CN116235111A - Photosensitive transfer material, manufacturing method of resin pattern, manufacturing method of circuit wiring, and manufacturing method of touch panel - Google Patents

Abstract

The present invention provides a photosensitive transfer material, a method for manufacturing a resin pattern using the photosensitive transfer material, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel, wherein the photosensitive transfer material comprises: a temporary support; and a photosensitive resin layer containing an alkali-soluble resin, an ethylenically unsaturated compound and a photopolymerization initiator, wherein the photosensitive resin layer is used for mJ/cm ² The width (W) of the double bond reaction region after exposure of the line and space pattern of 10 μm/10 μm in terms of exposure dose (Ep) per unit time was 3 hours ₃ ) Width of double bond reaction region (W) with passage of 24 hours ₂₄ ) Satisfy W ₂₄ /W ₃ ≤1.05。

Description

Photosensitive transfer material, method of manufacturing resin pattern, method of manufacturing circuit wiring And the manufacturing method of touch panel

technical field

The present invention relates to a photosensitive transfer material, a method for manufacturing a resin pattern, a method for manufacturing circuit wiring, and a method for manufacturing a touch panel.

Background technique

In a display device (such as an organic electroluminescent (EL) display device, a liquid crystal display device, etc.) equipped with a touch panel such as an electrostatic capacitive input device, the electrode pattern corresponding to the sensor of the visual recognition part is provided inside the touch panel, The conductive layer pattern of the peripheral wiring part and the wiring of the lead-out wiring part.

Generally, in the formation of a patterned layer, the number of steps for obtaining a desired pattern shape is small, so it is widely used to use a photosensitive transfer material to place on any substrate through a mask having a desired pattern. A method in which the upper layer of the photosensitive resin composition is exposed and then developed.

Moreover, the composition described in patent document 1 is known as a conventional photosensitive resin composition.

In Patent Document 1, a photosensitive resin composition is described, which is characterized in that it is stored after being exposed and cured so that the reaction rate of the ethylenically unsaturated compound contained as a photosensitive component in the exposed surface becomes 70%. In the dark, there was substantially no change in the reaction rate of the unsaturated compound throughout the plate, and the difference in the partial reaction rate between the exposed side and the non-exposed side remained at 20% or more after 24 hours.

Patent Document 1: Japanese Patent Laid-Open No. 2001-356493

Contents of the invention

The technical problem to be solved by the invention

In the process of forming wiring using a photosensitive transfer material, when exposing a photosensitive resin layer attached to a substrate having a conductive layer, in each photosensitive resin layer, the time from the completion of exposure to development is There is a difference in the elapsed time, and the difference may be several hours depending on the situation. In addition, the exposed photosensitive resin layer may not be developed immediately but left for a certain period of time, and in this case, the elapsed time from the completion of exposure will be further extended. The above-mentioned standing time after exposure tends to be longer because it takes time to convey from the unwinding portion of the roll to the core portion especially when the roll-to-roll process is performed.

An object to be solved by one embodiment of the present invention is to provide a photosensitive transfer material in which a change in the line width of a resin pattern is small with the lapse of a standing time after exposure.

Moreover, the problem to be solved by another embodiment of this invention is providing the manufacturing method of the resin pattern using the said photosensitive transfer material, the manufacturing method of a circuit wiring, and the manufacturing method of a touch panel.

Means for solving technical problems

Means for solving the above-mentioned problems include the following means.

<1> A photosensitive transfer material having: a temporary support; and a photosensitive resin layer comprising an alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator, wherein the photosensitive resin layer is used in mJ/ After exposing the line and space pattern of 10 μm/10 μm with the exposure amount Ep in cm ² , the double bond reaction area width W ₃ after 3 hours and the double bond reaction area width W ₂₄ after 24 hours satisfy W ₂₄ /W ₃ ≤1.05.

W ₃ and W ₂₄ are set as the width of the double bond reaction region obtained by secondary ion mass spectrometry after the exposed photosensitive transfer material is dyed with bromine,

The above Ep satisfies Ep=2×Eb,

The above-mentioned Eb is set to mean that after the above-mentioned photosensitive resin layer is pasted on the substrate, it is exposed through a high-pressure mercury lamp with an illuminance of 20 mW/cm ² through a 15-step wedge (stepwedge) at an exposure amount of 180 mJ/cm ² , and the development is given. After the layer thickness of the photosensitive resin layer ± 1% of the residual layer thickness order of the exposure amount.

<2> The photosensitive transfer material according to <1>, wherein,

After exposing the above-mentioned photosensitive resin layer with the above-mentioned exposure amount Ep in a line-and-space pattern of 10 μm/10 μm, the double-bond reaction region width W ₃ after 3 hours and the double-bond reaction region width W ₇₂ hours after 72 hours Satisfy W ₇₂ /W ₃ ≦1.10.

W ₇₂ is defined as the width of the double bond reaction region obtained by secondary ion mass spectrometry after bromine dyeing the exposed photosensitive transfer material.

<3> The photosensitive transfer material according to <1> or <2>, wherein,

The above-mentioned ethylenically unsaturated compound includes an ethylenically unsaturated compound having a bisphenol structure.

<4> The photosensitive transfer material according to any one of <1> to <3>, wherein,

The above-mentioned photopolymerization initiator includes a biimidazole compound and a benzophenone compound.

<5> The photosensitive transfer material according to any one of <1> to <4>, wherein,

The said photosensitive resin layer further contains a polymerization inhibitor.

<6> The photosensitive transfer material according to <5>, wherein

The polymerization inhibitor includes at least one compound selected from the group consisting of phenothiazine, phenoxazine, and compounds having a hindered phenol structure.

<7> The photosensitive transfer material according to <5> or <6>, wherein,

When content of the said photoinitiator in the said photosensitive resin layer is made into Rc, and content of the said polymerization inhibitor is made into Rd, the value of these mass ratio Rd/Rc is 0.02-0.1.

<8> The photosensitive transfer material according to <7>, wherein

The value of the above-mentioned mass ratio Rd/Rc is 0.03 or more and 0.05 or less.

<9> A method for producing a resin pattern, which sequentially includes: among the photosensitive transfer materials described in any one of <1> to <8>, one of the photosensitive transfer materials having a photosensitive resin layer relative to the temporary support. The step of bonding the outermost layer on the side to the substrate; the step of pattern-exposing the photosensitive resin layer; and the step of developing the exposed photosensitive resin layer to form a resin pattern.

<10> The method for producing a resin pattern according to <9>, wherein,

At least a part of the resin pattern includes a line and space pattern, and the total width of the line and space of at least one set of the line and space pattern is 20 μm or less.

<11> A method of manufacturing a circuit wiring, which sequentially includes: among the photosensitive transfer materials described in any one of <1> to <8>, which has a photosensitive resin layer on the temporary support. a step of laminating one outermost layer in contact with a substrate having a conductive layer; a step of pattern-exposing the above-mentioned photosensitive resin layer; a step of developing the exposed photosensitive resin layer to form a resin pattern; and A step of performing an etching process on the substrate in a region where the resin pattern is not arranged.

<12> A method for manufacturing a touch panel, comprising sequentially: making one of the photosensitive transfer materials described in any one of <1> to <8> that has a photosensitive resin layer on the temporary support The process of bonding the outermost layer on the side to the substrate with the conductive layer; the process of pattern-exposing the above-mentioned photosensitive resin layer; the process of developing the exposed photosensitive resin layer to form a resin pattern; and A step of performing an etching treatment on the substrate in a region where the resin pattern is not arranged.

Invention effect

According to one embodiment of the present invention, it is possible to provide a photosensitive transfer material in which a change in the line width of a resin pattern is small with the elapse of a standing time after exposure.

Moreover, according to another embodiment of this invention, the manufacturing method of the resin pattern using the said photosensitive transfer material, the manufacturing method of circuit wiring, and the manufacturing method of a touch panel can be provided.

Description of drawings

FIG. 1 is a schematic diagram illustrating an example of the structure of a photosensitive transfer material according to a first embodiment.

FIG. 2 is a schematic diagram illustrating an example of the structure of a photosensitive transfer material according to a second embodiment.

FIG. 3 is a schematic plan view showing pattern A. FIG.

FIG. 4 is a schematic plan view showing a pattern B. FIG.

Detailed ways

Hereinafter, the contents of the present invention will be described. In addition, although description is made with reference to drawings, a symbol may be abbreviate|omitted.

In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In addition, in this specification, "(meth)acrylic acid" means both or either of acrylic acid and methacrylic acid, and "(meth)acrylate" means both or either of acrylate and methacrylate. The term “(meth)acryloyl” means both or either of acryloyl and methacryloyl.

In addition, in this specification, regarding the amount of each component in a composition, when there exists a plurality of substances corresponding to each component in a composition, unless otherwise specified, it means the amount of the corresponding many in a composition. total amount of the substance.

In this specification, the term "process" not only refers to an independent process, but also includes in this term as long as the desired purpose of the process is achieved even if it cannot be clearly distinguished from other processes.

In the notation of a group (atomic group) in this specification, the notation of substitution and non-substitution includes a group having no substituent and a group having a substituent. For example, "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

Unless otherwise specified, "exposure" in this specification includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. In addition, as the light used for exposure, the bright line spectrum of a mercury lamp, the extreme ultraviolet rays represented by an excimer laser, the extreme ultraviolet rays (EUV light), X-rays, electron beams, etc. .

In addition, chemical structural formulas in this specification may also be described as abbreviated structural formulas in which hydrogen atoms are omitted.

In the present invention, "mass %" and "weight %" have the same meaning, and "mass part" and "weight part" have the same meaning.

Furthermore, in the present invention, a combination of two or more preferred forms is a more preferred form.

In addition, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in the present invention are molecular weights as follows: The gel permeation chromatography (GPC) analysis device of the column uses the solvent THF (tetrahydrofuran) and a differential refractometer for detection, and polystyrene is used as a standard substance for conversion.

In this specification, "total solid content" refers to the total mass of components excluding the solvent from the total composition of the composition. In addition, as mentioned above, "solid content" means the component after removing a solvent, For example, it may be a solid or a liquid at 25 degreeC.

(photosensitive transfer material)

The photosensitive transfer material related to the present invention has: a temporary support; and a photosensitive resin layer containing an alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator, and the photosensitive resin layer is used at mJ/cm ² After exposing the line and space pattern of 10μm/10μm with the exposure amount Ep as the unit, the double bond reaction area width W ₃ after 3 hours and the double bond reaction area width W ₂₄ after 24 hours satisfy W ₂₄ /W ₃ ≤1.05 .

W ₃ and W ₂₄ are set as the width of the double bond reaction region obtained by secondary ion mass spectrometry after the exposed photosensitive transfer material is dyed with bromine,

The above Ep satisfies Ep=2×Eb,

The above-mentioned Eb is set to mean that after the above-mentioned photosensitive resin layer is pasted on the substrate, it is exposed through a high-pressure mercury lamp with an illuminance of 20 mW/cm ² through a 15-step stepped wedge at an exposure amount of 180 mJ/cm ² , and the photosensitive resin layer after development is given. The exposure amount of the layer thickness of the permanent resin layer ± 1% of the order of the residual layer thickness.

As a result of detailed studies by the present inventors, the present inventors found that in a photosensitive transfer material having a conventional negative-type photosensitive resin layer formed of the photosensitive resin composition described in Patent Document 1, There is a problem that the line width of the resin pattern changes greatly with the elapse of the standing time after exposure.

In the photosensitive transfer material involved in the present invention, after exposing the photosensitive resin layer to a line and space pattern of 10 μm/10 μm with an exposure dose Ep in mJ/cm ² , the double bond reaction after 3 hours The region width W ₃ and the double bond reaction region width W ₂₄ after 24 hours satisfy W ₂₄ /W ₃ ≤ 1.05, and the photosensitive resin layer with a small time change in the double bond reaction region width is at the end of the exposed region The reaction in the half-exposed portion is sufficiently suppressed, and the difference between the degree of polymerization in the exposed region and the degree of polymerization in the unexposed region becomes large. Therefore, it is estimated as follows: Even if there is a slight change in developing conditions such as the standing time after exposure, the dissolution during development of the region where the polymerization reaction has sufficiently progressed is suppressed, and the line width of the resin pattern changes with the passing of the standing time after exposure ( Also known as "Placement Time Line Width Variation".) Small.

In the photosensitive transfer material according to the present invention, after exposing the above-mentioned photosensitive resin layer to a line and space pattern of 10 μm/10 μm at an exposure amount Ep in units of mJ/cm ² , the double bond reaction area after 3 hours The width W ₃ and the width W ₂₄ of the double bond reaction region after 24 hours satisfy W ₂₄ /W ₃ ≤ 1.05.

W ₃ and W ₂₄ are set as the width of the double bond reaction region obtained by secondary ion mass spectrometry after the exposed photosensitive transfer material is dyed with bromine,

The above Ep satisfies Ep=2×Eb,

The above-mentioned Eb is set to mean that after the above-mentioned photosensitive resin layer is pasted on the substrate, it is exposed through a high-pressure mercury lamp with an illuminance of 20 mW/cm ² through a 15-step stepped wedge at an exposure amount of 180 mJ/cm ² , and the photosensitive resin layer after development is given. The exposure amount of the layer thickness of the permanent resin layer ± 1% of the order of the residual layer thickness.

The photosensitive transfer material according to the present invention preferably satisfies W ₂₄ /W ₃ ≤1.04, more preferably satisfying W ₂₄ /W ₃ ≤1.03, especially preferably satisfying 1.00≤W ₂₄ /W ₃ ≤1.03.

In addition, in the photosensitive transfer material according to the present invention, from the standpoint of the change in the line width of the standing time and the change in the line width of the developing temperature, the above-mentioned photosensitive resin layer is treated with the above-mentioned exposure amount Ep at a line-and-space ratio of 10 μm/10 μm. After the pattern is exposed, the width W ₃ of the double bond reaction region after 3 hours and the width W ₇₂ of the double bond reaction region after 72 hours preferably satisfy W ₇₂ /W ₃ ≤ 1.15, more preferably satisfy W ₇₂ /W ₃ ≤ 1.10 , especially preferably satisfying 1.00≦W ₇₂ /W ₃ ≦1.10.

In addition, _W72 is made into the width|variety of the double bond reaction region obtained by the secondary ion mass spectrometry method after bromine dyeing the exposed photosensitive transfer material.

The measurement method of Eb and the calculation method of Ep in this invention are shown below.

The photosensitive transfer material was laminated on a substrate (a substrate in which a 200 nm-thick copper layer was formed on a 100 μm polyethylene terephthalate (PET) film by sputtering) using a sheet laminator. The lamination conditions were set at a roll temperature of 100° C., a lamination speed of 2 m/min, and a lamination pressure of 0.5 MPa.

A 15-step wedge (manufactured by Fujifilm Corporation) was arranged on the temporary support of the laminated photosensitive transfer material, and exposure was performed at 180 mJ/cm ² by a high-pressure mercury lamp of 20 mW/cm ² . After the exposure, the support was peeled off, developed for 30 seconds by using a 0.9% by mass sodium carbonate aqueous solution at 25° C., and Eb was calculated from the remaining film thickness in each step (meaning that after the above-mentioned photosensitive resin layer was attached to the substrate, it was separated by 15 The stepped wedge was exposed by a high-pressure mercury lamp with an illuminance of 20 mW/cm ² at an exposure dose of 180 mJ/cm ² , to give the photosensitive resin layer after development a layer thickness ± 1% of the remaining layer thickness in steps of exposure).

And, from the obtained Eb (mJ/cm ² ), Ep (mJ/cm ² ) was calculated by the following formula.

Ep=2×Eb

The method for measuring the double bond reaction region widths W ₃ , W ₂₄ and W ₇₂ obtained by secondary ion mass spectrometry after bromine dyeing the exposed photosensitive transfer material in the present invention is shown below.

The photosensitive transfer material was laminated on a substrate (a substrate in which a 200 nm-thick copper layer was formed on a 100 μm PET film by sputtering) using a sheet laminator. The lamination conditions were set at a roll temperature of 100° C., a lamination speed of 2 m/min, and a lamination pressure of 0.5 MPa.

A photomask of line and space=10 μm/10 μm was brought into contact with the temporary support, and the photosensitive transfer material laminated on the above substrate was exposed at Ep=2×Eb (mJ/cm ² ). After exposure, after 3 hours, 24 hours or 72 hours, use adhesive tape to peel off the temporary support body, thermoplastic resin layer and intermediate layer, take 5mL bromine water (0.2%) in a 50mL container, and use Method Fix the sample in the container and let it stand at room temperature (25°C) for 5 minutes. Thereafter, it was stored under high vacuum for half a day to degas residual bromine. In this way, a sample in which the carbon-carbon double bond portion was modified with bromine was prepared.

The sample was analyzed by secondary ion mass spectrometry (ION-TOF SIMS5, primary ion source: Bi ³⁺ (30kV), measurement range: 50mm, surface resolution: 512×512pixel, integration: 32 times, measurement mode: High spatial resolution mode (Fast Imaging: fast imaging), charging correction: using an electron gun), and the width of the C ₂ HBr ^-domain was evaluated. The width of the portion with low C ₂ HBr ^- intensity at three points was measured, and the average value of the measured values at the three points was obtained as the region width W ₃ , W ₂₄ or W ₇₂ at which polymerization proceeded.

The value of Eb in the photosensitive transfer material according to the present invention is preferably 20 mJ/cm ² to 200 mJ/cm ² , more preferably 30 mJ, from the viewpoint of line width change with standing time, line width change at developing temperature, and sensitivity. /cm ² to 150mJ/cm ² , more preferably 35mJ/cm ² to 100mJ/cm ² , especially preferably 35mJ/cm ² to 70mJ/cm ² .

In addition, from the standpoint of line width change with standing time, line width change at developing temperature, and sensitivity, the value of _W3 in the photosensitive transfer material according to the present invention is preferably 9.0 μm to 10.5 μm, more preferably 9.2 μm to 10.5 μm. 10.3 μm, especially preferably 9.5 μm to 10.2 μm.

The value of _W24 in the photosensitive transfer material according to the present invention is preferably from 9.0 μm to 11.0 μm, more preferably from 9.3 μm to 10.7 μm, from the standpoint of line width change with standing time, line width change at developing temperature, and sensitivity , especially preferably 9.5 μm to 10.5 μm.

The value of W ₇₂ in the photosensitive transfer material according to the present invention is preferably from 9.0 μm to 12.0 μm, more preferably from 9.5 μm to 11.5 μm, from the standpoint of line width change with standing time, line width change at developing temperature, and sensitivity , particularly preferably 9.7 μm to 11.0 μm.

The photosensitive transfer material which concerns on this invention has a temporary support body, and the photosensitive resin layer containing an alkali-soluble resin, an ethylenic unsaturated compound, and a photoinitiator.

In a photosensitive transfer material, a temporary support body and a photosensitive resin layer may be laminated|stacked directly without interposing another layer, and may be laminated|stacked via another layer. In addition, another layer may be laminated on the surface of the photosensitive resin layer opposite to the surface facing the temporary support.

As another layer other than a temporary support body and a photosensitive resin layer, a thermoplastic resin layer, an intermediate|middle layer, and a protective film are mentioned, for example.

Although an example of the form of the photosensitive transfer material which concerns on this invention is shown below, it is not limited to this.

(1) "Temporary support/photosensitive resin layer/refractive index adjustment layer/protective film"

(2) "Temporary support/photosensitive resin layer/protective film"

(3) "Temporary support body/intermediate layer/photosensitive resin layer/protective film"

(4) "Temporary support/thermoplastic resin layer/intermediate layer/photosensitive resin layer/protective film"

In addition, in each of the above structures, the photosensitive resin layer is preferably a negative photosensitive resin layer. In addition, the photosensitive resin layer is preferably a colored resin layer. As will be described later, the photosensitive transfer material according to the present invention can be used as a photosensitive transfer material for wiring protective films, or as a photosensitive transfer material for etching resists.

When it is set as the photosensitive transfer material for wiring protection films, as a structure of a photosensitive transfer material, for example, the structure of said (1) or (2) is preferable.

Moreover, when it is set as the photosensitive transfer material for etching resists, as a structure of a photosensitive transfer material, it is preferable to be the structure of (2)-(4) mentioned above, for example.

In the photosensitive transfer material, in the case where the side of the photosensitive resin layer opposite to the side of the temporary support also has a structure of another layer, the side of the photosensitive resin layer opposite to the side of the temporary support is arranged The total thickness of the other layers is preferably 0.1% to 30%, more preferably 0.1% to 20%, with respect to the layer thickness of the photosensitive resin layer.

Hereinafter, an example of a specific embodiment will be given and the photosensitive transfer material according to the present invention will be described. In addition, the photosensitive transfer material of the first embodiment below has a structure that can be preferably used for the photosensitive transfer material for etching resist, and the photosensitive transfer material of the second embodiment below is preferably used for the composition. Structure of photosensitive transfer material for line protection film.

[[Photosensitive Transfer Material of First Embodiment]]

Hereinafter, an example is given and the photosensitive transfer material of 1st Embodiment is demonstrated.

The photosensitive transfer material 20 shown in FIG. 1 has the temporary support body 11, the transfer layer 12 which consists of the thermoplastic resin layer 13, the intermediate|middle layer 15, and the photosensitive resin layer 17, and the protective film 19 in this order.

In addition, although the photosensitive transfer material 320 shown in FIG. 1 is the form which arrange|positioned the protective film 19, the protective film 19 may not be arrange|positioned.

Moreover, although the photosensitive transfer material 20 shown in FIG. 1 is the form which arrange|positioned the thermoplastic resin layer 13 and the intermediate layer 15, the thermoplastic resin layer 13 and the intermediate layer 15 may not be arrange|positioned.

Hereinafter, each requirement which comprises the photosensitive transfer material of 1st Embodiment is demonstrated.

〔Temporary support body〕

The photosensitive transfer material used in this invention has a temporary support body.

The temporary support body supports the photosensitive resin layer or the laminated body containing the photosensitive resin layer, and is a peelable support body.

It is preferable that a temporary support body has translucency from a viewpoint which can perform exposure of the photosensitive resin layer via a temporary support body at the time of pattern exposure to a photosensitive resin layer. In addition, in this specification, "having translucency" means that the transmittance of the light of the wavelength used for pattern exposure is 50 % or more.

From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the temporary support has a transmittance of light of a wavelength (more preferably a wavelength of 365 nm) used for pattern exposure of preferably 60% or more, more preferably 70% or more.

In addition, the so-called transmittance of the layer included in the photosensitive transfer material is the intensity of the emitted light emitted through the layer relative to the incident light when light is incident in a direction (thickness direction) perpendicular to the main surface of the layer. The intensity ratio was measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.

As a material which comprises a temporary support body, a glass substrate, a resin film, and paper are mentioned, for example, A resin film is preferable from a viewpoint of strength, flexibility, and translucency.

Examples of the resin film include a polyethylene terephthalate (PET:polyethylene terephthalate) film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, a PET film is preferable, and a biaxially stretched PET film is more preferable.

The thickness (layer thickness) of the temporary support is not particularly limited, and it can be obtained from the strength of the support, the flexibility required for bonding with the circuit wiring forming substrate, and the transparency required in the initial exposure process. From the point of view of light, it can be selected according to the material.

The thickness of the temporary support is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 50 μm, still more preferably in the range of 10 μm to 20 μm, and especially preferably in the range of 10 μm to 16 μm from the viewpoint of ease of handling and versatility .

In addition, the thickness of the temporary support is preferably 50 μm or less, more preferably 25 μm or less, from the viewpoint of resolution and linearity during exposure through the support.

Also, it is preferable that there are no deformations such as wrinkles, scratches, defects, etc. in the film used as the temporary support.

From the viewpoint of the pattern formation property and the transparency of the temporary support during pattern exposure through the temporary support, it is preferable that the number of fine particles, foreign matter, defects, precipitates, etc. contained in the temporary support is small. The number of fine particles, foreign substances, and defects with a diameter of 1 μm or more is preferably 50 particles/10 mm ² or less, more preferably 10 particles/10 mm ² or less, still more preferably 3 particles/10 mm ² or less, and especially preferably 0 particles/10 mm ² .

As a preferred form of the temporary support, for example, in paragraphs 0017 to 0018 of Japanese Patent Application Publication No. 2014-85643, paragraphs 0019 to 0026 of Japanese Patent Application Publication No. 2016-27363, and paragraphs 0041 to 0041 of International Publication No. 2012/081680 Paragraph 0057, paragraphs 0029 to 0040 of International Publication No. 2018/179370, and paragraphs 0012 to 0032 of Japanese Patent Application Laid-Open No. 2019-101405 are described, and the contents of these publications are incorporated in this specification.

〔Photosensitive resin layer〕

The photosensitive transfer material concerning this invention has a photosensitive resin layer.

The photosensitive resin layer is preferably a negative-type photosensitive resin layer in which the solubility of the exposed portion to the developing solution decreases by exposure and the non-exposed portion is removed by development.

The photosensitive resin layer contains an alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator, and preferably contains an alkali-soluble resin, an ethylenically unsaturated compound, The biimidazole compound and the benzophenone compound more preferably contain an alkali-soluble resin, an ethylenically unsaturated compound, a hexaarylbiimidazole compound, and a benzophenone compound.

In addition, it is preferable that the photosensitive resin layer further contains a polymerization inhibitor from the standpoint of line width changes in standing time, development temperature line width changes, and sensitivity.

The photosensitive resin layer preferably contains an alkali-soluble resin: 10% by mass to 90% by mass; an ethylenic unsaturated compound: 5% by mass to 70% by mass; and a photopolymerization initiator: 0.01 % by mass to 20% by mass.

Hereinafter, each component is demonstrated sequentially.

<Alkali-soluble resin>

The photosensitive resin layer contains alkali-soluble resin.

In addition, in this specification, "alkali solubility" means that the solubility in 100 g of 1 mass % aqueous solutions of sodium carbonate is 0.1 g or more at 22 degreeC.

Although it does not specifically limit as alkali-soluble resin, For example, the well-known alkali-soluble resin used for an etching resist is mentioned preferably.

Also, the alkali-soluble resin is preferably a binder polymer.

As the alkali-soluble resin, an alkali-soluble resin having an acidic group is preferable.

Among them, the polymer A described later is preferable as the alkali-soluble resin.

-Polymer A-

As the alkali-soluble resin, polymer A is preferably included.

The acid value of the polymer A is preferably 220 mgKOH/g or less, more preferably less than 200 mgKOH/g, and still more preferably less than 190 mgKOH/g, from the viewpoint of better resolution by suppressing swelling of the photosensitive resin layer caused by the developer.

The lower limit of the acid value of the polymer A is not particularly limited, but from the viewpoint of better developability, it is preferably 60 mgKOH/g or more, more preferably 120 mgKOH/g or more, still more preferably 150 mgKOH/g or more, and especially preferably It is more than 170 mgKOH/g.

In addition, the acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of the sample,

In this specification, the unit is described as mgKOH/g. The acid value can be calculated, for example, from the average content of acid groups in the compound.

The acid value of the polymer A may be adjusted according to the type of structural unit constituting the polymer A and the content of the acid group-containing structural unit.

The weight average molecular weight of polymer A is preferably 5,000 to 500,000. It is preferable to make weight average molecular weight into 500,000 or less from a viewpoint of improvement of resolution and developability. The weight average molecular weight is more preferably 100,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, it is preferable to set the weight average molecular weight to 5,000 or more from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film such as edge melting and chipping properties when forming a photosensitive resin laminate. The weight average molecular weight is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more. The edge melting property refers to the ease with which the photosensitive resin layer protrudes from the end surface of the roll when the photosensitive transfer material is wound up into a roll. The chipping property refers to the degree of ease of shavings flying when the unexposed film is cut with a knife. If this swarf adheres to the upper surface of the photosensitive resin laminate, etc., it will be transferred to the mask in the subsequent exposure process etc., and will become a cause of defective products. The degree of dispersion of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, and especially preferably 1.0 to 3.0. In the present invention, the molecular weight is a value measured using gel permeation chromatography. Also, the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).

It is preferable that the photosensitive resin layer contains a monomer component containing an aromatic hydrocarbon as the polymer A from the viewpoint of suppressing thickening of the line width and deterioration of the resolution when the focal position shifts during exposure. In addition, examples of such aromatic hydrocarbons include substituted or unsubstituted phenyl groups and substituted or unsubstituted aralkyl groups. The content ratio of the aromatic hydrocarbon-containing monomer component in the polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more, based on the total mass of the total monomer components. , especially preferably at least 45% by mass, and most preferably at least 50% by mass. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 85% by mass or less. In addition, when a plurality of polymers A are contained, the content ratio of the monomer component having an aromatic hydrocarbon was obtained as a weight average value.

Examples of monomers having aromatic hydrocarbons include monomers having aralkyl groups, styrene, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene , Acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among them, monomers having an aralkyl group or styrene are preferable. In one aspect, when the monomer component having an aromatic hydrocarbon in the polymer A is styrene, the content ratio of the styrene monomer component is preferably 20% by mass based on the total mass of the total monomer components. % to 50 mass%, more preferably 25 mass% to 45 mass%, further preferably 30 mass% to 40 mass%, especially preferably 30 mass% to 35 mass%.

Examples of the aralkyl group include substituted or unsubstituted phenylalkyl groups (excluding benzyl), substituted or unsubstituted benzyl groups, etc., preferably substituted or unsubstituted benzyl groups.

Examples of the monomer having a phenylalkyl group include phenylethyl (meth)acrylate and the like.

As a monomer having a benzyl group, (meth)acrylates having a benzyl group, for example, benzyl (meth)acrylate, chlorobenzyl (meth)acrylate, etc.; vinyl monomers having a benzyl group , for example, vinylbenzyl chloride, vinylbenzyl alcohol and the like. Among them, benzyl (meth)acrylate is preferable. In one embodiment, when the monomer component having an aromatic hydrocarbon in the polymer A is benzyl (meth)acrylate, the content ratio of the benzyl (meth)acrylate monomer component is calculated as the total of the total monomer components Based on mass, it is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, still more preferably 70% by mass to 90% by mass, particularly preferably 75% by mass to 90% by mass.

The polymer A containing a monomer component having an aromatic hydrocarbon is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon with at least one of the first monomers described below and/or at least one of the second monomers described below. And get.

Polymer A that does not contain a monomer component having an aromatic hydrocarbon is preferably obtained by polymerizing at least one of the first monomers described later, more preferably by combining at least one of the first monomers with a second monomer described later. It is obtained by copolymerizing at least one of dimonomers.

The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid half ester, and the like. Among these, (meth)acrylic acid is preferable.

The content ratio of the first monomer in the polymer A is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and even more preferably 15% by mass, based on the total mass of the total monomer components. % by mass to 30% by mass.

The copolymerization ratio of the first monomer is preferably 10% by mass to 50% by mass based on the total mass of the total monomer components. From the viewpoint of developing good developability and controlling edge melting properties, the copolymerization ratio is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. From the viewpoint of the high resolution of the resist pattern and the bead shape, and further from the viewpoint of the chemical resistance of the resist pattern, it is preferable to set the above-mentioned copolymerization ratio to 50% by mass or less, and more preferably 35% by mass in these viewpoints. Mass % or less, More preferably, it is 30 mass % or less, Especially preferably, it is 27 mass % or less.

The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylic acid n-butyl, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ring (meth)acrylate (meth)acrylates such as hexyl ester and 2-ethylhexyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile. Among these, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-butyl (meth)acrylate are preferable, and methyl (meth)acrylate is especially preferable.

The content ratio of the second monomer in the polymer A is preferably 5% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and even more preferably 20% by mass, based on the total mass of the total monomer components. % by mass to 45% by mass.

From the viewpoint of suppressing thickening of the line width and deterioration of resolution during exposure when the focal position shifts, it is preferable to contain an aralkyl-containing monomer and/or styrene as a monomer. For example, a copolymer containing methacrylic acid, benzyl methacrylate, and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene, and the like are preferable.

In one embodiment, the polymer A preferably contains 25% by mass to 40% by mass of the aromatic hydrocarbon-containing monomer component, 20% to 35% by mass of the first monomer component, and 30% to 45% by mass of the second monomer component. Polymers of two monomer components. Furthermore, in another aspect, it is preferable that it is a polymer containing 70 mass % - 90 mass % of monomer components containing an aromatic hydrocarbon, and 10 mass % - 25 mass % of a 1st monomer component.

The polymer A can be used individually by 1 type, or can also mix and use 2 or more types. When using two or more types in combination, it is preferable to mix and use two types of polymers A containing monomer components containing aromatic hydrocarbons, or to mix and use polymer A containing monomer components containing aromatic hydrocarbons and polymer A not containing aromatic hydrocarbons. Polymer A of the monomer component. In the latter case, the use ratio of the polymer A containing a monomer component having an aromatic hydrocarbon is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass, based on the entire polymer A. or more, especially preferably 90% by mass or more.

Polymer A may have a branched structure or an alicyclic structure in a side chain. In addition, the polymer A may have a linear structure in a side chain. For example, by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, a branched structure or an alicyclic structure can be introduced into the polymer (A) in the side chain. A group having an alicyclic structure may be monocyclic or polycyclic.

As a monomer containing a group having a branched structure in a side chain, for example, isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, (meth)acrylate, base) tert-butyl acrylate, isoamyl (meth)acrylate, tert-amyl (meth)acrylate, sec-pentyl (meth)acrylate, 2-octyl (meth)acrylate, 3-(meth)acrylate - Octyl and tert-octyl (meth)acrylate. Among the above, isopropyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate are preferred, isopropyl (meth)acrylate or tert-butyl (meth)acrylate are more preferred ester.

Specific examples of the monomer containing a group having an alicyclic structure in the side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group. Furthermore, (meth)acrylate which has an alicyclic hydrocarbon group with 5-20 carbon atoms is mentioned. As a monomer containing a group having an alicyclic structure in the side chain, for example, (meth)acrylate (bicyclo[2.2.1]heptyl-2)ester, (meth)acrylate-1-adamantane base ester, (meth)acrylate-2-adamantyl ester, (meth)acrylate-3-methyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-1- Adamantyl ester, (meth)acrylate-3-ethyladamantyl ester, (meth)acrylate-3-methyl-5-ethyl-1-adamantyl ester, (meth)acrylate-3 , 5,8-triethyl-1-adamantyl ester, (meth)acrylate-3,5-dimethyl-8-ethyl-1-adamantyl ester, (meth)acrylate 2-methyl Base-2-adamantyl ester, (meth)acrylate 2-ethyl-2-adamantyl ester, (meth)acrylate 3-hydroxyl-1-adamantyl ester, (meth)acrylate octahydro- 4,7-methanoindene (methanoindene)-5-yl ester, (meth)acrylic acid octahydro-4,7-methanoindene-1-yl methyl ester, (meth)acrylate-1-menthyl ester, ( Meth)acrylic acid tricyclodecane, (meth)acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl ester, (meth)acrylic acid-3,7,7- Trimethyl-4-hydroxy-bicyclo[4.1.0]heptyl ester, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fecundyl (meth)acrylate, (meth) ) 2,2,5-trimethylcyclohexyl acrylate and cyclohexyl (meth)acrylate. Among the above, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (meth)acrylate, Base) 2-adamantyl acrylate, fenzyl (meth)acrylate, 1-menthyl (meth)acrylate and tricyclodecane (meth)acrylate, more preferably cyclohexyl (meth)acrylate , (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 2-adamantyl (meth)acrylate, and tricyclodecane (meth)acrylate.

The synthesis of polymer A is preferably carried out as follows: Add an appropriate amount of benzene peroxide free radical polymerization initiators such as formyl and azoisobutyronitrile, and heated and stirred. Synthesis may also be performed while dropping a part of the mixture into the reaction liquid. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can be used.

The glass transition temperature Tg of the polymer A is preferably 30°C or higher and 135°C or lower. By using the polymer A having a Tg of 135° C. or less for the photosensitive resin layer, it is possible to suppress the line width from becoming thick and the deterioration of the resolution when the focus position shifts during exposure. From this viewpoint, the Tg of the polymer A is more preferably 130°C or lower, further preferably 120°C or lower, and particularly preferably 110°C or lower. Furthermore, it is preferable to use the polymer A which has Tg of 30 degreeC or more from a viewpoint of edge melting resistance improvement. From this viewpoint, the Tg of the polymer A is more preferably 40°C or higher, still more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

The photosensitive resin layer may contain resins other than alkali-soluble resin.

Examples of resins other than alkali-soluble resins include acrylic resins, styrene-acrylic acid copolymers (where the styrene content is 40% by mass or less), polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide Resin, polyester resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, polyimide resin, polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine and polyalkylene glycols.

Alkali-soluble resin can be used individually by 1 type, or may mix and use 2 or more types.

The ratio of the alkali-soluble resin to the total mass of the photosensitive resin layer is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, still more preferably 40% by mass to 60% by mass. From the viewpoint of controlling the development time, it is preferable to set the ratio of the alkali-soluble resin to the photosensitive resin layer to be 90% by mass or less. On the other hand, from the viewpoint of improving edge melting resistance, it is preferable to set the ratio of the alkali-soluble resin to the photosensitive resin layer to be 10% by mass or more.

(Ethylenically Unsaturated Compounds)

The photosensitive resin layer contains an ethylenic unsaturated compound.

In this specification, an "ethylenically unsaturated compound" refers to a compound that is polymerized by the action of a photopolymerization initiator described later, and is a compound different from the above-mentioned alkali-soluble resin.

As an ethylenic unsaturated compound, an ethylenic unsaturated compound is preferable.

An ethylenic unsaturated compound is a component which contributes to the photosensitivity (namely, photocurability) of a negative photosensitive resin layer, and the intensity|strength of a cured film.

Furthermore, an ethylenically unsaturated compound is a compound which has one or more ethylenically unsaturated groups.

The photosensitive resin layer preferably contains a difunctional or higher ethylenically unsaturated compound as the ethylenically unsaturated compound.

Here, the difunctional or more ethylenically unsaturated compound refers to a compound having two or more ethylenically unsaturated groups in one molecule.

As an ethylenic unsaturated group, a (meth)acryloyl group is more preferable.

As an ethylenic unsaturated compound, a (meth)acrylate compound is preferable.

Furthermore, the ethylenically unsaturated compound preferably includes an ethylenically unsaturated compound having a bisphenol structure from the standpoint of a change in line width with standing time, a change in line width at developing temperature, and sensitivity.

As an ethylenic unsaturated compound which has a bisphenol structure, the ethylenic unsaturated compound B1 which has a bisphenol structure mentioned later can be illustrated preferably.

The photosensitive resin layer preferably contains an ethylenically unsaturated compound having a polymerizable group.

The polymerizable group possessed by the ethylenically unsaturated compound is not particularly limited as long as it is a group that participates in a polymerization reaction, for example, vinyl, acryloyl, methacryloyl, styryl, maleic Groups having an ethylenically unsaturated group, such as an imide group; and groups having a cationic polymerizable group, such as an epoxy group and an oxetanyl group.

As the polymerizable group, a group having an ethylenically unsaturated group is preferable, and an acryloyl group or a methacryloyl group is more preferable.

As the ethylenically unsaturated compound, a compound (polyfunctional ethylenically unsaturated compound) containing two or more ethylenically unsaturated groups in one molecule is preferable from the viewpoint of better photosensitivity of the photosensitive resin layer. .

In addition, from the viewpoint of better resolution and peelability, the number of ethylenically unsaturated groups in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less, even more preferably 2 or less.

From the standpoint of a better balance of photosensitivity, resolution, and releasability of the photosensitive resin layer, the photosensitive resin layer preferably contains a bifunctional or trifunctional compound having 2 or 3 ethylenically unsaturated groups in one molecule. The functional ethylenically unsaturated compound more preferably contains a bifunctional ethylenically unsaturated compound having two ethylenically unsaturated groups in one molecule.

From the viewpoint of excellent releasability, the content of the bifunctional ethylenically unsaturated compound in the photosensitive resin layer is preferably 60% by mass or more, more preferably more than 70% by mass, and even more preferably More than 90% by mass. There is no particular limitation on the upper limit, and it may be 100% by mass. That is, all the ethylenically unsaturated compounds contained in the photosensitive resin layer may be bifunctional ethylenically unsaturated compounds.

Moreover, as an ethylenic unsaturated compound, the (meth)acrylate compound which has a (meth)acryloyl group as a polymeric group is preferable.

-Ethylenically unsaturated compound B1-

The photosensitive resin layer preferably contains an ethylenically unsaturated compound having an aromatic ring and two ethylenically unsaturated groups. The ethylenically unsaturated compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned ethylenically unsaturated compounds.

From the viewpoint of better resolution, the mass ratio of the content of the ethylenically unsaturated compound B1 to the content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 40% by mass or more, more preferably 50% by mass or more, and furthermore Preferably it is 55 mass % or more, Especially preferably, it is 60 mass % or more. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, particularly preferably 85% by mass or less, from the viewpoint of releasability.

Examples of the aromatic ring possessed by the ethylenically unsaturated compound include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings, thiophene rings, furan rings, pyrrole rings, imidazole rings, triazole rings, and pyridine rings. Aromatic heterocycles and their condensed rings are preferably aromatic hydrocarbon rings, more preferably benzene rings. In addition, the above-mentioned aromatic ring may have a substituent.

The ethylenically unsaturated compound P may have only one aromatic ring, or may have two or more aromatic rings.

From the viewpoint of improving resolution by suppressing swelling of the photosensitive resin layer due to a developer, the ethylenically unsaturated compound 10 preferably has a bisphenol structure.

As the bisphenol structure, for example, bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol A structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)propane), hydroxyphenyl)methane) and bisphenol B structures derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane), preferably bisphenol A structures.

Examples of the ethylenically unsaturated compound having a bisphenol structure include those having a bisphenol structure and two polymerizable groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. compound.

Both ends of the bisphenol structure and two polymerizable groups may be directly bonded, or may be bonded via one or more alkyleneoxy groups. As the alkyleneoxy group added to both ends of the bisphenol structure, an ethyleneoxy group or a propyleneoxy group is preferable, and an ethyleneoxy group is more preferable. The number of alkyleneoxy groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16 per molecule, more preferably 6 to 14.

The ethylenically unsaturated compound having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162, and the content described in the publication is incorporated in this specification.

As the ethylenically unsaturated compound, preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, more preferably 2,2-bis(4-((meth)acryloyloxypolyalkoxy)phenyl) propane.

Examples of 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane include 2,2-bis(4-(methacryloxydiethyl) oxy)phenyl)propane (FA-324M, manufactured by Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxyethoxypropoxy)phenyl)propane, 2 , 2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane (BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methyl 2,2-bis(4-(methacryloyloxydecamethacryloyloxytetrapropoxy)phenyl)propane (FA-3200MY, manufactured by Hitachi Chemical Co., Ltd. Pentaethoxy)phenyl)propane (BPE-1300, manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.) and ethoxylated (10) bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.).

The ethylenically unsaturated compound 10 preferably includes a compound represented by the following formula (Bis) from the standpoint of line width change over time, development temperature line width change, and sensitivity.

[chemical formula 1]

In formula (Bis), R ₁ and R ₂ independently represent a hydrogen atom or a methyl group, A is C ₂ H ₄ , B is C ₃ H ₆ , n ₁ and n ₃ are independently an integer of 1 to 39, and n ₁ +n ₃ is an integer of 2 to 40, n ₂ and n ₄ are each independently an integer of 0 to 29 and n ₂ +n ₄ is an integer of 0 to 30, -(AO)- and -(BO)- The arrangement of repeating units can be random or block. In addition, in the case of a block, either -(AO)- or -(BO)- may be on the side of the bisphenol structure.

In one embodiment, n ₁ +n ₂ +n ₃ +n ₄ is preferably an integer of 2-20, more preferably an integer of 2-16, and still more preferably an integer of 4-12. In addition, n ₂ +n ₄ is preferably an integer of 0-10, more preferably an integer of 0-4, still more preferably an integer of 0-2, especially preferably 0.

The ethylenic unsaturated compound B1 may be used individually by 1 type, and may use 2 or more types together.

From the viewpoint of further excellent resolution, the content of the ethylenically unsaturated compound B1 in the photosensitive resin layer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but from the viewpoint of transferability and edge melting (a phenomenon in which components in the photosensitive resin layer bleed out from the end of the photosensitive transfer material), it is preferably 70% by mass or less, more preferably Preferably it is 60 mass % or less.

The photosensitive resin layer may contain ethylenically unsaturated compounds other than the above-mentioned ethylenically unsaturated compounds.

The ethylenically unsaturated compound other than the ethylenically unsaturated compound F is not particularly limited, and can be appropriately selected from known compounds. Examples include compounds having one ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compound), bifunctional ethylenically unsaturated compounds not having an aromatic ring, and trifunctional or more functional ethylenically unsaturated compounds. unsaturated compounds.

Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethylsuccinate, polyethylene Glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate.

As bifunctional ethylenically unsaturated compounds not having an aromatic ring, for example, alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane Di(meth)acrylate and trimethylolpropane diacrylate.

Examples of the alkylene glycol di(meth)acrylate include tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), Methanol dimethacrylate (DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1 , 6-hexanediol diacrylate (A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl Diol di(meth)acrylate.

Examples of polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate. )Acrylate.

As the urethane di(meth)acrylate, for example, propylene oxide modified urethane di(meth)acrylate, ethylene oxide and propylene oxide modified urethane di(meth)acrylate, (meth)acrylates. As commercially available items, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.) and UA-1100H (manufactured by Shin-Nakamura Chemical Co. ., Ltd.).

Examples of ethylenically unsaturated compounds having three or more functions include dipentaerythritol (tri/tetra/penta/hexa)(meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, trimethylol propane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanurate tri(meth)acrylate, Glycerol tri(meth)acrylates and their alkylene oxide modifications.

Here, "(three/four/five/six) (meth)acrylates" include tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates and hexa(meth)acrylates. ) acrylate concept, "(three/tetra) (meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate. In one aspect, the photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound 10 and a trifunctional or more functional ethylenically unsaturated compound, more preferably contains the above-mentioned ethylenically unsaturated compound 11 and two or more kinds of trifunctional or more functional ethylenically unsaturated compounds. In this case, the mass ratio of the ethylenically unsaturated compound B1 to the ethylenically unsaturated compound having a trifunctional or higher function is preferably (the total mass of the ethylenically unsaturated compound B1 ): (the mass ratio of the ethylenically unsaturated compound having a trifunctional or higher function total mass)=1:1 to 5:1, more preferably 1.2:1 to 4:1, still more preferably 1.5:1 to 3:1.

Furthermore, in one aspect, the photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound and two or more kinds of trifunctional ethylenically unsaturated compounds.

Examples of alkylene oxide modified products of trifunctional or higher ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd. , Shin-Nakamura Chemical Co., Ltd. A-9300-1CL, etc.), alkylene oxide modified (meth)acrylate compounds (Nippon Kayaku Co., Ltd. KAYARAD RP-1040, Shin-Nakamura Chemical Co. ., Ltd. ATM-35E and A-9300, DAICEL-ALLNEX LTD. EBECRYL (registered trademark) 135, etc.), ethoxylated glycerin triacrylate (Shin-Nakamura Chemical Co., Ltd. A-GLY -9E, etc.), ARONIX (registered trademark) T0-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX M-520 (manufactured by TOAGOSEI CO., LTD.), and ARONIX M-510 (manufactured by TOAGOSEI CO., LTD.) .

Furthermore, as the ethylenically unsaturated compound other than the ethylenically unsaturated compound B1, an ethylenically unsaturated compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 can be used.

From the viewpoint of resolution and linearity, the ratio Mm/Mb of the content Mm of the ethylenically unsaturated compound in the photosensitive resin layer to the content Mb of the alkali-soluble resin is preferably 1.0 or less, more preferably 0.9 or less, and especially preferably It is 0.5 or more and 0.9 or less.

Moreover, it is preferable that the ethylenic unsaturated compound in a photosensitive resin layer contains a (meth)acryloxy compound from a viewpoint of curability and resolution.

In addition, from the viewpoint of curability, resolution and linearity, the ethylenically unsaturated compound in the photosensitive resin layer more preferably contains (meth)propylene oxide compound, and the content of the propylene oxide compound is relative to the content of the photosensitive resin layer. The total mass of the above-mentioned (meth)propylene oxide compound contained is 60 mass % or less.

The molecular weight (weight average molecular weight (Mw) in the case of distribution) of the ethylenically unsaturated compound containing the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 280 to 2,200, and even more preferably 300 to 2,200.

The ethylenic unsaturated compound may be used individually by 1 type, and may use 2 or more types together.

The content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and still more preferably 20% by mass, based on the total mass of the photosensitive resin layer ~50% by mass.

<Photopolymerization Initiator>

The photosensitive resin layer contains a photopolymerization initiator.

A photopolymerization initiator is a compound that initiates polymerization of an ethylenically unsaturated compound upon receiving activating light rays such as ultraviolet rays, visible rays, and X-rays. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used. Moreover, the photoinitiator in this invention contains a sensitizer further.

As a photoinitiator, a photoradical polymerization initiator and a photocationic polymerization initiator are mentioned, for example, A photoradical polymerization initiator is preferable.

Examples of photoradical polymerization initiators include photopolymerization initiators having an oxime ester structure, photopolymerization initiators having an α-aminoalkylphenone structure, and photopolymerization initiators having an α-hydroxyalkylphenone structure. Initiator, photopolymerization initiator with acyl phosphine oxide structure, photopolymerization initiator with N-phenylglycine structure and biimidazole compound.

Among them, the photopolymerization initiator preferably contains a biimidazole compound, more preferably contains a biimidazole compound and a benzophenone compound, from the viewpoint of line width change with standing time, line width change at developing temperature, and sensitivity.

Furthermore, as the biimidazole compound, preferably a hexaarylbiimidazole compound is mentioned.

Examples of biimidazole compounds include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxybenzene) base) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer And 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer.

The photosensitive resin layer may contain 1 type of biimidazole compound independently as a photoinitiator, and may contain 2 or more types.

The content of the biimidazole compound is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total mass of the photosensitive resin layer, from the standpoint of line width change over time, development temperature line width change, and sensitivity. More preferably, it is 3 mass % - 10 mass %, Especially preferably, it is 5 mass % - 10 mass %.

The photopolymerization initiator preferably contains a benzophenone compound, more preferably a dialkylaminobenzophenone compound, from the standpoint of a change in line width with standing time, a change in line width at developing temperature, and sensitivity.

Examples of benzophenone compounds include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxydiphenone, Benzophenone, 2-Chlorobenzophenone, 4-Chlorobenzophenone, 4-Bromobenzophenone, 2-Carboxybenzophenone, 2-Ethoxycarbonylbenzophenone, Benzophenone Ketonetetracarboxylic acid or its tetramethyl ester, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dicyclohexylamino)benzophenone, 4,4'-bis (Diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'- Dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-phenylbenzophenone, isobenzophenolphthalein, 4-benzoyl-4'-methylphenyl sulfide wait.

The photosensitive resin layer may contain one type of benzophenone compound alone as a photopolymerization initiator, or may contain two or more types.

The content of the benzophenone compound relative to the total mass of the photosensitive resin layer is preferably 0.05% by mass to 5% by mass, more preferably 0.1% by mass to 2% by mass, more preferably 0.2% by mass to 1.5% by mass, particularly preferably 0.4% by mass to 0.8% by mass.

In addition, when a biimidazole compound and a benzophenone compound are included as a photopolymerization initiator, the content of the above-mentioned benzophenone compound is preferably The content of the biimidazole compound is less than that of the above-mentioned biimidazole compound.

As the photoradical polymerization initiator, for example, polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064-0081 of JP-A-2015-14783 can be used.

As the photoradical polymerization initiator, for example, ethyl dimethylaminobenzoate (DBE, CASNo.10287-53-3), benzoin methyl ether, (p, p'-dimethoxybenzyl base) anisyl ester, TAZ-110 (trade name: manufactured by Midori Kagaku Co., Ltd.), benzophenone, TAZ-111 (trade name: manufactured by Midori Kagaku Co., Ltd.), IrgacureOXE01, OXE02, OXE03, OXE04 (manufactured by BASF), Omnirad651 and 369 (trade name: IGM Resins B.V.), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1 , 2'-biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).

Commercially available photoradical polymerization initiators include, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(o-benzoyl oxime) (commercial Name: IRGACURE (registered trademark) OXE-01, manufactured by BASF Corporation), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1- (o-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF Corporation), IRGACURE OXE-03 (manufactured by BASF Corporation), 2-(dimethylamino)-2-[(4-methylphenyl)methyl Base]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, manufactured by IGM Resins B.V.), 2-methyl-1-(4-methylthiobenzene base)-2-morpholinopropan-1-one (trade name: Omnirad 907, manufactured by IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl) Benzyl]phenyl}-2-methylpropan-1-one (trade name: Omnirad 127, manufactured by IGMResins B.V.), 2-benzyl-2-dimethylamino-1-(4-morpholinephenyl) Butanone-1 (trade name: Omnirad 369, manufactured by IGM Resins B.V.), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, manufactured by IGM Resins B.V.), 1-hydroxy Cyclohexylphenylketone (trade name: Omnirad 184, manufactured by IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, manufactured by IGM Resins B.V. ), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl) Phenylphosphine oxide (trade name: Omnired 819, manufactured by IGM Resins B.V.), oxime ester-based photopolymerization initiator (trade name: Lunar 6, manufactured by DKSH Holding Ltd.), 2,2'-bis(2-chlorobenzene base)-4,4',5,5'-tetraphenylbisimidazole (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer) (trade name: B-CIM, Hampford manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (trade name: BCTB, manufactured by Tokyo Chemical Industry Co., Ltd.).

Photocationic polymerization initiators (photoacid generators) are compounds that generate acid upon receiving activating light. The photocationic polymerization initiator is preferably a compound that generates acid in response to activating light with a wavelength of 300 nm or more, preferably 300 to 450 nm, but its chemical structure is not limited. And, for the photocationic polymerization initiator that is not directly responsive to activating light with a wavelength of 300 nm or more, as long as it is a compound that generates an acid in response to activating light with a wavelength of 300 nm or more by using it in combination with a sensitizer, it can be combined with the sensitizer and preferably used.

As the photocationic polymerization initiator, preferably a photocationic polymerization initiator that generates an acid with a pKa of 4 or less, more preferably a photocationic polymerization initiator that generates an acid with a pKa of 3 or less, especially preferably an acid that generates a pKa with a value of 2 or less photocationic polymerization initiator. There is no particular limitation on the lower limit of pKa, but it is preferably -10.0 or more, for example.

As a photocationic polymerization initiator, an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator are mentioned.

Examples of the ionic photocationic polymerization initiator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts.

As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-85643 can be used.

Examples of the nonionic photocationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. As the trichloromethyl-s-triazines, diazomethane compounds, and imidesulfonate compounds, compounds described in paragraphs 0083 to 0088 of JP-A-2011-221494 can be used. Furthermore, as the oxime sulfonate compound, compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 can be used.

The sensitizer is not particularly limited, and known sensitizers, dyes, and pigments can be used.

As the sensitizer, for example, dialkylaminobenzophenone compound, pyrazoline compound, anthracene compound, coumarin compound, xanthone (xanthone) compound, thioxanthone (thioxanthone) compound, acridine Pyridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalenedi Formimide compounds, triarylamine compounds and aminoacridine compounds.

The photosensitive resin layer may contain 1 type of photoinitiator independently, and may contain 2 or more types.

The content of the photopolymerization initiator in the photosensitive resin layer is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass relative to the total mass of the photosensitive resin layer %above. The upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive resin layer.

<pigment>

From the viewpoint of the visibility of the exposed part and the non-exposed part, and the pattern visibility and resolution after development, the photosensitive resin layer preferably contains a pigment, and more preferably contains a maximum absorption at a wavelength range of 400nm to 780nm during color development. A dye with a wavelength of 450 nm or more whose maximum absorption wavelength is changed by acid, alkali, or radicals (also referred to simply as "dye N"). When dye N is contained, although the detailed mechanism is not clear, the adhesion with adjacent layers (for example, a temporary support body and an intermediate layer) improves, and resolution becomes more excellent.

In this specification, the pigment "changes the maximum absorption wavelength by acid, alkali or free radical" may mean that the pigment in the color-developing state is decolorized by acid, alkali or free radicals, or the pigment in the decolorized state passes through Either one of the method of developing color by acid, alkali or radicals, and the method of changing the pigment in a color-developed state to a color-developed state of another hue.

Specifically, the dye N may be a compound that develops color from a decolorized state upon exposure, or may be a compound that decolorizes from a decolorized state upon exposure. In this case, it may be a pigment that generates and acts on the photosensitive resin layer by exposure to acid, alkali or free radicals to change the state of color development or decolorization, or it may be a pigment that is exposed to light by acid, alkali or free radicals. On the other hand, the state (for example, pH) in the photosensitive resin layer is changed, and the state of color development or decolorization is changed. In addition, it may be a dye that is directly stimulated by an acid, an alkali, or a free radical without exposure to light, thereby changing the state of color development or decolorization.

Among them, from the viewpoint of visibility and resolution of the exposed part and the non-exposed part, the dye N is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by a radical. of pigment.

From the viewpoint of visibility and resolution of the exposed portion and the non-exposed portion, the photosensitive resin layer preferably contains a dye whose maximum absorption wavelength is changed by radicals as both the dye N and the photoradical polymerization initiator.

In addition, the dye N is preferably a dye that develops color with an acid, an alkali, or a radical from the viewpoint of the visibility of the exposed portion and the non-exposed portion.

As an example of the color development mechanism of the dye N in the present invention, the method of adding a photoradical polymerization initiator, a photocationic polymerization initiator (photoacid generator) or a photobase generator to the photosensitive resin layer can be mentioned. , the radical reactive dye, acid reactive dye or base reactive dye (for example, without color pigment) for color development.

From the viewpoint of the visibility of the exposed part and the non-exposed part, the maximum absorption wavelength at the wavelength range of 400 nm to 780 nm during color development of the dye N is preferably 550 nm or more, more preferably 550 nm to 700 nm, and even more preferably 550 nm to 550 nm. 650nm.

In addition, the dye N may have only one maximum absorption wavelength in the wavelength range of 400 nm to 780 nm during color development, or may have two or more. When the dye N has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm for color development, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.

The maximum absorption wavelength of the dye N is obtained in the following manner: in the atmospheric environment gas, using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation), measuring the concentration of the solution (liquid temperature 25° C.) containing the dye N in the range of 400 nm to 780 nm. The transmission spectrum detects the wavelength at which the intensity of light becomes extremely small (maximum absorption wavelength).

As a coloring matter which develops or decolorizes by exposure, a colorless compound is mentioned, for example.

Examples of dyes decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. Department of pigment.

The dye N is preferably a colorless compound from the viewpoint of the visibility of the exposed portion and the non-exposed portion.

As the colorless compound, for example, a colorless compound having a triarylmethane skeleton (triarylmethane dye), a colorless compound having a spiropyran skeleton (spiropyran dye), a colorless compound having a fluoran skeleton, Chromatic compounds (fluorane pigments), colorless compounds with diarylmethane skeletons (diarylmethane pigments), colorless compounds with rhodamine lactam skeletons (rhodamine lactam pigments), indole A colorless compound (indolylphthalide dye) and a colorless compound (leuco auramine dye) with a leuco auramine skeleton.

Among them, triarylmethane-based dyes or fluoran-based dyes are preferable, and colorless compounds (triphenylmethane-based dyes) or fluoran-based dyes having a triphenylmethane skeleton are more preferable.

As a colorless compound, it is preferable to have a lactone ring, a sultone ring, or a sultone ring from the viewpoint of the visibility of an exposure part and a non-exposure part. Thereby, the lactone ring, sultone ring or sultone ring possessed by the colorless compound can be reacted with the radical generated by the photoradical polymerization initiator or the acid generated by the photocationic polymerization initiator, Thereby, the colorless compound becomes decolorized in a ring-closed state, or the colorless compound becomes colored in a ring-opened state. As a colorless compound, a compound having a lactone ring, a sultone ring or a sultone ring and the lactone ring, a sultone ring or a sultone ring developing color by radical or acid ring opening is preferred, More preferably, it is a compound having a lactone ring and the lactone ring is opened by a radical or an acid to develop a color.

Examples of the dye N include the following dyes and leuco compounds.

Specific examples of dyes in the dye N include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsine, methyl violet 2B, quinalidine red ( quinaldine red), rose bengal, metanil yellow, thymol sulfonphthalein, xylenol blue, methyl orange, p-methyl red, Congo red, benzene Benzopurpurine 4B, α-naphthalene red, nile blue 2B, nile blue A, methyl violet, malachite green, parafuchsin, victoria pure blue pure blue)-naphthalenesulfonate, Victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), oil blue #603 (manufactured by Orient Chemical Industries Co., Ltd.), oil pink #312 (manufactured by Orient Chemical Industries Co., Ltd.), oil red 5B (manufactured by Orient Chemical Industries Co., Ltd.), oil scarlet #308 (manufactured by Orient Chemical Industries Co., Ltd.), oil red OG (manufactured by Orient Chemical Industries Co., Ltd.), oil red RR (manufactured by Orient Chemical Industries Co., Ltd.), oil green #502 (manufactured by Orient Chemical Industries Co., Ltd.), spilonred BEH special (manufactured by Hodogaya Chemical Co., Ltd. ), m-cresyl violet, cresyl red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4- p-Diethylaminophenyliminonaphthoquinone, 2-carboxyoctadecylamino-4-p-N,N-bis(hydroxyethyl)amino-phenyliminonaphthoquinone, 1-phenyl-3 -Methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of the colorless compound in the dye N include p, p', p"-hexamethyltriaminotriphenylmethane (colorless crystal violet), Pergascript Blue SRB (manufactured by Ciba-Geigy), Crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(N-ethyl-p-toluidylamino)fluorane, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5 -Methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorane, 3-(N , N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N, N-diethylamino)-6-methyl-7-dimethylanilinofluorane, 3 -(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3- (N,N-diethylamino)-7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-di Ethylamino)-7-benzylaminofluorane, 3-(N,N-diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6- Methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-dimethylanilinofluoran, 3-hydropyridyl-6-methyl-7 -anilinofluoran, 3-pyrrolidinyl-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3 , 3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3 -(4-Diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(4- Diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1 (3H), 9'-[9H]xanthene-3-one.

From the viewpoint of the visibility of the exposed part and the non-exposed part, the pattern visibility after development, and the resolution, the dye N is preferably a dye whose maximum absorption wavelength changes by radicals, more preferably a dye that changes the maximum absorption wavelength by radicals. Chromogenic pigments.

The dye N is preferably leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalenesulfonate.

One type of pigment may be used alone, or two or more types may be used.

From the viewpoint of the visibility of the exposed portion and the non-exposed portion, and the pattern visibility and resolution after development, the content of the pigment is preferably 0.1% by mass or more, more preferably 0.1% by mass, relative to the total mass of the photosensitive resin layer. % to 10 mass%, more preferably 0.1 mass% to 5 mass%, especially preferably 0.1 mass% to 1 mass%.

In addition, from the viewpoint of the visibility of the exposed part and the non-exposed part, and the pattern visibility and resolution after development, the content of the dye N is preferably 0.1% by mass or more with respect to the total mass of the photosensitive resin layer, more preferably It is 0.1 mass % - 10 mass %, More preferably, it is 0.1 mass % - 5 mass %, Especially preferably, it is 0.1 mass % - 1 mass %.

The content of the dye N means the content of the dye when all the dye N contained in the photosensitive resin layer is in a colored state. Hereinafter, a method for quantifying the content of the dye N will be described by taking a dye that develops color by radicals as an example.

Two solutions in which 0.001 g or 0.01 g of the dye was dissolved in 100 mL of methyl ethyl ketone were prepared. A photoradical polymerization initiator Irgacure OXE01 (trade name, BASF Japan Ltd.) was added to each of the obtained solutions, and 365 nm light was irradiated to generate radicals to bring all the dyes into a color-developed state. Then, the absorbance of each solution at a liquid temperature of 25° C. was measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric atmosphere gas, and a calibration curve was prepared.

Next, except for dissolving 3 g of the photosensitive resin layer in methyl ethyl ketone instead of the dye, the absorbance of the solution in which all the dye was developed was measured in the same manner as above. From the absorbance of the obtained solution containing the photosensitive resin layer, the content of the dye contained in the photosensitive resin layer was calculated based on the calibration curve.

<Inhibitor>

It is preferable that the photosensitive resin layer further contains a polymerization inhibitor from the viewpoint of the storage stability, the line width change of standing time, and the development temperature line width change.

As a polymerization inhibitor, it is preferable to contain a radical polymerization inhibitor.

The polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used.

Examples of polymerization inhibitors include phenothiazine, phenoxazine, hydroquinone, chlorobenzoquinone, sodium phenindoxylate, m-aminophenol, p-methoxyphenol, di-tert-butyl-p-methyl Phenol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4- methyl-6-tert-butylphenol), N-nitrosophenyl hydroxylamine salt (ammonium salt, cerous salt, etc.), 2,2,6,6-tetramethylpiperidin-1-oxyl, etc. In addition, a polymerization inhibitor may also function as an antioxidant.

Moreover, as a polymerization inhibitor, the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784 is mentioned, for example.

Examples of other polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, diphenylnitrosoamine, and the like. In order not to impair the sensitivity of the photosensitive resin layer, nitrosophenylhydroxylamine aluminum salt is preferably used as a radical polymerization inhibitor.

Among them, as a polymerization inhibitor, it is preferable to include at least The one compound more preferably contains at least one compound selected from phenothiazine and phenoxazine, and especially preferably contains phenothiazine.

A polymerization inhibitor may be used individually by 1 type, and may use it in combination of 2 or more types.

From the standpoint of storage stability, line width change over time, development temperature line width change, and sensitivity, the content of the polymerization inhibitor is preferably 0.005% by mass to 2% by mass, more preferably 0.01% by mass, relative to the total mass of the photosensitive resin layer. % by mass to 1% by mass, more preferably 0.05% by mass to 0.5% by mass, particularly preferably 0.2% by mass to 0.4% by mass.

In addition, when the content of the above-mentioned photopolymerization initiator in the above-mentioned photosensitive resin layer is represented as Rc, and the content of the above-mentioned polymerization inhibitor is represented as Rd, the changes in the line width of the left time, the development temperature line width, and the sensitivity From a viewpoint, the value of their mass ratio Rd/Rc is preferably 0.01 to 0.2, more preferably 0.02 to 0.1, and particularly preferably 0.03 to 0.05.

<Heat-crosslinkable compound>

From the viewpoint of the strength of the cured film to be obtained and the adhesiveness of the uncured film to be obtained, the photosensitive resin layer preferably contains a thermally crosslinkable compound. In addition, in this specification, the heat-crosslinkable compound which has the ethylenically unsaturated group mentioned later is not handled as an ethylenically unsaturated compound, but is handled as a heat-crosslinkable compound.

Examples of the heat-crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoint of the strength of the cured film to be obtained and the adhesiveness of the uncured film to be obtained.

Since the blocked isocyanate compound reacts with a hydroxyl group and a carboxyl group, for example, when an alkali-soluble resin and/or an ethylenically unsaturated compound has at least one of a hydroxyl group and a carboxyl group, the hydrophilicity of the formed film decreases, thereby When using the film which hardened the photosensitive resin layer as a protective film, the function tends to strengthen.

In addition, the blocked isocyanate compound means "a compound having a structure in which an isocyanate group of an isocyanate is protected (so-called masked) by a blocking agent."

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, more preferably 130°C to 150°C.

The dissociation temperature of blocked isocyanate refers to "the temperature of the endothermic peak accompanying the deprotection reaction of blocked isocyanate when measured by DSC (Differential scanning calorimetry: differential scanning calorimetry) analysis using a differential scanning calorimeter." ".

As the differential scanning calorimeter, for example, a differential scanning calorimeter (model number: DSC6200) manufactured by Seiko Instruments Inc. can be preferably used. However, the differential scanning calorimeter is not limited to this.

As an end-capping agent with a dissociation temperature of 100°C to 160°C, active methylene compounds [malonate diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, etc.) Esters, di-2-ethylhexyl malonate, etc.)], oxime compounds (formaldoxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime and cyclohexanone oxime, etc. have -C(=N -OH)- the compound represented by the structure).

Among these, as a blocking agent having a dissociation temperature of 100° C. to 160° C., for example, an oxime compound is preferably contained from the viewpoint of storage stability.

For example, it is preferable that the blocked isocyanate compound has an isocyanurate structure from the viewpoint of improving film brittleness, improving adhesion to a transfer target, and the like.

A blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanurating and protecting hexamethylene diisocyanate.

Among the blocked isocyanate compounds having an isocyanurate structure, those having A compound of an oxime structure using an oxime compound as a blocking agent.

The blocked isocyanate compound may have a polymerizable group.

The polymerizable group is not particularly limited, and a known polymerizable group can be used, preferably a radical polymerizable group.

Examples of the polymerizable group include ethylenically unsaturated groups such as (meth)acryloyloxy groups, (meth)acrylamide groups, and styryl groups, and groups having epoxy groups such as glycidyl groups.

Among them, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloyloxy group, and even more preferably an acryloyloxy group.

As a blocked isocyanate compound, a commercial item can be used.

Examples of commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (the above are manufactured by SHOWA DENKO K.K.) . Duranate series of blocked type (for example, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Corporation).

Moreover, the compound of the following structure can also be used as a blocked isocyanate compound.

[chemical formula 2]

A heat-crosslinkable compound may be used individually by 1 type, and may use 2 or more types.

When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer. %.

<other ingredients>

The photosensitive resin layer may contain components other than the above-mentioned alkali-soluble resin, ethylenically unsaturated compound, photopolymerization initiator, dye, polymerization inhibitor, and thermally crosslinkable compound.

-Surfactant-

From the viewpoint of thickness uniformity, it is preferable that the photosensitive resin layer contains a surfactant.

Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, and nonionic surfactants are preferred.

Examples of the surfactant include those described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Application Laid-Open No. 2009-237362.

As the surfactant, a fluorine-based surfactant or a silicone-based surfactant is preferable.

Examples of commercially available fluorine-based surfactants include Megafac (trade name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F -143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A , F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP.MFS-330 , EXP.MFS-578, EXP.MFS-578-2, EXP.MFS-579, EXP.MFS-586, EXP.MFS-587, EXP.MFS-628, EXP.MFS-631, EXP.MFS-603 , R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (the above are manufactured by DIC Corporation), Fluorad (trade name) FC430, FC431, FC171 (the above are manufactured by Sumitomo 3M Limited), Surflon (trade name) S-382, SC-101, SC-103, SC-104, SC- 105, SC-1068, SC-381, SC-383, S-393, KH-40 (the above are manufactured by AGC Inc.), PolyFox (trade name) PF636, PF656, PF6320, PF6520, PF7002 (the above are OMNOVA Solutions Inc. Ftergent (trade name) 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (manufactured by Neos Company Limited), U-120E (Uni-chem Co., Ltd.), etc.

Furthermore, as the fluorine-based surfactant, an acrylic compound having a molecular structure including a fluorine-atom-containing functional group and in which the fluorine-atom-containing functional group is cut off when heat is applied to volatilize the fluorine atom can also be preferably used. Examples of such fluorine-based surfactants include DIC Corporation's Megafac (trade name) DS series (Chemical Industry Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), For example Megafac (trade name) DS-21.

Furthermore, as the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound and a hydrophilic vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group.

As the fluorine-based surfactant, a block polymer can be used. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound having fluorine atoms and a structure unit derived from a compound having 2 or more (preferably 5 or more) ) A structural unit of a (meth)acrylate compound of an alkyleneoxy group (preferably ethyleneoxy group, propyleneoxy group).

As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used. Examples thereof include Megafac (trade name) RS-101, RS-102, RS-718K, and RS-72-K (the above are manufactured by DIC Corporation).

As nonionic surfactants, glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerin propoxylate, glycerol ethoxylate, etc.) compounds, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, nonylphenol polyoxyethylene ether, polyethylene glycol dilaurel Ester, polyethylene glycol octacosanoate, sorbitan fatty acid ester, Pluronic (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF Corporation), Tetronic ( Product name) 304, 701, 704, 901, 904, 150R1, HYDROPALAT WE 3323 (the above are manufactured by BASF Corporation), Solsperse (product name) 20000 (the above are manufactured by Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN (trade name) D-1105, D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010 , Surfynol 104, 400, 440 (the above are manufactured by Nissin Chemical Co., Ltd.), etc.

As the fluorine-based surfactant, from the viewpoint of improving environmental adaptability, it is preferably a linear perfluoroalkyl group having 7 or more carbon atoms derived from perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Alternative materials for compounds of surfactants.

Examples of silicone-based surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminals.

Specific examples of silicone-based surfactants include EXP.S-309-2, EXP.S-315, EXP.S-503-2, and EXP.S-505-2 (manufactured by DIC Corporation) , DOWSIL (trade name) 8032ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are Dow Corning Toray Co. , Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-6191 , X-22-4515, KF-6004, KP-341, KF-6001, KF-6002, KP-101, KP-103, KP-104, KP-105, KP-106, KP-109, KP-112 , KP-120, KP-121, KP-124, KP-125, KP-301, KP-306, KP-310, KP-322, KP-323, KP-327, KP-341, KP-368, KP -369, KP-611, KP-620, KP-621, KP-626, KP-652 (manufactured by Shin-Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF- 4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), BYK300, BYK306, BYK307, BYK310, BYK320, BYK323, BYK325, BYK330, BYK313, BYK315N, BYK331, BYK333, BYK34 5. BYK347, BYK348, BYK349, BYK370, BYK377, BYK378 (the above are manufactured by BYK Chemie), etc.

And, in recent years, the environmental suitability of the compound that has the straight-chain perfluoroalkyl group that has 7 or more carbon atoms is worrying, so it is preferable to use a surfactant using perfluorooctanoic acid ( PFOA) and perfluorooctane sulfonic acid (PFOS) alternative materials.

The photosensitive resin layer may contain one type of surfactant alone, or may contain two or more types.

The content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass relative to the total mass of the photosensitive resin layer.

-additive-

The photosensitive resin layer may contain known additives as needed in addition to the above-mentioned components.

Examples of additives include plasticizers, heterocyclic compounds, benzotriazoles, carboxybenzotriazoles, pyridines (isonicotinamide, etc.), purine bases (adenine, etc.), and solvents. The photosensitive resin layer may contain each additive individually by 1 type, and may contain 2 or more types.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminoimide Methyl-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyethyl) Aminomethylene-1,2,3-benzotriazole, etc.

As carboxybenzotriazoles, for example, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N- Di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, N-(N,N- Di-2-ethylhexyl)aminoethylenecarboxybenzotriazole and the like. As carboxybenzotriazoles, for example, commercial items such as CBT-1 (JOHOKU CHEMICAL CO., LTD., brand name) can be used.

The total content of benzotriazoles and carboxybenzotriazoles is preferably 0.01% by mass to 3% by mass, more preferably 0.05% by mass to 1% by mass relative to the total mass of the photosensitive resin layer. It is preferable to make the said content into 0.01 mass % or more from a viewpoint of providing storage stability to a photosensitive resin layer. On the other hand, from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye, the content is preferably 3% by mass or less.

The photosensitive resin layer may contain at least one selected from plasticizers and heterocyclic compounds.

Examples of the plasticizer and the heterocyclic compound include compounds described in paragraphs 0097 to 0103 and 0111 to 0118 of International Publication No. 2018/179640.

The photosensitive resin layer may contain a solvent. When forming a photosensitive resin layer from the photosensitive resin composition containing a solvent, a solvent may remain in a photosensitive resin layer.

In addition, the photosensitive resin layer may contain metal oxide particles, antioxidants, dispersants, acid multiplying agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, etc. known additives such as additives, cross-linking agents and organic or inorganic anti-sedimentation agents.

About the additive contained in a photosensitive resin layer, it describes in paragraphs 0165-0184 of Unexamined-Japanese-Patent No. 2014-85643, and the content of this publication is incorporated in this specification.

<Impurities, etc.>

The photosensitive resin layer may contain a predetermined amount of impurities.

Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among them, since halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, it is preferable to set them to the following content.

The content of impurities in the photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, and further preferably 2 ppm or less on a mass basis. The content of impurities may be 1 ppb or more on a mass basis, and may be 0.1 ppm or more.

Examples of the method of keeping impurities within the above range include a method of selecting a raw material with a low content of impurities as a raw material of the composition, a method of preventing impurities from being mixed in the photosensitive resin layer, and a method of washing and removing them. By this method, the impurity amount can be set within the above-mentioned range.

Impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma: Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography, for example.

Benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide and The content of compounds such as hexane is small. The content of these compounds with respect to the total mass of the photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, and even more preferably 4 ppm or less on a mass basis.

The lower limit may be 10 ppb or more with respect to the total mass of the photosensitive resin layer on a mass basis, and may be 100 ppb or more. These compounds can suppress the content by the same method as the impurities of the above-mentioned metals. In addition, it can be quantified by a known measurement method.

The content of water in the photosensitive resin layer is preferably from 0.01% by mass to 1.0% by mass, more preferably from 0.05% by mass to 0.5% by mass, from the viewpoint of improving reliability and laminability.

<Residual Monomer>

The photosensitive resin layer may contain residual monomers corresponding to each structural unit of the above-mentioned alkali-soluble resin.

From the viewpoint of patternability and reliability, the residual monomer content is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and still more preferably 500 mass ppm or less, based on the total mass of the alkali-soluble resin. The lower limit is not particularly limited, but is preferably 1 mass ppm or more, more preferably 10 mass ppm or more.

From the viewpoint of patternability and reliability, the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and even more preferably 100 mass ppm with respect to the total mass of the photosensitive resin layer. Mass ppm or less. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more.

It is also preferable to set the residual monomer amount of the monomer in the case of synthesizing the alkali-soluble resin by polymer reaction within the above-mentioned range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate and a carboxylic acid side chain, it is preferable to make content of glycidyl acrylate into the said range.

The amount of residual monomers can be measured by known methods such as liquid chromatography and gas chromatography.

<Physical properties, etc.>

From the viewpoint of developability and resolution, the thickness of the photosensitive resin layer is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, particularly preferably 1 μm or more and 5 μm or less.

The thickness of each layer of the photosensitive transfer material is measured by observing a cross-section in a direction perpendicular to the main surface of the photosensitive transfer material with a scanning electron microscope (SEM: Scanning Electron Microscope), based on In the obtained observation image, the thickness of each layer was measured at 10 points or more, and the average value thereof was calculated.

Furthermore, from the viewpoint of more excellent adhesiveness, the transmittance of light having a wavelength of 365 nm of the photosensitive resin layer is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

<Formation method>

The method for forming the photosensitive resin layer is not particularly limited as long as it is a method capable of forming a layer containing the above components.

As a method for forming the photosensitive resin layer, for example, a method of preparing a photosensitive resin composition containing an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, a solvent, etc. The photosensitive resin composition is applied and formed by drying the coating film of the photosensitive resin composition.

As a photosensitive resin composition used for formation of a photosensitive resin layer, the composition containing alkali-soluble resin, an ethylenic unsaturated compound, a photoinitiator, the said arbitrary component, and a solvent is mentioned, for example.

In order to adjust the viscosity of a photosensitive resin composition and form a photosensitive resin layer easily, it is preferable that a photosensitive resin composition contains a solvent.

-Solvent-

The solvent contained in the photosensitive resin composition is not particularly limited as long as it can dissolve or disperse the alkali-soluble resin, ethylenically unsaturated compound, photopolymerization initiator, and any of the above-mentioned components, and known solvents can be used. .

Examples of solvents include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol and ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic Hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N,N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents, amide solvents, lactone solvents, and 2 solvents including these more than one mixed solvent.

In the case of producing a photosensitive transfer material with a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer, the photosensitive resin composition preferably contains an alkylene glycol ether solvent and an alkylene glycol ether solvent. At least one of ether acetate solvents. Among them, it is more preferable to include at least one kind of mixed solvent selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents and at least one mixed solvent selected from ketone solvents and cyclic ether solvents, and more preferably At least one kind selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and three mixed solvents of a ketone solvent and a cyclic ether solvent are included.

Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, and diethylene glycol dialkyl ether. , Dipropylene glycol monoalkyl ether and dipropylene glycol dialkyl ether.

Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and diethylene glycol monoalkyl ether acetate. Propylene Glycol Monoalkyl Ether Acetate.

As the solvent, solvents described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and solvents described in paragraph 0014 of JP-A-2018-177889 can be used, and these contents are incorporated herein.

The photosensitive resin composition may contain 1 type of solvent independently, and may contain 2 or more types.

The content of the solvent when coating the photosensitive resin composition is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solids in the photosensitive resin composition .

The preparation method of the photosensitive resin composition is not particularly limited, and the following method is mentioned: a solution obtained by dissolving each component in the above-mentioned solvent is prepared in advance, and the obtained solution is mixed in a predetermined ratio, thereby preparing Photosensitive resin composition.

Before forming the photosensitive resin layer, it is preferable to filter the photosensitive resin composition using a filter having a pore diameter of 0.2 μm to 30 μm.

The coating method of the photosensitive resin composition is not particularly limited, and it may be coated by a known method. Examples of coating methods include printing, spray coating, roll coating, bar coating, curtain coating, spin coating, and die coating (ie, slit coating).

Moreover, the photosensitive resin layer can also be formed by apply|coating and drying the photosensitive resin composition on the protective film mentioned later.

As a method of drying the coating film of the photosensitive resin composition, heat drying and reduced-pressure drying are preferable.

The drying temperature is preferably 80°C or higher, more preferably 90°C or higher. In addition, the upper limit thereof is preferably 130°C or lower, more preferably 120°C or lower. It is also possible to continuously change the temperature and dry it.

In addition, the drying time is preferably at least 20 seconds, more preferably at least 40 seconds, and even more preferably at least 60 seconds. Also, the upper limit is not particularly limited, but is preferably 600 seconds or less, more preferably 300 seconds or less.

〔Thermoplastic resin layer〕

The photosensitive transfer material may also include a thermoplastic resin layer.

The photosensitive transfer material preferably has a thermoplastic resin layer between the temporary support and the photosensitive resin layer. This is because the photosensitive transfer material is equipped with a thermoplastic resin layer between the temporary support body and the photosensitive resin layer, and the followability to the substrate in the bonding process with the substrate is improved, so that the substrate and the photosensitive transfer material The mixing of air bubbles between them is suppressed, and the adhesiveness with the adjacent layer (for example, a temporary support body) is improved.

<Alkali-soluble resin>

The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.

Examples of alkali-soluble resins include acrylic resins, polystyrene resins, styrene-acrylic acid copolymers, polyurethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resins, polyester resins, epoxy resins, Polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.

As the alkali-soluble resin, an acrylic resin is preferable from the viewpoint of developability and adhesiveness with an adjacent layer.

Here, the acrylic resin means having at least one structure selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylate esters, and structural units derived from (meth)acrylamides. unit resin.

As the acrylic resin, the total content of the structural unit derived from (meth)acrylic acid, the structural unit derived from (meth)acrylate, and the structural unit derived from (meth)acrylamide is preferably More than 50% by mass.

Among them, the total content of the structural unit derived from (meth)acrylic acid and the structural unit derived from (meth)acrylate is preferably 30% by mass to 100% by mass, more preferably 50% by mass, based on the total mass of the acrylic resin. ~100% by mass.

Also, the alkali-soluble resin is preferably a polymer having an acid group.

Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group and a phosphonic acid group, and a carboxyl group is preferable.

From the viewpoint of developability, the alkali-soluble resin is more preferably an alkali-soluble resin having an acid value of 60 mgKOH/g or more, and further preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more.

The upper limit of the acid value of the alkali-soluble resin is not particularly limited, but is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less.

The carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited, and can be appropriately selected from known resins and used.

For example, among the polymers described in paragraph 0025 of JP-A-2011-95716, alkali-soluble resins of acrylic resins containing carboxyl groups having an acid value of 60 mgKOH/g or more, and JP-A-2010-237589 Carboxyl group-containing acrylic resins having an acid value of 60 mgKOH/g or more in polymers described in paragraphs 0033 to 0052 and acid values of 60 mgKOH in alkali-soluble resins described in paragraphs 0053 to 0068 of JP-A-2016-224162 /g or more carboxyl-containing acrylic resins.

The copolymerization ratio of the structural unit having a carboxyl group in the above-mentioned carboxyl group-containing acrylic resin is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and still more preferably 12% by mass, based on the total mass of the acrylic resin. % to 30% by mass.

As the alkali-soluble resin, an acrylic resin having a structural unit derived from (meth)acrylic acid is particularly preferable from the viewpoint of developability and adhesiveness with an adjacent layer.

Alkali-soluble resins may have reactive groups. As the reactive group, as long as it is a group capable of addition polymerization, there may be mentioned ethylenically unsaturated groups; polycondensable groups such as hydroxyl groups and carboxyl groups; epoxy groups, (block) isocyanate groups, etc. polyreactive groups.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and still more preferably 20,000 to 50,000.

The thermoplastic resin layer may contain one type of alkali-soluble resin alone, or may contain two or more types.

The content of the alkali-soluble resin is preferably 10% by mass to 99% by mass, more preferably 20% by mass to 90% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of developability and adhesiveness to adjacent layers. , more preferably 40% by mass to 80% by mass, particularly preferably 50% by mass to 70% by mass.

<pigment>

The thermoplastic resin layer preferably contains a pigment (also simply referred to as "pigment B") whose maximum absorption wavelength is 450nm or more in the wavelength range of 400nm to 780nm when the pigment develops color, and the maximum absorption wavelength occurs due to acid, alkali or free radicals. Variety.

A preferred aspect of the dye B is the same as that of the dye N except for the points described below.

The dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, more preferably a dye whose maximum absorption wavelength is changed by an acid, from the viewpoint of visibility and resolution of the exposed part and the non-exposed part.

From the viewpoint of the visibility and resolution of the exposed portion and the non-exposed portion, the thermoplastic resin layer preferably contains both a dye that changes the maximum absorption wavelength by an acid as the dye B and a compound that generates an acid by light as described later. By.

One type of dye B may be used alone, or two or more types may be used.

From the viewpoint of the visibility of the exposed portion and the non-exposed portion, the content of the dye B is preferably 0.2% by mass or more, more preferably 0.2% by mass to 6% by mass, and even more preferably 0.2% by mass relative to the total mass of the thermoplastic resin layer. % by mass to 5% by mass, particularly preferably 0.25% by mass to 3.0% by mass.

Here, the content of the dye B refers to the content of the dye when all the dye B contained in the thermoplastic resin layer is in a colored state. Hereinafter, a method for quantifying the content of the dye B will be described by taking a dye that develops color by radicals as an example.

A solution in which 0.001 g and 0.01 g of a dye were dissolved in 100 mL of methyl ethyl ketone was prepared. A photoradical polymerization initiator Irgacure OXE0 1 (trade name, BASF Japan Ltd.) was added to each of the obtained solutions, and irradiated with light of 365 nm, thereby generating radicals and bringing all the dyes into a color-developed state. Then, the absorbance of each solution at a liquid temperature of 25° C. was measured using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric atmosphere gas, and a calibration curve was prepared.

Next, except for dissolving 0.1 g of the thermoplastic resin layer in methyl ethyl ketone instead of the dye, the absorbance of the solution in which all the dye was developed was measured in the same manner as above. From the absorbance of the obtained solution containing the thermoplastic resin layer, and based on the calibration curve, the amount of the dye contained in the thermoplastic resin layer was calculated.

<Compounds that generate acids, bases, or radicals by light>

The thermoplastic resin layer may contain a compound (also simply referred to as "compound C") that generates an acid, a base, or a radical by light.

Compound C is preferably a compound that generates an acid, a base, or a radical upon receiving activating light such as ultraviolet light or visible light.

As the compound C, known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators) can be used. Among them, photoacid generators are preferable.

-Photoacid Generator-

From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator.

As a photoacid generator, the photocationic polymerization initiator which the above-mentioned photosensitive resin layer may contain is mentioned, and the preferable aspect is the same except the point mentioned later.

The photoacid generator preferably contains at least one compound selected from onium salt compounds and oxime sulfonate compounds from the viewpoint of sensitivity and resolution, and more preferably from the viewpoint of sensitivity, resolution and adhesion. Contains oxime sulfonate compounds.

Moreover, as a photoacid generator, the photoacid generator which has the following structure is also preferable.

[chemical formula 3]

- Photoradical polymerization initiator -

The thermoplastic resin layer may contain a photoradical polymerization initiator (photoradical polymerization initiator).

As a photoradical polymerization initiator, the photoradical polymerization initiator which may be contained in the above-mentioned photosensitive resin layer is mentioned, and a preferable aspect is also the same.

-Photobase Generator-

The thermoplastic resin layer may contain a photobase generator.

The photobase generator is not particularly limited as long as it is a known photobase generator, for example, 2-nitrobenzylcyclohexyl carbamate, triphenylmethanol, o-carbamoyl hydroxyamide, o-carbamoyl oxime, {[(2,6-dinitrobenzyl)oxy]carbonyl}cyclohexylamine, bis{[(2-nitrobenzyl)oxy]carbonyl}hexane-1,6 -diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylamino Propane, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaaminocobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl) butanone, 2,6-dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 2,6- Dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4-dihydropyridine.

The thermoplastic resin layer may contain 1 type alone or may contain 2 or more types of compound C.

From the viewpoint of visibility and resolution of the exposed portion and the non-exposed portion, the content of the compound C is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, based on the total mass of the thermoplastic resin layer. %.

<plasticizer>

The thermoplastic resin layer preferably contains a plasticizer from the viewpoint of resolution, adhesiveness with adjacent layers, and developability.

The molecular weight of the plasticizer (weight average molecular weight (Mw) in the case of an oligomer or a polymer) is preferably smaller than that of the alkali-soluble resin. The molecular weight (weight average molecular weight (Mw)) of the plasticizer is preferably 200 to 2,000.

The plasticizer is not particularly limited as long as it is a compound that is compatible with an alkali-soluble resin and exhibits plasticity. From the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule, and more preferably It is a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer more preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.

In addition, it is preferable that the plasticizer contains a (meth)acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution, and adhesiveness with adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin, and the plasticizer contains a (meth)acrylate compound.

As a (meth)acrylate compound used as a plasticizer, the (meth)acrylate compound described as an ethylenic unsaturated compound contained in the said photosensitive resin layer is mentioned.

In the photosensitive transfer material, when the thermoplastic resin layer and the photosensitive resin layer are laminated in direct contact, it is preferable that both the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound. This is because when the thermoplastic resin layer and the photosensitive resin layer each contain the same (meth)acrylate compound, interlayer component diffusion is suppressed and storage stability improves.

When the thermoplastic resin layer contains a (meth)acrylate compound as a plasticizer, it is preferable that the (meth)acrylate compound does not polymerize in the exposed portion after exposure from the viewpoint of adhesion to the adjacent layer. .

In addition, from the viewpoint of resolution, adhesion with adjacent layers, and developability, as a (meth)acrylate compound used as a plasticizer, it is preferable to have two or more (methyl) Acryloyl polyfunctional (meth)acrylate compound.

Moreover, as a (meth)acrylate compound used as a plasticizer, the (meth)acrylate compound or urethane (meth)acrylate compound which has an acid group is also preferable.

The thermoplastic resin layer may contain one type of plasticizer alone, or may contain two or more types.

The content of the plasticizer is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 60% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of resolution, adhesion to adjacent layers, and developability. % by mass is particularly preferably 20% by mass to 50% by mass.

<Surfactant>

From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant.

Examples of the surfactant include surfactants that may be contained in the above-mentioned photosensitive resin layer, and preferred embodiments are also the same.

The thermoplastic resin layer may contain one type of surfactant alone, or may contain two or more types.

The content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the thermoplastic resin layer.

<Sensitizer>

The thermoplastic resin layer may contain a sensitizer.

It does not specifically limit as a sensitizer, The sensitizer which may be contained in the above-mentioned photosensitive resin layer is mentioned.

The thermoplastic resin layer may contain one type of sensitizer alone, or may contain two or more types.

The content of the sensitizer can be appropriately selected according to the purpose, but it is preferably 0.01% by mass to The range of 5% by mass, more preferably the range of 0.05% by mass to 1% by mass.

<Additives, etc.>

The thermoplastic resin layer may contain known additives as needed in addition to the above components.

In addition, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of JP 2014-85643 A, and the contents described in this publication are incorporated in this specification.

<Physical properties, etc.>

The layer thickness of the thermoplastic resin layer is not particularly limited, but is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesiveness with adjacent layers. The upper limit is not particularly limited, but from the viewpoint of developability and resolution, it is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less.

<Formation method>

The method for forming the thermoplastic resin layer is not particularly limited as long as it can form a layer containing the above components.

As a method of forming a thermoplastic resin layer, for example, the following method can be mentioned: by preparing a thermoplastic resin composition containing the above-mentioned components and a solvent, coating the thermoplastic composition on the surface of a support, etc., and coating the thermoplastic resin composition formed by drying.

In order to adjust the viscosity of the thermoplastic resin composition to facilitate formation of the thermoplastic resin layer, the thermoplastic resin composition preferably contains a solvent.

-Solvent-

The solvent contained in the thermoplastic resin composition is not particularly limited as long as it can dissolve or disperse the above-mentioned components contained in the thermoplastic resin layer.

Examples of the solvent contained in the thermoplastic resin composition include solvents that may be contained in the above-mentioned photosensitive resin composition, and preferred embodiments are also the same.

The solvent contained in a thermoplastic resin composition may be single type, or may be two or more types.

The content of the solvent when coating the thermoplastic resin composition is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass relative to 100 parts by mass of the total solids in the thermoplastic resin composition.

What is necessary is just to follow the preparation method of the said photosensitive resin composition and the formation method of the photosensitive resin layer about preparation of a thermoplastic resin composition, and formation of a thermoplastic resin layer.

For example, after preparing in advance a solution in which each component contained in the thermoplastic resin layer is dissolved in the above-mentioned solvent, and mixing the obtained solution at a predetermined ratio to prepare a thermoplastic resin composition, the surface of the temporary support The obtained thermoplastic resin composition is coated on the substrate, and the coating film of the thermoplastic resin composition is dried to form a thermoplastic resin layer.

Moreover, after forming a photosensitive resin layer and an intermediate layer on the protective film mentioned later, you may form a thermoplastic resin layer on the surface of an intermediate layer.

〔middle layer〕

The photosensitive transfer material preferably includes an intermediate layer between the thermoplastic resin layer and the photosensitive resin layer. By providing an intermediate layer, it is possible to suppress mixing of components when applying multiple layers and when storing after application.

The intermediate layer is preferably a water-soluble layer from the viewpoint of developability and suppression of mixing of components when applying multiple layers and when storing after application.

In addition, in this specification, "water solubility" means that the solubility with respect to 100 g of water of pH7.0 whose liquid temperature is 22 degreeC is 0.1 g or more.

Examples of the intermediate layer include an oxygen barrier layer having an oxygen barrier function described in JP-A-5-72724 as a "separation layer". When the intermediate layer is an oxygen barrier layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and productivity is improved, so it is preferable.

The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers described in the aforementioned publications and the like. Among them, an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (a 1 mass % aqueous solution of sodium carbonate at 22° C.) is preferable.

The intermediate layer preferably contains resin.

Examples of the resin contained in the intermediate layer include polyvinyl alcohol-based resins, polyvinylpyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, and vinyl ether-based resins. resins, polyamide resins and their copolymers and other resins.

The resin contained in the intermediate layer is preferably a water-soluble resin.

In addition, from the viewpoint of suppressing mixing of components between multiple layers, the resin contained in the intermediate layer is preferably a polymer A contained in the photosensitive resin layer and a thermoplastic resin contained in the thermoplastic resin layer (such as , alkali-soluble resin) are different resins.

The intermediate layer preferably contains polyvinyl alcohol, and more preferably contains both polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of oxygen barrier properties and suppression of mixing of components during multilayer coating and storage after coating.

The intermediate layer may contain one kind of the above-mentioned resins alone, or may contain two or more kinds thereof.

The content of the resin in the intermediate layer is not particularly limited, but it is preferably 50% to the total mass of the intermediate layer from the viewpoint of oxygen barrier properties and suppression of mixing of components when applying multiple layers and when storing after coating. % by mass to 100% by mass, more preferably 70% by mass to 100% by mass, still more preferably 80% by mass to 100% by mass, particularly preferably 90% by mass to 100% by mass.

In addition, the intermediate layer may contain additives such as surfactants as needed.

The layer thickness of the intermediate layer is not particularly limited, but is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm.

This is because, if the thickness of the intermediate layer is within the above range, it is possible to suppress the mixing of components when applying multiple layers and during storage after coating without reducing the oxygen barrier property, and it is possible to suppress the removal of the intermediate layer during development. increase in time.

There is no particular limitation on the formation method of the intermediate layer. For example, the following method can be mentioned: prepare an intermediate layer composition containing the above resin and any additives, apply it on the surface of the thermoplastic resin layer or the photosensitive resin layer, And the coating film of the intermediate layer composition is dried, thereby forming an intermediate layer.

In order to adjust the viscosity of the intermediate layer composition to facilitate formation of the intermediate layer, the intermediate layer composition preferably contains a solvent.

The solvent contained in the intermediate layer composition is not particularly limited as long as it can dissolve or disperse the above-mentioned resin, but is preferably at least one selected from water and water-miscible organic solvents, more preferably water or a mixture of water and water Mixed solvents of neutral organic solvents.

Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, preferably alcohols having 1 to 3 carbon atoms, and more preferably methanol or ethanol.

〔Protective film〕

It is preferable that a photosensitive transfer material is equipped with the protective film which contacts the surface which does not oppose a temporary support body of a photosensitive resin layer.

Examples of the material constituting the protective film include resin films and paper, and resin films are preferred from the viewpoint of strength and flexibility.

As a resin film, a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film are mentioned. Among them, a polyethylene film, a polypropylene film, or a polyethylene terephthalate film is preferable.

The thickness (layer thickness) of the protective film is not particularly limited, but is preferably 5 μm to 100 μm, more preferably 10 to 50 μm.

And, from the standpoint of more excellent resolution, the arithmetic average roughness Ra value of the surface of the protective film in contact with the photosensitive resin layer (hereinafter also simply referred to as "the surface of the protective film") is preferably 0.3 μm or less, more preferably It is 0.1 μm or less, more preferably 0.05 μm or less. This is considered to be because the uniformity of the layer thickness of the photosensitive resin layer and the formed resin pattern improves when the Ra value of the surface of a protective film exists in the said range.

The lower limit of the Ra value of the surface of the protective film is not particularly limited, but is preferably 0.001 μm or more.

The Ra value of the surface of the protective film was measured by the following method.

Using a three-dimensional optical profiler (New View7300, manufactured by Zygo Corporation), the surface of the protective film was measured under the following conditions to obtain the surface profile of the optical film.

As measurement and analysis software, Microscope Application of MetroPro ver8.3.2 was used. Next, use the above analysis software to display the Surface Map screen, and obtain the histogram data on the Surface Map screen. The arithmetic mean roughness was calculated from the obtained histogram data to obtain the Ra value of the surface of the protective film.

When the protective film is bonded to the photosensitive transfer material, the protective film may be peeled from the photosensitive transfer material, and the Ra value of the surface on the peeled side may be measured.

It does not specifically limit about the method of bonding a protective film to a photosensitive resin layer etc., A well-known method is mentioned.

As an apparatus which bonds a protective film to a photosensitive resin layer etc., well-known laminators, such as a vacuum laminator and an automatic cutting laminator, are mentioned.

The laminator is preferably equipped with any heatable roller such as a rubber roller, and is capable of pressurization and heating.

The photosensitive transfer material may include layers (hereinafter also referred to as "other layers") other than the above-mentioned layers. As other layers, for example, a contrast enhancement layer can be mentioned.

Regarding the contrast enhancement layer, it is described in paragraph 0134 of International Publication No. 2018/179640. In addition, other layers are described in paragraphs 0194 to 0196 of JP-A-2014-85643. The contents of these gazettes are incorporated into this specification.

From the viewpoint of further exhibiting the effects of the present invention, the total thickness of the layers in the photosensitive transfer material other than the temporary support and the protective film is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, Especially preferably, it is 2 μm or more and 8 μm or less.

In addition, from the viewpoint of further exerting the effects of the present invention, the total thickness of the photosensitive resin layer, intermediate layer, and thermoplastic resin layer in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less, especially preferably not less than 2 μm and not more than 8 μm.

The photosensitive transfer material according to the present invention can be preferably used in various applications requiring precise microfabrication by photolithography. After patterning the photosensitive resin layer, the photosensitive resin layer may be etched as a film, or electroforming mainly by electroplating may be performed. Furthermore, the cured film obtained by patterning can be used as a permanent film, for example, an interlayer insulating film, a wiring protection film, a wiring protection film having a refractive index matching layer, and the like. In addition, the photosensitive transfer material according to the present invention can be preferably used in semiconductor packages, printed circuit boards, various wiring formation applications of sensor substrates, touch panels, electromagnetic shield materials, conductive films such as film heaters, liquid crystal sealing, etc. In applications such as the formation of structures in the fields of materials, micromechanics, or microelectronics.

[Manufacturing method of photosensitive transfer material]

The method for producing the photosensitive transfer material used in the present invention is not particularly limited, and a known production method, for example, a known method for forming each layer can be used.

Hereinafter, with reference to FIG. 1, the manufacturing method of the photosensitive transfer material which concerns on this invention is demonstrated. However, the photosensitive transfer material according to the present invention is not limited to the photosensitive transfer material having the structure shown in FIG. 1 .

FIG. 1 is a schematic cross-sectional view illustrating an example of a layer structure in an embodiment of a photosensitive transfer material according to the present invention. The photosensitive transfer material 20 shown in FIG. 1 has the structure which laminated|stacked the temporary support body 11, the thermoplastic resin layer 13, the water-soluble resin layer 15, the photosensitive resin layer 17, and the protective film 19 in this order.

As a method for producing the above-mentioned photosensitive transfer material 20, for example, a method including the steps of coating the thermoplastic resin composition on the surface of the temporary support 11, drying the coating film of the thermoplastic resin composition, and The process of thus forming the thermoplastic resin layer 13; after coating the water-soluble resin layer composition on the surface of the thermoplastic resin layer 13, drying the coating film of the water-soluble resin layer composition to form the water-soluble resin layer 15; and A step of forming the photosensitive resin layer 17 by drying the coating film of the photosensitive resin composition after coating the photosensitive resin composition containing an alkali-soluble resin and an ethylenically unsaturated compound on the surface of the water-soluble resin layer 15 .

In the above production method, it is preferable to use the following composition: containing at least one thermoplastic resin composition selected from an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent; At least one water-soluble resin layer composition in miscible organic solvents; and containing alkali-soluble resins, ethylenically unsaturated compounds, and solvents selected from alkylene glycol ether solvents and alkylene glycol ether acetate solvents At least one photosensitive resin composition in. Thereby, the application of the water-soluble resin layer composition to the surface of the thermoplastic resin layer 13 and/or the thermoplastic resin layer 13 during storage of the laminate having the coating film of the water-soluble resin layer composition can be suppressed. The ingredients contained in the water-soluble resin layer 15 can be mixed with the ingredients contained in the water-soluble resin layer 15, and the coating of the photosensitive resin composition on the surface of the water-soluble resin layer 15 and/or the coating film with the photosensitive resin composition can be suppressed. Mixing of components contained in the water-soluble resin layer 15 and components contained in the photosensitive resin layer 17 during storage of the laminated body.

The photosensitive transfer material 20 is manufactured by press-bonding the protective film 19 to the photosensitive resin layer 17 of the laminated body manufactured by the above-mentioned manufacturing method.

As the method for producing the photosensitive transfer material used in the present invention, it is preferable to manufacture a photosensitive transfer material comprising the temporary support 11, thermoplastic resin layer, etc. 13. The photosensitive transfer material 20 of the water-soluble resin layer 15 , the photosensitive resin layer 17 and the protective film 19 .

After the photosensitive transfer material 20 is produced by the above-mentioned production method, the photosensitive transfer material 20 can be wound up to produce and store the photosensitive transfer material in roll form. The photosensitive transfer material in roll form can be directly supplied in this form to the bonding process with the board|substrate in the roll-to-roll system mentioned later.

The photosensitive transfer material according to the present invention can be preferably used in various applications requiring precise microfabrication by photolithography. After patterning the photosensitive resin layer, the photosensitive resin layer may be etched as a film, or electroforming mainly by electroplating may be performed. Furthermore, the cured film obtained by patterning can be used as a permanent film, for example, an interlayer insulating film, a wiring protection film, a wiring protection film having a refractive index matching layer, and the like. In addition, the photosensitive transfer material according to the present invention can be preferably used in semiconductor packages, printed circuit boards, various wiring formation applications of sensor substrates, touch panels, electromagnetic shield materials, conductive films such as film heaters, liquid crystal sealing, etc. In applications such as the formation of structures in the fields of materials, micromechanics, or microelectronics.

In addition, the photosensitive transfer material of the first embodiment may preferably include an aspect in which the photosensitive resin layer contains a pigmented colored resin layer.

As the use of the colored resin layer, in addition to the above, for example, it is suitable for forming a liquid crystal display device (LCD) and a solid-state imaging element [for example, CCD (charge-coupled device: charge-coupled device) and CMOS (complementary metal oxide semiconductor: Complementary Metal Oxide Semiconductor)] colored pixels or black matrix applications such as color filters.

About the aspect other than a pigment in a colored resin layer, it is the same as the above-mentioned aspect.

<pigment>

The photosensitive resin layer may be a colored resin layer containing a pigment.

In order to protect the liquid crystal display window included in recent electronic devices, a cover glass in which a black frame-shaped light-shielding layer is formed on the back peripheral portion of a transparent glass substrate or the like is sometimes attached. In order to form such a light-shielding layer, a colored resin layer can be used.

As a pigment, what is necessary is just to select suitably according to desired hue, and can select from black pigment, white pigment, and color pigments other than black and white. Among them, when forming a black-based pattern, it is preferable to select a black pigment as the pigment.

Known black pigments (organic pigments, inorganic pigments, etc.) can be appropriately selected as the black pigment within a range that does not impair the effects of the present invention. Among them, from the viewpoint of optical density, examples of the black pigment preferably include carbon black, titanium oxide, titanium carbide, iron oxide, graphite, and the like, and carbon black is particularly preferable. As carbon black, carbon black in which at least a part of the surface is coated with a resin is preferable from the viewpoint of surface resistance.

From the viewpoint of dispersion stability, the particle size of the black pigment is preferably from 0.001 μm to 0.1 μm, more preferably from 0.01 μm to 0.08 μm, as a number average particle size.

Here, the particle diameter refers to the diameter of a circle when the area of the pigment particle is calculated from the photographic image of the pigment particle taken with an electron microscope and a circle having the same area as the area of the pigment particle is considered, and the number average particle diameter refers to the number average particle diameter for any 100 particles. The above-mentioned particle diameter was obtained, and the average value obtained by averaging 100 obtained particle diameters was obtained.

As the pigments other than the black pigment, the white pigments described in paragraphs 0015 and 0114 of JP-A-2005-007765 can be used as the white pigment. Specifically, among white pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate are preferred as inorganic pigments, and titanium oxide or oxide Zinc is more preferably titanium oxide. As the inorganic pigment, rutile-type or anatase-type titanium oxide is more preferable, and rutile-type titanium oxide is especially preferable.

Furthermore, the surface of titania may be treated with silica, alumina, titania, zirconia, or organic matter, or two or more treatments may be performed. Thereby, the catalytic activity of titanium oxide is suppressed, and heat resistance, delustering properties, and the like are improved.

From the viewpoint of reducing the thickness of the photosensitive resin layer after heating, as the surface treatment on the surface of titanium oxide, at least one of alumina treatment and zirconia treatment is preferred, and alumina treatment and zirconia treatment are particularly preferred. handle both.

Furthermore, when the photosensitive resin layer is a colored resin layer, it is also preferable that the photosensitive resin layer further contains color pigments other than the black pigment and the white pigment from the viewpoint of transferability. When a color pigment is included, the particle size of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of better dispersibility.

Examples of color pigments include Victoria Pure Blue BO (Color Index (Color Index) (hereinafter C.I.) 42595), Auramine (C.I. 41000), Fat Black (fat black) HB (C.I. 26150), Monolite Yellow (monolight yellow) GT (C.I. Pigment Yellow 12), permanent yellow (permanent yellow) GR (C.I. Pigment Yellow 17), permanent yellow HR (C.I. Pigment Yellow 83), permanent carmine (permanent carmine) FBB (C.I. Pigment Red 146 ), Herstaperm red (hostaperm red) ESB (C.I. Pigment Violet 19), permanent ruby red (permanent ruby) FBH (C.I. Pigment Red 11), Fastel pink (pastel pink) B Supura (supura ) (C.I. Pigment Red 81), monastralfast blue (C.I. Pigment Blue 15), Monolette Fast Black B (C.I. Pigment Black 1) and Carbon, C.I. Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15: 4. C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64 and C.I. Pigment Violet 23, etc. Among them, C.I. Pigment Red 177 is preferable.

When the photosensitive resin layer contains a pigment, the content of the pigment is preferably more than 3% by mass and not more than 40% by mass, more preferably more than 3% by mass and not more than 35% by mass, and still more preferably More than 5% by mass and not more than 35% by mass, particularly preferably not less than 10% by mass and not more than 35% by mass.

When the photosensitive resin layer contains pigments (white pigments and color pigments) other than black pigments, the content of pigments other than black pigments is preferably 30% by mass or less, more preferably 1% by mass to 20% by mass, based on the black pigment. % by mass, more preferably 3% by mass to 15% by mass.

In addition, when the photosensitive resin layer contains a black pigment, and the photosensitive resin layer is formed of a photosensitive resin composition, the black pigment (preferably carbon black) is preferably introduced into the photosensitive resin composition in the form of a pigment dispersion. .

The dispersion liquid can be prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent (or vehicle) and dispersing it with a disperser. What is necessary is just to select a pigment dispersant according to a pigment and a solvent, For example, a commercially available dispersant can be used. In addition, the carrier refers to the part of the medium that disperses the pigment when preparing the pigment dispersion liquid. It is liquid and contains a binder component that maintains the black pigment in a dispersed state and a solvent component (organic solvent) that dissolves and dilutes the binder component. .

The dispersing machine is not particularly limited, and examples thereof include a kneader, a roll mill, an attritor, a super mill, a dissolver, and a homo mixer. and a known dispersing machine such as a sand mill. In addition, it is also possible to perform fine pulverization by mechanical pulverization using frictional force. Regarding the disperser and the fine pulverization, the description in "Paint Dictionary" (by Kuni Asakura, first edition, Asakura Shoten, 2000, pages 438 and 310) can be referred to.

[[Photosensitive Transfer Material of Second Embodiment]]

Hereinafter, an example is given and the photosensitive transfer material of 2nd Embodiment is demonstrated.

The photosensitive transfer material 10 shown in FIG. 2 has the temporary support body 1, the transfer layer 2 containing the photosensitive resin layer 3 and the refractive index adjustment layer 5, and the protective film 7 in this order.

Moreover, although the photosensitive transfer material 10 shown in FIG. 2 is the form which arrange|positioned the refractive index adjustment layer 5, the refractive index adjustment layer 5 may not be arrange|positioned.

Hereinafter, each requirement which comprises the photosensitive transfer material of 2nd Embodiment is demonstrated.

The temporary support body and protective film used in the photosensitive transfer material of 2nd Embodiment are the same as the temporary support body and protective film in the photosensitive transfer material of 1st Embodiment, and a preferable form is also the same.

〔Photosensitive resin layer〕

The photosensitive transfer material has a photosensitive resin layer.

After the photosensitive resin layer is transferred onto the to-be-transferred body, a pattern can be formed on the to-be-transferred body by exposing and developing.

Hereinafter, components which may be contained in the photosensitive resin layer will be described in detail.

<Alkali-soluble resin>

The photosensitive resin layer contains alkali-soluble resin.

Examples of alkali-soluble resins include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenolic resins, ester resins, urethane resins, Epoxy acrylate resin obtained by reaction of epoxy resin and (meth)acrylic acid, and acid-modified epoxy acrylate resin obtained by reaction of epoxy acrylate resin and acid anhydride.

As one of the preferable aspects of alkali-soluble resin, (meth)acrylic resin is mentioned from a viewpoint which is excellent in alkali developability and film formability.

In addition, in this specification, a (meth)acrylic resin means resin which has a structural unit derived from a (meth)acrylic compound. The content of the structural unit derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, based on all the structural units of the (meth)acrylic resin.

A (meth)acrylic resin may consist only of a structural unit derived from a (meth)acrylic compound, or may have a structural unit derived from a polymerizable monomer other than a (meth)acrylic compound. That is, the upper limit of content of the structural unit derived from a (meth)acrylic compound is 100 mass % or less with respect to all the structural units of a (meth)acrylic resin.

As a (meth)acrylic compound, (meth)acrylic acid, (meth)acrylate, (meth)acrylamide, and (meth)acrylonitrile are mentioned, for example.

Examples of (meth)acrylates include alkyl (meth)acrylates, tetrahydrofurfuryl (meth)acrylates, dimethylaminoethyl (meth)acrylates, (meth)acrylic acid Diethylaminoethyl ester, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate and 2,2,3,3-tetra Fluoropropyl (meth)acrylates, preferably alkyl (meth)acrylates.

As (meth)acrylamide, acrylamides, such as diacetone acrylamide, are mentioned, for example.

Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate, ) pentyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, ( Alkyl (meth)acrylates having an alkyl group having 1 to 12 carbon atoms, such as decyl meth)acrylate, undecyl (meth)acrylate, and dodecyl (meth)acrylate.

The (meth)acrylate is preferably an alkyl (meth)acrylate having an alkyl group having 1 to 4 carbon atoms, more preferably methyl (meth)acrylate or ethyl (meth)acrylate.

The (meth)acrylic resin may have structural units other than the structural unit derived from the (meth)acrylic compound.

The polymerizable monomer forming the above-mentioned structural unit is not particularly limited as long as it is a compound other than a (meth)acrylic compound that can be copolymerized with a (meth)acrylic compound. For example, styrene, vinyl Styrenic compounds such as toluene and α-methylstyrene that may have substituents at the α position or on the aromatic ring, vinyl alcohol esters such as acrylonitrile and vinyl n-butyl ether, maleic acid, maleic anhydride, maleic acid Maleic acid monoesters such as monomethyl, monoethyl maleate, and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid.

These polymerizable monomers may be used alone or in combination of two or more.

Moreover, it is preferable that a (meth)acrylic resin contains the structural unit which has an acid group from a viewpoint of making alkali developability more favorable. As an acidic group, a carboxyl group, a sulfo group, a phosphoric acid group, and a phosphonic acid group are mentioned, for example.

Among them, the (meth)acrylic resin more preferably contains a structural unit having a carboxyl group, and further preferably has a structural unit derived from the above-mentioned (meth)acrylic acid.

From the viewpoint of excellent developability, the content of the structural unit having an acid group (preferably a structural unit derived from (meth)acrylic acid) in the (meth)acrylic resin is preferably 10% by mass or more. In addition, the upper limit is not particularly limited, but from the viewpoint of excellent alkali resistance, it is preferably 50% by mass or less, more preferably 40% by mass or less.

Moreover, it is more preferable that a (meth)acrylic resin has the structural unit derived from the said alkyl (meth)acrylate.

The content of the structural unit derived from the alkyl (meth)acrylate in the (meth)acrylic resin is preferably 50% by mass to 90% by mass, more preferably 60% by mass, based on all the structural units of the (meth)acrylic resin % to 90% by mass, more preferably 65% to 90% by mass.

The (meth)acrylic resin is preferably a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from an alkyl (meth)acrylate, more preferably a resin composed only of (meth)acrylic acid A resin composed of a structural unit derived from acrylic acid and a structural unit derived from an alkyl (meth)acrylate.

Furthermore, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.

Furthermore, from the viewpoint of more excellent effects of the present invention, the (meth)acrylic resin preferably has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from alkyl methacrylates, preferably It has both a structural unit derived from methacrylic acid and a structural unit derived from an alkyl methacrylate.

From the viewpoint that the effect of the present invention is more excellent, the total content of the structural unit derived from methacrylic acid and the structural unit derived from alkyl methacrylate in the (meth)acrylic resin relative to the (meth)acrylic resin All the structural units of are preferably 40% by mass or more, more preferably 60% by mass or more. The upper limit is not particularly limited, and may be 100% by mass or less, preferably 80% by mass or less.

In addition, from the viewpoint that the effects of the present invention are more excellent, the (meth)acrylic resin preferably has at least one selected from the group consisting of structural units derived from methacrylic acid and structural units derived from alkyl methacrylates and At least one selected from structural units derived from acrylic acid and structural units derived from alkyl acrylates.

From the viewpoint that the effect of the present invention is more excellent, the total content of the structural unit derived from methacrylic acid and the structural unit derived from alkyl methacrylate is relative to the structural unit derived from acrylic acid and the content of alkyl acrylate derived The total content of the structural units is preferably 60/40 to 80/20 by mass ratio.

It is preferable that the (meth)acrylic resin has an ester group at the terminal from the viewpoint of being excellent in the developability of the photosensitive resin layer after transfer.

In addition, the terminal portion of the (meth)acrylic resin is constituted by a portion derived from a polymerization initiator used for synthesis. A (meth)acrylic resin having an ester group at a terminal can be synthesized by using a polymerization initiator that generates a radical having an ester group.

In addition, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH/g or more, for example, from the viewpoint of developability.

And, for example, from the viewpoint of thermally crosslinking with a crosslinking component by heating to easily form a firm film, the alkali-soluble resin is more preferably a resin having a carboxyl group with an acid value of 60 mgKOH/g or more (so-called carboxyl group-containing resin) , more preferably a (meth)acrylic resin having a carboxyl group (so-called carboxyl group-containing (meth)acrylic resin) having an acid value of 60 mgKOH/g or more.

If the alkali-soluble resin is a resin having a carboxyl group, for example, by adding a heat-crosslinkable compound such as a blocked isocyanate compound, thermal crosslinking can be performed to increase the three-dimensional crosslink density. Moreover, when the carboxyl group of the resin which has a carboxyl group is dehydrated and hydrophobized, heat-and-moisture resistance can be improved.

The carboxyl group-containing (meth)acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited as long as it satisfies the above acid value conditions, and can be appropriately selected from known (meth)acrylic resins.

For example, the carboxyl group-containing acrylic resin described in paragraph 0025 of JP-A-2011-095716 and the acrylic resin described in paragraphs 0033-0052 of JP-A-2010-237589 can be preferably used. Among the described polymers are carboxyl group-containing acrylic resins with an acid value of 60 mgKOH/g or more.

As another preferred embodiment of the alkali-soluble resin, a styrene-acrylic acid copolymer is mentioned. In addition, in this specification, a styrene-acrylic acid copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound, and the structural unit derived from the above-mentioned styrene compound and its source The total content of the structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, relative to all the structural units of the above-mentioned copolymer.

Furthermore, the content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 5% by mass to 80% by mass based on all the structural units of the copolymer.

In addition, the content of the structural unit derived from the above-mentioned (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass to 95% by mass of all the structural units of the above-mentioned copolymer. %.

From the viewpoint of more excellent effects in the present invention, the alkali-soluble resin preferably has an aromatic ring structure, and more preferably has a structural unit including an aromatic ring structure.

Examples of monomers that form structural units having an aromatic ring structure include styrene compounds such as styrene, tert-butoxystyrene, methylstyrene, and α-methylstyrene, and benzyl (meth)acrylate. wait.

Among them, styrene compounds are preferable, and styrene is more preferable.

Moreover, it is more preferable that the alkali-soluble resin has the structural unit (structural unit derived from styrene) represented by following formula (S) from the viewpoint of the more excellent effect in this invention.

[chemical formula 4]

When the alkali-soluble resin contains a structural unit having an aromatic ring structure, the content of the structural unit having an aromatic ring structure relative to all the structural units of the alkali-soluble resin is preferably 5 from the viewpoint of more excellent effects in the present invention. % by mass to 90% by mass, more preferably 10% by mass to 70% by mass, still more preferably 20% by mass to 60% by mass.

And, from the viewpoint of more excellent effects in the present invention, the content of the structural unit having an aromatic ring structure in the alkali-soluble resin is preferably 5 mol % to 70 mol %, more preferably It is 10 mol% - 60 mol%, More preferably, it is 20 mol% - 60 mol%.

In addition, from the viewpoint of more excellent effects in the present invention, the content of the structural unit represented by the above formula (S) in the alkali-soluble resin is preferably 5 mol% to 70 mol% with respect to all the structural units of the alkali-soluble resin. , more preferably 10 mol% to 60 mol%, still more preferably 20 mol% to 60 mol%, especially preferably 20 mol% to 50 mol%.

In addition, in this specification, when content of a "structural unit" is prescribed|regulated by molar ratio, the said "structural unit" has the same meaning as a "monomer unit." In addition, in the present specification, the above-mentioned "monomer unit" may be modified after being polymerized by a polymer reaction or the like. The same applies to the following.

The alkali-soluble resin preferably has an aliphatic hydrocarbon ring structure from the viewpoint of more excellent effects in the present invention. That is, the alkali-soluble resin preferably contains a structural unit having an aliphatic hydrocarbon ring structure. Among them, the alkali-soluble resin more preferably has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.

Examples of the ring constituting the aliphatic hydrocarbon ring structure in the structural unit having the aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane (norbornane) ring, and an isoborane ring. alkane ring.

Among them, from the viewpoint of more excellent effects in the present invention, a ring formed by condensing two or more aliphatic hydrocarbon rings is preferable, and a tetrahydrodicyclopentadiene ring (tricyclo[5.2.1.0 ^{2 , 6} ] decane ring).

As a monomer which forms the structural unit which has an aliphatic hydrocarbon ring structure, dicyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate are mentioned.

And, from the viewpoint of the more excellent effects in the present invention, the alkali-soluble resin more preferably has the structural unit represented by the following formula (Cy), more preferably has the structural unit represented by the above-mentioned formula (S) and the following formula ( The structural unit represented by Cy).

[chemical formula 5]

In formula (Cy), R ^M represents a hydrogen atom or a methyl group, and R ^Cy represents a monovalent group having an aliphatic hydrocarbon ring structure.

R ^M in formula (Cy) is preferably methyl.

From the viewpoint of more excellent effects in the present invention, R ^Cy in the formula (Cy) is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, more preferably a group having 6 carbon atoms The monovalent group having an aliphatic hydrocarbon ring structure of ∼16 carbon atoms is more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms.

The aliphatic hydrocarbon ring structure in R ^Cy of the formula (Cy) may be a monocyclic structure or a polycyclic structure.

And, from the viewpoint of more excellent effects in the present invention, the aliphatic hydrocarbon ring structure in R ^Cy of formula (Cy) is preferably a cyclopentane ring structure, a cyclohexane ring structure, tetrahydrodicyclopentadiene The ring structure, norbornane ring structure, or isoborane ring structure is more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and is still more preferably a tetrahydrodicyclopentadiene ring structure.

In addition, from the viewpoint of more excellent effects in the present invention, the aliphatic hydrocarbon ring structure in R ^Cy of formula (Cy) is preferably a ring structure in which two or more aliphatic hydrocarbon rings are condensed, more preferably 2 A ring formed by condensing aliphatic hydrocarbon rings of ~4 rings.

In addition, R ^Cy in the formula (Cy) is preferably such that the oxygen atom of -C(=O)O- in the formula (Cy) is directly bonded to the aliphatic hydrocarbon ring structure from the viewpoint of a more excellent effect in the present invention. The group is an aliphatic hydrocarbon ring group, more preferably cyclohexyl or dicyclopentyl, even more preferably dicyclopentyl.

Alkali-soluble resin may have 1 type of structural unit which has an aliphatic hydrocarbon ring structure independently, and may have 2 or more types.

In the case where the alkali-soluble resin contains a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure relative to all the structural units of the alkali-soluble resin is Preferably it is 5 mass % - 90 mass %, More preferably, it is 10 mass % - 80 mass %, More preferably, it is 20 mass % - 70 mass %.

And, from the viewpoint of more excellent effects in the present invention, the content of the structural unit having the aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably 5 mol% to 70 mol% with respect to all the structural units of the alkali-soluble resin, More preferably, it is 10 mol% - 60 mol%, More preferably, it is 20 mol% - 50 mol%.

In addition, from the viewpoint of more excellent effects in the present invention, the content of the structural unit represented by the above formula (Cy) in the alkali-soluble resin is preferably 5 mol% to 70 mol% with respect to all the structural units of the alkali-soluble resin. , more preferably 10 mol % to 60 mol %, still more preferably 20 mol % to 50 mol %.

In the case where the alkali-soluble resin includes a structural unit having an aromatic ring structure and a structural unit having an aliphatic hydrocarbon ring structure, from the viewpoint of more excellent effects in the present invention, the structural unit having an aromatic ring structure and the structural unit having an aliphatic hydrocarbon The total content of structural units of the ring structure is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 40% by mass to 75% by mass, based on all the structural units of the alkali-soluble resin.

And, from the viewpoint of more excellent effects in the present invention, the total content of structural units having an aromatic ring structure and structural units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is preferably It is 10 mol% - 80 mol%, More preferably, it is 20 mol% - 70 mol%, More preferably, it is 40 mol% - 60 mol%.

In addition, from the viewpoint of more excellent effects in the present invention, the total content of the structural unit represented by the above-mentioned formula (S) and the structural unit represented by the above-mentioned formula (Cy) in the alkali-soluble resin is relative to the total content of the alkali-soluble resin. The structural unit is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, and still more preferably 40 mol% to 60 mol%.

And, from the viewpoint of more excellent effects in the present invention, the molar amount nS of the structural unit represented by the above-mentioned formula (S) in the alkali-soluble resin and the molar amount nCy of the structural unit represented by the above-mentioned formula (Cy) are preferably It satisfies the relationship represented by the following formula (SCy), more preferably satisfies the following formula (SCy-1), and further preferably satisfies the following formula (SCy-2).

0.2≤nS/(nS+nCy)≤0.8 Formula (SCy)

0.30≤nS/(nS+nCy)≤0.75 Formula (SCy-1)

0.40≤nS/(nS+nCy)≤0.70 Formula (SCy-2)

From the viewpoint of more excellent effects in the present invention, the alkali-soluble resin preferably includes a structural unit having an acidic group.

Examples of the above-mentioned acid groups include carboxyl groups, sulfo groups, phosphonic acid groups, and phosphoric acid groups, and carboxyl groups are preferred.

As the above-mentioned structural unit having an acid group, a structural unit derived from (meth)acrylic acid shown below is preferable, and a structural unit derived from methacrylic acid is more preferable.

[chemical formula 6]

Alkali-soluble resins may have one type of structural unit having an acid group alone, or may have two or more types.

When the alkali-soluble resin contains a structural unit having an acid group, the content of the structural unit having an acid group is preferably 5% by mass relative to all the structural units of the alkali-soluble resin from the viewpoint of a more excellent effect in the present invention. -50% by mass, more preferably 5% by mass to 40% by mass, still more preferably 10% by mass to 30% by mass.

And, from the viewpoint of more excellent effects in the present invention, the content of the structural unit having an acid group in the alkali-soluble resin is preferably 5 mol % to 70 mol %, more preferably 10 mol% to 50 mol%, more preferably 20 mol% to 40 mol%.

In addition, from the viewpoint of more excellent effects in the present invention, the content of the structural unit derived from (meth)acrylic acid in the alkali-soluble resin is preferably 5 mol % to 70 mol % with respect to all the structural units of the alkali-soluble resin. , more preferably 10 mol % to 50 mol %, still more preferably 20 mol % to 40 mol %.

From the viewpoint of more excellent effects in the present invention, the alkali-soluble resin preferably has a reactive group, and more preferably contains a structural unit having a reactive group.

The reactive group is preferably a radical polymerizable group, more preferably an ethylenically unsaturated group. Furthermore, when the alkali-soluble resin has an ethylenically unsaturated group, the alkali-soluble resin preferably includes a structural unit having an ethylenically unsaturated group in the side chain.

In this specification, "main chain" means the relatively longest linking chain in the molecule of the polymer compound constituting the resin, and "side chain" means an atomic group branched from the main chain.

As the ethylenically unsaturated group, an allyl group or a (meth)acryloyloxy group is more preferable.

As an example of the structural unit which has a reactive group, the structural unit shown below is mentioned, However, It is not limited to these.

[chemical formula 7]

The alkali-soluble resin may have one type of structural unit having a reactive group alone, or may have two or more types.

In the case where the alkali-soluble resin contains a structural unit having a reactive group, from the viewpoint of a more excellent effect in the present invention, the content of the structural unit having a reactive group is preferably It is 5 mass % - 70 mass %, More preferably, it is 10 mass % - 50 mass %, More preferably, it is 20 mass % - 40 mass %.

In addition, from the viewpoint that the effect of the present invention is more excellent, the content of the structural unit having a reactive group in the alkali-soluble resin is preferably 5 mol % to 70 mol %, more preferably It is 10 mol% - 60 mol%, More preferably, it is 20 mol% - 50 mol%.

As a method for introducing reactive groups into alkali-soluble resins, compounds such as epoxy compounds, blocked isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds, and carboxylic anhydrides, etc. , carboxyl group, primary amino group, secondary amino group, acetoacetyl group (acetoacetyl group) and sulfo group and other functional groups to react.

As a preferred example of the method for introducing reactive groups into alkali-soluble resins, after synthesizing a polymer having a carboxyl group by polymerization reaction, reacting glycidyl (meth)acrylate with the obtained resin by polymer reaction A method of introducing a (meth)acryloyloxy group into a polymer by reacting a part of the carboxyl group. By this method, the alkali-soluble resin which has a (meth)acryloyloxy group in a side chain can be obtained.

The above-mentioned polymerization reaction is preferably carried out at a temperature of 70°C to 100°C, more preferably at a temperature of 80°C to 90°C. As the polymerization initiator used in the above-mentioned polymerization reaction, an azo-based initiator is preferable, for example, V-601 (trade name) or V-65 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation is more preferable. The above polymer reaction is preferably carried out at a temperature of 80°C to 110°C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

As the alkali-soluble resin, the resins shown below are preferable from the viewpoint that the effect in the present invention is more excellent. In addition, the content ratio (a-d) of each structural unit shown below, weight average molecular weight Mw, etc. can be changed suitably according to the objective.

[chemical formula 8]

[chemical formula 9]

In addition, the alkali-soluble resin may contain a polymer (hereinafter also referred to as "polymer X") including a structural unit having a carboxylic anhydride structure.

The carboxylic anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but is preferably a cyclic carboxylic anhydride structure.

The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 5-membered ring.

The structural unit having a carboxylic anhydride structure is preferably a structural unit comprising a divalent group formed by removing two hydrogen atoms from a compound represented by the following formula P-1 in the main chain, or a structural unit derived from the following formula P-1. In the compound represented by 1, a structural unit in which a monovalent group obtained by removing one hydrogen atom is bonded to the main chain directly or via a divalent linking group.

[chemical formula 10]

In formula P-1, R ^A1a represents a substituent, n ^1a of R ^A1a may be the same or different, and Z ^1a represents a divalent group forming a ring including -C(=O)-OC(=O)- , n ^1a represents an integer of 0 or more.

As a substituent represented by R ^A1a , an alkyl group is mentioned, for example.

Z ^1a is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and even more preferably an alkylene group having 2 carbon atoms.

n ^1a represents an integer of 0 or more. When Z ^1a represents an alkylene group having 2 to 4 carbon atoms, n ^1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and still more preferably 0.

When n ^1a represents an integer of 2 or greater, the plurality of R ^A1a may be the same or different. In addition, a plurality of R ^A1a may be bonded to each other to form a ring, but it is preferable not to bond to each other to form a ring.

The structural unit having a carboxylic anhydride structure is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic anhydride, and even more preferably a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride. The structural unit is particularly preferably a structural unit derived from maleic anhydride or itaconic anhydride, most preferably a structural unit derived from maleic anhydride.

Hereinafter, although the specific example of the structural unit which has a carboxylic anhydride structure is mentioned, the structural unit which has a carboxylic anhydride structure is not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH ₂ OH group or a CF ₃ group, and Me represents a methyl group.

[chemical formula 11]

[chemical formula 12]

The structural unit having a carboxylic anhydride structure in the polymer X may be a single type, or may be two or more types.

The total content of structural units having a carboxylic anhydride structure is preferably 0 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, and still more preferably 10 mol% to 35 mol% with respect to all structural units of the polymer X %.

The photosensitive resin layer may contain only 1 type of polymer X, and may contain 2 or more types.

When the photosensitive resin layer contains the polymer X, the content of the polymer X is preferably 0.1% by mass to 30% by mass relative to the total mass of the photosensitive resin layer, from the viewpoint of a more excellent effect in the present invention, More preferably, it is 0.2 mass % - 20 mass %, More preferably, it is 0.5 mass % - 20 mass %, More preferably, it is 1 mass % - 20 mass %.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 10,000 to 50,000, particularly preferably 20,000 to 30,000, from the viewpoint of more excellent effects in the present invention.

The acid value of the alkali-soluble resin is preferably 10 mgKOH/g to 200 mgKOH/g, more preferably 60 mgKOH/g to 200 mgKOH/g, even more preferably 60 mgKOH/g to 150 mgKOH/g, and especially preferably 60 mgKOH/g to 110 mgKOH/g.

In addition, the acid value of alkali-soluble resin is the value measured according to the method described in JISK0070:1992.

The photosensitive resin layer may contain only 1 type of alkali-soluble resin, and may contain 2 or more types.

From the viewpoint of more excellent effects in the present invention, the content of the alkali-soluble resin is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, relative to the total mass of the photosensitive resin layer, More preferably, it is 30 mass % - 70 mass %.

<Ethylenically unsaturated compound>

The photosensitive resin layer contains an ethylenically unsaturated compound.

As the ethylenically unsaturated group, a (meth)acryloyloxy group is preferable.

In addition, the ethylenically unsaturated compound in this specification is a compound other than the said alkali-soluble resin, Preferably it is a molecular weight less than 5,000.

Furthermore, as a preferable aspect of the ethylenic unsaturated compound used in 2nd Embodiment, the preferable aspect of the ethylenic unsaturated compound used in 1st Embodiment mentioned above is mentioned.

As one of the preferred embodiments of the ethylenically unsaturated compound, a compound represented by the following formula (M) (also simply referred to as "compound M") is exemplified.

Q ² -R ¹ -Q ¹ formula (M)

In the formula (M), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group, and R ¹ represents a divalent linking group having a chain structure.

Q ¹ and Q ² in the formula (M) are preferably the same group from the viewpoint of easiness of synthesis.

In addition, Q ¹ and Q ² in the formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.

R ¹ in the formula (M) is preferably an alkylene group, an alkyleneoxyalkylene group (-L ¹ -OL ¹ -) or a polyalkyleneoxy group from the viewpoint of more excellent effects in the present invention. An alkylene group (-(L ¹ -O) _p -L ¹ -), more preferably a hydrocarbon group or a polyalkyleneoxyalkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 4 to 20 carbon atoms The alkyl group is particularly preferably a linear alkylene group having 6 to 18 carbon atoms.

The above-mentioned hydrocarbon group is not particularly limited as long as at least a part thereof has a chain structure, and the part other than the above-mentioned chain structure is not particularly limited. Any one of an alkyl group, an arylene group, an ether bond, and combinations thereof, preferably an alkylene group or a combination of two or more alkylene groups and one or more arylene groups, more preferably an alkylene group group, more preferably a linear alkylene group.

In addition, the above L ¹ each independently represent an alkylene group, preferably an ethylene group, a propylene group or a butylene group, more preferably an ethylene group or a 1,2-propylene group.

p represents an integer of 2 or more, preferably an integer of 2-10.

In addition, from the viewpoint of more excellent effects in the present invention, the number of atoms in the shortest connecting chain connecting ^Q1 and ^Q2 in compound M is preferably 3 to 50, and more preferably 4 to 40. , more preferably 6 to 20, particularly preferably 8 to 12.

In this specification, "the number of atoms of the shortest link linking ^Q1 and ^Q2 " is the shortest link linking from the atom in ^R1 linking to ^Q1 to the atom in ^R1 linking ^Q2 atomic number.

Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate , 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9- Nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, tricyclodecane dimethanol dimethacrylate (meth)acrylate, di(meth)acrylate of hydrogenated bisphenol A, di(meth)acrylate of hydrogenated bisphenol F, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate base) acrylate, poly(ethylene glycol/propylene glycol) di(meth)acrylate and polytetramethylene glycol di(meth)acrylate. The aforementioned ester monomers can also be used as mixtures.

Among the above-mentioned compounds, from the viewpoint of more excellent effects in the present invention, preferably selected from 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate At least one compound selected from esters, 1,10-decanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate, more preferably selected from 1,6-hexanediol di(meth)acrylate base) acrylate, 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate, more preferably selected from 1,9- At least one compound selected from nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate.

Moreover, as one of the preferable aspects of an ethylenic unsaturated compound, the ethylenic unsaturated compound more than bifunctional is mentioned.

In this specification, a "difunctional or higher ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule.

As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryloyl group is preferable.

As an ethylenic unsaturated compound, a (meth)acrylate compound is preferable.

The bifunctional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds.

Tricyclodecane dimethanol di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate are mentioned as a bifunctional ethylenically unsaturated compound other than the said compound M.

Commercially available difunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (trade name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), tricyclodecane Decane dimethanol dimethacrylate (trade name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (trade name: NK Ester A-NOD-N , manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.).

It does not specifically limit as a trifunctional or more ethylenically unsaturated compound, It can select suitably from well-known compounds.

Examples of ethylenically unsaturated compounds having trifunctional or higher functions include dipentaerythritol (tri/tetra/penta/hexa)(meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, trimethylolpropane Tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and glycerol tri(meth)acrylate skeleton (meth)acrylate compound .

Here, "(three/four/five/six) (meth)acrylates" include tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates and hexa(meth)acrylates. ) acrylate concept, "(three/tetra) (meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate.

Examples of ethylenically unsaturated compounds include caprolactone-modified compounds of (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura Chemical Co., Ltd., A-9300-1CL, etc.), alkylene oxide-modified compounds of (meth)acrylate compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura Chemical Co., Ltd. ATM-35E, A-9300, EBECRYL (registered trademark) 135 of DAICEL-ALLNEX LTD., etc.), ethoxylated glycerin triacrylate (NK Ester A-GLY manufactured by Shin-Nakamura Chemical Co., Ltd. -9E etc.).

As an ethylenic unsaturated compound, a urethane (meth)acrylate compound is also mentioned.

Urethane (meth)acrylates include urethane di(meth)acrylates, for example, propylene oxide-modified urethane di(meth)acrylates and cyclic Ethylene oxide and propylene oxide modified urethane di(meth)acrylate.

Furthermore, examples of the urethane (meth)acrylate include trifunctional or higher urethane (meth)acrylates. The lower limit of the number of functional groups is more preferably hexafunctional or more, and still more preferably octafunctional or more. In addition, the upper limit of the number of functional groups is preferably 20 functional groups or less. Urethane (meth)acrylates with more than trifunctionality include, for example, 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin-Nakamura Chemical Co., Ltd.) , U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd., and UA -306H, UA-306T, UA-306I, UA-51OH, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.), etc.

As one of the preferable aspects of an ethylenic unsaturated compound, the ethylenic unsaturated compound which has an acidic group is mentioned.

Examples of the acid group include a phosphoric acid group, a sulfo group, and a carboxyl group.

Among these, as the acid group, a carboxyl group is preferable.

Examples of the ethylenically unsaturated compound having an acid group include a trifunctional to tetrafunctional ethylenically unsaturated compound having an acid group [the ethylenically unsaturated compound having a carboxyl group introduced into the skeleton of pentaerythritol tri- and tetraacrylate (PETA) (acid value: 80mgKOH/g～120mgKOH/g)], five- to six-functional ethylenically unsaturated compounds with acid groups (ethylenically unsaturated compounds with carboxyl groups introduced into dipentaerythritol penta- and hexaacrylate (DPHA) Compound [acid value: 25mgKOH/g～70mgKOH/g)], etc.

These trifunctional or more functional ethylenically unsaturated compounds having an acid group can be used in combination with a bifunctional ethylenically unsaturated compound having an acid group as needed.

As the ethylenically unsaturated compound having an acid group, at least one selected from difunctional or higher ethylenically unsaturated compounds having a carboxyl group and their carboxylic acid anhydrides are preferable.

When the ethylenically unsaturated compound which has an acidic group is at least 1 sort(s) chosen from the ethylenically unsaturated compound which has a carboxyl group and more than a function, and its carboxylic acid anhydride, developability and film strength will improve further.

There are no particular limitations on the difunctional or higher ethylenically unsaturated compound having a carboxyl group, and it can be appropriately selected from known compounds.

Examples of difunctional or higher ethylenically unsaturated compounds having a carboxyl group include ARONIX (registered trademark) TO-2349 (manufactured by TOAGOSEI CO., LTD.), ARONIX (registered trademark) M-520 (TOAGOSEI CO., LTD. Manufactured by ARONIX (registered trademark) M-510 (manufactured by TOAGOSEI CO., LTD.).

As the ethylenically unsaturated compound having an acid group, polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942 are preferred, and the contents described in this publication are incorporated in this specification. .

Examples of ethylenically unsaturated compounds include compounds obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol, and compounds obtained by reacting an α,β-unsaturated carboxylic acid with a glycidyl group-containing compound. The resulting compound, a urethane monomer such as a (meth)acrylate compound having a urethane bond, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl - Phthalate, β-Hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate and β-Hydroxypropyl-β'-(meth)acryloyl Phthalate-based compounds such as oxyethyl-phthalate and alkyl (meth)acrylates.

These can be used individually or in combination of 2 or more types.

Examples of compounds obtained by reacting an α,β-unsaturated carboxylic acid with a polyhydric alcohol include 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl) Propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane and 2,2-bis(4-((meth)acryloxypolyethoxypolypropylene) Bisphenol A-based (meth)acrylate compounds such as oxy)phenyl)propane, polyethylene glycol di(meth)acrylate with 2 to 14 oxirane groups, and the number of propylene oxide groups Polypropylene glycol di(meth)acrylate with 2 to 14, polyethylene polypropylene glycol di(meth)acrylate with 2 to 14 ethylene oxide groups and 2 to 14 propylene oxide groups, Trimethylolpropane Di(meth)acrylate, Trimethylolpropane Tri(meth)acrylate, Trimethylolpropane Ethoxylate Tri(meth)acrylate, Trimethylolpropane Diethoxylate trimethylolpropane triethoxytri(meth)acrylate, trimethylolpropane tetraethoxytri(meth)acrylate, trimethylolpropane pentaethyl Oxytri(meth)acrylate, Di(trimethylolpropane)tetraacrylate, Tetramethylolmethane tri(meth)acrylate, Tetramethylolmethane tetra(meth)acrylate, Dipentaerythritol Tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

Among them, preferred are ethylenically unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure, more preferably tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylic acid ester, trimethylolpropane tri(meth)acrylate or di(trimethylolpropane)tetraacrylate.

As the ethylenically unsaturated compound, caprolactone-modified compounds of the ethylenically unsaturated compound (for example, Nippon Kayaku Co., Ltd. KAYARAD (registered trademark) DPCA-20, Shin-Nakamura Chemical Co., Ltd. .A-9300-1CL, etc.), alkylene oxide-modified compounds of ethylenically unsaturated compounds (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E manufactured by Shin-Nakamura Chemical Co., Ltd. , A-9300, EBECRYL (registered trademark) 135, etc. manufactured by DAICEL-ALLNEX LTD.), ethoxylated glycerin triacrylate (A-GLY-9E, etc. manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

Among them, ethylenic unsaturated compounds containing an ester bond are also preferable from the viewpoint of excellent developability of the photosensitive resin layer after transfer as the ethylenic unsaturated compound.

The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but it preferably has a tetramethylolmethane structure or trimethylolpropane from the viewpoint of excellent effects in the present invention. Structure ethylenically unsaturated compounds, more preferably tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate or di (Trimethylolpropane) tetraacrylate.

From the viewpoint of imparting reliability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an aliphatic group having 6 to 20 carbon atoms and the aforementioned tetramethylolmethane structure or trimethylolpropane structure of ethylenically unsaturated compounds.

Examples of the ethylenically unsaturated compound having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate and 1,10-decanediol di(meth)acrylate. and tricyclodecane dimethanol di(meth)acrylate.

As one of the preferable aspects of an ethylenically unsaturated compound, the ethylenically unsaturated compound (preferably a bifunctional ethylenically unsaturated compound) which has an aliphatic hydrocarbon ring structure is mentioned.

The above-mentioned ethylenically unsaturated compound is preferably an ethylenically unsaturated compound having a ring structure (preferably a structure selected from a tricyclodecane structure and a tricyclodecene structure) in which two or more rings are condensed with aliphatic hydrocarbon rings. , more preferably a bifunctional ethylenically unsaturated compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed, and even more preferably tricyclodecane dimethanol di(meth)acrylate.

The aliphatic hydrocarbon ring structure is preferably a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, a tricyclodecene structure, a norbornane structure, or an iso Borane structure.

The molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, particularly preferably 300 to 2,200.

The ratio of the content of ethylenically unsaturated compounds with a molecular weight of 300 or less among the ethylenically unsaturated compounds contained in the photosensitive resin layer is preferably 30% by mass relative to the content of all ethylenically unsaturated compounds contained in the photosensitive resin layer % or less, more preferably 25 mass % or less, even more preferably 20 mass % or less.

As one of the preferred forms of the photosensitive resin layer, the photosensitive resin layer preferably contains a difunctional or higher ethylenically unsaturated compound, more preferably a trifunctional or higher ethylenically unsaturated compound, and further preferably a trifunctional or tetrafunctional ethylenic unsaturated compound. It is an unsaturated compound.

Furthermore, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an alkali-soluble resin including a structural unit having an aliphatic hydrocarbon ring.

And, as one of the preferred forms of the photosensitive resin layer, the photosensitive resin layer preferably contains the compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, and more preferably contains 1,9-nonanediol diacrylic acid ester, tricyclodecane dimethanol diacrylate and polyfunctional ethylenically unsaturated compounds with carboxylic acid groups, further preferably including 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and dimethanol diacrylate A succinic acid modified form of pentaerythritol pentaacrylate.

And, as one of the preferred forms of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a heat-crosslinkable compound described later, more preferably A compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a blocked isocyanate compound described later.

And, as one of the preferred forms of the photosensitive resin layer, the photosensitive resin layer preferably contains a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound), a trifunctional or higher ethylenically unsaturated compound, compound (preferably a trifunctional or higher (meth)acrylate compound).

Furthermore, as one of the preferred aspects of the photosensitive resin layer, it is preferable that the photosensitive resin layer contains the compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust resistance.

In addition, as one of the preferred forms of the photosensitive resin layer, from the viewpoint of substrate adhesion, development residue suppression and rust prevention, the photosensitive resin layer preferably contains compound M and an ethylenically unsaturated compound having an acidic group, More preferably, it contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acidic group, and further preferably contains compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure. Compounds, trifunctional or higher ethylenically unsaturated compounds and ethylenically unsaturated compounds with acid groups, particularly preferably compounds including compound M, bifunctional ethylenically unsaturated compounds with aliphatic hydrocarbon ring structures, trifunctional or higher ethylenically unsaturated compounds Saturated compounds, ethylenically unsaturated compounds having acid groups, and urethane (meth)acrylate compounds.

In addition, as one of the preferred forms of the photosensitive resin layer, the photosensitive resin layer preferably contains 1,9-nonanediol diacrylate and carboxylated Polyfunctional ethylenically unsaturated compounds with acid groups, more preferably 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and polyfunctional ethylenically unsaturated compounds with carboxylic acid groups, more preferably Containing 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate and ethylenically unsaturated compounds with carboxylic acid groups, especially preferably containing 1,9-nonanediol diacrylate Acrylates, tricyclodecanedimethanol diacrylate, ethylenically unsaturated compounds having carboxylic acid groups, and urethane acrylate compounds.

The photosensitive resin layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.

The content of the difunctional or higher ethylenically unsaturated compound among the above-mentioned ethylenically unsaturated compounds is preferably 60 mass % to 100 mass % with respect to the total content of all the ethylenically unsaturated compounds contained in the photosensitive resin layer, more preferably Preferably it is 80 mass % - 100 mass %, More preferably, it is 90 mass % - 100 mass %.

The ethylenic unsaturated compound may be used individually by 1 type, and may use 2 or more types together.

The content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 70% by mass, and still more preferably 5% by mass, based on the total mass of the photosensitive resin layer ~60% by mass, especially preferably 5% to 50% by mass.

<Photopolymerization Initiator>

The photosensitive resin layer contains a photopolymerization initiator.

As a preferable aspect of the photoinitiator used in 2nd Embodiment, the preferable aspect of the photoinitiator used in 1st Embodiment mentioned above is mentioned.

A photopolymerization initiator may be used individually by 1 type, and may use 2 or more types together.

The content of the photopolymerization initiator is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, and still more preferably at least 1.0% by mass, based on the total mass of the photosensitive resin layer. And as the upper limit, it is preferable that it is 10 mass % or less with respect to the total mass of a photosensitive resin layer, and it is more preferable that it is 5 mass % or less.

<Heterocyclic compound>

The photosensitive resin layer may contain a heterocyclic compound.

The heterocyclic ring possessed by the heterocyclic compound may be any of monocyclic and polycyclic heterocyclic rings.

Examples of the hetero atom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably has at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably has a nitrogen atom.

Examples of heterocyclic compounds include triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, Benzoxazole compounds and pyrimidine compounds.

Among the above, the heterocyclic compound is preferably selected from triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzo At least one compound among oxazole compounds, more preferably selected from triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds at least 1 of the compounds.

Preferred specific examples of heterocyclic compounds are shown below. Examples of the triazole compound and the benzotriazole compound include the following compounds.

[chemical formula 13]

[chemical formula 14]

As the tetrazole compound, the following compounds can be exemplified.

[chemical formula 15]

[chemical formula 16]

As the thiadiazole compound, the following compounds can be illustrated.

[chemical formula 17]

As the triazine compound, the following compounds can be exemplified.

[chemical formula 18]

As the rhodanine compound, the following compounds can be exemplified.

[chemical formula 19]

As the thiazole compound, the following compounds can be exemplified.

[chemical formula 20]

As the benzothiazole compound, the following compounds can be exemplified.

[chemical formula 21]

As the benzimidazole compound, the following compounds can be exemplified.

[chemical formula 22]

[chemical formula 23]

As the benzoxazole compound, the following compounds can be exemplified.

[chemical formula 24]

The heterocyclic compound may be used alone or in combination of two or more.

When the photosensitive resin layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01% by mass to 20.0% by mass, more preferably 0.10% by mass to 10.0% by mass, and furthermore, relative to the total mass of the photosensitive resin layer. Preferably it is 0.30 mass % - 8.0 mass %, Especially preferably, it is 0.50 mass % - 5.0 mass %.

<Aliphatic Thiol Compound>

The photosensitive resin layer may contain an aliphatic thiol compound.

When the photosensitive resin layer contains the aliphatic thiol compound, ene-thiol reaction proceeds between the aliphatic thiol compound and the ethylenically unsaturated compound, thereby suppressing cure shrinkage of the formed film and relaxing stress.

As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, a difunctional or more functional aliphatic thiol compound) is preferable.

Among the above, the aliphatic thiol compound is more preferably a polyfunctional aliphatic thiol compound from the viewpoint of the adhesiveness of the formed pattern (especially the adhesiveness after exposure).

In this specification, a "polyfunctional aliphatic thiol compound" means the aliphatic compound which has 2 or more thiol groups (it is also called a "mercapto group") in a molecule|numerator.

As the polyfunctional aliphatic thiol compound, a low-molecular compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and still more preferably 150 to 1,000.

As the number of functional groups of the polyfunctional aliphatic thiol compound, for example, from the viewpoint of the adhesiveness of the formed pattern, it is preferably bifunctional to decafunctional, more preferably bifunctional to octafunctional, and even more preferably bifunctional to octafunctional. 6 functions.

As polyfunctional aliphatic thiol compounds, for example, trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis( 3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-tri Ketone, trimethylolethane tris(3-mercaptobutyrate), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptopropionic acid) ester), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), ethylene glycol dithiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2, 2'-(ethylenedithio)diethanethiol, meso (mes ₀ )-2,3-dimercaptosuccinic acid and bis(mercaptoethyl)ether.

Among the above, as the polyfunctional aliphatic thiol compound, it is preferably selected from trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane and At least one compound of 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

Examples of monofunctional aliphatic thiol compounds include 1-octyl mercaptan, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl- 3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate and octadecyl-3-mercaptopropionate.

The photosensitive resin layer may contain one type of aliphatic thiol compound alone, or may contain two or more types of aliphatic thiol compounds.

When the photosensitive resin layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5% by mass to 50% by mass, and further preferably 5% by mass to the total mass of the photosensitive resin layer. Preferably it is 5 mass % - 30 mass %, Especially preferably, it is 8 mass % - 20 mass %.

<Heat-crosslinkable compound>

From the viewpoint of the strength of the cured film to be obtained and the adhesiveness of the uncured film to be obtained, the photosensitive resin layer preferably contains a thermally crosslinkable compound.

As the thermally crosslinkable compound used in the photosensitive resin layer of the second embodiment, it is preferable to use the thermally crosslinkable compound described above in the photosensitive resin layer of the first embodiment.

A heat-crosslinkable compound may be used individually by 1 type, and may use 2 or more types together.

When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer. %.

<Surfactant>

The photosensitive resin layer may contain a surfactant.

As the surfactant used in the photosensitive resin layer of the second embodiment, it is preferable to use the surfactant described above in the photosensitive resin layer of the first embodiment.

Surfactants may be used alone or in combination of two or more.

When the photosensitive resin layer contains a surfactant, the content of the surfactant is preferably 0.01% by mass to 3.0% by mass, more preferably 0.01% by mass to 1.0% by mass, and even more preferably It is 0.05 mass % - 0.80 mass %.

<Inhibitor>

The photosensitive resin layer may contain a polymerization inhibitor.

The polymerization inhibitor refers to a compound having a function of delaying or prohibiting a polymerization reaction. As a polymerization inhibitor, the well-known compound used as a polymerization inhibitor can be used, for example.

As a polymerization inhibitor, for example, phenothiazine compounds such as phenothiazine, bis-(1-dimethylbenzyl) phenothiazine and 3,7-dioctyl phenothiazine; bis[3-( 3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl]-o-cresol, 1, 3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl ), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine and pentaerythritol tetra-3-(3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate and other hindered phenolic compounds; 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexyl hydroxylamine and N -Nitroso compounds such as nitrosophenylhydroxylamine or their salts; quinone compounds such as methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone and 4-benzoquinone; 4-methoxyphenol , 4-methoxy-1-naphthol and tert-butylcatechol and other phenolic compounds; copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate And metal salt compounds such as manganese diphenyldithiocarbamate.

Among them, from the viewpoint of more excellent effects in the present invention, the polymerization inhibitor is preferably at least one selected from the group consisting of phenothiazine compounds, nitroso compounds or their salts, and hindered phenol compounds, and more preferably phenothiazine compounds. Oxyzine, bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid][ethylenebis(oxyethylene)]2,4-bis[(laurylthio)methyl ]-o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) and N-nitrosophenylhydroxylamine aluminum salt.

A polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together.

When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 5.0% by mass with respect to the total mass of the photosensitive resin layer, and furthermore Preferably, it is 0.04 mass % - 3.0 mass %.

<Hydrogen donating compound>

The photosensitive resin layer may contain a hydrogen donating compound.

The hydrogen-donating compound has the functions of further improving the sensitivity of the photopolymerization initiator to active light and suppressing the polymerization hindrance of the ethylenically unsaturated compound caused by oxygen.

Examples of hydrogen-donating compounds include amines and amino acid compounds.

Examples of the amines include M.R. Sander et al. "Journal of Polymer Society", Vol. 10, p. 3173 (1972), Japanese Patent Application Publication No. 44-020189, Japanese Patent Application Laid-Open Publication No. 51-082102, Japanese Patent Application Laid-Open Publication No. 51-082102, JP-A-52-134692, JP-A-59-138205, JP-A-60-084305, JP-A-62-018537, JP-A-64-033104 and Research Disclosure 33825 Compounds described in No. etc. More specifically, 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (another name: leuco crystal violet), triethanolamine, p- Ethyl Dimethylaminobenzoate, p-Formyldimethylaniline, and p-Methylthiodimethylaniline.

Among them, the amines are preferably selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane from the viewpoint of more excellent effects in the present invention. At least 1 of them.

Examples of amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.

Among them, N-phenylglycine is preferable as the amino acid compound from the viewpoint of more excellent effects in the present invention.

In addition, as the hydrogen-donating compound, for example, organometallic compounds (tributyltin acetate, etc.) described in Japanese Patent Publication No. 48-042965, and organometallic compounds described in Japanese Patent Publication No. 55-034414 can also be mentioned. Hydrogen and sulfur compounds (trithiane, etc.) described in JP-A-6-308727.

The hydrogen-donating compound may be used alone or in combination of two or more.

When the photosensitive resin layer contains a hydrogen-donating compound, the content of the hydrogen-donating compound is preferably 0.01 mass by mass relative to the total mass of the photosensitive resin layer from the viewpoint of increasing the curing rate by the balance between the polymerization growth rate and chain transfer % to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, still more preferably 0.03% by mass to 5.0% by mass.

<Impurities, etc.>

The photosensitive resin layer may contain a predetermined amount of impurities.

About the impurity in the photosensitive resin layer of 2nd Embodiment, it is the same as the preferable aspect of the said impurity in the photosensitive resin layer of 1st Embodiment.

<Residual Monomer>

The photosensitive resin layer may contain residual monomers corresponding to each structural unit of the above-mentioned alkali-soluble resin.

For the residual monomer corresponding to each structural unit of the alkali-soluble resin in the photosensitive resin layer of the second embodiment, and the residual monomer corresponding to each structural unit of the above-mentioned alkali-soluble resin in the photosensitive resin layer of the first embodiment The preferred mode of the residual monomer is the same.

<other ingredients>

The photosensitive resin layer may contain components (hereinafter also referred to as "other components") other than the above-described components. Examples of other components include colorants, antioxidants, and particles (eg, metal oxide particles). Furthermore, as other components, other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706 can also be mentioned.

-particle-

As the particles, metal oxide particles are preferable.

Metals in the metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.

For example, the average primary particle diameter of the particles is preferably from 1 nm to 200 nm, more preferably from 3 nm to 80 nm, from the viewpoint of transparency of the cured film.

The average primary particle diameter of the particles is calculated by measuring the particle diameters of arbitrary 200 particles using an electron microscope and calculating the arithmetic mean of the measurement results. In addition, when the shape of a particle is not spherical, let the longest side be a particle diameter.

When the photosensitive resin layer contains particles, it may contain only one type of particles different in metal type and size, or may contain two or more types.

Preferably, when the photosensitive resin layer does not contain particles or the photosensitive resin layer contains particles, the content of the particles is more than 0% by mass and not more than 35% by mass relative to the total mass of the photosensitive resin layer, more preferably no particles or the content of the particles Relative to the total mass of the photosensitive resin layer, it is more than 0% by mass and not more than 10% by mass, more preferably no particles or the content of particles is more than 0% by mass and not more than 5% by mass relative to the total mass of the photosensitive resin layer, more preferably not Particles are contained or the content of particles is more than 0 mass % and 1 mass % or less with respect to the total mass of the photosensitive resin layer, and it is particularly preferable not to contain particles.

-Colorant-

The photosensitive resin layer may contain a colorant (pigment, dye, etc.), but preferably does not substantially contain a colorant, for example, from the viewpoint of transparency.

When the photosensitive resin layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the photosensitive resin layer.

-Antioxidants-

As an antioxidant, for example, 1-phenyl-3-pyrazolidone (alias: phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone and other 3-pyrazolidinones; hydroquinone, catechol, pyrogallol, methylhydroquinone and chlorhydroquinone and other polyhydroxybenzenes; p-methylaminophenol, p-aminophenol, p-hydroxyphenylglycine and p-phenylenediamine.

Among these, 3-pyrazolidinones are preferred as antioxidants, and 1-phenyl-3-pyrazolidinone is more preferred from the viewpoint of more excellent effects in the present invention.

When the photosensitive resin layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and still more preferably 0.01% by mass or more, based on the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 1% by mass or less.

<Layer thickness of photosensitive resin layer>

The layer thickness of the photosensitive resin layer is not particularly limited, but it is often 30 μm or less, and from the viewpoint of more excellent effects in the present invention, it is preferably 20 μm or less, more preferably 15 μm or less, even more preferably 10 μm or less , especially preferably 5.0 μm or less. The lower limit is preferably 0.60 μm or more, more preferably 1.5 μm or more, from the viewpoint of excellent strength of a film obtained by curing the photosensitive resin layer.

The thickness of the photosensitive resin layer can be calculated as an average value of arbitrary five points measured by cross-sectional observation with a scanning electron microscope (SEM), for example.

<Refractive Index of Photosensitive Resin Layer>

The refractive index of the photosensitive resin layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.

<Color of photosensitive resin layer>

The photosensitive resin layer is preferably achromatic. Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) in the CIE1976 (L ^* , a ^* , b ^* ) color space, the L ^* value is preferably 10 to 90, a The ^* value is preferably -1.0 to 1.0, and the b ^* value is preferably -1.0 to 1.0.

Moreover, it is preferable that the pattern obtained by hardening a photosensitive resin layer (cured film of a photosensitive resin layer) is achromatic.

Specifically, total reflection (incident angle 8°, light source: D-65 (2° field of view)) in the CIE1976 (L ^* , a ^* , b ^* ) color space, the L ^* value of the pattern is preferably 10 to 90 , the a ^* value of the pattern is preferably -1.0 to 1.0, and the b ^* value of the pattern is preferably -1.0 to 1.0.

[Refractive index adjustment layer]

The photosensitive transfer material preferably has a refractive index adjustment layer.

As the refractive index adjustment layer, known refractive index adjustment layers can be applied. Examples of materials contained in the refractive index adjusting layer include alkali-soluble resins, ethylenically unsaturated compounds, metal salts, and particles.

The method of controlling the refractive index of the refractive index adjusting layer is not particularly limited, and examples thereof include a method of using a resin having a predetermined refractive index alone, a method of using resin and particles, and a method of using a composite of a metal salt and a resin.

As an alkali-soluble resin and an ethylenic unsaturated compound, the alkali-soluble resin and ethylenic unsaturated compound demonstrated in the said "photosensitive resin layer" section are mentioned, for example.

Examples of the particles include metal oxide particles and metal particles.

The type of metal oxide particles is not particularly limited, and known metal oxide particles can be used. Metals in the metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.

For example, the average primary particle diameter of the particles is preferably from 1 nm to 200 nm, more preferably from 3 nm to 80 nm, from the viewpoint of transparency of the cured film.

The average primary particle diameter of the particles is calculated by measuring the particle diameters of arbitrary 200 particles using an electron microscope and calculating the arithmetic mean of the measurement results. In addition, when the shape of a particle is not spherical, let the longest side be a particle diameter.

Specifically, the metal oxide particles are preferably selected from zirconia particles (ZrO ₂ particles), Nb ₂ O ₅ particles, titanium oxide particles (TiO ₂ particles), silica particles (SiO ₂ particles) and those. at least one of the composite particles.

Among these, the metal oxide particles are more preferably at least one kind selected from zirconia particles and titania particles, for example, from the viewpoint of easy adjustment of the refractive index.

Commercially available metal oxide particles include calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F04), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F74), Calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F75), calcined zirconia particles (manufactured by CIK NanoTek Corporation, product name: ZRPGM15WT%-F76), zirconia particles (NanoUse OZ-S30M, Nissan Chemical Industries , Ltd.) and zirconia particles (NanoUse OZ-S30K, Nissan Chemical Industries, Ltd.).

The particles may be used alone or in combination of two or more.

The content of the particles in the refractive index adjusting layer is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and even more preferably 40% by mass to 85% by mass, based on the total mass of the refractive index adjusting layer. .

When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass with respect to the total mass of the refractive index adjusting layer, and furthermore Preferably it is 40 mass % - 85 mass %.

The refractive index of the refractive index adjustment layer is preferably higher than the refractive index of the photosensitive resin layer.

The refractive index of the refractive index adjusting layer is preferably 1.50 or higher, more preferably 1.55 or higher, still more preferably 1.60 or higher, and particularly preferably 1.65 or higher. The upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or less, more preferably 1.85 or less, further preferably 1.78 or less, and particularly preferably 1.74 or less.

The layer thickness of the refractive index adjusting layer is preferably 50 nm to 500 nm, more preferably 55 nm to 110 nm, and still more preferably 60 nm to 100 nm.

<Method for Manufacturing Photosensitive Transfer Material of Second Embodiment>

The method for producing the photosensitive transfer material of the second embodiment is not particularly limited, and a known method can be used.

As a method of manufacturing the photosensitive transfer material 10 shown in FIG. 2 , for example, a method including the steps of applying a photosensitive resin composition on the surface of the temporary support 1 to form a coating film, and further The film is dried to form the photosensitive resin layer 3 ; and the composition for forming a refractive index adjusting layer is applied on the surface of the photosensitive resin layer 3 to form a coating film, and the coating film is further dried to form the refractive index adjusting layer 5 .

The photosensitive transfer material 10 is manufactured by crimping the protective film 7 on the refractive index adjustment layer 5 of the laminate manufactured by the above-mentioned manufacturing method.

As the method of manufacturing the photosensitive transfer material of the first embodiment, it is preferable to include the step of providing the protective film 7 so that the surface of the refractive index adjustment layer 5 on the side opposite to the side having the temporary support 1 is in contact. The photosensitive transfer material 10 provided with the temporary support body 1, the photosensitive resin layer 3, the refractive index adjustment layer 5, and the protective film 7 was manufactured.

The photosensitive transfer material 10 in roll form can be produced and stored by winding up the photosensitive transfer material 10 after manufacturing the photosensitive transfer material 10 by the above-mentioned manufacturing method. The photosensitive transfer material in roll form can be directly supplied in this form to the bonding process with the board|substrate in the roll-to-roll system mentioned later.

Furthermore, as a method of manufacturing the photosensitive transfer material 10 described above, a method may be employed in which the refractive index adjustment layer 5 is formed on the protective film 7 and then the photosensitive resin layer 3 is formed on the surface of the refractive index adjustment layer 5 .

And, as the manufacturing method of the above-mentioned photosensitive transfer material 10, the photosensitive resin layer 3 may be formed on the temporary support body 1, and the refractive index adjustment layer 5 may be formed on the protective film 7, and the photosensitive resin layer 3 may be formed on the protective film 7. A method of bonding and forming the refractive index adjustment layer 5 .

The formation method of the photosensitive resin composition and photosensitive resin layer in 2nd Embodiment is the same as the formation method of the photosensitive resin composition and photosensitive resin layer mentioned above in 1st Embodiment, and a preferable form is also the same.

<Composition for Refractive Index Adjustment Layer Formation and Method for Forming Refractive Index Adjustment Layer>

The composition for forming a refractive index adjusting layer preferably contains various components and a solvent for forming the above-mentioned refractive index adjusting layer. In addition, in the composition for forming a refractive index adjusting layer, the preferred ranges of the content of each component relative to the total solid content of the composition are the same as the above-mentioned preferred ranges of the content of each component relative to the total mass of the refractive index adjusting layer.

The solvent is not particularly limited as long as it can dissolve or disperse the components contained in the refractive index adjusting layer. It is preferably at least one selected from water and water-miscible organic solvents, more preferably water or water-water-miscible organic solvents. solvent mixtures.

Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, preferably alcohols having 1 to 3 carbon atoms, and more preferably methanol or ethanol.

A solvent may be used individually by 1 type, and may use 2 or more types.

The content of the solvent is preferably 50 to 2,500 parts by mass, more preferably 50 to 1,900 parts by mass, and even more preferably 100 to 900 parts by mass with respect to 100 parts by mass of the total solid content of the composition. .

The method for forming the refractive index adjusting layer is not particularly limited as long as it is a method capable of forming a layer containing the above components. For example, known coating methods (slit coating, spin coating, curtain coating, and spray coating) can be mentioned. ink coating, etc.).

And the photosensitive transfer material of 2nd Embodiment can be manufactured by bonding a protective film to a refractive index adjustment layer.

The method of bonding the protective film to the refractive index adjustment layer is not particularly limited, and known methods can be used.

As an apparatus for bonding the protective film to the refractive index adjusting layer, known laminators such as a vacuum laminator and an automatic cutting laminator can be mentioned.

The laminator is preferably equipped with any heatable roller such as a rubber roller, and can be pressurized and heated.

(Manufacturing method of resin pattern and manufacturing method of laminated body)

The manufacturing method of the resin pattern which concerns on this invention is a manufacturing method of the resin pattern which forms a resin pattern on a board|substrate using the photosensitive transfer material which has a temporary support body and a photosensitive resin layer.

As a method for producing a resin pattern, it is preferable to sequentially include the steps of bringing the outermost layer of the photosensitive transfer material according to the present invention on the side having the photosensitive resin layer with respect to the temporary support body into contact with the substrate. The process of bonding (hereinafter also referred to as "bonding process"); the process of pattern exposure of the photosensitive resin layer (hereinafter also referred to as "exposure process"); and the exposed photosensitive resin A layer is developed to form a resin pattern (hereinafter also referred to as "development process").

In addition, in the method for producing a resin pattern according to the present invention, from the viewpoint of further exerting the effects of the present invention, it is preferable to include a line and space pattern in at least a part of the resin pattern, and it is more preferable to include a line and space pattern in at least a part of the resin pattern. The line and space pattern is included in , and the total width of the line and space of at least one set of the line and space pattern is 20 μm or less.

The manufacturing method of the laminated body which concerns on this invention is a manufacturing method of the laminated body which has a resin pattern on a board|substrate using the photosensitive transfer material which concerns on this invention.

As a manufacturing method of a laminated body, the method which sequentially includes the said protective film peeling process, the said bonding process, the said exposure process, and the said image development process is preferable.

<Laminating process>

It is preferable that the manufacturing method of the resin pattern or the manufacturing method of a laminated body includes a bonding process.

In the bonding step, it is preferable to make the outermost layer on the side having the photosensitive resin layer with respect to the above-mentioned temporary support in the photosensitive transfer material and the substrate (when a conductive layer is provided on the surface of the substrate, it is conductive). layer) contact, so that the photosensitive transfer material is pressed against the substrate. According to the above aspect, the adhesiveness between the outermost layer on the side of the photosensitive transfer material having the photosensitive resin layer on the above-mentioned temporary support body and the substrate will be improved, so it can be preferably used as a substrate after exposure and development. Etching resist when patterning the conductive layer of the photosensitive resin layer for etching.

Moreover, when a photosensitive transfer material is equipped with a protective film, you may bond after removing a protective film from the surface of a photosensitive resin layer.

And, in the bonding step, the photosensitive transfer material is further provided with a layer other than the protective film (for example, a high refractive index layer and/or a low refractive index layer) on the surface of the photosensitive resin layer that is not opposed to the temporary support. In the case of the layer), the surface of the photosensitive resin layer on the side not having the temporary support body and the substrate are bonded via the layer.

The method of pressure-bonding the substrate and the photosensitive transfer material is not particularly limited, and known transfer methods and lamination methods can be used.

The bonding of the photosensitive transfer material to the substrate is preferably carried out by overlapping the outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer with respect to the above-mentioned temporary support with the substrate, and using a mechanism such as a roller. Pressurized and heated. For bonding, a known laminator such as a laminator, a vacuum laminator, and an automatic cutting laminator capable of further improving productivity can be used.

Although it does not specifically limit as lamination temperature, For example, 70 degreeC - 130 degreeC is preferable.

It is preferable to carry out by the roll-to-roll system about the manufacturing method of the resin pattern which includes a bonding process, and the manufacturing method of circuit wiring.

Next, the roll-to-roll method will be described.

The roll-to-roll method refers to a method in which a substrate that can be rolled up and unwound is used as the substrate, and the method of manufacturing a resin pattern or the method of manufacturing a circuit wiring includes either unwinding the substrate or including The process of the structure of the substrate (also referred to as the "unwinding process"), and the process of winding the substrate or the structure including the substrate after any of the processes (also referred to as the "winding process"), and while carrying The substrate or the structure including the substrate is subjected to at least any one of the steps (preferably all the steps, or all the steps except the heating step).

The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and known methods may be used in the production method to which the roll-to-roll method is applied.

<substrate>

As the substrate used in the method for producing a resin pattern or the method for producing a laminate according to the present invention, known substrates can be used, but preferably have a conductive layer, and more preferably have a conductive layer on the surface of the substrate.

The substrate may have any layer other than the conductive layer as needed.

As a substrate, a resin substrate, a glass substrate, and a semiconductor substrate are mentioned, for example.

As a preferred embodiment of the substrate, for example, the embodiment described in paragraph 0140 of International Publication No. 2018/155193 can be mentioned, and the content thereof is incorporated in this specification.

Examples of base materials constituting the substrate include glass, silicon, and films.

The base material constituting the substrate is preferably transparent. In this specification, "transparent" means that the transmittance of light having a wavelength of 400 nm to 700 nm is 80% or more.

In addition, the refractive index of the substrate constituting the substrate is preferably 1.50 to 1.52.

Examples of the transparent glass substrate include tempered glass represented by Corning Incorporated's Gorilla Glass. Furthermore, as the transparent glass substrate, materials used in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492 can be used.

In the case of using a film substrate as the substrate, it is preferable to use a film substrate with small optical strain and/or high transparency. Examples of such film substrates include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymers.

As a board|substrate, when manufacturing by a roll-to-roll method, it is preferable that it is a film board|substrate. Moreover, when manufacturing the circuit wiring for touch panels by a roll-to-roll system, it is preferable that a board|substrate is a sheet-shaped resin composition.

As a conductive layer which a board|substrate has, the conductive layer used for normal circuit wiring and touch panel wiring is mentioned.

The conductive layer is preferably at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer from the viewpoint of conductivity and fine line formation, It is more preferably a metal layer, still more preferably a copper layer or a silver layer.

The substrate may have one conductive layer alone, or may have two or more layers. When having two or more conductive layers, it is preferable to have conductive layers of different materials.

Examples of the material of the conductive layer include metals and conductive metal oxides.

Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.

Examples of conductive metal oxides include ITO (indium tin oxide), IZ0 (indium zinc oxide), and Si0 ₂ .

In addition, in this specification, "conductivity" means that the volume resistivity is less than 1×10 ⁶ Ωcm. The volume resistivity of the conductive metal oxide is preferably less than 1×10 ⁴ Ωcm.

When producing a resin pattern using a substrate having a plurality of conductive layers, at least one conductive layer among the plurality of conductive layers preferably contains a conductive metal oxide.

As the conductive layer, an electrode pattern of a sensor corresponding to a viewing portion used in a capacitive touch panel or wiring of a peripheral lead-out portion is preferable.

As a preferred embodiment of the conductive layer, for example, the embodiment described in paragraph 0141 of International Publication No. 2018/155193 can be mentioned, and the contents thereof are incorporated in this specification.

As a substrate having a conductive layer, a substrate having at least one of a transparent electrode and routing wiring is preferable. The substrate as described above can be preferably used as a substrate for a touch panel.

The transparent electrode can preferably function as an electrode for a touch panel. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) or IZO (indium zinc oxide), and metal thin wires such as a metal mesh and silver nanowires.

Examples of thin metal wires include thin wires such as silver and copper. Among them, silver conductive materials such as silver mesh and silver nanowire are preferable.

As a material of the routing wiring, metal is preferable.

Examples of the metal used as a material for the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, and alloys composed of two or more of these metal elements. As a material of the routing wiring, copper, molybdenum, aluminum, or titanium is preferable, and copper is particularly preferable.

For the purpose of protecting electrodes and the like (that is, at least one of touch panel electrodes and touch panel wiring), the electrode protective film for touch panels formed using the photosensitive transfer material according to the present invention is preferably directly or via other layer to cover electrodes and the like.

<Exposure process>

It is preferable that the manufacturing method of the resin pattern or the manufacturing method of a laminated body include the process (exposure process) of exposing a pattern to a photosensitive resin layer after the said bonding process.

In addition, here, "pattern exposure" means exposure in the form of pattern exposure, ie, the exposure in which the exposed part and the non-exposed part exist.

The positional relationship between the exposed area and the unexposed area in the pattern exposure is not particularly limited, and can be appropriately adjusted.

There are no particular limitations on the detailed arrangement and specific dimensions of the patterns in the pattern exposure. For example, in order to improve the display quality of a display device (such as a touch panel) provided with an input device having a circuit wiring manufactured by a method of manufacturing a circuit wiring, and to reduce the area occupied by the lead wiring, at least a part of the pattern (preferably The electrode pattern of the touch panel and/or the lead wiring portion) preferably includes thin lines with a width of 20 μm or less, and more preferably includes thin lines with a width of 10 μm or less.

The light source used for exposure can be suitably selected and used as long as it irradiates the light (for example, 365 nm or 405 nm) of the wavelength which can expose a photosensitive resin layer. Specifically, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode: light emitting diode) are mentioned.

The exposure amount is preferably 5 mJ/cm ² to 200 mJ/cm ² , more preferably 10 mJ/cm ² to 100 mJ/cm ² .

As a preferable aspect of the light source used for exposure, exposure amount, and an exposure method, the aspect described in paragraph 0146-0147 of international publication 2018/155193 is mentioned, for example, These content is incorporated in this specification.

In the exposure process, pattern exposure may be performed after the temporary support is peeled off from the photosensitive resin layer, or pattern exposure may be performed through the temporary support before peeling the temporary support, and then the temporary support may be peeled off. When peeling off a temporary support body before exposure, a mask may contact and expose to a photosensitive resin layer, and may expose without contacting and bringing it close. When performing exposure without peeling off a temporary support body, a mask may contact a temporary support body, and may expose, and may expose without contacting and bringing it close. In order to prevent contamination of the mask due to contact between the photosensitive resin layer and the mask and to avoid influence on exposure due to foreign matter adhering to the mask, it is preferable to perform pattern exposure without peeling off the temporary support. In addition, regarding the exposure method, in the case of contact exposure, a contact exposure method can be appropriately selected and used, and in the case of a non-contact exposure method, a proximity exposure method, projection exposure of a lens system, or a mirror system can be appropriately selected and used. method, a direct exposure method using an exposure laser or the like. In the case of projection exposure by a lens system or a mirror system, an exposure machine having an appropriate number of apertures (NA) of lenses can be used depending on required resolution and depth of focus. In the case of the direct exposure method, the photosensitive resin layer may be drawn directly, or the photosensitive resin layer may be subjected to reduced projection exposure through a lens. In addition, exposure may be performed not only in air, but also under reduced pressure or vacuum, and may also be performed with a liquid such as water interposed between the light source and the photosensitive resin layer.

<Peel off process>

The manufacturing method of the resin pattern or the manufacturing method of a laminated body may include the peeling process of peeling off a temporary support body between a bonding process and an exposure process, or between an exposure process and a development process.

The peeling method of the temporary support body is not particularly limited, and the same mechanism as the cover film peeling mechanism described in paragraphs 0161 to 0162 of JP-A-2010-072589 can be used.

<Development process>

In the manufacturing method of a resin pattern, it is preferable to include the process (development process) of developing the exposed photosensitive resin layer and forming a resin pattern after the said exposure process.

When the photosensitive transfer material has a thermoplastic resin and an intermediate layer, the thermoplastic resin layer and intermediate layer in the non-exposed area are also removed together with the photosensitive resin layer in the non-exposed area in the image development process. In addition, in the developing step, the thermoplastic resin layer and the intermediate layer in the exposed portion may be removed in the form of being dissolved or dispersed in the developing solution.

The image development of the exposed photosensitive resin layer in an image development process can be performed with a developing solution.

The developer is not particularly limited as long as it can remove the non-image portion (non-exposed portion) of the photosensitive resin layer. For example, known developers such as those described in JP-A-5-72724 can be used.

The developing solution is preferably an alkaline aqueous developing solution containing a compound having pKa=7 to 13 at a concentration of 0.05 mol/L to 5 mol/L (liter). The developer may contain a water-soluble organic solvent and/or a surfactant.

As the basic compound that can be contained in the alkaline aqueous solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, tetramethylammonium hydroxide, tetraethyl hydroxide ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide).

As the developing solution, those described in paragraph 0194 of International Publication No. 2015/093271 are also preferably used. As an image development method preferably used, for example, the image development method described in paragraph 0195 of International Publication No. 2015/093271 can be mentioned.

The image development method is not particularly limited, and may be any of spin-on-submerge image development, shower image development, shower-and-rotary image image development, and immersion image image development. The shower development is a development process of removing a non-exposed portion by spraying a developing solution onto the exposed photosensitive resin layer by a shower.

It is preferable to remove development residues while wiping with a brush after spraying a cleaning agent with a shower after the development step.

The liquid temperature of the developer is not particularly limited, but is preferably 20°C to 40°C.

<Protective film peeling process>

When the photosensitive transfer material is equipped with a protective film, it is preferable that the manufacturing method of a resin pattern or the manufacturing method of a laminated body includes the process of peeling a protective film from a photosensitive transfer material. There is no limitation on the method of peeling off the protective film, and a known method can be applied.

<Post-exposure process and post-drying process>

The manufacturing method of the resin pattern or the manufacturing method of a laminated body may have the process of exposing the resin pattern obtained by the said developing process (post-exposure process) and/or the process of heating (post-baking process).

When including both the post-exposure process and the post-baking process, it is preferable to perform post-baking after post-exposure.

<Other processes>

The manufacturing method of the resin pattern or the manufacturing method of a laminated body may include arbitrary process (other process) other than the said process. For example, the steps described in the manufacturing method of the circuit wiring shown below or the manufacturing method of the touch panel etc. are mentioned below, However, It is not limited to these steps.

<purpose>

The resin pattern manufactured by the manufacturing method of the resin pattern which concerns on this invention, and the laminated body manufactured by the manufacturing method of the laminated body which concerns on this invention can be applied to various apparatuses. As a device provided with the said laminated body, an input device etc. are mentioned, for example, Preferably it is a touch panel, More preferably, it is a capacitance type touch panel. Furthermore, the above-mentioned input device can be applied to display devices such as organic electroluminescence display devices and liquid crystal display devices.

When the laminate is applied to a touch panel, the formed resin pattern is preferably used as a protective film for touch panel electrodes or touch panel wiring. That is, the photosensitive transfer material according to the present invention is preferably used to form an electrode protective film for a touch panel or wiring for a touch panel.

(Manufacturing method of circuit wiring)

The method for producing the circuit wiring according to the present invention is not particularly limited as long as it is a method using the photosensitive transfer material according to the present invention.

The method for producing circuit wiring according to the present invention preferably sequentially includes the step of forming the outermost layer on the side having the photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to the present invention. A step of bonding the substrate having a conductive layer in contact with it; a step of pattern-exposing the above-mentioned photosensitive resin layer; a step of developing the exposed photosensitive resin layer to form a resin pattern; A step (hereinafter, also referred to as "etching step") of performing an etching process on the above-mentioned substrate in a pattern region.

Hereinafter, each step included in the manufacturing method of the circuit wiring will be described, but the content described for each step included in the manufacturing method of the resin pattern is also applicable to the manufacturing of the circuit wiring steps involved in the method.

<Etching process>

It is preferable that the manufacturing method of circuit wiring includes the process (etching process) of etching the said board|substrate in the area|region where the said resin pattern is not arrange|positioned.

In an etching process, the etching process of a conductive layer is performed using the resin pattern formed from the photosensitive resin layer as an etching resist.

As the method of etching treatment, known methods can be applied, for example, the method described in paragraphs 0209 to 0210 of Japanese Patent Application Laid-Open No. 2017-120435, the method described in paragraphs 0048 to 0054 of Japanese Patent Laid-Open No. 2010-152155, etc. The method described in the paragraph, the wet etching method of immersing in an etchant, and the method of dry etching by plasma etching or the like.

As the etchant used in wet etching, an acidic or alkaline etchant can be appropriately selected according to the object to be etched.

As an acidic etchant, for example, an aqueous solution of an acidic component selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid, and an acidic component selected from ferric chloride, ammonium fluoride, and A mixed aqueous solution of salts in potassium permanganate. An acidic component may be a combination of some acidic components.

As an alkaline etchant, an aqueous solution of an alkali component alone selected from sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (tetramethylammonium hydroxide, etc.), and an alkali component and A mixed aqueous solution of salt (potassium permanganate, etc.). The alkali component may be a combination of a plurality of alkali components.

<Removal process>

In the manufacturing method of circuit wiring, it is preferable to perform the process (removal process) of removing the remaining resin pattern.

The removal step is not particularly limited and can be performed as needed, but is preferably performed after the etching step.

The method of removing the remaining resin pattern is not particularly limited, and a method of removing it by chemical treatment is mentioned, and a method of removing it using a removing liquid is preferable.

As a method for removing the photosensitive resin layer, immersing the substrate having the remaining resin pattern in a stirring removal solution having a liquid temperature of preferably 30°C to 80°C, more preferably 50°C to 80°C, for 1 minute ~30 minutes method.

Examples of the removal liquid include those obtained by dissolving an inorganic base component or an organic base component in water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solution thereof. As an inorganic base component, sodium hydroxide and potassium hydroxide are mentioned, for example. Examples of the organic base component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium compounds.

In addition, it may be removed by a known method such as a spraying method, a shower method, or a spin-on-dip method using a removing liquid.

<Other processes>

The manufacturing method of the circuit wiring may include arbitrary steps (other steps) other than the above-mentioned steps. For example, the following steps can be mentioned, but it is not limited to these steps.

Moreover, as an exposure process, a development process, and other processes applicable to the manufacturing method of a circuit wiring, the process described in paragraph 0035-0051 of Unexamined-Japanese-Patent No. 2006-23696 is mentioned.

In addition, as other steps, for example, the step of reducing the reflectance of visible light described in paragraph 0172 of International Publication No. 2019/022089, the step of reducing the reflectance of the insulating film described in paragraph 0172 of International Publication No. 2019/022089, The process of forming a new conductive layer on it, etc., but is not limited to these processes.

-Process of reducing reflectance of visible light-

The method of manufacturing the circuit wiring may include the step of performing a process of reducing the visible light reflectance of a part or all of the plurality of conductive layers included in the substrate.

An oxidation treatment is mentioned as a treatment for reducing the reflectance of visible light. When the substrate has a conductive layer containing copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to form copper oxide and blackening the conductive layer.

The treatment for reducing the reflectance of visible light is described in paragraphs 0017 to 0025 of JP-A-2014-150118, and paragraphs 0041, 0042, 0048, and 0058 of JP-A-2013-206315. The content described in these gazettes is incorporated into this specification.

-Step of forming an insulating film, and step of forming a new conductive layer on the surface of the insulating film-

The method of manufacturing the circuit wiring preferably includes the step of forming an insulating film on the surface of the circuit wiring and the step of forming a new conductive layer on the surface of the insulating film.

Through the above steps, the second electrode pattern insulated from the first electrode pattern can be formed.

The step of forming an insulating film is not particularly limited, and a known method for forming a permanent film can be used. In addition, an insulating film having a desired pattern can be formed by photolithography using an insulating photosensitive material.

The step of forming a new conductive layer on the insulating film is not particularly limited. For example, a photosensitive material having conductivity may be used to form a new conductive layer in a desired pattern by photolithography.

Also in the method of manufacturing circuit wiring, it is preferable to use a substrate having a plurality of conductive layers on both surfaces of the substrate, and to sequentially or simultaneously form circuits on the conductive layers formed on both surfaces of the substrate. With such a configuration, it is possible to form circuit wiring for a touch panel in which the first conductive pattern is formed on one surface of the substrate and the second conductive pattern is formed on the other surface. Furthermore, it is also preferable to form the circuit wiring for a touch panel having such a structure from both surfaces of the substrate in a roll-to-roll manner.

<Applications of Circuit Wiring>

The circuit wiring manufactured by the manufacturing method of circuit wiring can be applied to various apparatuses. As a device provided with the circuit wiring manufactured by the above-mentioned manufacturing method, an input device is mentioned, for example, Preferably it is a touch panel, More preferably, it is a capacitive type touch panel. Furthermore, the input device described above can be applied to display devices such as organic EL display devices and liquid crystal display devices.

(Manufacturing method of touch panel)

The method for manufacturing the touch panel according to the present invention is not particularly limited as long as it is a method using the photosensitive transfer material according to the present invention.

As the manufacturing method of the touch panel concerning this invention, it is preferable to include the following process sequentially: The outermost layer of the side which has a photosensitive resin layer with respect to the said temporary support body in the photosensitive transfer material concerning this invention and The process of bonding the substrates with the conductive layer in contact; the process of pattern-exposing the photosensitive resin layer; the process of developing the exposed photosensitive resin layer to form a resin pattern; The above-mentioned substrate in the area is subjected to the process of etching treatment.

The specific form of each step in the manufacturing method of the touch panel and the order in which the respective steps are performed are as described in the above-mentioned "Manufacturing method of resin pattern" and "Manufacturing method of circuit wiring" The preferred way is also the same.

Regarding the manufacturing method of the touch panel, in addition to forming the wiring for a touch panel by the above-mentioned method, reference can also be made to a known manufacturing method of the touch panel.

Furthermore, the manufacturing method of the touch panel may include arbitrary steps (other steps) other than the above.

An example of the pattern of the mask used for manufacture of a touch panel is shown in FIG.3 and FIG.4.

In the pattern A shown in FIG. 3 and the pattern B shown in FIG. 4 , GR is a non-image portion (shielding portion), EX is an image portion (exposed portion), and DL is a virtual alignment frame. In the manufacturing method of the touch panel, for example, by exposing the above-mentioned photosensitive resin layer through a mask having the pattern A shown in FIG. touch panel. Specifically, it can be produced by the method described in FIG. 1 of International Publication No. 2016/190405. In an example of the manufactured touch panel, the central part (pattern part where the four corners are connected) of the exposure part EX is a part where a transparent electrode (electrode for a touch panel) is formed, and the peripheral part (thin line part) of the exposure part EX is The part that forms the wiring of the peripheral lead-out part.

A touch panel having at least wiring for a touch panel is manufactured by the above-mentioned method of manufacturing a touch panel. The touch panel preferably has a transparent substrate, electrodes, insulating layer or protective layer.

Examples of the detection method in the touch panel include known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the capacitive method is preferable.

As the touch panel type, the so-called built-in type (for example, the content described in Fig. 5, Fig. 6, Fig. 7, and Fig. 8 of JP2012-517051A), the so-called , the content described in Figure 19 of Japanese Patent Application Laid-Open No. 2013-168125, and the content recorded in Figure 1 and Figure 5 of Japanese Patent Application Publication No. 2012-89102), OGS (One Glass Solution: single glass contact control technology) type, TOL (Touch-on-Lens: overlay touch) type (for example, the content described in Fig. 2 of Japanese Patent Application Laid-Open No. G2, GFF, GF2, GF1, G1F, etc.) and other structures (for example, the content described in FIG. 6 of Japanese Patent Laid-Open No. 2013-164871).

As a touch panel, the touch panel described in paragraph 0229 of Unexamined-Japanese-Patent No. 2017-120435 is mentioned, for example.

Example

Below, an Example is given and the embodiment of this invention is demonstrated more concretely. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the spirit of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "part" and "%" are mass standards.

The details of the abbreviations of the compounds used in Examples and Comparative Examples are shown below.

<Alkali-soluble resin>

A-1: Styrene/methacrylic acid/methyl methacrylate=32/28/40 (mass %), Mw=40,000

A-2: Styrene/methacrylic acid/methyl methacrylate=52/29/19 (mass %), Mw=60,000

A-3: benzyl methacrylate/methacrylic acid=81/19 (mass %), Mw=40,000

A-4: Propylene glycol monomethyl ether acetate solution of a copolymer of benzyl methacrylate/methacrylic acid/acrylic acid=75/10/15 (solid content concentration: 30.0%, Mw=30,000, acid value: 153 mgKOH/g)

A-5: Kuraray Poval PVA-205 (polyvinyl alcohol, manufactured by KURARAY CO., LTD.)

A-6: Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.)

<Ethylenically unsaturated compound>

B-1: NK ester BPE-500 (2,2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.)

B-2: NK ester BPE-200 (2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd.)

B-3: Dimethacrylate of polyethylene glycol with an average of 1 to 5 moles of ethylene oxide and an average of 2 moles of propylene oxide added to both ends of bisphenol A

B-4: LIGHT ACRYLATE DPE-6A (dipentaerythritol hexaacrylate, manufactured by KYOEISHA CHEMICAL CO., LTD.)

B-5: ARONIX M-270 (polypropylene glycol diacrylate, manufactured by TOAGOSEI CO., LTD.)

B-6: NK ester A-TMPT (trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

B-7: Sartomer SR-454 (ethoxylated (3) trimethylolpropane triacrylate, manufactured by Arkema)

B-8: Sartomer SR-502 (ethoxylated (9) trimethylolpropane triacrylate, manufactured by Arkema)

B-9: NK ester A-9300-CL1 (ε-caprolactone-modified tris-(2-acryloyloxyethyl)isocyanurate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

B-10: NK ester A—DCP (tricyclodecane dimethanol diacrylate, manufactured by Shin—Nakamura Chemical Co., Ltd.)

B-11: 8UX-015A (urethane acrylate, TAISEI FINE CHEMICAL CO, .LTD.)

B-12: ARONIX TO-2349 (polyfunctional ethylenically unsaturated compound having a carboxylic acid group, manufactured by TOAGOSEI CO., LTD.)

<Photopolymerization Initiator>

C-1: B-CIM (2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, manufactured by KUROGANE KASEI Co., Ltd.)

C-2: SB-PI 701 (4,4'-bis(diethylamino)benzophenone, available from Sanyo Trading Co., Ltd.)

C-3: Omnifad 907 (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, manufactured by IGM Resins B.V.)

C-4: Irgacure OXE02 (1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(o-acetyl oxime), manufactured by BASF Corporation ),

C-5: 4,4'-bis(diethylamino)benzophenone (manufactured by KANTO CHEMICAL CO., INC.)

<Inhibitor>

D-1: TDP-G (phenothiazine, manufactured by Kawaguchi Chemical Industry Co., LTD.)

D-2: Phenoxazine (manufactured by Tokyo Chemical Industry Co., Ltd.)

D-3: Irganox245 (hindered phenolic polymerization inhibitor, manufactured by BASF Corporation)

D-4: N-nitrosophenylhydroxylamine aluminum salt (manufactured by FUJIFILM Wako Pure Chemical Corporation)

D-5: MQ (4-methoxyphenol, manufactured by Kawaguchi Chemical Industry Co., LTD.)

<Other additives>

E-1: Colorless crystal violet (color developer, manufactured by Tokyo Chemical Industry Co., Ltd.)

E-2: N-phenylcarbamoylmethyl-N-carboxymethylaniline (color developer, manufactured by FUJIFILM Wako Pure Chemical Corporation)

E-3: bright green (color developer, manufactured by Tokyo Chemical Industry Co., Ltd.)

E-4: CBT-1 (rust inhibitor, carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD)

E-5: 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole 1:1 (mass ratio) mixture, rust inhibitor

E-6: phenidone (antioxidant, manufactured by Tokyo Chemical Industry Co., Ltd.)

E-7: Megafac F-552 (fluorosurfactant, manufactured by DIC Corporation)

E-8: Megafac F-444 (fluorosurfactant, manufactured by DIC Corporation)

<solvent>

F-1: methyl ethyl ketone (manufactured by SANKYO CHEMICAL Co., Ltd.)

F-2: Propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K.)

F-3: Ion exchanged water

F-4: Methanol (manufactured by Mitsubishi Gas Chemical Company, Inc.)

<Preparation of thermoplastic resin composition>

The following components were mixed to prepare a thermoplastic resin composition.

A-4: 42.85 copies

B-10: 4.63 copies

B-11: 2.31 copies

· B-12: 0.77 copies

E-7: 0.03 parts

· F-1: 39.50 copies

· F-2: 9.51 copies

A compound (photoacid generator, a compound synthesized according to the method described in paragraph 0227 of JP-A-2013-47765) of the structure shown below: 0.32 parts

[chemical formula 25]

・Compound with the structure shown below (pigment that develops color with acid): 0.08 part

[chemical formula 26]

<Preparation of Intermediate Layer Composition>

The following components were mixed to prepare an intermediate layer composition.

A-5: 3.22 parts

A-6: 1.49 copies

E-8: 0.0015 copies

· F-3: 38.12 copies

· F-4: 57.17 copies

<Preparation of Photosensitive Resin Composition>

Each photosensitive resin composition used in the Example and the comparative example was prepared with the composition described in Table 1 mentioned later.

(Examples 1-16 and Comparative Examples 1-3)

<Production of photosensitive transfer material>

As a temporary support, a polyethylene terephthalate (PET) film with a thickness of 30 μm was prepared. On the surface of the temporary support body, the above-mentioned thermoplastic resin composition was applied using a slit-shaped nozzle so that the coating width would be 1.0 m and the layer thickness after drying would be 4.0 μm. The formed coating film of the thermoplastic resin composition was dried at 80° C. for 40 seconds to form a thermoplastic resin layer.

On the surface of the formed thermoplastic resin layer, the above-mentioned intermediate layer composition was applied using a slit-shaped nozzle so that the coating width would be 1.0 m and the layer thickness after drying would be 1.2 μm. The coating film of the intermediate layer composition was dried at 80° C. for 40 seconds to form an intermediate layer.

On the surface of the formed intermediate layer, the composition described in Table 1 was applied using a slit nozzle so that the coating width became 1.0 m and the layer thickness after drying became the layer thickness described in Table 1. photosensitive resin composition. The photosensitive resin layer was formed by drying the coating film of the photosensitive resin composition at 80 degreeC for 40 second.

On the surface of the formed photosensitive resin layer, a PET film (manufactured by TORAY INDUSTRIES, INC., Lumirror 16QS62) was pressure-bonded as a protective film, and photosensitive transfer materials of Examples and Comparative Examples were produced, respectively.

<Evaluation of photosensitive transfer material>

-laminated-

The protective film was peeled off from the obtained photosensitive transfer material, and the peeled photosensitive transfer material was laminated on a substrate (a 200 nm-thick copper layer was formed by sputtering on a 100 μm PET film) using a sheet laminator. The lamination conditions were set at a roll temperature of 100° C., a lamination speed of 2 m/min, and a lamination pressure of 0.5 MPa.

-Measurement of Eb and Evaluation of Sensitivity-

A 15-step wedge (manufactured by Fujifilm Corporation) was arranged on the temporary support of the laminated photosensitive transfer material, and exposure was performed at 180 mJ/cm ² by a high-pressure mercury lamp of 20 mW/cm ² . After exposure, the support was peeled off, developed in a 0.9% by mass sodium carbonate aqueous solution at 25° C. for 30 seconds, and Eb was calculated from the remaining film thickness in each step.

In addition, as the value of Eb, there is a range of preferable values from the viewpoint of adaptability to general photolithography processes. When Eb is 25 mJ/cm ² or more, the sensitivity is moderate and the followability of the device is excellent, and when Eb is 90 mJ/cm ² or less, the exposure time can be shortened and the productivity is excellent.

The sensitivity was evaluated according to the following criteria based on the value of Eb (mJ/cm ² ). As the photosensitive transfer material, A to C are preferable, and A or B is more preferable.

A: 35≤Eb(mJ/cm ² )≤70

B: 25≤Eb(mJ/cm ² )＜35 or 70＜Eb(mJ/cm ² )≤90

C: 90<Eb(mJ/cm ² )

D: Eb(mJ/cm ² )＜25

-Measurement of W3-

A photomask of line and space=10 μm/10 μm was brought into contact with the temporary support, and the photosensitive transfer material laminated on the above substrate was exposed at Ep=2×Fb (mJ/cm ² ). After exposure, after 3 hours, the temporary support body, thermoplastic resin layer, and intermediate layer were peeled off with adhesive tape, and 5 mL of bromine water (0.2%) was separated into a 50 mL container, and fixed in the container so that it did not come into contact with the separation liquid. The sample was allowed to stand at room temperature (25° C.) for 5 minutes. Thereafter, it was stored under high vacuum for half a day to degas residual bromine. Thus, a sample in which a carbon-carbon double bond portion was modified with bromine was produced.

The sample was analyzed by secondary ion mass spectrometry (SIMS5 of ION-TOF Company, primary ion source: Bi ³⁺ (30kV), measurement range: 50mm, surface resolution: 512×512pixel, integration: 32 times, measurement mode: In high spatial resolution mode (FastImaging: fast imaging), charging correction: using an electron gun), the width of the C ₂ HBr ^-domain was evaluated. The portion where the C ₂ HBr ^- intensity is low is defined as the region width in which the polymerization proceeds. The region width in which the polymerization proceeded was measured at three places, and the average value thereof was defined as W ₃ .

- Determination of W ₂₄ -

Except for changing the elapsed time after exposure, the width W ₂₄ of the polymerization progress region 24 hours after the pattern exposure was obtained in the same manner as the measurement of W ₃ . And, the value of W ₂₄ /W ₃ was calculated.

- Determination of W ₇₂ -

Except for changing the elapsed time after exposure, the polymerization progress region width W ₇₂ after 72 hours after the pattern exposure was obtained in the same manner as the measurement of W ₃ . And, the value of W ₇₂ /W ₃ was calculated.

<Change in line width when left for 24 hours after exposure>

A photomask of line and space=10 μm/10 μm was brought into contact with the temporary support, and the photosensitive transfer material laminated on the above substrate was exposed at Ep=2×Fb (mJ/cm ² ). After 3 hours or 24 hours after the exposure, the temporary support was peeled off, and a 1% sodium carbonate aqueous solution at 25° C. was sprayed to dissolve the unexposed portion to obtain a resist pattern. From the scanning electron microscope (SEM) image of the cross section of the obtained resist pattern, the line width of the part where the photosensitive resin layer contacts a board|substrate was measured. Wr ₂₄ /Wr 3 was obtained by setting the line width developed 3 hours after exposure to Wr ₃ and the line width developed ₂₄ hours after development to Wr ₂₄ . The closer this ratio is to 1, the smaller the change in line width when left to stand after exposure, which can be said to have preferable performance. Wr ₂₄ /Wr ₃ was evaluated according to the following criteria. As a photosensitive transfer material, A or B is preferable.

A: Wr ₂₄ /Wr ₃ <1.03

B: 1.03≤Wr ₂₄ /Wr ₃ <1.05

C: 1.05≤Wr ₂₄ /Wr ₃ <1.1

D: 1.1≤Wr ₂₄ /Wr ₃

<Change in line width when developing temperature changes>

A photomask of line and space=10 μm/10 μm was brought into contact with the temporary support, and the photosensitive transfer material laminated on the above substrate was exposed at Ep=2×Eb (mJ/cm ² ). After exposure, 3 hours later, the temporary support body was peeled off, and the 1% sodium carbonate aqueous solution of 30 degreeC was sprayed, and the unexposed part was melt|dissolved, and the resist pattern was obtained. The line width Wr _3b was measured from the cross-sectional SEM image of the obtained resist pattern to obtain Wr _3b /Wr ₃ . The closer this ratio is to 1, the smaller the change in line width when the developing temperature fluctuates, and the wider the process robustness, which is preferable. Wr _3b /Wr ₃ was evaluated based on the following criteria. As a photosensitive transfer material, A or B is preferable.

A: Wr _3b /Wr ₃ <1.03

B: 1.03≤Wr _3b /Wr ₃ <1.05

C: 1.05≤Wr _3b /Wr ₃

The measurement results and evaluation results are summarized in Table 2.

[Table 1]

[Table 2]

As shown in Table 1 and Table 2 above, compared with the photosensitive transfer materials of Comparative Examples 1 to 3, the photosensitive transfer materials of Examples 1 to 16 showed that the line of the resin pattern decreased with the elapse of the standing time after exposure. Width variation is small.

Moreover, in the photosensitive transfer material of Examples 1-16, the line width change of the resin pattern accompanying the change of image development temperature was small, and it was excellent also in sensitivity.

(Example 101 (second time: PET peeling exposure))

On a PET substrate with a thickness of 100 micrometers, an ITO film was formed as a conductive layer of the second layer with a thickness of 150 nm by sputtering, and a copper film was formed as a conductive layer of the first layer with a thickness of 200 nm by a vacuum evaporation method. It became a substrate for circuit formation.

The photosensitive transfer material obtained in Example 1 was laminated on the copper layer (lamination roll temperature 120° C., line pressure 0.8 MPa, line speed 1.0 m/min.). The laminated laminate was subjected to contact pattern exposure using a photomask provided with pattern A shown in FIG. 3 , which has a structure in which conductive layer pads are bonded in one direction without peeling off the temporary support. . After that, the temporary support was peeled off, image development and water washing were performed, and pattern A was obtained. Next, after etching the copper layer using a copper etchant (KANTOCHEMICAL CO., Cu-02 manufactured by INC.), the ITO layer was etched using an ITO etchant (ITO-02 manufactured by KANTO CHEMICAL CO., INC.), thereby A substrate in which both copper and ITO were drawn by the pattern A was obtained.

The remaining photosensitive resin layer (pattern A) was peeled off using a stripping liquid (KP-301 manufactured by KANTO CHEMICAL CO., INC.), and the photosensitive transfer material (layer A) obtained in Example 1 was laminated again on the copper layer. Roller temperature 120°C, line pressure 0.8MPa, line speed 1.0m/min.).

Next, in an aligned state, pattern exposure was performed using the photomask of pattern B shown in FIG. 4 , and development and water washing were performed. Thereafter, the copper layer was etched using Cu-02, and the remaining photosensitive resin layer (pattern B) was peeled off using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.

As a result of observing the obtained circuit wiring board with a microscope, there were no peeling, chipping, etc., and it was a perfect pattern.

In addition, in pattern A shown in FIG. 3 , GR, which is a gray part, is a light-shielding part, EX is an exposure part, and DL, which is a dotted line part, represents an alignment frame virtually.

In the pattern B shown in FIG. 4 , similarly to FIG. 3 , GR, which is a gray part, is a light-shielding part, EX is an exposure part, and DL, which is a dotted line part, represents an alignment frame virtually.

Regarding the disclosure of Japanese Patent Application No. 2020-156353 filed on September 17, 2020, the entire contents thereof are incorporated herein by reference.

All documents, patent applications and technical standards described in this specification are incorporated by reference to the same extent as if each document, patent application and technical standard incorporated by reference is specifically and individually stated. middle.

Symbol Description

1, 11-temporary support, 2, 12-transfer layer, 3, 17-photosensitive resin layer, 5-refractive index adjustment layer, 13-thermoplastic resin layer, 15-intermediate layer, 10, 20-photosensitive transfer layer Printing material, GR-shading part (non-image part), EX-exposure part (image part), DL-alignment frame.

Claims (12)

1. A photosensitive transfer material, comprising:

a temporary support; and

a photosensitive resin layer containing an alkali-soluble resin, an ethylenically unsaturated compound, and a photopolymerization initiator,

the photosensitive resin layer is used for mJ/cm ² The width W of the double bond reaction region after exposure of the line and space pattern of 10 μm/10 μm with the exposure dose Ep of unit time of 3 hours ₃ Width of double bond reaction region W after 24 hours ₂₄ Satisfy W ₂₄ /W ₃ ≤1.05，

W ₃ W and W ₂₄ The width of the double bond reaction region obtained by secondary ion mass spectrometry after bromine staining the exposed photosensitive transfer material,

the Ep satisfies ep=2×eb,

The Eb is set to be 20mW/cm of illuminance passing through a 15-step wedge after the photosensitive resin layer is attached to a substrate ² Is exposed to 180mJ/cm ² Exposure is performed to give an exposure amount of an order of ±1% of the residual layer thickness of the developed photosensitive resin layer.

2. The photosensitive transfer material according to claim 1, wherein,

the double bond reaction area width W after 3 hours after exposing the photosensitive resin layer to the exposure Ep in a line and space pattern of 10 μm/10 μm ₃ Width of double bond reaction region W at 72 hours ₇₂ Satisfy W ₇₂ /W ₃ ≤1.10，

W ₇₂ The width of the double bond reaction region obtained by the secondary ion mass spectrometry after bromine staining the exposed photosensitive transfer material was set.

3. The photosensitive transfer material according to claim 1 or 2, wherein,

the ethylenically unsaturated compound comprises an ethylenically unsaturated compound having a bisphenol structure.

4. The photosensitive transfer material according to any one of claims 1 to 3, wherein,

the photopolymerization initiator includes a biimidazole compound and a benzophenone compound.

5. The photosensitive transfer material according to any one of claims 1 to 4, wherein,

The photosensitive resin layer further comprises a polymerization inhibitor.

6. The photosensitive transfer material according to claim 5, wherein,

the polymerization inhibitor contains at least 1 compound selected from phenothiazine, phenoxazine and a compound having a hindered phenol structure.

7. The photosensitive transfer material according to claim 5 or 6, wherein,

when Rc is the content of the photopolymerization initiator and Rd is the content of the polymerization inhibitor in the photosensitive resin layer, the mass ratio Rd/Rc is 0.02 or more and 0.1 or less.

8. The photosensitive transfer material according to claim 7, wherein,

the mass ratio Rd/Rc is 0.03 or more and 0.05 or less.

9. A method for manufacturing a resin pattern, comprising, in order:

a step of bringing an outermost layer of the photosensitive transfer material according to any one of claims 1 to 8, which is on the side having the photosensitive resin layer with respect to the temporary support, into contact with a substrate and bonding the outermost layer;

a step of exposing the photosensitive resin layer to a pattern; and

And developing the exposed photosensitive resin layer to form a resin pattern.

10. The method for producing a resin pattern according to claim 9, wherein,

At least a part of the resin pattern includes a line-and-space pattern, and at least 1 group of lines and spaces in the line-and-space pattern have a total width of 20 μm or less.

11. A method for manufacturing a circuit wiring includes, in order:

a step of bonding the outermost layer of the photosensitive transfer material according to any one of claims 1 to 8 on the side having the photosensitive resin layer with respect to the temporary support, by contacting the outermost layer with a substrate having a conductive layer;

a step of exposing the photosensitive resin layer to a pattern;

developing the exposed photosensitive resin layer to form a resin pattern; and

And a step of etching the substrate in the region where the resin pattern is not arranged.

12. A method for manufacturing a touch panel, which comprises the following steps in order:

a step of bonding the outermost layer of the photosensitive transfer material according to any one of claims 1 to 8 on the side having the photosensitive resin layer with respect to the temporary support, by contacting the outermost layer with a substrate having a conductive layer;

a step of exposing the photosensitive resin layer to a pattern;

developing the exposed photosensitive resin layer to form a resin pattern; and

And a step of etching the substrate in the region where the resin pattern is not arranged.

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