WO2022181431A1

WO2022181431A1 - Photosensitive composition, transfer film, pattern formation method, production method for circuit wiring, and production method for touch panel

Info

Publication number: WO2022181431A1
Application number: PCT/JP2022/006314
Authority: WO
Inventors: 圭吾山口; 邦彦児玉
Original assignee: 富士フイルム株式会社
Priority date: 2021-02-26
Filing date: 2022-02-17
Publication date: 2022-09-01
Also published as: CN116888535A; JPWO2022181431A1

Abstract

The first problem to be addressed by the present invention is to provide a photosensitive composition that makes it possible to form a pattern that has excellent corrosion prevention performance in wet heat environments. The second problem to be addressed by the present invention is to provide a transfer film that is formed using the photosensitive composition. The third problem to be addressed by the present invention is to provide a pattern formation method, a production method for circuit wiring, and a production method for a touch panel.　This photosensitive composition satisfies condition A1 and condition B1.　Condition A1: The glass transition temperature of an exposed photosensitive layer obtained by means of procedure X is at least 65°C.　Condition B1: The water content at 40°C and 90% RH of the exposed photosensitive layer obtained by means of procedure X is less than 2.0 mass%.

Description

Photosensitive composition, transfer film, pattern forming method, circuit wiring manufacturing method, touch panel manufacturing method

The present invention relates to a photosensitive composition, a transfer film, a pattern forming method, a circuit wiring manufacturing method, and a touch panel manufacturing method.

In a display device having a touch panel such as a capacitive input device (specifically, as a display device, an organic electroluminescence (EL) display device, a liquid crystal display device, etc.), an electrode pattern corresponding to a sensor in the visual recognition part , peripheral wiring portions, and lead-out wiring portions, and other conductive patterns are provided inside the touch panel.

On this conductive pattern, a pattern made of resin is usually placed as a protective film (permanent film) for the purpose of preventing problems such as metal corrosion, increased electrical resistance between electrodes and drive circuits, and disconnection. may have been.

In general, a photosensitive composition is used for pattern formation, and in particular, since the number of steps for obtaining the required pattern shape is small, a temporary support and a photosensitive composition are used. A method using a transfer film having a formed photosensitive layer is widely used. Examples of the method of forming a pattern using a transfer film include a method of exposing and developing a photosensitive layer transferred from a transfer film onto an arbitrary substrate through a mask having a predetermined pattern shape. be done. For example, if the photosensitive layer is a negative-acting photosensitive layer, the hardening of the exposed areas can create a dissolution contrast with the unexposed areas. As a result, a pattern can be formed by removing only the unexposed area during development.

As a photosensitive composition and a transfer film, for example, in Patent Document 1, "on a substrate, a binder polymer having a carboxyl group having an acid value of 75 mgKOH/g or more, a photopolymerizable compound, a photopolymerization initiator, and a photosensitive element comprising a support film and a photosensitive layer comprising the above-mentioned photosensitive resin composition provided on the above-mentioned support film.

International Publication No. 2013/084886

By the way, a pattern used as a protective film for a conductive pattern formed from a metal material is also required to have the ability to suppress metal corrosion (hereinafter also referred to as "corrosion prevention").

The inventors of the present invention formed a pattern using the photosensitive composition described in Patent Document 1 and studied it, and found that there is room for further improvement, particularly in the corrosion prevention property in a moist heat environment. .

Accordingly, an object of the present invention is to provide a photosensitive composition capable of forming a pattern having excellent corrosion resistance in a moist and hot environment.
Another object of the present invention is to provide a transfer film formed using the photosensitive composition.
Another object of the present invention is to provide a pattern forming method, a circuit wiring manufacturing method, and a touch panel manufacturing method.

As a result of intensive studies aimed at solving the above problems, the inventors found that the above problems can be solved with the following configuration, and completed the present invention.

[1] A photosensitive composition that satisfies both requirements A1 and B1 shown below.
Requirement A1: The glass transition temperature of the post-exposure photosensitive layer obtained by the following procedure X is 65° C. or higher.
Requirement B1: The moisture content at 40° C. and 90% RH of the post-exposure photosensitive layer obtained by the following procedure X is less than 2.0% by mass.
Procedure X: A laminate having a glass substrate, a photosensitive layer formed from the photosensitive composition, and a resin film in this order is obtained. Next, from the side opposite to the glass substrate side of the laminate, an ultrahigh-pressure mercury lamp was used to irradiate the photosensitive layer in the laminate so that the integrated exposure amount at a wavelength of 365 nm was 80 mJ/cm ² . expose. After the exposure, the laminate is left in an environment of 25° C. and 50% RH for 30 minutes, and then the resin film is peeled off. Then, the photosensitive layer is exposed again from the side where the resin film is peeled off using a high-pressure mercury lamp so that the cumulative exposure amount at a wavelength of 365 nm is 1000 mJ/cm ² , After exposure a photosensitive layer is obtained.
[2] The photosensitive composition of [1], which further satisfies the following requirement A2.
Requirement A2: The glass transition temperature of the post-exposure photosensitive layer obtained by the above procedure X is 165° C. or lower.
[3] The photosensitive composition according to [2], wherein the glass transition temperature in requirement A2 is 120°C or lower.
[4] The photosensitive composition according to any one of [1] to [3], wherein the glass transition temperature in requirement A1 is 85°C or higher.
[5] The photosensitive composition according to any one of [1] to [4], which further satisfies the following requirement B2.
Requirement B2: The moisture content at 40°C and 90% RH of the post-exposure photosensitive layer obtained by procedure X above is greater than 0% by mass.
[6] The photosensitive composition according to [5], wherein the moisture content in requirement B2 is 0.5% by mass or more.
[7] The photosensitive composition according to any one of [1] to [6], wherein the glass transition temperature in requirement A1 is 100° C. or higher.
[8] The photosensitive composition contains a compound A having an acid group,
The photosensitive composition according to any one of [1] to [7], wherein the content of the acid group in the photosensitive composition is reduced by exposure to actinic rays or radiation.
[9] The photosensitive composition according to any one of [1] to [8], wherein the photosensitive composition satisfies either the following requirement (V01) or the following requirement (W01).
Requirements (V01)
The photosensitive composition contains a compound A having an acid group, and a compound β having a structure that reduces the amount of the acid group contained in the compound A upon exposure to light.
Requirement (W01)
The photosensitive composition contains a compound A having an acid group, and the compound A further contains a structure that reduces the amount of the acid group upon exposure.
[10] In the requirement (V01), the compound β is a compound B having a structure capable of accepting electrons from the acid group contained in the compound A in a photoexcited state,
The photosensitive composition according to [9], wherein in the requirement (W01), the structure is a structure capable of accepting electrons from the acid group in a photoexcited state.
[11] A compound B that satisfies the above requirements (V01) and has a structure in which the compound β is capable of accepting an electron from the acid group contained in the compound A in a photoexcited state;
In the photosensitive composition, the total number of the structures capable of accepting electrons contained in the compound B is 1 mol% or more with respect to the total number of acid groups contained in the compound A, [9] or [10] ].
[12] The photosensitive composition according to any one of [1] to [11], wherein the compound A contains a polymer having an acid group.
[13] The photosensitive composition of [12], wherein the polymer has a polymerizable group.
[14] The photosensitive composition according to any one of [1] to [13], further comprising a polymerizable compound.
[15] The photosensitive composition according to any one of [1] to [14], further comprising a photopolymerization initiator.
[16] A transfer film comprising a temporary support and a photosensitive layer formed from the photosensitive composition according to any one of [1] to [15].
[17] A step of bonding the transfer film and the base material together by bringing the surface of the photosensitive layer in the transfer film described in [16] on the side opposite to the temporary support side into contact with the base material;
a step of patternwise exposing the photosensitive layer;
A pattern forming method comprising, in this order, the step of developing the exposed photosensitive layer with an alkaline developer to form a pattern.
[18] The surface of the photosensitive layer in the transfer film described in [16] on the side opposite to the temporary support side is brought into contact with the conductive layer in the substrate having a conductive layer to form the transfer film and the A step of bonding a substrate having a conductive layer;
a step of patternwise exposing the photosensitive layer;
developing the exposed photosensitive layer with an alkaline developer to form a patterned etching resist film;
and a step of etching the conductive layer in a region where the etching resist film is not disposed, in this order.
[19] The surface of the photosensitive layer in the transfer film described in [16] on the side opposite to the temporary support side is brought into contact with the conductive layer in the substrate having a conductive layer, whereby the transfer film and the above A step of bonding a substrate having a conductive layer;
a step of patternwise exposing the photosensitive layer;
and developing the exposed photosensitive layer with an alkaline developer to form a patterned protective film or insulating film of the conductive layer, in this order.

Therefore, according to the present invention, it is possible to provide a photosensitive composition capable of forming a pattern having excellent corrosion resistance in a moist and hot environment.
Moreover, according to this invention, the transfer film formed using the said photosensitive composition can be provided.

It is a schematic diagram showing an example of layer composition of a transfer film concerning an embodiment.

The present invention will be described in detail below.
In this specification, the numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
Further, in the numerical ranges described stepwise in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of the numerical range described in other steps. good. Moreover, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the values shown in the examples.

In addition, the term "step" in this specification is not only an independent step, but even if it cannot be clearly distinguished from other steps, if the intended purpose of the step is achieved included.

As used herein, “transparent” means that the average transmittance of visible light with a wavelength of 400 to 700 nm is 80% or more, preferably 90% or more. Therefore, for example, a “transparent resin layer” refers to a resin layer having an average transmittance of 80% or more for visible light with a wavelength of 400 to 700 nm.
Also, the average transmittance of visible light is a value measured using a spectrophotometer, and can be measured using, for example, a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

As used herein, "actinic ray" or "radiation" means, for example, g-line, h-line, and i-line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X ray, electron beam (EB), and the like. Moreover, in the present invention, light means actinic rays or radiation.

In this specification, unless otherwise specified, the term "exposure" means not only exposure by far ultraviolet rays, extreme ultraviolet rays, X-rays, and EUV light typified by mercury lamps and excimer lasers, but also electron beams, ion beams, and the like. lithography by particle beam is also included in the exposure. In addition, in this specification, "irradiation of actinic rays or radiation" and "exposure" may be used synonymously.

In this specification, unless otherwise specified, the content ratio of each structural unit of the polymer is a molar ratio.
Moreover, in this specification, unless otherwise specified, the refractive index is a value measured by an ellipsometer at a wavelength of 550 nm.

In this specification, unless otherwise specified, the molecular weight when there is a molecular weight distribution is the weight average molecular weight.
In the present specification, the weight average molecular weight of the resin is the weight average molecular weight obtained by gel permeation chromatography (GPC) in terms of polystyrene.

As used herein, "(meth)acrylic acid" is a concept that includes both acrylic acid and methacrylic acid, and "(meth)acryloyl group" is a concept that includes both acryloyl and methacryloyl groups. .

In the present specification, a layer or the like constituting a compound or a transfer film being “alkali-soluble” means that the dissolution rate determined by the following method is 0.01 μm/second or more.
A propylene glycol monomethyl ether acetate solution in which the concentration of the target (e.g., resin) is 25% by mass is applied onto a glass substrate, and then heated in an oven at 100 ° C. for 3 minutes to form a coating film of the target (e.g., resin). thickness 2.0 μm). The dissolution rate (μm/sec) of the coating film is determined by immersing the coating film in a 1% by mass sodium carbonate aqueous solution (liquid temperature: 30° C.).
If the target does not dissolve in propylene glycol monomethyl ether acetate, the target is dissolved in an organic solvent (eg, tetrahydrofuran, toluene, or ethanol) with a boiling point of less than 200° C. other than propylene glycol monomethyl ether acetate.

As used herein, "water-soluble" means that the solubility in 100 g of water at pH 7.0 at a liquid temperature of 22°C is 0.1 g or more. Thus, for example, by water-soluble resin is intended a resin that satisfies the solubility conditions set forth above.

The "solid content" of the composition means a component that forms a composition layer (e.g., photosensitive layer) formed using the composition, and the composition contains a solvent (e.g., organic solvent, water, etc.). When included, it means all ingredients except solvent. In addition, as long as it is a component that forms a composition layer, a liquid component is also regarded as a solid content.

In this specification, unless otherwise specified, the thickness of a layer (film thickness) is the average thickness measured using a scanning electron microscope (SEM) for thicknesses of 0.5 μm or more, and less than 0.5 μm. is the average thickness measured using a transmission electron microscope (TEM). The average thickness is an average thickness obtained by forming a section to be measured using an ultramicrotome, measuring the thickness at arbitrary five points, and arithmetically averaging them.

[Photosensitive composition]
The photosensitive composition of the present invention satisfies both Requirement A1 and Requirement B1 described later.
Requirement A1: The glass transition temperature of the post-exposure photosensitive layer obtained by procedure X described later is 65° C. or higher.
Requirement B1: The moisture content at 40° C. and 90% RH of the post-exposure photosensitive layer obtained by procedure X described later is less than 2.0% by mass.
The pattern obtained from the photosensitive composition having the above constitution is excellent in corrosion prevention properties in a moist and hot environment. Although this is not clear in detail, the present inventors presume as follows. The pattern formed by the post-exposure photosensitive layer obtained from the photosensitive composition of the present invention has a small molecular movement because the glass transition temperature of the post-exposure photosensitive layer is a predetermined temperature or higher, and the water content is a predetermined value. It is estimated that the hygroscopicity is remarkably low because it is less than the value. As a result, the pattern obtained with the photosensitive composition of the present invention is considered to be excellent in corrosion prevention properties in a moist and hot environment.
In addition, in the following description, the fact that the pattern formed by the photosensitive composition of the present invention has more excellent corrosion prevention properties in a moist and heat environment may also be referred to as "the effect of the present invention is more excellent".
The features of the photosensitive composition of the present invention are described in detail below.

[Requirement A1]
The photosensitive composition of the present invention satisfies requirement A1 explained below. Moreover, the photosensitive composition of the present invention also preferably satisfies requirement A2 described below.
Requirement A1:
The glass transition temperature of the post-exposure photosensitive layer obtained by procedure X described later is 65° C. or higher.
Requirement A2:
The glass transition temperature of the post-exposure photosensitive layer obtained by procedure X described later is 165° C. or lower.

Above all, the glass transition temperature in the requirement A1 is preferably 85°C or higher, more preferably 100°C or higher, from the viewpoint that the effects of the present invention are more excellent. Moreover, the above glass transition temperature in the above requirement A2 is preferably 120° C. or lower in terms of the effect of the present invention being more excellent. In the following, the procedure X will be described first, and then the method for measuring the glass transition temperature will be described.

<<Procedure X>>
Procedure X: A laminate having a glass substrate, a photosensitive layer formed from a photosensitive composition, and a resin film in this order is obtained. Next, the photosensitive layer in the laminate is exposed from the side opposite to the glass substrate side of the laminate using an extra-high pressure mercury lamp so that the cumulative exposure amount at a wavelength of 365 nm is 80 mJ/cm ² . After the exposure, the laminate is left in an environment of 25° C. and 50% RH for 30 minutes, and then the resin film is peeled off. Next, the photosensitive layer is exposed again from the side where the resin film has been peeled off using a high-pressure mercury lamp so that the integrated exposure amount at a wavelength of 365 nm is 1000 mJ/cm ² , and after exposure. Get a sex layer.

In procedure X, exposure processing is performed using a high-pressure mercury lamp such that the integrated exposure amount at a wavelength of 365 nm is 1000 mJ/cm ² . When the irradiation conditions described above are carried out, it can generally be said that each reaction of the photosensitive layer (for example, a curing reaction, a decarboxylation reaction of a carboxylic acid, which will be described later, etc.) is substantially completed. As will be described later, the laminate includes a case where another layer is interposed between the photosensitive layer and the resin film. When exposure processing is performed using a high-pressure mercury lamp such that the integrated exposure amount at a wavelength of 365 nm is 1000 mJ/cm ² , the curing reaction of the photosensitive layer and the decarboxylation reaction of carboxylic acid, which will be described later, are inhibited. hard to do. In other words, even if another layer is interposed between the photosensitive layer and the resin film, the laminate can be obtained by using a high-pressure mercury lamp if the layer is laminated on the transfer film, for example. Each reaction of the photosensitive layer is substantially completed when exposure processing is carried out so that the integrated exposure amount at a wavelength of 365 nm becomes 1000 mJ/cm ² .

In Procedure X, the illuminance during exposure with an extra-high pressure mercury lamp is preferably 5 to 100 mW/cm ² , more preferably 10 to 50 mW/cm ² .
Also, the illuminance during exposure with a high-pressure mercury lamp is preferably 10 to 200 mW/cm ² , more preferably 15 to 100 mW/cm ² .

In Procedure X, the film thickness of the photosensitive layer in the laminate is preferably 0.1 to 20 μm, more preferably 1 to 9 μm.
Moreover, the photosensitive composition may be a coating composition or a layered composition.
The case where the above-mentioned photosensitive composition is in the form of a layer means, for example, the case where a photosensitive layer is formed by drying a coating film of the photosensitive composition. Specifically, a photosensitive layer contained in a transfer film or the like corresponds to the layered photosensitive composition.
In addition, when performing procedure X on the photosensitive layer contained in the transfer film, in the above-described laminate, between the glass and the photosensitive layer, the photosensitive layer and the temporary support (resin film) Other layers may be included in between.

Procedure X will be specifically described below, separately for the case where the photosensitive composition is in the form of a coating composition and the case where the photosensitive composition is in the form of a layer.

<Procedure X when the photosensitive composition is a coating composition>
An example of procedure X in the case where the photosensitive composition is a coating composition will be described below.
After spin-coating the photosensitive composition on a glass substrate (e.g., Corning "Eagle XG"), it is dried using a hot plate (e.g., 80 ° C. for 2 minutes) to form a film (photosensitive layer: A film thickness of 2 μm, for example, is obtained.
Next, a resin film (e.g., polyethylene terephthalate film (PET film; e.g., "16KS40" manufactured by Toray Industries, Inc.)) is crimped from the upper surface of the obtained film (photosensitive layer) to form a glass substrate, a photosensitive layer, Then, a laminate is produced by laminating the resin films in this order. The pressure bonding conditions between the resin film and the photosensitive layer are, for example, laminating temperature: 25° C., pressure: 0.6 Pa, linear pressure: 3 N/cm, and conveying speed: 4 m/min.
Next, the glass substrate side of the laminate is exposed to the photosensitive layer in the laminate using an ultra-high pressure mercury lamp (for example, a proximity type exposure machine having an ultra-high pressure mercury lamp (Hitachi High-Tech Electronic Engineering Co., Ltd.)). It is exposed from the opposite side (through the resin film) so that the cumulative exposure amount at a wavelength of 365 nm is 80 mJ/cm ² . The above exposure amount of 80 mJ/cm ² is the cumulative exposure amount of light having a wavelength of 365 nm that reaches the photosensitive layer through the resin film. When the resin film is a resin film other than a PET film (for example, a polypropylene film (PP film) or a polyethylene film (PE film), it is preferable to perform exposure through a filter that cuts wavelengths of 350 nm or less. It is preferable that the exposure is carried out through a filter that cuts the wavelength and that the integrated exposure amount measured with a 365 nm illuminometer is 80 mJ/cm ² .

After exposure, the laminate is left in an environment of 25° C. and 50% RH for 30 minutes, and then the resin film is peeled off.
Then, from the side exposed by peeling the resin film, the photosensitive layer is irradiated with a high-pressure mercury lamp (for example, an ultraviolet irradiation conveyor device having a high-pressure mercury lamp (Igraphics Co., Ltd.)) at a wavelength of 365 nm. Exposure is performed so that the integrated exposure amount is 1000 mJ/cm ² .
The exposure at a wavelength of 365 nm with an integrated exposure amount of 1000 mJ/cm ² is an exposure with an integrated exposure amount of 1000 mJ/cm ² measured with a 365 nm illuminometer.

Then, the post-exposure photosensitive layer on the glass substrate is scraped off to prepare a 100 mg powdery test sample (hereinafter referred to as sample X). If the scraped post-exposure photosensitive layer is not powdery, it is pulverized before use.

<Procedure X when the photosensitive composition is in the form of a layer>
An example of procedure X when the photosensitive composition is in the form of a layer is described below.
The case where the photosensitive composition is in a layered form means the case where the photosensitive composition constitutes a photosensitive layer. In the following, a transfer film comprising at least a temporary support (resin film) and a photosensitive layer composed of a photosensitive composition will be exemplified, and a predetermined post-exposure photosensitive layer from the photosensitive layer in the transfer film will be described. A method for obtaining (Sample X) will be described.

First, a transfer film is crimped (laminated) onto a glass substrate (for example, "Eagle XG" manufactured by Corning). When laminating the transfer film, the surface of the photosensitive layer in the transfer film opposite to the temporary support (resin film) side is brought into contact with the substrate, and the transfer film and the glass substrate are bonded together. Moreover, when the transfer film has a cover film, lamination is performed after peeling the cover film from the transfer film. The conditions for lamination are, for example, lamination temperature: 100° C., linear pressure: 3 N/cm, and conveying speed: 1 m/min. Thus, a laminate is obtained.
In addition, when the transfer film has other layers in addition to the cover film, the photosensitive layer, and the temporary support, the above other layers can be obtained based on the normal usage of the transfer film. Laminate the transfer film, including , onto the glass. In this case, the laminate may have the other layer, for example, between the temporary support and the photosensitive layer and/or on the opposite side of the photosensitive layer to the temporary support. .

Next, using an ultra-high pressure mercury lamp (for example, a proximity type exposure machine (Hitachi High-Tech Electronic Engineering Co., Ltd.) having an ultra-high pressure mercury lamp) is used to expose the laminate from the side opposite to the glass substrate side of the laminate. The layer is exposed to an integrated exposure dose of 80 mJ/cm ² at a wavelength of 365 nm. The above exposure amount of 80 mJ/cm ² is the cumulative exposure amount of light having a wavelength of 365 nm that reaches the photosensitive layer through the resin film. When the resin film is a resin film other than a PET film (for example, a polypropylene film (PP film) or a polyethylene film (PE film), it is preferable to perform exposure through a filter that cuts wavelengths of 350 nm or less. It is preferable that the exposure is carried out through a filter that cuts the wavelength and that the integrated exposure amount measured with a 365 nm illuminometer is 80 mJ/cm ² .

After the exposure, the laminate is left in an environment of 25° C. and 50% RH for 30 minutes, and then the temporary support (resin film) is peeled off.
Then, a high-pressure mercury lamp (for example, an ultraviolet irradiation conveyor device having a high-pressure mercury lamp (Igraphics Co., Ltd.)) is applied to the photosensitive layer from the side exposed by peeling the temporary support (resin film). The exposure is performed so that the integrated exposure amount at a wavelength of 365 nm is 1000 mJ/cm ² .
The exposure at a wavelength of 365 nm with an integrated exposure amount of 1000 mJ/cm ² is an exposure with an integrated exposure amount of 1000 mJ/cm ² measured with a 365 nm illuminometer.

In the laminate obtained by laminating the transfer film on the glass substrate, when the other layers (for example, the thermoplastic resin layer and the intermediate layer) are present between the temporary support and the photosensitive layer, the above-mentioned It is preferable to remove the other layers after exposure at a wavelength of 365 nm to an integrated exposure amount of 1000 mJ/cm ² . The removal method is not particularly limited, and the other layers can be removed from the laminate by, for example, treatment such as alkali development treatment, solvent washing, and tape peeling. The photosensitive layer is exposed as the outermost layer by the removal treatment described above.
However, in the above treatment, it is preferable not to heat-treat the laminate.
Moreover, the above treatment is carried out so as not to alter the quality of the photosensitive layer as much as possible.

<<Measurement of glass transition temperature of post-exposure photosensitive layer formed by procedure X>>
Using 5 to 6 mg of sample X prepared by procedure X, temperature modulated differential scanning calorimetry is performed under the following conditions. Measurement conditions using temperature-modulated differential scanning calorimetry are preferably the following conditions.
Apparatus: DSC2500 manufactured by TA Instruments (using a Tzero aluminum pan for sealing the sample)
Measurement conditions: nitrogen atmosphere, temperature range -70 to 200°C (5°C/min), temperature modulation condition ±1°C/min (N = 2)))
Then, the temperature (midpoint) at which the baseline shifts in the reversing heat flow (Rev. Heat Flow) is defined as the glass transition temperature (average value of n2).

[Requirement B1]
The photosensitive composition of the present invention satisfies requirement B1 explained below. Moreover, the photosensitive composition of the present invention preferably also satisfies requirement B2 described below.
Requirement B1:
The moisture content at 40° C. and 90% RH of the post-exposure photosensitive layer formed by procedure X described later is less than 2.0% by mass.
Requirement B2:
The moisture content at 40° C. and 90% RH of the post-exposure photosensitive layer formed by procedure X described later is greater than 0 mass %.

Above all, the water content at 40°C and 90% RH in requirement B2 is preferably 0.5% by mass or more in terms of the effect of the present invention being more excellent.

The procedure X and the method for measuring the moisture content are described below. The method for measuring the moisture content has steps (1) to (9) described later.

<<Procedure X>>
Procedure X is the same as <<procedure X>> in the description of requirement A.

<<Measurement of moisture content at 40°C and 90% RH of the post-exposure photosensitive layer formed by procedure X>>
(1) Weigh 11 to 12 mg of sample X prepared according to procedure X in a laboratory at 23° C. and 50% RH. Let the mass of the weighed sample X be a [mg].

(2) Next, the weighed sample X is put into the furnace of the heating and expelling device heated to 150° C., and the water content is measured for 15 minutes using a Karl Fischer moisture meter.
As the Karl Fischer moisture meter, for example, "AQ-2100" manufactured by Hiranuma Sangyo Co., Ltd. can be used. Also, as a heating and expelling device, for example, “EV-2000” manufactured by Hiranuma Sangyo Co., Ltd. can be used.

(3) Then, from the measured moisture content, the moisture content x [mass %] at 23°C and 50% RH is obtained by the following formula.
(Moisture content/a) x 100 = x [% by mass]

(4) Weigh 11 to 12 mg of sample X prepared according to procedure X in a laboratory at 23° C. and 50% RH. Let b [mg] be the mass of the sample X weighed here.

(5) Next, the weighed sample X is stored in a constant temperature and humidity chamber at 40° C. and 90% RH for 24 hours.

(6) Immediately after being taken out of the constant temperature and high humidity chamber, the sample X is put into the furnace of the heating and expelling device heated to 150° C., and the moisture content is measured for 15 minutes using a Karl Fischer moisture meter.
As the Karl Fischer moisture meter, for example, "AQ-2100" manufactured by Hiranuma Sangyo Co., Ltd. can be used. Also, as a heating and expelling device, for example, “EV-2000” manufactured by Hiranuma Sangyo Co., Ltd. can be used.

(7) Next, from the measured water content, the (apparent) water content y [mass %] at 40°C and 90% RH is obtained by the following formula.
(Moisture content/b) x 100 = y [% by mass]

(8) Using the x and y values obtained in (3) and (7) above, the water content at 40° C. and 90% RH is calculated by the following equation.
{Moisture content / (dry mass + moisture content)} × 100 [mass%] = [(b × y / 100) / {b × (100-x) / 100 + b × y / 100}] × 100 [mass%] = {y / (100-x + y)} × 100 [mass%]

(9) The moisture content is measured five times through the series of steps (1) to (8) described above, and the arithmetic mean is taken as the moisture content (% by mass) at 40° C. and 90% RH.

[Photosensitive composition]
Specific embodiments of the photosensitive composition satisfying both the requirements A1 and B1 described above are shown below.
The photosensitive composition preferably contains compound A having an acid group, and is a photosensitive composition in which the content of acid groups in the photosensitive composition is reduced by exposure to actinic rays or radiation.
In the photosensitive layer formed using the photosensitive composition having such a structure, the content of acid groups is reduced by exposure. That is, the polarity of the photosensitive layer changes before and after exposure, and this changes the solubility in developing solutions (alkaline developing solutions and organic solvent-based developing solutions). Therefore, if pattern exposure is performed on such a photosensitive layer, a dissolution contrast in the developing solution can occur between the exposed area and the non-exposed area, so that a pattern can be formed.

An example of a photosensitive composition having a mechanism for reducing the content of acid groups includes a compound A having a carboxyl group, and decarboxylation of the carboxyl group by exposure causes a decarboxylation reaction in the photosensitive composition. A photosensitive composition having a mechanism for reducing the content of carboxyl groups is mentioned.
A photosensitive layer formed using a photosensitive composition having such a structure exhibits excellent pattern formability with respect to developers (alkaline developers and organic solvent-based developers). In addition, since the amount of acid groups in the photosensitive layer is reduced by exposure, the moisture permeability resulting from the presence of acid groups is reduced, and as a result, the anticorrosion property is superior in a moist and hot environment. Therefore, the pattern formed from the photosensitive layer can be suitably used, for example, as a protective film (permanent film) such as a conductive pattern.

Moreover, as described later, the photosensitive composition preferably contains a polymerizable compound.
In the photosensitive layer formed using the photosensitive composition having such a structure, for example, when the acid group (eg, carboxyl group) is eliminated (eg, decarboxylation reaction), the acid group in compound A is eliminated. Radicals can be generated at the timed part. Radical polymerization of the polymerizable compound is initiated by such radicals, and the compound A in the exposed area can be crosslinked.

Furthermore, as described later, the photosensitive composition preferably contains a polymerizable compound and a photopolymerization initiator.
The photosensitive layer formed using the photosensitive composition having such a structure can cause the elimination of the acid group (such as the carboxyl group) and the polymerization initiation reaction to occur at different timings as described above. . For example, the photosensitive layer formed using the photosensitive composition having the above structure is first exposed at a wavelength or exposure amount that hardly causes the elimination of acid groups, and photopolymerization is performed. Curing may be achieved by allowing initiator-based polymerization to proceed. The cured photosensitive layer may then be subjected to a second exposure to cause elimination of the acid groups. Note that the first exposure is patterned exposure, a development step is performed to remove the unexposed portion or the exposed portion before the second exposure, and then the second exposure is performed to obtain a pattern. may

<<Requirement (V01), Requirement (W01)>>
The photosensitive composition is preferably a photosensitive composition that satisfies either requirement (V01) or requirement (W01) shown below. The photosensitive composition may be a photosensitive composition that satisfies both requirements (V01) and requirements (W01).
Requirements (V01)
The photosensitive composition contains a compound A having an acid group, and a compound β having a structure (hereinafter also referred to as “specific structure S0”) that reduces the amount of the acid group contained in the compound A upon exposure.
Requirement (W01)
The photosensitive composition contains a compound A having an acid group, and the compound A further contains a structure (specific structure S0) that reduces the amount of the acid group by exposure.

The above-mentioned specific structure S0 is a structure that exhibits the action of reducing the amount of acid groups contained in compound A when exposed to light. The specific structure S0 is preferably a structure that transitions from a ground state to an excited state upon exposure and exhibits an effect of reducing acid groups in compound A in the excited state. Specific structure S0 includes, for example, a structure (specific structure S1 described later) that can accept electrons from an acid group contained in compound A upon being exposed to light and being photoexcited.

The requirement (V01) is preferably the requirement (V1) shown below, and the requirement (W01) is preferably the requirement (W1) shown below. That is, in the requirement (V01), the compound β is preferably the compound B having a structure capable of accepting electrons from the acid group contained in the compound A in a photoexcited state. Further, in the requirement (W01), the structure is preferably a structure capable of accepting electrons from an acid group contained in compound A in a photoexcited state.
Requirement (V1): The photosensitive composition contains a compound A having an acid group, and a compound B having a structure (specific structure S1) capable of accepting electrons from the acid group contained in the compound A in a photoexcited state. .
Requirement (W1): The photosensitive composition contains a compound A having an acid group, and the compound A further contains a structure (specific structure S1) capable of accepting electrons from the acid group in a photoexcited state.
The photosensitive composition may be a photosensitive composition that satisfies both requirement (V1) and requirement (W1).

More preferably, the photosensitive composition is a photosensitive composition that satisfies either requirement (V1-C) or requirement (W1-C). Requirement (V1-C) corresponds to the aspect of requirement (V1) in which the acid group is a carboxy group, and requirement (W1-C) corresponds to the aspect of requirement (W1) in which the acid group is a carboxy group.
Requirements (V1-C)
The photosensitive composition contains a compound A having a carboxy group, and a compound B having a structure capable of accepting electrons from the carboxy group in compound A in a photoexcited state (hereinafter also referred to as “specific structure S1”).
Requirement (W1-C)
The photosensitive composition contains a compound A having a carboxy group, and the compound A further contains a structure (specific structure S1) capable of accepting electrons from the carboxy group in compound A in a photoexcited state.
The photosensitive composition may be a photosensitive composition that satisfies both requirements (V1-C) and requirement (W1-C).

Hereinafter, the photosensitive composition contains polyacrylic acid as compound A and quinoline as compound β (compound B) as an example, and the content of acid groups (carboxy groups) derived from compound A is reduced by exposure The mechanism for estimating
As illustrated below, the carboxy group of polyacrylic acid and the nitrogen atom of quinoline form hydrogen bonds in the presence of each other. When quinoline is exposed to light, its electron acceptability increases, and electrons are transferred from the carboxy group of polyacrylic acid (step 1: photoexcitation). The carboxyl group of polyacrylic acid becomes unstable when electrons are transferred to quinoline, and is released as carbon dioxide (step 2: decarboxylation reaction). After the decarboxylation reaction described above, radicals are generated in the polyacrylic acid residue, and the radical reaction proceeds. A radical reaction can occur between polyacrylic acid residues, between polyacrylic acid residues and optionally contained polymerizable compounds (monomer (M)), and hydrogen atoms in the atmosphere (step 3: polarity conversion, cross-linking/polymerization reaction). After completion of the radical reaction, compound β is regenerated and can contribute to the decarboxylation process of compound A again (step 4: regeneration of compound β (catalyst)).

Note that the mechanism by which the content of acid groups derived from compound A is reduced by exposure is not limited to the decarboxylation method described above, and is a known method capable of reducing the content of acid groups derived from compound A. can be selected as appropriate.

The photosensitive composition has an acid group (preferably a carboxyl group) content derived from the compound A by exposure to 5 mol% or more in that it has a more excellent pattern-forming ability, particularly with respect to an alkaline developer. preferably at a reduction rate of 10 mol% or more, more preferably at a reduction rate of 20 mol% or more, even more preferably at a reduction rate of 31 mol% or more It is more preferable to reduce at a reduction rate of 40 mol% or more, particularly preferably at a reduction rate of 51 mol% or more, and most preferably at a reduction rate of 71 mol% or more. preferable. Although the upper limit is not particularly limited, it is, for example, 100 mol % or less.
The amount of decrease in the content of acid groups (preferably carboxy groups) derived from compound A due to exposure of the photosensitive composition is the decrease in the content of carboxy groups derived from compound A in the photosensitive layer in the transfer film described later. It can be quantified by the same method as the rate.

<<Example of Embodiment of Photosensitive Composition>>
Moreover, below, an example of embodiment of a photosensitive composition is shown.
- Photosensitive composition of embodiment X-1-a1 A photosensitive composition that satisfies at least one of the requirements (V01) or (W01) and does not substantially contain a polymerizable compound and a photopolymerization initiator be.
Photosensitive Composition of Embodiment X-1-a2 A photosensitive composition that satisfies at least either requirement (V01) or requirement (W01) and is substantially free of a photopolymerization initiator.
Photosensitive layer of embodiment X-1-a3 A photosensitive composition that satisfies at least either requirement (V01) or requirement (W01) and contains a polymerizable compound and a photopolymerization initiator.

In the photosensitive composition of Embodiment X-1-a1, "the photosensitive composition substantially does not contain a polymerizable compound" means that the content of the polymerizable compound is the total solid of the photosensitive composition. It may be less than 3% by mass, preferably 0 to 1% by mass, more preferably 0 to 0.1% by mass, based on the minute.
Further, in the photosensitive compositions of Embodiments X-1-a1 and X-1-a2, the phrase "the photosensitive composition substantially does not contain a photopolymerization initiator" means that a photopolymerization initiator is contained. The amount may be less than 0.1% by mass, preferably 0 to 0.05% by mass, and preferably 0 to 0.01% by mass, based on the total solid content of the photosensitive composition. more preferred.

The photosensitive compositions of Embodiments X-1-a1 and X-1-a2 are preferably applied to the pattern forming method of Embodiment 1, which will be described later. Further, the photosensitive composition of Embodiment X-1-a3 is preferably applied to the pattern forming method of Embodiment 2, which will be described later.
Further, as the embodiment of the photosensitive composition, the photosensitive compositions of Embodiments X-1-a1-C to X-1-a3-C are more preferred. In addition, Embodiment X-1-a1-C to Embodiment X-1-a3-C are Embodiments X-1-a1 to X-1-a3 in which the requirement (V01) and the requirement (W01) are They correspond to the aspects of requirement (V1-C) and requirement (W1-C), respectively.

<< Various Ingredients >>
<Compound A having an acid group>
The photosensitive composition contains compound A having an acid group (compound A).
The acid group contained in compound A is preferably a proton-dissociating group with a pKa of 12 or less. Specific examples of the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group, with the carboxy group being preferred.
The compound A may be a low-molecular-weight compound or a high-molecular-weight compound (hereinafter also referred to as a "polymer"), but preferably contains a polymer (a polymer having an acid group). It is more preferable to include a polymer having
Examples of the polymerizable group include ethylenically unsaturated groups (e.g., (meth)acryloyl group, vinyl group, styryl group, etc.), and cyclic ether groups (e.g., epoxy group, oxetanyl group, etc.). , an ethylenically unsaturated group is preferred, and a (meth)acryloyl group is more preferred.
When compound A is a low-molecular-weight compound, the molecular weight of compound A is preferably less than 5,000, more preferably 2,000 or less, even more preferably 1,000 or less, particularly preferably 500 or less, most preferably 400 or less. preferable.
When the compound A is a polymer, the lower limit of the weight average molecular weight of the compound A is 5 in terms of excellent formability of the photosensitive layer (in other words, excellent film-forming ability for forming the photosensitive layer). ,000 or more is preferable, 10,000 or more is more preferable, and 15,000 or more is still more preferable. Although the upper limit is not particularly limited, it is preferably 50,000 or less from the viewpoint of better adhesion (laminate adhesion) when laminating (transferring) to any substrate.

Further, when compound A is a polymer, from the viewpoint of developability, the acid value of compound A, which is a polymer, is preferably 60 to 300 mgKOH/g, more preferably 60 to 275 mgKOH/g, and further 75 to 250 mgKOH/g. preferable.
As used herein, the acid value of a resin is a value measured by the titration method specified in JIS K0070 (1992).

Compound A also preferably contains a structure (specific structure S0) that reduces the amount of acid groups contained in compound A upon exposure. In the following, compound A not containing specific structure S0 is also referred to as "compound Aa", and compound A containing specific structure S0 is also referred to as "compound Ab". Incidentally, the compound Ab is preferably a polymer.
Compound A does not contain specific structure S0 means that compound A does not substantially contain specific structure S0. For example, the content of specific structure S0 in compound Aa is relative to the total mass of compound Aa is less than 1% by mass, preferably 0 to 0.5% by mass, more preferably 0 to 0.05% by mass.
The content of the specific structure S0 in the compound Ab is preferably 1% by mass or more, more preferably 1 to 50% by mass, and even more preferably 5 to 40% by mass, relative to the total mass of the compound Ab. preferable.
When compound A contains compound Ab, the content of compound Ab is preferably 5 to 100% by mass relative to the total mass of compound A.
Here, the specific structure S0 is a structure that exhibits an effect of reducing the amount of acid groups contained in the compound A upon exposure to light, as described above. The specific structure S0 is preferably a structure that transitions from a ground state to an excited state upon exposure and exhibits an effect of reducing acid groups in compound A in the excited state.
Specific structure S0 of compound A includes a structure (specific structure S1) that can accept electrons from an acid group contained in compound A in a photoexcited state.
Such a specific structure S1 includes a heteroaromatic ring.

The heteroaromatic ring may be monocyclic or polycyclic, and is preferably polycyclic. A polycyclic heteroaromatic ring is formed by condensing a plurality of (for example, 2 to 5) aromatic ring structures, and at least one of the plurality of aromatic ring structures has a heteroatom as a ring member atom. have.
The heteroaromatic ring has one or more heteroatoms (nitrogen atom, oxygen atom, sulfur atom, etc.) as ring member atoms, preferably 1 to 4 heteroatoms. In addition, the heteroaromatic ring preferably has one or more (eg, 1 to 4) nitrogen atoms as ring member atoms.
The number of ring member atoms in the above heteroaromatic ring is preferably 5-15.

Examples of the heteroaromatic ring include monocyclic heteroaromatic rings such as pyridine ring, pyrazine ring, pyrimidine ring, and triazine ring; cyclic heteroaromatic rings; heteroaromatic rings in which three rings are condensed, such as acridine ring, phenanthridine ring, phenanthroline ring, and phenazine ring.

The heteroaromatic ring may have one or more (for example, 1 to 5) substituents, and examples of the substituents include alkyl groups, aryl groups, halogen atoms, acyl groups, alkoxycarbonyl groups, and arylcarbonyl groups. , carbamoyl, hydroxy, cyano, and nitro groups. Moreover, when the aromatic ring has two or more substituents, the plurality of substituents may be combined to form a non-aromatic ring.
It is also preferred that the heteroaromatic ring is directly bonded to the carbonyl group.
It is also preferred that the heteroaromatic ring is bonded to the imide group to form a heteroaromatic imide group. The imide group in the heteroaromatic imide group may or may not form an imide ring together with the heteroaromatic ring.

In compound A, multiple aromatic rings (e.g., 2 to 5 aromatic rings) include single bonds, carbonyl groups, and multiple bonds (e.g., optionally substituted vinylene groups, —C≡C -, -N=N-, etc.), forming a series of aromatic ring structures linked by a structure selected from the group consisting of, and one of a plurality of aromatic rings constituting the series of aromatic ring structures When the above are the above heteroaromatic rings, the entire series of the above aromatic ring structures is regarded as one specific structure S1.

Further, some or all of the acid groups of compound A may or may not be anionized in the photosensitive composition, and both anionized acid groups and non-anionized acid groups are included. are called acid groups. That is, compound A may or may not be anionized in the photosensitive composition.

As the compound A, a compound having a carboxy group is particularly preferable because the pattern forming performance of the photosensitive composition is more excellent and the film-forming property is more excellent.
The compound having a carboxy group is preferably a monomer containing a carboxy group (hereinafter also referred to as a "carboxy group-containing monomer") or a polymer containing a carboxy group (hereinafter also referred to as a "carboxy group-containing polymer"). A carboxyl group-containing polymer is more preferable in that the pattern forming performance of the liquid composition is more excellent and the film-forming property is more excellent.

Some or all of the carboxy groups (--COOH) possessed by the carboxy group-containing monomer and the carboxy group-containing polymer may or may not be anionized in the photosensitive composition. Both (—COO ⁻ ) and non-anionized carboxy groups are referred to as carboxy groups.
In other words, the carboxy group-containing monomer may or may not be anionized in the photosensitive composition, and both anionized carboxy group-containing monomers and non-anionized carboxy group-containing monomers may be included. It is called contained monomer.
In other words, the carboxy group-containing polymer may or may not be anionized in the photosensitive composition, and both the anionized carboxy group-containing polymer and the non-anionized carboxy group-containing polymer are included in the carboxy group-containing polymer. It is called the contained polymer.

As described above, compound A containing a carboxy group may contain specific structure S0 (preferably specific structure S1). In other words, the carboxy group-containing monomer and the carboxy group-containing polymer may contain specific structure S0 (preferably specific structure S1). When the compound A containing a carboxy group contains the specific structure S0 (preferably the specific structure S1), it is particularly preferably a carboxy group-containing polymer containing the specific structure S0 (preferably the specific structure S1). A carboxy group-containing polymer containing

In the photosensitive composition, the lower limit of the content of compound A is preferably 1% by mass or more, more preferably 25% by mass or more, more preferably 30% by mass or more, relative to the total solid content of the photosensitive composition. Preferably, 45% by mass or more is even more preferable, and 50% by mass or more is particularly preferable. The upper limit of the content of compound A is preferably 100% by mass or less, more preferably 99% by mass or less, still more preferably 97% by mass or less, and 93% by mass or less, relative to the total solid content of the photosensitive composition. is particularly preferred, 85% by mass or less is more preferred, and 75% by mass or less is most preferred. In addition, when the photosensitive composition satisfies the requirement W01, the upper limit of the content of the compound A is preferably 99% by mass or less with respect to the total solid content of the photosensitive composition.
Compound A may be used alone or in combination of two or more.

(Carboxy group-containing monomer)
Examples of the carboxy group-containing monomer include polymerizable compounds containing a carboxy group and one or more (eg, 1 to 15) ethylenically unsaturated groups.
Examples of ethylenically unsaturated groups include (meth)acryloyl groups, vinyl groups, and styryl groups, with (meth)acryloyl groups being preferred.
As the carboxy group-containing monomer, a bifunctional or higher functional monomer containing a carboxy group is preferable from the viewpoint of better film-forming properties. The bifunctional or higher monomer means a polymerizable compound having two or more (eg, 2 to 15) ethylenically unsaturated groups in one molecule.
The carboxy group-containing monomer may further have an acid group other than the carboxy group as an acid group. Examples of acid groups other than carboxy groups include phenolic hydroxyl groups, phosphoric acid groups, and sulfonic acid groups.

The bifunctional or higher functional monomer containing a carboxy group is not particularly limited, and can be appropriately selected from known compounds.
Examples of bifunctional or higher monomers containing a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.), and Aronix M-510 (manufactured by Toagosei Co., Ltd.). manufactured by Toagosei Co., Ltd.) and the like.

Further, as the bifunctional or higher monomer containing a carboxy group, for example, a tri- to tetra-functional polymerizable compound having a carboxy group (pentaerythritol tri- and tetraacrylate [PETA] having a carboxy group introduced into its skeleton (acid value = 80 to 120 mgKOH/g)), and 5- to 6-functional polymerizable compounds containing carboxy groups (dipentaerythritol penta and hexaacrylate [DPHA] skeletons with carboxy groups introduced therein (acid value = 25 to 70 mg KOH/g). ) and the like. In the case of using the above-mentioned tri- or more functional monomer containing a carboxy group, it is also preferable to use a bi- or more functional monomer containing a carboxy group together from the viewpoint of better film formability.

Examples of bifunctional or higher functional monomers containing a carboxy group include polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942. The contents of this publication are incorporated herein.

(Carboxy group-containing polymer)
Carboxy group-containing polymers are usually alkali-soluble resins. The definition and measurement method of alkali solubility are as described above.

The carboxy group-containing polymer may further have an acid group other than the carboxy group as the acid group. Examples of acid groups other than carboxy groups include phenolic hydroxyl groups, phosphoric acid groups, and sulfonic acid groups.

From the standpoint of developability, the acid value of the carboxy group-containing polymer is preferably 60-300 mgKOH/g, more preferably 60-275 mgKOH/g, even more preferably 75-250 mgKOH/g.

<<Repeating unit having a carboxy group>>
The carboxy group-containing polymer preferably has a repeating unit having a carboxy group.
Examples of repeating units having a carboxy group include repeating units represented by the following general formula (A).

In general formula (A), R ^A1 represents a hydrogen atom, a halogen atom, or an alkyl group.
The above alkyl groups may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1.
In general formula (A), A ¹ represents a single bond or a divalent linking group.
Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO ₂ -, -NR ^N - (R ^N is a hydrogen atom or a alkyl groups), hydrocarbon groups (eg, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups such as phenylene groups, etc.), and linking groups in which a plurality of these are linked.

Examples of monomers from which repeating units having a carboxy group are derived include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. Among them, (meth)acrylic acid is preferable from the viewpoint of excellent patterning properties. That is, the repeating unit having a carboxy group is preferably a repeating unit derived from (meth)acrylic acid.

The content of repeating units having a carboxy group in the carboxy group-containing polymer is preferably 5 to 100 mol%, more preferably 10 to 65 mol%, and 15 to 45 mol, based on the total repeating units of the carboxy group-containing polymer. % is more preferred.
Further, the content of repeating units having a carboxy group in the carboxy group-containing polymer is preferably 1 to 100% by mass, more preferably 5 to 70% by mass, more preferably 12 to 12% by mass, based on the total repeating units of the carboxy group-containing polymer. 50% by mass is more preferred.
A repeating unit having a carboxy group may be used alone or in combination of two or more.

<<Repeating unit having a polymerizable group>>
The carboxy group-containing polymer preferably has a repeating unit having a polymerizable group in addition to the repeating units described above.
Examples of the polymerizable group include ethylenically unsaturated groups (e.g., (meth)acryloyl group, vinyl group, styryl group, etc.), and cyclic ether groups (e.g., epoxy group, oxetanyl group, etc.). An ethylenically unsaturated group is preferred, and a (meth)acryloyl group is more preferred.
Examples of repeating units having a polymerizable group include repeating units represented by the following general formula (B).

In general formula (B), X ^B1 and X ^B2 each independently represent -O- or -NR ^N -.
^RN represents a hydrogen atom or an alkyl group. The alkyl group may be linear or branched, and preferably has 1 to 5 carbon atoms.
L represents an alkylene group or an arylene group. The alkylene group may be linear or branched, and preferably has 1 to 5 carbon atoms. The arylene group may be monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms. The alkylene group and the arylene group may have a substituent, and the substituent is preferably a hydroxyl group, for example.
R ^B1 and R ^B2 each independently represent a hydrogen atom or an alkyl group. The above alkyl groups may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1.

The content of repeating units having a polymerizable group in the carboxy group-containing polymer is preferably 3 to 60 mol%, more preferably 5 to 40 mol%, more preferably 10 to 30, based on the total repeating units of the carboxy group-containing polymer. Mole % is more preferred.
The content of repeating units having a polymerizable group in the carboxy group-containing polymer is preferably 1 to 70% by mass, more preferably 5 to 50% by mass, more preferably 12 to 45% by mass, based on the total repeating units of the carboxy group-containing polymer. % by mass is more preferred.
The repeating units having a polymerizable group may be used singly or in combination of two or more.

<<Repeating unit having specific structure S0>>
The carboxy group-containing polymer also preferably has a repeating unit having a specific structure S0 (preferably a specific structure S1) in addition to the repeating units described above.
The specific structure S0 and the specific structure S1 are as described above.
In the repeating unit having the specific structure S0 (preferably the specific structure S1), the specific structure S0 (preferably the specific structure S1) may be present in the main chain, may be present in the side chain, or may be present in the side chain. preferably present in When the specific structure S0 (preferably specific structure S1) is present in the side chain, the specific structure S0 (preferably specific structure S1) is bound to the main chain of the polymer via a single bond or a linking group.
A repeating unit having a specific structure S0 (preferably a specific structure S1) is, for example, a monomer having a heteroaromatic ring (specifically, a vinyl heteroaromatic ring such as vinylpyridine and vinyl (iso)quinoline, and a heteroaromatic It is a repeating unit based on a (meth)acrylate monomer having a ring).
Specific examples of the repeating unit having the specific structure S0 (preferably specific structure S1) are shown below, but are not limited thereto.

When the carboxy group-containing polymer has a repeating unit having the specific structure S0 (preferably specific structure S1), the content thereof is preferably 3 to 75 mol% with respect to the total repeating units of the carboxy group-containing polymer. ~60 mol% is more preferred, and 10 to 50 mol% is even more preferred.
When the carboxy group-containing polymer has a repeating unit having the specific structure S0 (preferably specific structure S1), the content thereof is preferably 1 to 75% by mass with respect to the total repeating units of the carboxy group-containing polymer, and 3 ~60% by mass is more preferable, and 5 to 30% by mass is even more preferable.
The repeating units having the specific structure S0 (preferably specific structure S1) may be used singly or in combination of two or more.

<<Repeating unit having an aromatic ring>>
The carboxy group-containing polymer preferably has a repeating unit having an aromatic ring (preferably an aromatic hydrocarbon ring) in addition to the repeating units described above. Examples thereof include repeating units based on (meth)acrylates having aromatic rings, and repeating units based on styrene and polymerizable styrene derivatives.
Examples of (meth)acrylates having an aromatic ring include benzyl (meth)acrylate, phenethyl (meth)acrylate, phenoxyethyl (meth)acrylate, and the like.
Styrene and polymerizable styrene derivatives include methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimers, styrene trimers, and the like.
As the repeating unit having an aromatic ring, for example, repeating units represented by the following general formula (C) are also preferable.

In general formula (C), R ^C1 represents a hydrogen atom, a halogen atom, or an alkyl group. The above alkyl groups may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1.
Ar ^C represents a phenyl group or a naphthyl group. The phenyl group and naphthyl group may have one or more substituents, and examples of the substituents include alkyl groups, alkoxy groups, aryl groups, halogen atoms, and hydroxy groups.
Examples of repeating units having an aromatic ring are shown below.

Among them, the following structure is preferable as a repeating unit having an aromatic ring.

The content of repeating units having an aromatic ring in the carboxy group-containing polymer is preferably 5 to 80 mol%, more preferably 15 to 75 mol%, and 30 to 70 mol, based on the total repeating units of the carboxy group-containing polymer. % is more preferred.
The content of repeating units having an aromatic ring in the carboxy group-containing polymer is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and 30 to 70% by mass, based on the total repeating units of the carboxy group-containing polymer. % is more preferred.
A repeating unit having an aromatic ring may be used alone or in combination of two or more.

<<Repeating unit having an alicyclic structure>>
The carboxy group-containing polymer preferably has a repeating unit having an alicyclic structure in addition to the repeating units described above. The alicyclic structure may be monocyclic or polycyclic.
Alicyclic structures include, for example, dicyclopentanyl ring structures, dicyclopentenyl ring structures, isobornyl ring structures, adamantane ring structures, and cyclohexyl ring structures.
Monomers from which repeating units having an alicyclic structure are derived include, for example, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and cyclohexyl ( meth)acrylates.

The content of repeating units having an alicyclic structure in the carboxy group-containing polymer is preferably 3 to 70 mol%, more preferably 5 to 60 mol%, more preferably 10 to 55 mol % is more preferred.
The content of repeating units having an alicyclic structure in the carboxy group-containing polymer is preferably 3 to 90% by mass, more preferably 5 to 70% by mass, and 25 to 60% by mass is more preferred.
The repeating units having an alicyclic structure may be used alone or in combination of two or more.

≪Other repeating units≫
The carboxy group-containing polymer may have other repeating units in addition to the repeating units described above.
Examples of monomers from which the other repeating units are derived include (meth)acrylic acid alkyl esters, and examples of alkyl groups include alkyl groups having a chain structure. The chain structure may be either a linear structure or a branched structure. The alkyl group may have a substituent such as a hydroxy group. The number of carbon atoms in the alkyl group is 1-50, preferably 1-10. A specific example is methyl (meth)acrylate.
The content of other repeating units in the carboxy group-containing polymer is preferably 1 to 70 mol%, more preferably 2 to 50 mol%, and 3 to 20 mol%, based on the total repeating units of the carboxy group-containing polymer. More preferred.
The content of other repeating units in the carboxy group-containing polymer is preferably 1 to 70% by mass, more preferably 2 to 50% by mass, more preferably 5 to 35% by mass, based on the total repeating units of the carboxy group-containing polymer. More preferred.
Other repeating units may be used singly or in combination of two or more.
The weight average molecular weight of the carboxy group-containing polymer is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and most preferably 11,000 to 49,000.

The content of the polymer (preferably carboxy group-containing polymer) in compound A is preferably 75 to 100% by mass, more preferably 85 to 100% by mass, and 90 to 100% by mass, relative to the total content of compound A. % is more preferred, and 95 to 100% by mass is particularly preferred.

The content of the monomer (preferably a carboxy group-containing monomer) in compound A is preferably 0 to 25% by mass, more preferably 0 to 10% by mass, and 0 to 5% by mass, based on the total content of compound A. % is more preferred.

The content of compound A is preferably 25 to 100% by mass based on the total solid content of the photosensitive composition. However, if the photosensitive composition satisfies the requirements (V01) and/or requirements (V1) (that is, if the photosensitive composition contains compound β and/or compound B), the content of compound A is 25 to 99% by weight is preferred relative to the total solid content of the composition.
Among them, in the photosensitive composition of Embodiment X-1-a1, the content of compound A is preferably 40 to 98% by mass, more preferably 50 to 96% by mass, based on the total solid content of the photosensitive composition. is more preferable, and 60 to 93% by mass is more preferable.
In the photosensitive composition of Embodiment X-1-a2, the content of compound A is preferably 30 to 85% by mass, more preferably 45 to 75% by mass, based on the total solid content of the photosensitive composition. .
In the photosensitive composition of Embodiment X-1-a3, the content of compound A is preferably 30 to 85% by mass, more preferably 45 to 75% by mass, based on the total solid content of the photosensitive composition. .

<Compound β>
The photosensitive composition preferably contains compound β.
Compound β is a compound having a structure (specific structure S0) that reduces the amount of acid groups contained in compound A upon exposure. Note that the specific structure S0 is as described above.
The specific structure S0 of the compound β may be the entire structure that constitutes the entire compound β, or a partial structure that constitutes a part of the compound β.
The compound β may be a high-molecular compound or a low-molecular compound, preferably a low-molecular-weight compound.
The molecular weight of compound β, which is a low-molecular compound, is preferably less than 5,000, more preferably less than 1,000, even more preferably 65-300, and particularly preferably 75-250.

Among others, the specific structure S0 is preferably a structure (specific structure S1) that can accept electrons from the acid group contained in the compound A in a photoexcited state. That is, the compound β is preferably a compound B having a structure (specific structure S1) capable of accepting electrons from an acid group contained in the compound A in a photoexcited state.

Compound β (preferably compound B) is described below.
The compound β (preferably the compound B) is preferably an aromatic compound in terms of better pattern forming ability and/or lower moisture permeability of the formed pattern.
Here, the aromatic compound is a compound having one or more aromatic rings.
Only one aromatic ring or a plurality of aromatic rings may be present in compound β (preferably compound B). When a plurality of aromatic rings are present, for example, the aromatic ring may be present in a side chain of the resin or the like.
In compound β (preferably compound B), the aromatic ring can be used as a structure (specific structure S1) capable of accepting electrons from the acid group contained in compound A in the photoexcited state. The aromatic ring may be an entire structure that constitutes the entire compound β (preferably compound B), or a partial structure that constitutes a part of the compound β (preferably compound B).
The aromatic ring may be monocyclic or polycyclic, and is preferably polycyclic. The polycyclic aromatic ring is, for example, an aromatic ring formed by condensing a plurality of (for example, 2 to 5) aromatic ring structures, and at least one of the plurality of aromatic ring structures has a heteroatom as a ring member atom. It is preferable to have
The aromatic ring may be a heteroaromatic ring, preferably has 1 or more (eg, 1 to 4) heteroatoms (nitrogen atom, oxygen atom, sulfur atom, etc.) as ring member atoms, and More preferably, it has 1 or more (eg, 1 to 4) nitrogen atoms.
The number of ring member atoms in the aromatic ring is preferably 5-15.

Examples of the aromatic ring include monocyclic aromatic rings such as pyridine ring, pyrazine ring, pyrimidine ring, and triazine ring; Aromatic ring: aromatic ring in which three rings are condensed, such as acridine ring, phenanthridine ring, phenanthroline ring, and phenazine ring.

The aromatic ring may have one or more (for example, 1 to 5) substituents, and examples of the substituents include alkyl groups, aryl groups, halogen atoms, acyl groups, alkoxycarbonyl groups, arylcarbonyl groups, Carbamoyl groups, hydroxy groups, cyano groups, amino groups, and nitro groups are included. Moreover, when the aromatic ring has two or more substituents, the plurality of substituents may be combined to form a non-aromatic ring.
It is also preferred that the aromatic ring is directly bonded to the carbonyl group to form an aromatic carbonyl group in compound β (preferably compound B). It is also preferred that multiple aromatic rings are linked via a carbonyl group.
It is also preferred that the aromatic ring is bonded to the imide group to form an aromatic imide group in compound β (preferably compound B). The imide group in the aromatic imide group may or may not form an imide ring together with the aromatic ring.
In addition, a plurality of aromatic rings (e.g., 2 to 5 aromatic rings) include single bonds, carbonyl groups, and multiple bonds (e.g., optionally substituted vinylene groups, -C≡C-, -N= N—, etc.), when a series of aromatic ring structures linked together are formed, the series of aromatic ring structures as a whole is regarded as one specific structure S1.
Moreover, one or more of the plurality of aromatic rings constituting the series of aromatic ring structures is preferably the heteroaromatic ring.

Compound β (preferably compound B) has one or more of the following requirements (1) to (4) (for example, 1 to 4) are preferred. Above all, it is preferable that at least requirement (2) is satisfied, and that at least a nitrogen atom be included as the heteroatom possessed by the heteroaromatic ring.
(1) It has a polycyclic aromatic ring.
(2) having a heteroaromatic ring;
(3) having an aromatic carbonyl group;
(4) It has an aromatic imide group.

Specific examples of compound β (preferably compound B) include pyridine and pyridine derivatives, pyrazine and pyrazine derivatives, pyrimidine and pyrimidine derivatives, and monocyclic aromatic compounds such as triazine and triazine derivatives; quinoline and quinoline derivatives; Compounds in which two rings are fused to form an aromatic ring, such as isoquinoline and isoquinoline derivatives, quinoxaline and quinoxaline derivatives, and quinazoline and quinazoline derivatives; acridine and acridine derivatives, phenanthridine and phenanthridine derivatives, phenanthroline and Compounds in which three or more rings are condensed to form an aromatic ring, such as phenanthroline derivatives and phenazine and phenazine derivatives.
Among them, compound β (preferably compound B) is preferably one or more selected from the group consisting of pyridine and pyridine derivatives, quinoline and quinoline derivatives, and isoquinoline and isoquinoline derivatives. And, it is more preferably one or more selected from the group consisting of isoquinoline and isoquinoline derivatives, and more preferably one or more selected from the group consisting of isoquinoline and isoquinoline derivatives.
These compounds and derivatives thereof may further have a substituent, and examples of the substituent include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, A cyano group, an amino group, or a nitro group is preferable, an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, or a nitro group is more preferable, and an alkyl group , an aryl group, an acyl group, an alkoxycarbonyl group, an arylcarbonyl group, a carbamoyl group, a hydroxy group, a cyano group, or a nitro group are more preferable, and an alkyl group (for example, a linear or branched chain having 1 to 10 carbon atoms) alkyl groups) are particularly preferred.

In addition, the compound β (preferably compound B) is an aromatic compound having a substituent (compound β (preferably is a compound having substituents on the constituent atoms of the aromatic ring contained in compound B)), satisfies one or more (for example, 1 to 4) of the above requirements (1) to (4), and further A compound having a substituent is more preferred.
The position of the substituent is, for example, when the compound β (preferably compound B) is a quinoline or a quinoline derivative, the point at which the pattern forming ability is superior and/or the point at which the formed pattern has lower moisture permeability. and preferably have substituents at least at the 2- and 4-positions on the quinoline ring. Further, for example, when the compound β (preferably the compound B) is an isoquinoline or an isoquinoline derivative, the pattern forming ability is superior and/or the moisture permeability of the formed pattern is lower. It is preferred that at least the 1-position of has a substituent. As the substituent, an alkyl group (for example, a linear or branched alkyl group having 1 to 10 carbon atoms) is preferable.

When compound β (preferably compound B) is a polymer, it may be a polymer in which specific structure S0 (preferably specific structure S1) is bound to the main chain of the polymer via a single bond or a linking group.
Compound β (preferably compound B), which is a polymer, is, for example, a monomer having a heteroaromatic ring (specifically, a vinyl heteroaromatic ring and/or a specific structure S0 (preferably a specific structure S1, and more It is preferably obtained by polymerizing a (meth)acrylate monomer) having a heteroaromatic ring). You may copolymerize with another monomer as needed.

The molar absorption coefficient (molar absorption coefficient ε) of compound β (preferably compound B) for light at a wavelength of 365 nm is , for example, 1×10 ³ (cm·mol/L) ⁻¹ or less, preferably 1×10 ³ (cm·mol/L) ⁻¹ or less, and 5×10 ² (cm·mol/L) It is more preferably less than ⁻¹ , and even more preferably 1×10 ² (cm·mol/L) ⁻¹ or less. The lower limit of the molar extinction coefficient ε is not particularly limited, and is, for example, greater than 0 (cm·mol/L) ⁻¹ .
The fact that the molar extinction coefficient ε of the compound β (preferably compound B) is within the above range is particularly effective when exposing a photosensitive layer formed from a photosensitive composition through a temporary support (preferably PET film). There are advantages.
That is, when the acid group of the compound A having an acid group is a carboxy group, the molar absorption coefficient ε is moderately low, so that the generation of bubbles due to decarboxylation can be controlled even when exposed through the temporary support, and the pattern shape can be improved. deterioration can be prevented.
Further, when the photosensitive composition is used for producing a protective film (permanent film), coloration of the film can be suppressed by setting the molar extinction coefficient ε of the compound β (preferably compound B) within the above range.
As the compound having such a molar extinction coefficient ε, the above-described monocyclic aromatic compounds or aromatic compounds in which two rings are condensed to form an aromatic ring are preferable, and pyridine or pyridine derivatives, quinoline or quinoline Derivatives, or isoquinolines or isoquinoline derivatives are more preferred, and isoquinolines or isoquinoline derivatives are even more preferred.

In addition, in that the pattern forming ability is better and / or the moisture permeability of the formed pattern is lower, the molar absorption coefficient (molar absorption coefficient ε ') of the compound β (preferably compound B) at 313 nm The ratio of the molar extinction coefficient (molar extinction coefficient ε) of compound β (preferably compound B) at 365 nm (that is, the ratio represented by molar extinction coefficient ε/molar extinction coefficient ε′) is preferably 3 or less. , is more preferably 2 or less, and even more preferably less than 1. The lower limit is not particularly limited, and is, for example, 0.01 or more.

The molar extinction coefficient (molar extinction coefficient ε) of compound β (preferably compound B) for light at a wavelength of 365 nm (molar extinction coefficient ε) and the molar extinction coefficient (molar extinction coefficient ε′) for light at a wavelength of 313 nm are the compound β (preferably compound B ) is dissolved in acetonitrile and measured. If compound β (preferably compound B) does not dissolve in acetonitrile, the solvent for dissolving compound β (preferably compound B) may be changed as appropriate.

Specific examples of compound β (preferably compound B) include 5,6,7,8-tetrahydroquinoline, 4-acetylpyridine, 4-benzoylpyridine, 1-phenylisoquinoline, 1-n-butylisoquinoline, 1-n -butyl-4-methylisoquinoline, 1-methylisoquinoline, 2,4,5,7-tetramethylquinoline, 2-methyl-4-methoxyquinoline, 2,4-dimethylquinoline, phenanthridine, 9-methylacridine, 9-phenylacridine, pyridine, isoquinoline, quinoline, acridine, 4-aminopyridine, 2-chloropyridine and the like.

The lower limit of the pKa in the ground state of the compound β (preferably compound B) is preferably 0.50 or more, and the pattern forming ability is more excellent and/or the moisture permeability of the formed pattern is lower. point, 2.00 or more is more preferable. Further, the upper limit of pKa in the ground state of compound β (preferably compound B) is preferably 10.00 or less, more preferably 9.00 or less, still more preferably 8.00 or less, and 7.00 or less. Especially preferred. The ground-state pKa of compound β (preferably compound B) means the pKa of compound β (preferably compound B) in an unexcited state, and can be determined by acid titration. When the compound β (preferably compound B) is a nitrogen-containing aromatic compound, the ground state pKa of the compound β (preferably compound B) is the base of the conjugate acid of compound β (preferably compound B). The pKa under conditions is intended.

In the case of forming a photosensitive layer by coating, it is difficult to volatilize in the coating process, and the residual rate in the photosensitive layer is superior (and thus the pattern forming ability is superior, and / or formed The molecular weight of compound β (preferably compound B) is more preferably 120 or more, more preferably 130 or more, even more preferably 150 or more, in terms of lowering the moisture permeability of the pattern. Although the upper limit of the molecular weight of compound β (preferably compound B) is not particularly limited, it is, for example, 50,000 or less.

Further, when the compound β (preferably compound B) is a compound exhibiting a cationic state (for example, a nitrogen-containing aromatic compound), the energy of the HOMO (highest occupied molecular orbital) in the cationic state of the compound β (preferably compound B) The level is preferably −7.50 eV or less, and more preferably −7.80 eV or less in terms of better pattern forming ability and/or lower moisture permeability of the formed pattern. . Although the lower limit is not particularly limited, it is more preferably -13.60 eV or higher.
In this specification, the energy level of the HOMO (HOMO in the first electron excited state) in the cation state of compound β (preferably compound B) is calculated using a quantum chemical calculation program Gaussian09 (Gaussian 09, Revision A.02, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2009.).
As a calculation method, the time-dependent density functional theory using B3LYP as the functional and 6-31+G(d, p) as the basis function was used. In addition, in order to capture the solvent effect, the PCM method based on the parameters of chloroform set in Gaussian09 was also used. By this method, the structure optimization calculation of the first electron excited state was performed, the structure with the minimum energy was obtained, and the HOMO energy in that structure was calculated.

The HOMO energy level (eV) of the cation state of a representative example of compound β (preferably compound B) is shown below. In addition, the molecular weight is also shown together.

The content of compound β (preferably compound B) in the photosensitive composition is preferably 0.1 to 50% by mass based on the total solid content of the photosensitive composition.
Among them, in the photosensitive composition of Embodiment X-1-a1, the content of compound β (preferably compound B) is 2.0 to 40% by mass relative to the total solid content of the photosensitive composition. is preferred, 4 to 35 mass % is more preferred, and 8 to 30 mass % is even more preferred.
In the photosensitive composition of Embodiment X-1-a2, the content of compound β (preferably compound B) is preferably 0.5 to 20% by mass based on the total solid content of the photosensitive composition, 1.0 to 10% by mass is more preferable.
In the photosensitive composition of Embodiment X-1-a3, the content of compound β (preferably compound B) is preferably 0.3 to 20% by mass based on the total solid content of the photosensitive composition, 0.5 to 8% by mass is more preferable.
Compound β (preferably compound B) may be used alone or in combination of two or more.

When compound β is compound B, the total number of electron-accepting structures (specific structure S1) possessed by compound B in the photosensitive composition is the same as the acid group possessed by compound A, since the effect of the present invention is more excellent. (preferably carboxy groups), the total number is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, particularly preferably 10 mol% or more, most preferably 20 mol% or more. preferable.
Although there is no particular upper limit on the total number of electron-accepting structures (specific structure S1) possessed by compound B, the total number of acid groups (preferably carboxyl groups) possessed by compound A is considered from the viewpoint of the film quality of the resulting film. is preferably 200 mol % or less, more preferably 100 mol % or less, and even more preferably 80 mol % or less.

<Polymerizable compound>
The photosensitive composition also preferably contains a polymerizable compound. This polymerizable compound is a component different from the compound A having an acid group, and preferably does not contain an acid group.

The polymerizable compound is preferably a component different from compound A. For example, it is preferably a compound having a molecular weight (weight average molecular weight if it has a molecular weight distribution) of less than 5,000, and is a polymerizable monomer. is also preferred.

A polymerizable compound is a polymerizable compound having one or more (eg, 1 to 15) ethylenically unsaturated groups in one molecule.
The polymerizable compound preferably contains a polymerizable compound having a functionality of two or more.
Here, the bifunctional or higher polymerizable compound means a polymerizable compound having two or more (for example, 2 to 15) ethylenically unsaturated groups in one molecule.
Examples of ethylenically unsaturated groups include (meth)acryloyl groups, vinyl groups, and styryl groups, with (meth)acryloyl groups being preferred.
(Meth)acrylates are preferred as the polymerizable compound.

The photosensitive composition contains a bifunctional polymerizable compound (preferably a difunctional (meth)acrylate) and/or a trifunctional or higher polymerizable compound (preferably a trifunctional or higher (meth)acrylate). is preferred.

The bifunctional polymerizable compound is not particularly limited and can be appropriately selected from known compounds.
Examples of bifunctional polymerizable compounds include tricyclodecanedimethanol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,6 - hexanediol di(meth)acrylates.
As the bifunctional polymerizable compound, more specifically, for example, tricyclodecanedimethanol diacrylate (manufactured by A-DCP Shin-Nakamura Chemical Co., Ltd.), tricyclodecane dimenanol dimethacrylate (DCP Shin-Nakamura Kagaku Kogyo Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (A-HD-N Shin-Nakamura Chemical Kogyo Co., Ltd.) and the like.

The trifunctional or higher polymerizable compound is not particularly limited and can be appropriately selected from known compounds.
Examples of trifunctional or higher polymerizable compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth)acrylate, pentaerythritol (tri/tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, Examples include ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.

Here, "(tri/tetra/penta/hexa) (meth)acrylate" is a concept including tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. , "(tri/tetra)(meth)acrylate" is a concept including tri(meth)acrylate and tetra(meth)acrylate.

Other polymerizable compounds include, for example, caprolactone-modified compounds of (meth)acrylate compounds (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd. etc.), alkylene oxide-modified compounds of (meth)acrylate compounds (KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) manufactured by Daicel Allnex ) 135 etc.), and ethoxylated glycerin triacrylate (A-GLY-9E etc. manufactured by Shin-Nakamura Chemical Co., Ltd.).

The polymerizable compound also includes urethane (meth)acrylates (preferably trifunctional or higher urethane (meth)acrylates). The lower limit of the number of functional groups is more preferably hexafunctional or more, still more preferably octafunctional or more. The upper limit of the number of functional groups is, for example, 20 or less.
Trifunctional or higher urethane (meth)acrylates include, for example, 8UX-015A (manufactured by Taisei Fine Chemicals Co., Ltd.): UA-32P, U-15HA, and UA-1100H (all manufactured by Shin-Nakamura Chemical Co., Ltd.). : AH-600 (trade name) manufactured by Kyoeisha Chemical Co., Ltd.: UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000 (all manufactured by Nippon Kayaku Co., Ltd.), etc. be done.

The weight average molecular weight (Mw) of the polymerizable compound that can be contained in the photosensitive composition is preferably 200-3000, more preferably 250-2600, and even more preferably 280-2200.
When the photosensitive composition contains a polymerizable compound, among all the polymerizable compounds contained in the photosensitive composition, the molecular weight of the one with the smallest molecular weight is preferably 250 or more, more preferably 280 or more.

When the photosensitive composition contains a polymerizable compound, the content thereof is preferably 3 to 70% by mass, more preferably 10 to 70% by mass, based on the total solid content of the photosensitive composition, and 20 to 55% by mass. % is particularly preferred.
When the photosensitive composition contains a polymerizable compound, the mass ratio of the polymerizable compound to compound A (mass of polymerizable compound/mass of compound A) is preferably 0.2 to 2.0, and 0.4 to 0. .9 is more preferred.
A polymerizable compound may be used individually by 1 type, and may be used 2 or more types.

Further, when the photosensitive composition contains a bifunctional polymerizable compound and a trifunctional or higher polymerizable compound, the content of the bifunctional polymerizable compound is On the other hand, 10 to 90% by mass is preferable, 20 to 85% by mass is more preferable, and 30 to 80% by mass is even more preferable.
Further, the content of the trifunctional or higher polymerizable compound is preferably 10 to 100% by mass, more preferably 15 to 100% by mass, and 20 to 100% by mass with respect to all polymerizable compounds contained in the photosensitive composition. % is more preferred. 70 to 100% by weight is particularly preferred.

Moreover, when the photosensitive composition contains a bifunctional or higher-functional polymerizable compound, the photosensitive composition may further contain a monofunctional polymerizable compound.
However, when the photosensitive composition contains a bifunctional or higher polymerizable compound, it is preferable that the difunctional or higher polymerizable compound is the main component in the polymerizable compounds that the photosensitive composition may contain.
Specifically, when the photosensitive composition contains a bifunctional or higher polymerizable compound, the content of the bifunctional or higher polymerizable compound is relative to the total content of the polymerizable compounds contained in the photosensitive composition. , preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass.

<Photoinitiator>
The photosensitive composition preferably also contains a photoinitiator.
The photopolymerization initiator may be a radical photopolymerization initiator, a cationic photopolymerization initiator, or an anionic photopolymerization initiator, and is preferably a radical photopolymerization initiator.

The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used.
As the photopolymerization initiator, an oxime ester compound (photopolymerization initiator having an oxime ester structure) or an alkylphenone compound (photopolymerization initiator having an alkylphenone structure) is preferable, and at least one of these compounds may be included. , may include both. When both the above compounds are included, the content of the oxime ester compound is preferably 5 to 90% by mass, more preferably 15 to 50% by mass, relative to the total content of both compounds. The alkylphenone compound is also preferably an aminoacetophenone compound (a photopolymerization initiator having an aminoacetophenone structure).
The photopolymerization initiator may be used in combination with other photopolymerization initiators, such as hydroxyacetophenone compounds, acylphosphine oxide compounds, and bistriphenylimidazole compounds.

Further, as the photopolymerization initiator, for example, polymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-095716 and paragraphs 0064-0081 of JP-A-2015-014783 may be used.

Specific examples of the photopolymerization initiator include the following photopolymerization initiators.
Examples of oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)] (trade name: IRGACURE OXE-01, IRGACURE series are products of BASF) ), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF) , [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazolyl][2-(2,2,3,3-tetrafluoropropoxy) Phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpenta Non-1-(O-acetyloxime) (trade name: IRGACURE OXE-04, manufactured by BASF, and trade name: Lunar 6, manufactured by DKSH Japan Co., Ltd.), 1-[4-(phenylthio)phenyl]-3- Cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, manufactured by Changzhou Power Electronics New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[ 9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.) , 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.).
Examples of aminoacetophenone compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379, The Omnirad series is a product of IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907), APi-307 (1-( biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).
Other photopolymerization initiators include, for example, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one ( Trade name: Omnirad 127), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (trade name: Omnirad 369), 2-hydroxy-2-methyl-1-phenyl-propane -1-one (trade name: Omnirad 1173), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Omnirad 184), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819).

When the photosensitive composition contains a photopolymerization initiator, its content is preferably 0.01 to 15% by mass, more preferably 0.05 to 10% by mass, based on the total solid content of the photosensitive composition. , 0.1 to 5 mass % is more preferable.
A photoinitiator may be used individually by 1 type, and may be used 2 or more types.

<Surfactant>
The photosensitive composition may contain a surfactant.
Surfactants include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, with nonionic surfactants being preferred.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. mentioned.

As the surfactant, for example, surfactants described in paragraphs 0120 to 0125 of WO 2018/179640 can also be used.
As the surfactant, the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362 can also be used.
Examples of commercially available fluorosurfactants include MEGAFACE F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, and F-144. , F-437, 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, MFS-578, MFS-579, MFS -586, MFS-587, 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 (manufactured by DIC Corporation), Florado FC430, FC431, FC171 (manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC -105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Corporation), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), Futergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured by NEOS Co., Ltd.) etc.
In addition, as the fluorosurfactant, an acrylic compound that has a molecular structure with a functional group containing a fluorine atom and in which the portion of the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes when heat is applied. can also be suitably used. Examples of such fluorine-based surfactants include Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafac and DS-21.
As the fluorosurfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
A block polymer can also be used as the fluorosurfactant.
Further, the fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). A fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound can also be preferably used.
As the fluorosurfactant, a fluoropolymer having an ethylenically unsaturated bond-containing group in a side chain can also be used. Megafac RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation) and the like.

As fluorine-based surfactants, from the viewpoint of improving environmental suitability, compounds having linear perfluoroalkyl groups having 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), are used. Surfactants derived from alternative materials are preferred.
Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2 , 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW -1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil Co., Ltd.), Olphine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.

Examples of silicone-based surfactants include straight-chain polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups are introduced into side chains and terminals.

Specific examples of surfactants include DOWSIL 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (Toray Dow Corning Co.) 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 (manufactured by Shin-Etsu Silicone Co., Ltd.), F-4440, TSF-4300, TSF-4445 , TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), BYK307, BYK323, BYK330 (manufactured by BYK-Chemie) and the like.

The content of the surfactant is preferably 0.0001 to 10% by mass, more preferably 0.001 to 5% by mass, and further 0.005 to 3% by mass, based on the total solid content of the photosensitive composition. preferable.
One type of surfactant may be used alone, or two or more types may be used.

<Solvent>
As the solvent, commonly used solvents can be used without particular limitation.
Organic solvents are preferred as solvents.
Examples of organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, and caprolactam. , n-propanol, 2-propanol, and mixed solvents thereof.
The solvent is preferably a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate, a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate, or a mixed solvent of methyl ethyl ketone, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. .

When the photosensitive composition contains a solvent, the content of the solvent is preferably 20 to 95% by mass, more preferably 60 to 95% by mass, more preferably 70 to 95% by mass, based on the total mass of the photosensitive composition. More preferred.
A solvent may be used individually by 1 type, and may be used 2 or more types.

When the photosensitive composition contains a solvent, the viscosity (25° C.) of the photosensitive composition is preferably 1 to 50 mPa s, more preferably 2 to 40 mPa s, more preferably 3 to 30 mPa s, from the viewpoint of coating properties. is more preferred.
Viscosity is measured using, for example, VISCOMETER TV-22 (manufactured by TOKI SANGYO CO. LTD).
When the photosensitive composition contains a solvent, the surface tension (25° C.) of the photosensitive composition is preferably 5 to 100 mN/m, more preferably 10 to 80 mN/m, more preferably 15 to 40 mN/m, from the viewpoint of coatability. m is more preferred.
Surface tension can be measured, for example, with an Automatic Surface Tensiometer
It is measured using CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).

Solvents can also be used as described in paragraphs 0054 and 0055 of US Published Application 2005/282073, the contents of which are incorporated herein.
Also, as the solvent, an organic solvent having a boiling point of 180 to 250° C. (high boiling point solvent) can be used as necessary.

In addition, when the photosensitive composition of the present invention forms a photosensitive layer in a transfer film or the like, which will be described later, the photosensitive layer preferably does not substantially contain a solvent. The term “substantially solvent-free” means that the content of the solvent may be less than 1% by mass relative to the total mass of the photosensitive composition (photosensitive layer), and is 0 to 0.5% by mass. is preferred, and 0 to 0.001% by mass is more preferred.

<Other additives>
The photosensitive composition may contain other additives as needed.
Other additives include, for example, plasticizers, sensitizers, heterocyclic compounds, alkoxysilane compounds, and the like.
Plasticizers, sensitizers, heterocyclic compounds, and alkoxysilane compounds include, for example, those described in paragraphs 0097 to 0119 of WO 2018/179640.

In addition, the photosensitive composition contains other additives such as rust inhibitors, metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, colorants, and thermal radical polymerization initiators. , a thermal acid generator, an ultraviolet absorber, a thickener, a cross-linking agent, and an organic or inorganic suspending agent.
Preferred aspects of these components are described in paragraphs 0165 to 0184 of JP-A-2014-085643, respectively, and the contents of this publication are incorporated herein.

The photosensitive composition may contain impurities.
Impurities include, for example, sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogens, and ions thereof. Among them, halide ions, sodium ions, and potassium ions tend to be mixed as impurities, so the following contents are particularly preferable.

The content of impurities in the photosensitive composition is preferably 80 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 2 ppm by mass or less, relative to the total solid content of the photosensitive composition. The content of impurities in the photosensitive composition may be 1 mass ppb or 0.1 mass ppm or more with respect to the total solid content of the photosensitive composition.

As a method of making the impurities within the above range, for example, a raw material of the photosensitive composition with a low impurity content is selected, contamination of impurities is prevented during the formation of the photosensitive composition, and washing is performed. removal. By such a method, the amount of impurities can be made within the above range.

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

In addition, the content of compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, and hexane in the photosensitive composition is Less is preferred. The content of these compounds in the photosensitive composition is preferably 100 mass ppm or less, more preferably 20 mass ppm or less, and even more preferably 4 mass ppm or less, relative to the total solid content of the photosensitive composition.
The lower limit of the content may be 10 mass ppb or more, or 100 mass ppb or more, relative to the total solid content of the photosensitive composition. The content of these compounds can be suppressed in the same manner as the metal impurities described above. Moreover, it can quantify by a well-known measuring method.

The content of water in the photosensitive composition is preferably 0.01 to 1.0% by mass, preferably 0.05 to 0.5%, based on the total solid content of the photosensitive composition, from the viewpoint of improving patterning properties. % by mass is more preferred.

[Transfer film]
The transfer film of the invention has a temporary support and a photosensitive layer (hereinafter also simply referred to as "photosensitive layer") formed using the photosensitive composition of the invention.

The transfer film of the present invention will be described in detail below.
FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of the transfer film of the present invention.
The transfer film 100 shown in FIG. 1 comprises a temporary support 12, a photosensitive layer (a photosensitive layer formed using the photosensitive composition of the present invention) 14, and a cover film 16 laminated in this order. configuration.
The cover film 16 may be omitted.

<<temporary support>>
The temporary support is a support that supports the photosensitive layer and is peelable from the photosensitive layer.
The temporary support preferably has light transmittance in that the photosensitive layer can be exposed through the temporary support when patternwise exposing the photosensitive layer.
Here, "having light transmittance" means that the transmittance of the main wavelength of light used for exposure (either pattern exposure or overall exposure) is 50% or more. The transmittance of the dominant wavelength of light used for exposure is preferably 60% or more, more preferably 70% or more, from the viewpoint of better exposure sensitivity. As a method of measuring transmittance, a method of measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd. can be mentioned.
Regarding the transmittance of the temporary support, more specifically, the transmittance at 313 nm, 365 nm, 313 nm, 405 nm, and 436 nm is more preferably 70% or more, still more preferably 80% or more, and particularly preferably 90% or more. . Preferred values of transmittance include, for example, 87%, 92%, and 98%.

Specific examples of the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is preferable in terms of superior strength, flexibility, and the like. Examples of resin films include polyethylene terephthalate (PET) films, cellulose triacetate films, polystyrene films, and polycarbonate films. Among them, a biaxially stretched polyethylene terephthalate film is preferred.

From the viewpoints of pattern formability during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the number of particles, foreign substances, and defects contained in the temporary support is small. The number of fine particles, foreign substances, and defects with a diameter of 2 μm or more is preferably 50/10 mm ² or less, more preferably 10/10 mm ² or less, and even more preferably 3/10 mm ² or less. . Although the lower limit is not particularly limited, it can be 1 piece/10 mm ² or more.
The temporary support has a layer in which particles with a diameter of 0.5 to 5 μm are present at a rate of 1/mm ² or more on the side opposite to the side on which the photosensitive layer is formed, in order to further improve handling properties. more preferably 1 to 50/mm ² .

The thickness of the temporary support is not particularly limited, and is preferably 5 to 200 μm, more preferably 10 to 150 μm, from the viewpoint of ease of handling and excellent versatility.
The thickness of the temporary support depends on the material, considering the strength of the support, the flexibility required for lamination with the substrate for circuit wiring formation, and the light transmittance required in the first exposure step. can be selected as appropriate.
The temporary support may be a recycled product. Recycled products include those obtained by washing used films, cutting them into chips, and making films using these as materials. A specific example of the recycled product is Ecouse series manufactured by Toray Industries, Inc.

Preferred aspects of the temporary support include, for example, paragraphs 0017 to 0018 of JP-A-2014-085643, paragraphs 0019-0026 of JP-A-2016-027363, paragraphs 0041 to 0057 of WO2012/081680A1, and WO2018/ 179370A1, paragraphs 0029-0040, the contents of which are incorporated herein.

Temporary supports include, for example, Cosmoshine (registered trademark) A4100, Cosmoshine (registered trademark) A4160, and Cosmoshine (registered trademark) A4360 (all manufactured by Toyobo Co., Ltd.), and Lumirror (registered trademark). ) 16FB40, Lumirror (registered trademark) 16QS62 (16KS40), Lumirror (registered trademark) #38-U48, Lumirror (registered trademark) #75-U34, and Lumirror (registered trademark) #25-T60 (all of the above are Toray ( Co., Ltd.) may be used.
Further, particularly preferred embodiments of the temporary support include a 16 μm thick biaxially stretched polyethylene terephthalate film, a 12 μm thick biaxially stretched polyethylene terephthalate film, and a 9 μm thick biaxially stretched polyethylene terephthalate film.

<<Photosensitive layer>>
The photosensitive layer in the transfer film is a layer formed using the photosensitive composition of the present invention. For example, the photosensitive layer is a layer consisting essentially of the solid component of the photosensitive composition described above. is preferred. That is, the photosensitive composition that constitutes the photosensitive layer preferably contains solid components (components other than the solvent) that can be contained in the above-described photosensitive composition in the above-described content.
However, when a photosensitive composition containing a solvent is applied and dried to form a photosensitive layer, the solvent remains in the photosensitive layer even after drying. may contain.

The photosensitive layer has an acid group (preferably a carboxyl group) content of 5 mol% or more derived from the compound A upon exposure in terms of having superior pattern forming ability, particularly in an alkaline developer. It is preferably reduced at a reduction rate of 10 mol% or more, more preferably at a reduction rate of 10 mol% or more, even more preferably at a reduction rate of 20 mol% or more, and reduced at a reduction rate of 31 mol% or more is more preferable, it is particularly preferable that the reduction rate is 40 mol% or more, it is particularly preferable that the reduction rate is 51 mol% or more, and it is most preferable that the reduction rate is 71 mol% or more. . Although the upper limit is not particularly limited, it is, for example, 100 mol % or less.
When the acid group derived from compound A is a carboxy group, the rate of decrease in the content of carboxy groups derived from compound A in the photosensitive layer can be obtained by measuring the amount of carboxy groups in the photosensitive layer before and after exposure. can be calculated by When measuring the amount of carboxy groups in the photosensitive layer before exposure, it can be analyzed and quantified by, for example, potentiometric titration. When measuring the amount of carboxy groups in the photosensitive layer after exposure, the hydrogen atoms of the carboxy groups are replaced with metal ions such as lithium, and the amount of metal ions is measured by ICP-OES (Inductivity coupled plasma optical emission spectrometer). It can be calculated by analytical quantification.
In addition, the reduction rate of the content of acid groups derived from compound A in the photosensitive layer can be obtained by measuring the IR (infrared) spectrum of the photosensitive layer before and after exposure, and calculating the reduction rate of the peaks derived from the acid groups. You can get it though.

<Average thickness of photosensitive layer>
The average thickness of the photosensitive layer is preferably 0.5-20 μm. When the average thickness of the photosensitive layer is 20 μm or less, the resolution of the pattern is more excellent, and when the average thickness of the photosensitive layer is 0.5 μm or more, it is preferable from the viewpoint of pattern linearity. The average thickness of the photosensitive layer is more preferably 0.8 to 15 μm, still more preferably 1.0 to 10 μm. Specific examples of the average thickness of the photosensitive layer include 3.0 μm, 5.0 μm, and 8.0 μm.

<Method for forming photosensitive layer>
The photosensitive layer can be formed by applying and drying the photosensitive composition of the present invention. When forming a photosensitive layer from the photosensitive composition of the present invention, the photosensitive composition should be filtered using, for example, a filter having a pore size of 0.2 to 30 μm before being subjected to formation. is preferred.
A photosensitive layer can be formed by applying the photosensitive composition onto a temporary support or a cover film and drying it.
The coating method is not particularly limited, and includes known methods such as slit coating, spin coating, curtain coating, and inkjet coating.
Moreover, when forming other layers described later on the temporary support or the cover film, the photosensitive layer may be formed on the above other layers.

The 365 nm transmittance of the photosensitive layer is preferably 20% or more, more preferably 65% or more, more preferably 90%, in terms of better pattern formation ability and/or lower moisture permeability of the formed pattern. % or more is more preferable. Although the upper limit is not particularly limited, it is 100% or less.

In addition, the ratio of the 365 nm transmittance of the photosensitive layer to the 313 nm transmittance of the photosensitive layer (ratio represented by the 365 nm transmittance of the photosensitive layer/the 313 nm transmittance of the photosensitive layer) is more excellent in pattern formation ability. 1 or more is preferable, and 1.5 or more is more preferable in terms of point and/or the moisture permeability of the formed pattern becomes lower. Although the upper limit is not particularly limited, it is, for example, 1000 or less.

In the photosensitive layer, the acid group possessed by compound A is preferably a carboxy group. Furthermore, the photosensitive layer preferably has a carboxyl group content that is reduced at a rate of 5 mol % or more by irradiation with actinic rays or radiation. Such a photosensitive layer is more preferably a photosensitive layer that satisfies either the requirement (V1-C) or the requirement (W1-C) described above.
In addition, as an embodiment of the photosensitive layer, the above-described photosensitive layers of Embodiments X-1-a1-C to X-1-a3-C are more preferable.

The visible light transmittance per 1.0 μm film thickness of the photosensitive layer is preferably 80% or more, more preferably 90% or more, and most preferably 95% or more.
As for the visible light transmittance, it is preferable that all of the average transmittance at a wavelength of 400 to 800 nm, the minimum transmittance at a wavelength of 400 to 800 nm, and the transmittance at a wavelength of 400 nm satisfy the above.
Preferable values of the visible light transmittance per 1.0 μm film thickness of the photosensitive layer are, for example, 87%, 92%, 98%, and the like.
The dissolution rate of the photosensitive layer in a 1.0% by mass aqueous solution of sodium carbonate is preferably 0.01 μm/second or more, more preferably 0.10 μm/second or more, and more preferably 0.20 μm/second from the viewpoint of suppressing residue during development. The above is more preferable. From the point of view of the edge shape of the pattern, it is preferably 5.0 μm/sec or less. Specific preferable numerical values include, for example, 1.8 μm/second, 1.0 μm/second, and 0.7 μm/second.
The dissolution rate per unit time of the photosensitive layer in a 1.0% by mass sodium carbonate aqueous solution is measured as follows.
A photosensitive layer formed on a glass substrate from which the solvent has been sufficiently removed (thickness within the range of 1.0 to 10 μm) is dissolved at 25 ° C. using a 1.0% by mass sodium carbonate aqueous solution. Perform shower development until cut (however, up to 2 minutes).
It is obtained by dividing the film thickness of the photosensitive layer by the time required for the photosensitive layer to melt completely. In addition, when it does not melt completely in 2 minutes, it calculates similarly from the film thickness change amount until then.
For development, a 1/4 MINJJX030PP shower nozzle manufactured by Ikeuchi Co., Ltd. is used, and the shower spray pressure is 0.08 MPa. Under the above conditions, the shower flow rate per unit time is 1,800 mL/min.

From the viewpoint of pattern formability, the number of foreign substances having a diameter of 1.0 μm or more in the photosensitive layer is preferably 10/mm ² or less, more preferably 5/mm ² or less.
The number of foreign objects shall be measured as follows.
Any five regions (1 mm × 1 mm) on the surface of the photosensitive layer from the normal direction of the surface of the photosensitive layer are visually observed using an optical microscope, and a diameter of 1 in each region Measure the number of foreign matter of 0 μm or more, and calculate the number of foreign matter by arithmetically averaging them.
Specific preferable numerical values include, for example, 0/mm ² , 1/mm ² , 4/mm ² , and 8/mm ² .
From the viewpoint of suppressing the generation of aggregates during development, the haze of a solution obtained by dissolving 1.0 cm ³ of a photosensitive layer in 1.0 liter of a 30° C. aqueous solution of 1.0% by weight sodium carbonate is 60% or less. is preferably 30% or less, more preferably 10% or less, and most preferably 1% or less.
Haze shall be measured as follows.
First, a 1.0% by mass sodium carbonate aqueous solution is prepared and the liquid temperature is adjusted to 30°C. 1.0 cm ³ of photosensitive layer is placed in 1.0 L of sodium carbonate aqueous solution. Stir at 30° C. for 4 hours, taking care not to introduce air bubbles. After stirring, the haze of the solution in which the photosensitive resin layer is dissolved is measured. Haze is measured using a haze meter (product name “NDH4000”, manufactured by Nippon Denshoku Industries Co., Ltd.) using a liquid measurement unit and a liquid measurement dedicated cell with an optical path length of 20 mm.
Specific preferable numerical values include, for example, 0.4%, 1.0%, 9%, and 24%.

<< cover film >>
The transfer film of the present invention may further have a cover film on the side opposite to the temporary support when viewed from the photosensitive layer.
When the transfer film of the present invention includes a high refractive index layer described later, the cover film is arranged on the side opposite to the temporary support (that is, the side opposite to the photosensitive layer) when viewed from the high refractive index layer. is preferred. In this case, the transfer film is a laminate in which, for example, "temporary support/photosensitive layer/high refractive index layer/cover film" are laminated in this order.

The number of fisheyes having a diameter of 80 μm or more contained in the cover film is preferably 5/m ² or less. In addition, the term "fish eye" refers to material foreign matter, undissolved matter, and/or Alternatively, an oxidative degradation product or the like is taken into the film.

The number of particles having a diameter of 3 μm or more contained in the cover film is preferably 30 particles/mm ² or less, more preferably 10 particles/mm ² or less, and even more preferably 5 particles/mm ² or less. As a result, it is possible to suppress defects caused by the unevenness caused by the particles contained in the cover film being transferred to the photosensitive resin layer.

The arithmetic mean roughness Ra of the surface of the cover film is preferably 0.01 µm or more, more preferably 0.02 µm or more, and even more preferably 0.03 µm or more. If Ra is within such a range, for example, when the transfer film is elongated, it is possible to improve the take-up property when the transfer film is taken up.
From the viewpoint of suppressing defects during transfer, Ra is preferably less than 0.50 μm, more preferably 0.40 μm or less, and even more preferably 0.30 μm or less.

Cover films include, for example, polyethylene terephthalate films, polypropylene films, polystyrene films, and polycarbonate films.
As the cover film, for example, those described in paragraphs 0083 to 0087 and 0093 of JP-A-2006-259138 may be used.

As the cover film, for example, Alphan (registered trademark) FG-201 manufactured by Oji F-Tex Co., Ltd., Alphan (registered trademark) E-201F manufactured by Oji F-Tex Co., Ltd., Toray Advanced Film Co., Ltd. Therapeal (registered trademark) 25WZ manufactured by Toray Industries, Inc. or Lumirror (registered trademark) 16QS62 (16KS40) manufactured by Toray Industries, Inc. may also be used.

<<Other Layers>>
The transfer film may have other layers than those mentioned above.
Other layers include, for example, a high refractive index layer.
Moreover, when forming a high refractive index layer on a temporary support or a cover film, the photosensitive layer may be formed on the high refractive index layer.

<High refractive index layer>
The high refractive index layer is preferably arranged adjacent to the photosensitive layer, and is also preferably arranged on the opposite side of the temporary support from the photosensitive layer.
The high refractive index layer is not particularly limited except that it is a layer having a refractive index of 1.50 or more at a wavelength of 550 nm.
The refractive index of the high refractive index layer is preferably 1.55 or higher, more preferably 1.60 or higher.
Although the upper limit of the refractive index of the high refractive index layer is not particularly limited, it is preferably 2.10 or less, more preferably 1.85 or less, still more preferably 1.78 or less, and particularly preferably 1.74 or less.
Moreover, the refractive index of the high refractive index layer is preferably higher than the refractive index of the photosensitive layer.

The high refractive index layer may be photocurable (that is, photosensitive), thermosetting, or both photocurable and thermosetting. .
The embodiment in which the high refractive index layer is photosensitive has the advantage that after transfer, the photosensitive layer and the high refractive index layer transferred onto the base material can be patterned together by photolithography once.
The high refractive index layer preferably has alkali solubility (for example, solubility in a weakly alkaline aqueous solution).
Also, the high refractive index layer is preferably a transparent layer.

The thickness of the high refractive index layer is preferably 500 nm or less, more preferably 110 nm or less, and even more preferably 100 nm or less.
The thickness of the high refractive index layer is preferably 20 nm or more, more preferably 55 nm or more, still more preferably 60 nm or more, and particularly preferably 70 nm or more.

After transfer, the high refractive index layer may form a laminate together with the transparent electrode pattern (preferably ITO pattern) and the photosensitive layer by being sandwiched between the transparent electrode pattern and the photosensitive layer. In this case, light reflection is further reduced by reducing the refractive index difference between the transparent electrode pattern and the high refractive index layer and the refractive index difference between the high refractive index layer and the photosensitive layer. This further improves the concealability of the transparent electrode pattern.
For example, when a transparent electrode pattern, a high refractive index layer, and a photosensitive layer are laminated in this order, the transparent electrode pattern becomes less visible when viewed from the transparent electrode pattern side.

The refractive index of the high refractive index layer is preferably adjusted according to the refractive index of the transparent electrode pattern.
When the refractive index of the transparent electrode pattern is in the range of 1.8 to 2.0 as in the case of forming using oxides of In and Sn (ITO), the refractive index of the high refractive index layer is 1.60 or more is preferable. Although the upper limit of the refractive index of the high refractive index layer in this case is not particularly limited, it is preferably 2.1 or less, more preferably 1.85 or less, even more preferably 1.78 or less, and particularly preferably 1.74 or less.
When the refractive index of the transparent electrode pattern exceeds 2.0 as in the case of forming using an oxide of In and Zn (IZO; Indium Zinc Oxide), the refractive index of the high refractive index layer is 1.0. 70 or more and 1.85 or less are preferable.

The method for controlling the refractive index of the high refractive index layer is not particularly limited. A method using a complex with, and the like.

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

The average primary particle size of the particles (metal oxide particles or metal particles) is, for example, preferably 1 to 200 nm, more preferably 3 to 80 nm, from the viewpoint of transparency.
The average primary particle diameter of particles is calculated by measuring the particle diameters of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particles is not spherical, the longest side is taken as the particle diameter.
Specific examples of metal oxide particles include zirconium oxide particles ₍ ZrO2 particles), _Nb2O5 particles, titanium oxide particles ( _TiO2 particles), silicon dioxide particles ₍ _SiO2 particles), and composites thereof. At least one selected from the group consisting of particles is preferred.
Among these, as the metal oxide particles, for example, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles from the viewpoint that the refractive index of the high refractive index layer can be easily adjusted to 1.6 or more. more preferred.

When the high refractive index layer contains metal oxide particles, the high refractive index layer may contain only one type of metal oxide particles, or may contain two or more types of metal oxide particles.

The content of the particles (metal oxide particles or metal particles) improves the concealability of the object to be hidden, such as the electrode pattern, and effectively improves the visibility of the object to be hidden. It is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 40 to 85% by mass, relative to the total mass.
When titanium oxide is used as the metal oxide particles, the content of the titanium oxide particles is preferably 1 to 95% by mass, more preferably 20 to 90% by mass, based on the total mass of the high refractive index layer. It is preferably 40 to 85% by mass, and more preferably 40 to 85% by mass.

Commercially available metal oxide particles include calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F04), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F74), Baked zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F75), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F76), zirconium oxide particles (Nanouse OZ-S30M, Nissan Kagaku Kogyo Co., Ltd.) zirconium oxide particles (Nanouse OZ-S30K, Nissan Chemical Industries, Ltd.).

The high refractive index layer includes inorganic particles (metal oxide particles or metal particles) having a refractive index of 1.50 or more (more preferably 1.55 or more, still more preferably 1.60 or more), and a refractive index of 1.50 or more (more preferably 1.55 or more, still more preferably 1.60 or more), and a polymer having a refractive index of 1.50 or more (more preferably 1.55 or more, still more preferably 1.60 or more) It preferably contains one or more selected from the group consisting of toxic compounds.
In this aspect, it is easy to adjust the refractive index of the high refractive index layer to 1.50 or more (more preferably 1.55 or more, particularly preferably 1.60 or more).

Also, the high refractive index layer preferably contains a binder polymer, a polymerizable monomer, and particles.
Regarding the components of the high refractive index layer, the components of the curable transparent resin layer described in paragraphs 0019 to 0040 and 0144 to 0150 of JP 2014-108541, paragraphs 0024 to 0035 of JP 2014-010814 and components of the transparent layer described in WO 2016/009980, components of compositions having ammonium salts described in paragraphs 0034 to 0056 of WO 2016/009980, and the like.

Also, the high refractive index layer preferably contains a metal oxidation inhibitor.
When the high refractive index layer contains a metal oxidation inhibitor, when the high refractive index layer is transferred onto the substrate (i.e., the object to be transferred), a member that is in direct contact with the high refractive index layer (e.g., on the substrate) conductive member) can be surface-treated. This surface treatment imparts a metal oxidation suppressing function (protective property) to the member that is in direct contact with the high refractive index layer.

The metal oxidation inhibitor is preferably a compound having an aromatic ring containing a nitrogen atom. A compound having an aromatic ring containing a nitrogen atom may have a substituent.
The aromatic ring containing a nitrogen atom is preferably an imidazole ring, a triazole ring, a tetrazole ring, a thiazole ring, a thiadiazole ring, or a condensed ring of any one of these and another aromatic ring, such as an imidazole ring, a triazole ring, and a tetrazole ring. Alternatively, any one of these is more preferably a condensed ring with another aromatic ring.
The "other aromatic ring" forming the condensed ring may be a monocyclic ring or a heterocyclic ring, but is preferably a monocyclic ring, more preferably a benzene ring or a naphthalene ring, and still more preferably a benzene ring.

The metal oxidation inhibitor is preferably imidazole, benzimidazole, tetrazole, 5-amino-1H-tetrazole, mercaptothiadiazole or benzotriazole, more preferably imidazole, benzimidazole, 5-amino-1H-tetrazole or benzotriazole.
A commercial product may be used as the metal oxidation inhibitor, and as a commercial product, for example, BT120 manufactured by Johoku Chemical Industry Co., Ltd. containing benzotriazole can be preferably used.

When the high refractive index layer contains a metal oxidation inhibitor, the content of the metal oxidation inhibitor is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the high refractive index layer. is more preferred, and 1 to 5% by mass is even more preferred.

The high refractive index layer may contain components other than the components described above.
Other components that the high refractive index layer may contain include the same components as other components that the photosensitive layer may contain.
The high refractive index layer also preferably contains a surfactant.

The method for forming the high refractive index layer is not particularly limited.
As a method for forming the high refractive index layer, for example, a composition for forming a high refractive index layer containing an aqueous solvent is applied onto the above photosensitive layer formed on a temporary support, and dried if necessary. A method of forming by causing the

The composition for forming a high refractive index layer may contain each component of the high refractive index layer described above.
The composition for forming a high refractive index layer contains, for example, a binder polymer, a polymerizable monomer, particles, and an aqueous solvent.
Further, as the composition for forming a high refractive index layer, compositions containing an ammonium salt described in paragraphs 0034 to 0056 of WO 2016/009980 are also preferable.

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

<Other layers>
The transfer film may include layers other than the layers described above (hereinafter also referred to as "other layers"). Other layers include, for example, an intermediate layer and a thermoplastic resin layer, and known layers can be used as appropriate.

Preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP-A-2014-085643, and preferred embodiments of layers other than the above are described in paragraphs 0194-0196 of JP-A-2014-085643. Yes, the contents of this publication are incorporated herein.

<<Manufacturing method of transfer film>>
The production method of the transfer film is not particularly limited, and known production methods can be applied.
The method for producing the transfer film preferably includes a step of forming a photosensitive layer from the photosensitive composition of the present invention on the temporary support, and after the step of forming the photosensitive layer, the photosensitive More preferably, the step of placing a cover film over the adhesive layer is included.
Further, after the step of forming the photosensitive layer, a step of forming a high refractive index layer by applying and drying a composition for forming a high refractive index layer may be included. In this case, it is more preferable to further include a step of disposing a cover film on the high refractive layer after the step of forming the high refractive layer.

[Pattern formation method]
The pattern forming method related to the present invention (also referred to as the "pattern forming method of the present invention") is not particularly limited as long as it is a pattern forming method using the photosensitive composition of the present invention. A step of forming a photosensitive layer on a base material, a step of pattern-exposing the photosensitive layer, and a step of developing (in particular, alkali development) the exposed photosensitive layer, in this order. is preferred. When the development is organic solvent development, it is preferable to include a step of further exposing the obtained pattern.
In addition, in forming a photosensitive layer on a substrate using the photosensitive composition of the present invention, the above-described transfer film is produced using the photosensitive composition, and such a transfer film is used to form the substrate. A method of forming a photosensitive layer thereon may also be used. Specifically, as such a method, the surface of the photosensitive layer in the above-described transfer film opposite to the temporary support side is brought into contact with the base material, and the transfer film and the base material are bonded together, and the transfer film is A method of using the photosensitive layer in (1) as a photosensitive layer on the base material.
Specific embodiments of the pattern forming method of the present invention include the pattern forming methods of the first and second embodiments.
Each step of the pattern forming method of Embodiments 1 and 2 will be described in detail below.

[Pattern Forming Method of Embodiment 1]
The pattern formation method of Embodiment 1 has steps X1 to X3. The following step X2 corresponds to the step of reducing the content of acid groups derived from compound A in the photosensitive layer by exposure. However, when the developer in step X3 is an organic solvent-based developer, it is preferable to further include step X4 after step X3.
Step X1: The surface of the photosensitive layer in the transfer film opposite to the temporary support side is brought into contact with the substrate, and the transfer film and the substrate are bonded together Step X2: Pattern exposure of the photosensitive layer Step X3: A step of developing the photosensitive layer using a developer (e.g., an alkaline developer or an organic solvent-based developer). Step X4: After the development step of step X3, a step of exposing a pattern formed by development.

When an alkaline developer is used as the developer in step X3, the photosensitive layer is preferably the photosensitive layer of Embodiments X-1-a1 and X-1-a2. When an organic solvent-based developer is used as the developer in step X3, the photosensitive layer is preferably the photosensitive material of Embodiment X-1-a1.
The patterning method of Embodiment 1 is preferably applied to transfer films comprising the photosensitive layers of Embodiments X-1-a1 and X-1-a2 described above.

Further, the pattern forming method of Embodiment 1 preferably has a step of peeling off the temporary support between the steps X1 and X2 or between the steps X2 and X3.

<<Step X1>>
The pattern forming method of Embodiment 1 has a step of bringing the surface of the photosensitive layer in the transfer film opposite to the temporary support side into contact with the substrate, and bonding the transfer film and the substrate together.

<<Base material>>
The substrate is not particularly limited, and examples thereof include glass substrates, silicon substrates, resin substrates, and substrates having a conductive layer. Examples of substrates included in the substrate having a conductive layer include glass substrates, silicon substrates, and resin substrates.
The substrate is preferably transparent.
The refractive index of the substrate is preferably 1.50 to 1.52.
The substrate may be composed of a translucent substrate such as a glass substrate. For example, tempered glass such as Corning Gorilla Glass can be used. Materials used in JP-A-2010-086684, JP-A-2010-152809, and JP-A-2010-257492 are also preferable as the material contained in the base material.
When the substrate includes a resin substrate, it is more preferable to use a resin film with small optical distortion and/or high transparency as the resin substrate. Specific materials include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, cycloolefin polymer, and the like.

The substrate included in the substrate having the conductive layer is preferably a resin substrate, and more preferably a resin film, from the viewpoint of roll-to-roll production.

The conductive layer includes any conductive layer used for general circuit wiring or touch panel wiring.
As the conductive layer, one or more selected from the group consisting of a metal layer (metal foil, etc.), 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. is preferred, a metal layer is more preferred, and a copper or silver layer is even more preferred.
Further, the conductive layer in the substrate having the conductive layer may be one layer or two layers or more.
When a substrate having a conductive layer includes two or more conductive layers, each conductive layer is preferably made of a material different from each other.
Materials for the conductive layer include simple metals and conductive metal oxides.
Examples of simple metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au.
Conductive metal oxides include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ₂ . The term “conductivity” refers to a volume resistivity of less than 1×10 ⁶ Ωcm, preferably less than 1×10 ⁴ Ωcm.

When there are two or more conductive layers in a substrate having conductive layers, at least one of the conductive layers preferably contains a conductive metal oxide.
The conductive layer is preferably an electrode pattern corresponding to the sensor of the visual recognition portion used in the capacitive touch panel or the wiring of the peripheral extracting portion.
Also, the conductive layer is preferably a transparent layer.

<<Procedure of step X1>>
The step X1 is preferably a bonding step by pressing and heating with rolls or the like. A known laminator such as a laminator, a vacuum laminator, and an autocut laminator can be used for bonding.
The step X1 is preferably carried out by a roll-to-roll method, and therefore the base material to which the transfer film is attached is preferably a resin film or a resin film having a conductive layer.
The roll-to-roll method will be described below.
In the roll-to-roll method, a base material that can be wound and unwound is used as a base material, and the step of unwinding the base material ("winding (Also referred to as "unloading step"), and after any of the steps, a step of winding the base material (also referred to as "winding step"), at least any of the steps (preferably, all steps, or all the steps other than the heating step) while conveying the substrate.
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 manufacturing methods to which a roll-to-roll system is applied.

<<Step X2>>
The pattern forming method of Embodiment 1 includes a step of pattern-exposing the photosensitive layer (step X2) after step X1. Step X2 corresponds to the step of reducing the content of acid groups derived from compound A in the photosensitive layer by exposure. More specifically, specific structure S0 (preferably specific structure S1) in compound β (preferably compound B) in the photosensitive layer (for requirement V01) and specific structure S0 in compound A (preferably specific structure It is preferred to patternwise expose the photosensitive layer with light of a wavelength that excites S1) (for requirement W01).

In the exposure process, the detailed arrangement and specific size of the pattern are not particularly limited.
For example, when the pattern formation method of Embodiment 1 is applied to manufacture of circuit wiring, the display quality of a display device (for example, a touch panel) provided with an input device having circuit wiring manufactured by the pattern formation method of Embodiment 1 is improved. Also, from the point of view that the area occupied by the lead-out wiring can be made as small as possible, at least a part of the pattern (especially the part corresponding to the electrode pattern and the lead-out wiring of the touch panel) is preferably a thin wire of 100 μm or less, and 70 μm or less. is more preferable.

As the light source used for exposure, light in a wavelength range capable of reducing the content of acid groups derived from compound A in the photosensitive layer (compound β in the photosensitive layer (preferably compound B) Light having a wavelength that excites the specific structure S0 (preferably the specific structure S1) (in the case of requirement V01) and the specific structure S0 (preferably the specific structure S1) (in the case of requirement W01) in compound A. For example, if the photosensitive layer is In the case of the photosensitive layer described above, light in a wavelength range of 254 nm, 313 nm, 365 nm, 405 nm, etc. can be used.) can be appropriately selected. Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).

The exposure amount is preferably 10-10000 mJ/cm ² , more preferably 50-3000 mJ/cm ² .

In step X2, pattern exposure may be performed after peeling the temporary support from the photosensitive layer, and before peeling the temporary support, pattern exposure is performed through the temporary support, and then the temporary support is peeled. may In order to prevent contamination of the mask due to contact between the photosensitive layer and the mask and to avoid the influence of foreign matter adhering to the mask on the exposure, it is preferable to carry out pattern exposure without peeling off the temporary support. The pattern exposure may be exposure through a mask, or may be direct exposure using a laser or the like.
The temporary support is peeled off from the photosensitive layer before step X3, which will be described later.

<<Process X3>>
The pattern forming method of Embodiment 1 includes a step (step X3) of developing the pattern-exposed photosensitive layer with a developer (especially an alkaline developer) after step X2.
In the photosensitive layer that has undergone step X2, the content of acid groups in the photosensitive layer in the exposed area is reduced, so that there is a difference in solubility (dissolution contrast) between the exposed area and the unexposed area in a developer. is occurring. Formation of the dissolution contrast in the photosensitive layer enables pattern formation in step X3. In addition, when the developer in the step X3 is an alkaline developer, the unexposed portion is removed by performing the step X3 to form a negative pattern. On the other hand, when the developer in the step X3 is an organic solvent-based developer, the exposed portion is removed by performing the step X3 to form a positive pattern. The resulting positive pattern is subjected to a treatment for reducing the content of acid groups derived from compound A in step X4, which will be described later.

(Alkaline developer)
The alkaline developer is not particularly limited as long as it can remove the unexposed portion of the photosensitive resin layer.
As the alkaline developer, for example, an aqueous alkaline developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol/L (liter) is preferable.
Moreover, the alkaline developer may further contain a water-soluble organic solvent, a surfactant, and the like. As the alkaline developer, for example, the developer described in paragraph 0194 of International Publication No. 2015/093271 is preferable.
The concentration of water in the alkaline developer is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. In addition, as an upper limit, it is less than 100 mass %, for example.

(Organic solvent-based developer)
The organic solvent-based developer is not particularly limited as long as it can remove the exposed portion of the photosensitive resin layer. A developer containing an organic solvent such as a hydrogen-based solvent can be used.
In the organic solvent-based developer, a plurality of organic solvents may be mixed, or an organic solvent other than the above or water may be mixed and used. However, in order to fully exhibit the effects of the present invention, the water content of the organic solvent-based developer as a whole is preferably less than 10% by mass, and more preferably substantially free of water. The concentration of the organic solvent (in the case of multiple mixtures, the total) in the organic solvent-based developer is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 85% by mass or more, and particularly preferably 90% by mass or more. , 95 mass % or more is most preferable. In addition, as an upper limit, it is 100 mass % or less, for example.

The development method is not particularly limited, and may be any of puddle development, shower development, spin development, dip development, and the like. Here, shower development will be described. Unnecessary portions can be removed by spraying a developer onto the exposed photosensitive resin layer by showering. After development, it is also preferable to remove development residues while spraying a detergent or the like with a shower and rubbing with a brush or the like. The liquid temperature of the developer is preferably 20 to 40.degree.

The pattern forming method of Embodiment 1 may or may not further include a post-baking step of heat-treating the pattern including the photosensitive layer obtained by development.
Post-baking is preferably performed in an environment of 8.1 to 121.6 kPa, more preferably in an environment of 50.66 kPa or higher. On the other hand, it is more preferable to carry out under the environment of 111.46 kPa or less, and further preferably under the environment of 101.3 kPa or less.
The post-baking temperature is preferably 80 to 250.degree. C., more preferably 110 to 170.degree. C., even more preferably 130 to 150.degree.
The post-baking time is preferably 1 to 60 minutes, more preferably 2 to 50 minutes, even more preferably 5 to 40 minutes.
Post-baking may be performed in an air environment or in a nitrogen-substituted environment.

<<Process X4>>
When the developer used in the step X3 is an organic solvent-based developer, the positive pattern obtained is subjected to the step X4. Step X4 corresponds to the step of exposing the positive pattern obtained in step X3 to reduce the content of acid groups derived from compound A. More specifically, specific structure S0 (preferably specific structure S1) in compound β (preferably compound B) in the photosensitive layer (for requirement V01) and specific structure S0 in compound A (preferably specific structure It is preferred to patternwise expose the photosensitive layer with light of a wavelength that excites S1) (for requirement W01).

The light source and exposure amount used for exposure are the same as the light source and exposure amount described in step X1, and the preferred embodiments are also the same.

[Pattern Forming Method of Embodiment 2]
The pattern forming method of Embodiment 2 has step Y1, step Y2P, and step Y3 in this order, and further includes step Y2Q (a step of further exposing the photosensitive layer exposed in step Y2P). Between Y2P and step Y3, or after step Y3.
Step Y1: The surface of the photosensitive layer in the transfer film opposite to the temporary support side is brought into contact with the substrate, and the transfer film and the substrate are bonded together Step Y2P: The step of exposing the photosensitive layer Step Y3: Step of developing the photosensitive layer

As described above, the pattern forming method of Embodiment 2 corresponds to an aspect applicable when the photosensitive layer further contains a photopolymerization initiator and a polymerizable compound. Therefore, the patterning method of Embodiment 2 is preferably applied to a transfer film including the photosensitive layer of Embodiment X-1-a3 described above.
The pattern forming method of Embodiment 2 will be described below. Processes Y1 and Y3 are the same as the processes X1 and X3, respectively, and description thereof will be omitted.
Note that the step Y3 may be performed at least after the step Y2P, and the step Y3 may be performed between the steps Y2P and Y2Q.
The pattern forming method of Embodiment 2 may or may not have a post-baking step of heat-treating the pattern including the photosensitive layer obtained by development after step Y3. good. The post-baking process can be performed by the same method as the post-baking process that the pattern forming method of the first embodiment may have. When step Y3 is performed between step Y2P and step Y2Q, the post-baking step may be performed before step Y2Q or after step Y2Q as long as it is performed after step Y3. may have been

Further, the pattern forming method of Embodiment 2 preferably has a step of peeling off the temporary support between step Y1 and step Y2P or between step Y2P and step Y3.

<<Process Y2P, Process Y2Q>>
The pattern forming method of Embodiment 2 includes a step of exposing the photosensitive layer that has passed through step Y1 (step Y2P), and a step of further exposing the exposed photosensitive layer (step Y2Q).
One of the exposure treatments (steps Y2P and Y2Q) is mainly exposure for reducing the content of acid groups derived from compound A by exposure, and the other of the exposure treatments (steps Y2P and Y2Q). mainly corresponds to exposure for causing a polymerization reaction of a polymerizable compound based on a photopolymerization initiator. Further, the exposure processing (steps Y2P and Y2Q) may be either full-surface exposure or pattern exposure, but one of the exposure processing is pattern exposure.
For example, when step Y2P is pattern exposure for reducing the content of acid groups derived from compound A by exposure, the developer used in step Y3 may be an alkaline developer or an organic solvent-based developer. may be However, when developing with an organic solvent-based developer, step Y2Q is usually performed after step Y3, and in the developed photosensitive layer (pattern), the polymerization reaction of the polymerizable compound based on the photopolymerization initiator. The content of acid groups (preferably carboxyl groups) derived from compound A decreases as the acid groups are generated.
Further, for example, when step Y2P is pattern exposure for causing a polymerization reaction of a polymerizable compound based on a photopolymerization initiator, the developer used in step Y3 is usually an alkaline developer. In this case, process Y2Q may be performed before or after process Y3, and process Y2Q performed before process Y3 is normal pattern exposure.

In steps Y2P and Y2Q, the light source used for exposure is light in a wavelength range capable of reducing the content of acid groups derived from compound A in the photosensitive layer (compound β in the photosensitive layer ( Light of a wavelength that excites the specific structure S0 (preferably specific structure S1) in compound B) (for requirement V01) and the specific structure S0 (preferably specific structure S1) in compound A (for requirement W01). For example, when the photosensitive layer is the photosensitive layer described above, light in the wavelength range of 254 nm, 313 nm, 365 nm, 405 nm, etc.), or a polymerizable compound based on the photopolymerization initiator in the photosensitive layer (light having a wavelength that sensitizes the photopolymerization initiator, for example, 254 nm, 313 nm, 365 nm, 405 nm, etc.) can be selected as appropriate. Specific examples include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and LEDs (Light Emitting Diodes).

In exposure for reducing the content of acid groups derived from compound A in the photosensitive layer, the exposure amount is preferably 10 to 10,000 mJ/cm ² , more preferably 50 to 3,000 mJ/cm ² .
In the exposure for causing the reaction of the polymerizable compound based on the photopolymerization initiator in the photosensitive layer, the exposure amount is preferably 5-200 mJ/cm ² , more preferably 10-150 mJ/cm ² .

In steps Y2P and Y2Q, pattern exposure may be performed after peeling the temporary support from the photosensitive layer, and before peeling the temporary support, pattern exposure is performed via the temporary support, and then the temporary support is exposed. may be peeled off. In order to prevent contamination of the mask due to contact between the photosensitive layer and the mask and to avoid the influence of foreign matter adhering to the mask on the exposure, it is preferable to carry out pattern exposure without peeling off the temporary support. The pattern exposure may be exposure through a mask, or may be direct exposure using a laser or the like.

In the exposure process, the detailed arrangement and specific size of the pattern are not particularly limited.
For example, when the pattern formation method of Embodiment 2 is applied to the manufacture of circuit wiring, the display quality of a display device (for example, a touch panel) provided with an input device having circuit wiring manufactured by the pattern formation method of Embodiment 2 is improved. Also, from the point of view that the area occupied by the lead-out wiring can be made as small as possible, at least a part of the pattern (especially the part corresponding to the electrode pattern and the lead-out wiring of the touch panel) is preferably a thin wire of 100 μm or less, and 70 μm or less. is more preferable.

<<Preferred embodiment>>
The pattern forming method of Embodiment 2 preferably includes process Y1, process Y2A, process Y3, and process Y2B in this order. In step Y2A and step Y2B, one is an exposure step for reducing the content of acid groups derived from compound A by exposure, and the other is a polymerization reaction of a polymerizable compound based on a photopolymerization initiator. It is also preferred that it is an exposure step for generating.
Step Y1: A step of bringing the surface of the photosensitive layer in the transfer film opposite to the temporary support side into contact with the substrate, and bonding the transfer film and the substrate together Step Y2A: Step of exposing the photosensitive layer in a pattern Step Y3: Step of developing the photosensitive layer with an alkaline developer to form a pattern Step Y2B: Step of exposing the pattern obtained in Step Y3

In addition, the pattern forming method preferably has a step of peeling off the temporary support between step Y1 and step Y2A or between step Y2A and step Y3.

The step Y2A is preferably an exposure step for causing a polymerization reaction of a polymerizable compound based on a photopolymerization initiator, and the step Y2B reduces the content of acid groups derived from compound A by exposure. It is preferable that the exposure step is for

[Optional steps that the pattern forming methods of Embodiments 1 and 2 may have]
The pattern formation methods of Embodiments 1 and 2 may include arbitrary steps (other steps) other than those described above. Examples include, but are not limited to, the following steps.

<<Cover film peeling process>>
When the transfer film has a cover film, the pattern forming method preferably includes a step of peeling off the cover film of the transfer film (hereinafter also referred to as a “cover film peeling step”). A method for peeling off the cover film is not particularly limited, and a known method can be applied.

<<Step of reducing visible light reflectance>>
When the substrate is a substrate having a conductive layer, the patterning method may further include the step of treating the conductive layer to reduce the reflectance of visible light. Note that when the substrate has a plurality of conductive layers, the treatment for reducing the visible light reflectance may be performed on some of the conductive layers or may be performed on all the conductive layers. may
The treatment for reducing the visible light reflectance includes oxidation treatment. For example, the visible light reflectance of the conductive layer can be reduced by oxidizing copper to form copper oxide, thereby blackening the copper.
Preferred aspects of the treatment for reducing visible light reflectance are described in paragraphs 0017 to 0025 of JP-A-2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of JP-A-2013-206315. and the contents of this publication are incorporated herein.

<< Etching process >>
When the substrate is a substrate having a conductive layer, the pattern forming method uses the pattern formed in step X3 (or step X4) and step Y3 as an etching resist film to form a conductive layer in a region where the etching resist film is not disposed. It is preferable to include a step of etching the layer (etching step).
As the etching treatment method, a wet etching method described in paragraphs 0048 to 0054 of JP-A-2010-152155, etc., and a known dry etching method such as plasma etching can be applied.

For example, as an etching treatment method, there is a commonly used wet etching method in which the substrate is immersed in an etchant. As the etchant used for wet etching, an acidic type or alkaline type etchant may be appropriately selected according to the object to be etched.
Acid type etching solutions include aqueous solutions of acidic components alone such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and acidic component and salts such as ferric chloride, ammonium fluoride, or potassium permanganate. A mixed aqueous solution and the like are exemplified. As the acidic component, a component obtained by combining a plurality of acidic components may be used.
Alkaline etching solutions include aqueous solutions of alkali components alone, such as sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines such as tetramethylammonium hydroxide, and alkali components and potassium permanganate. For example, a mixed aqueous solution with a salt such as As the alkaline component, a component obtained by combining a plurality of alkaline components may be used.

Although the temperature of the etching solution is not particularly limited, it is preferably 45° C. or lower. In the method for producing circuit wiring of the present invention, the pattern formed in step X3 (or step X4) and step Y3 (or step Y2B), which is used as an etching resist film, is acidic and alkaline in a temperature range of 45 ° C. or less. It is preferable to exhibit particularly excellent resistance to the etchant. With the above structure, the etching resist film is prevented from peeling off during the etching process, and the portions where the etching resist film does not exist are selectively etched.
After the etching process, a cleaning process for cleaning the etched substrate and a drying process for drying the cleaned substrate may be performed as necessary in order to prevent contamination of the process line.

<<other embodiments>>
In the above pattern forming method, it is also preferable to use a substrate having a plurality of conductive layers on both surfaces and pattern the conductive layers formed on both surfaces sequentially or simultaneously.
With such a configuration, the first conductive pattern can be formed on one surface of the substrate and the second conductive pattern can be formed on the other surface. Forming from both sides of the substrate by roll-to-roll is also preferable.

〔pattern〕
The patterns formed by the pattern forming methods of Embodiments 1 and 2 have a low acid group content, and thus have low polarity, low moisture permeability, and low relative permittivity.
The content of acid groups in the pattern is preferably reduced by 5 mol% or more, and preferably 10 mol% or more, relative to the content of acid groups in the photosensitive layer formed in step X1 or step Y1. It is more preferably reduced, even more preferably reduced by 20 mol% or more, still more preferably reduced by 31 mol% or more, and particularly preferably reduced by 40 mol% or more. A decrease of mol % or more is particularly preferred, and a decrease of 71 mol % or more is most preferred. Although the upper limit is not particularly limited, it is, for example, 100 mol % or less.
The moisture permeability of the pattern is preferably reduced by 5% or more, more preferably by 10% or more, relative to the moisture permeability of the photosensitive layer formed in step X1 or step Y1. % or more is more preferable. Although the upper limit is not particularly limited, it is, for example, 100% or less.
The dielectric constant of the pattern is preferably reduced by 5% or more, more preferably by 10% or more, relative to the dielectric constant of the photosensitive layer formed in step X1 or step Y1. , is more preferably reduced by 15% or more. Although the upper limit is not particularly limited, it is, for example, 100% or less.

The average thickness of the pattern formed by the pattern forming method described above is preferably 0.5 to 20 μm. The average thickness of the pattern is more preferably 0.8 to 15 μm, still more preferably 1.0 to 10 μm.

The pattern formed by the pattern forming method described above is preferably achromatic. Specifically, total internal reflection (incidence angle 8°, light source: D-65 (2° field of view)) is applied to the CIE1976 (L ^* , a ^* , b ^* ) color space, and the L ^* value of the pattern is 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.

The application of the pattern formed by the pattern forming method described above is not particularly limited, and can be used as various protective films or insulating films.
Specifically, it is used as a protective film (permanent film) for protecting conductive patterns, as an interlayer insulating film between conductive patterns, and as an etching resist film in the production of circuit wiring. Since the pattern is excellent in low moisture permeability, it is particularly preferably used as a protective film (permanent film) for protecting the conductive pattern or an interlayer insulating film between the conductive patterns.
The pattern is, for example, a protective film (permanent film) or a conductive film that protects conductive patterns such as electrode patterns corresponding to sensors in the visual recognition portion, peripheral wiring portions, and lead-out wiring portions provided inside the touch panel. It can be used as an interlayer insulating film between patterns.

[Method for producing circuit wiring]
The invention also relates to a method of manufacturing circuit traces.
The method for producing circuit wiring related to the present invention (also referred to as "the method for producing circuit wiring of the present invention") is not particularly limited as long as it is a method for producing circuit wiring using the photosensitive composition described above. It is preferable that it is a method for manufacturing circuit wiring using the transfer film of No.
As a method for producing circuit wiring using the transfer film described above, the surface of the photosensitive layer in the transfer film described above on the side opposite to the temporary support side is brought into contact with the conductive layer in the substrate having the conductive layer, A step of bonding a transfer film and a substrate having a conductive layer (bonding step), a step of pattern-exposing the photosensitive layer in the bonded transfer film (first exposure step), and exposing the exposed photosensitive layer to A step of forming a patterned etching resist film by developing with an alkaline developer (etching resist film forming step), and a step of etching the conductive layer in the region where the etching resist film is not arranged (etching treatment step) and , in this order. Further, the etching resist film forming step includes a step of developing the exposed photosensitive layer obtained through the first exposure step with an alkali developer to form a pattern (alkali development step); and a step of exposing the formed pattern to form an etching resist film (second exposure step).
In the circuit wiring manufacturing method of the present invention, the bonding step, the first exposure step, the alkali development step, and the second exposure step are all the steps Y1, Y2A, and Y2A of the pattern forming method of Embodiment 2 described above. It can be implemented by the same procedures as those of Step Y3 and Step Y2B. The etching resist film forming step may be performed by the same method as the step Y3. Moreover, the substrate having a conductive layer used in the method for manufacturing circuit wiring of the present invention is the same as the substrate having a conductive layer used in the step X1 described above. Moreover, the method for manufacturing the circuit wiring of the present invention may have other steps than the steps described above. Other steps include the same arbitrary steps that the pattern forming methods of the first and second embodiments may have.

In the circuit wiring manufacturing method of the present invention, four steps of the bonding step, the first exposure step, the development step, the second exposure step, and the etching step are set as one set and are repeated multiple times. It is also preferable to have
The film used as the etching resist film can also be used as a protective film (permanent film) for the formed circuit wiring.

[Manufacturing method of touch panel]
The present invention also relates to a method of manufacturing a touch panel.
The method for producing a touch panel according to the present invention (also referred to as "the method for producing a touch panel of the present invention") is not particularly limited as long as it is a method for producing a touch panel using the photosensitive composition described above. is preferably a method for manufacturing a touch panel using
As a method for producing a touch panel of the present invention, the surface of the photosensitive layer in the above-described transfer film opposite to the temporary support side is coated with a conductive layer (preferably a patterned conductive layer, specifically, A step of bonding a transfer film and a substrate having a conductive layer (bonding step) by contacting a conductive layer in a substrate having a conductive pattern such as a touch panel electrode pattern or wiring), and photosensitive in the bonded transfer film A step of pattern-exposing a layer (first exposure step), and a step of developing the exposed photosensitive layer with an alkaline developer to form a patterned protective film or insulating film of the conductive layer ( protective film or insulating film forming step) in this order. In addition, the protective film or insulating film forming step includes a step of developing the exposed photosensitive layer obtained through the first exposure step using an alkali developer to form a pattern (alkali development step); It is preferable to include a step of exposing the obtained pattern to form a protective film or an insulating film for the conductive layer (second exposure step).
The protective film functions as a film that protects the surface of the conductive layer. In addition, the insulating film functions as an interlayer insulating film between conductive layers. When forming an insulating film of a conductive layer, the touch panel manufacturing method of the present invention further includes a conductive layer (preferably a patterned conductive layer) on the insulating film, specifically, a touch panel electrode pattern or It is preferable to have a step of forming a conductive pattern such as wiring.
In the method for manufacturing a touch panel of the present invention, the bonding step, the first exposure step, the alkali development step, and the second exposure step are all the step Y1, step Y2A, and step Y1 of the pattern forming method of Embodiment 2 described above. It can be implemented by the same procedures as Y3 and step Y2B. The protective film or insulating film forming step may be performed by the same procedure as the step Y3. Further, the substrate having a conductive layer used in the method for manufacturing a touch panel of the present invention is the same as the substrate having a conductive layer used in step X1 described above. Other steps include the same arbitrary steps that the pattern forming methods of the first and second embodiments may have.

As for the method for manufacturing the touch panel of the present invention, a known method for manufacturing a touch panel can be referred to for configurations other than those described above.

The touch panel manufactured by the touch panel manufacturing method of the present invention preferably has a transparent substrate, electrodes, and a protective layer (protective film).
As a detection method for the touch panel, any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Among them, the capacitance method is preferable.
As the touch panel type, the so-called in-cell type (for example, those described in FIGS. 5, 6, 7, and 8 of JP-A-2012-517051), the so-called on-cell type (for example, JP-A-2013-168125 19 of the publication, those described in FIGS. 1 and 5 of JP-A-2012-089102), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP-A 2013-054727), other configurations (for example, those described in FIG. 6 of JP-A-2013-164871), and various out-cell types (so-called GG, G1 G2, GFF , GF2, GF1, G1F, etc.).

The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed to be limited by the examples shown below. "Parts" and "%" are based on mass unless otherwise specified. Further, in the following examples, the weight average molecular weight of the resin is the weight average molecular weight determined by gel permeation chromatography (GPC) in terms of polystyrene.

[Preparation of photosensitive composition]
A photosensitive composition was prepared by mixing and stirring each component so as to obtain the composition and formulation shown in Table 2 shown in the latter part. In addition, the numerical value of the content (parts by mass) of the polymer in Table 2 intends the amount of solid content (other than the solvent).

[Components of the photosensitive composition]
The various components used in Table 2 are shown below.

<Compound having an acid group>
Synthesized compounds (polymers 1 to 9) having an acid group were used.
A method for synthesizing polymer 8 is shown below as an example. Other polymers were synthesized in the same manner by changing the type and amount of charged monomers.

- Method for synthesizing polymer 8 (DCPMA/AA/AA-GMA copolymer [composition ratio (mass ratio): 68/16/16, weight average molecular weight (Mw): 15000]);
A flask was charged with 77.2 g of propylene glycol monomethyl ether and heated to 90° C. under a nitrogen stream. Dicyclopentanyl methacrylate (manufactured by Showa Denko Materials Co., Ltd.) 89.8 g of this liquid, a solution obtained by dissolving 28.3 g of acrylic acid in 30 g of propylene glycol monomethyl ether, and a polymerization initiator V-601 (FUJIFILM Wako Pure Chemical Industries, Ltd. At the same time, a solution of 5.5 g of propylene glycol monomethyl ether dissolved in 30 g of propylene glycol monomethyl ether was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was allowed to react at 90° C. for 1 hour, and then 0.7 g of V-601 was added. After that, the reaction was further continued for 3 hours. After that, it was diluted with 60.4 g of propylene glycol monomethyl ether acetate and 26.4 g of propylene glycol monomethyl ether. The reaction solution was heated to 100° C. under an air stream, and 0.47 g of tetraethylammonium bromide and 0.23 g of p-methoxyphenol were added. To this, 14.0 g of glycidyl methacrylate (Blenmer G manufactured by NOF Corporation) was added dropwise over 20 minutes. This was reacted at 100° C. for 7 hours to obtain a polymer 8 solution. The solid content concentration of the obtained solution was 36.3% by mass. The weight average molecular weight in terms of standard polystyrene in GPC was 15000, the degree of dispersion was 2.2, and the acid value of the polymer was 125 mgKOH/g. The amount of residual monomer measured using gas chromatography was less than 0.1% by mass based on the polymer solid content for any monomer.
In addition, each polymer is synthesized in a state contained in a solution, but when using a polymer as a component of a photosensitive composition, only the solid content (polymer) contained in the solution is added to the photosensitive composition. added as an ingredient. For example, the photosensitive compositions used in the transfer films of Examples 1 and 2 contained 100 parts by weight of Polymer 1 itself, not 100 parts by weight of the solution.

Polymer 1: St/MAA/MMA/MAA-GMA copolymer [composition ratio (mass ratio): St/MAA/MMA/MAA-GMA = 47.7/19/1.3/32, weight average Molecular weight (Mw): 18,000]
Polymer 2: CHMA/MAA/MMA/MAA-GMA copolymer [composition ratio (mass ratio): 55.1/14.5/1.3/29.1, weight average molecular weight (Mw): 27 , 000]
- Polymer 3: IBMA/MAA copolymer [composition ratio (mass ratio): 80/20, weight average molecular weight (Mw): 12000]
- Polymer 4: DCPMA/MAA copolymer [composition ratio (mass ratio): 80/20, weight average molecular weight (Mw): 30000]
- Polymer 5: DCPMA/AA copolymer [composition ratio (mass ratio): 83/17, weight average molecular weight (Mw): 20000]
Polymer 6: IBMA/IBA/AA copolymer [composition ratio (mass ratio): 20/63/17, weight average molecular weight (Mw): 33000]
Polymer 7: DCPMA/AA/AA-GMA copolymer [composition ratio (mass ratio): 74/16/10, weight average molecular weight (Mw): 24000]
Polymer 8: DCPMA/AA/AA-GMA copolymer [composition ratio (mass ratio): 68/16/16, weight average molecular weight (Mw): 15000]
Polymer 9: DCPMA/AA/AA-GMA copolymer [composition ratio (mass ratio): 52/16/32, weight average molecular weight (Mw): 16000]

The abbreviations in the above polymers are shown below.
・St: repeating unit based on styrene ・MAA: repeating unit based on methacrylic acid ・MMA: repeating unit based on methyl methacrylate ・MAA-GMA: obtained by reacting the carboxy group of the repeating unit based on methacrylic acid with glycidyl methacrylate Repeating unit CHMA: Repeating unit based on cyclohexyl methacrylate DCPMA: Repeating unit based on dicyclopentanyl methacrylate AA: Repeating unit based on acrylic acid AA-GMA: Glycidyl methacrylate is added to the carboxy group of the repeating unit based on acrylic acid Repeating unit obtained by reacting IBMA: Repeating unit based on isobornyl methacrylate IBA: Repeating unit based on isobornyl acrylate

<Compound β>
・ 1-Me isoquinoline (manufactured by Fujifilm Wako Pure Chemical Industries)
・2,4-dimethylquinoline (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)

<Polymerizable compound>
・ TMPTA: trimethylolpropane triacrylate (A-TMPT manufactured by Shin-Nakamura Chemical Co., Ltd.)
・ DTMPTA: ditrimethylolpropane tetraacrylate (KAYARAD T-1420 (T) manufactured by Nippon Kayaku Co., Ltd.)
・ DPHA: Dipenerythritol hexaacrylate (A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.)
・ A-NOD-N: 1,9-nonanediol diacrylate (A-NOD-N manufactured by Shin-Nakamura Chemical Co., Ltd.)

<Initiator>
- Irg379: Omnirad 379 (manufactured by IGM Resins B.V., alkylphenone compound)
・Oxe02: Irgacure OXE02 (manufactured by BASF, oxime ester compound) Molar extinction coefficient for light with a wavelength of 365 nm in acetonitrile 2700 (cm mol / L) ^-1
· Api307: (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one (manufactured by Shenzhen UV-ChemTech LTD)

<Surfactant>
・F551A: Megaface F551 (manufactured by DIC)

<Solvent>
・MEK: Methyl ethyl ketone ・PGMEA: Propylene glycol monomethyl ether acetate ・MFG: Propylene glycol monomethyl ether

[Various measurements]
[Preparation of test sample (sample X)]
After spin-coating the prepared photosensitive composition onto a glass substrate (“Eagle XG” manufactured by Corning), it was dried at 80 ° C. for 2 minutes using a hot plate to form a film with a thickness of 2 μm (photosensitive layer) was obtained. Next, a polyethylene terephthalate film (PET film, Toray "16KS40") is pressed from the upper surface of the obtained film (photosensitive layer) to form a laminate in which the glass substrate, the photosensitive layer, and the PET film are laminated in this order. made the body. The pressure bonding conditions were laminating temperature: 25° C., pressure: 0.6 Pa, linear pressure: 3 N/cm, and conveying speed: 4 m/min. Then, the photosensitive layer in the laminate is exposed through a PET film using a proximity exposure machine (Hitachi High-Tech Electronic Engineering Co., Ltd.) having an ultra-high pressure mercury lamp at a wavelength of 365 nm. The exposure was made to be cm ² . After exposure, the laminate was allowed to stand in an environment of 25° C. and 50% RH for 30 minutes, after which the PET film was peeled off. Next, the photosensitive layer exposed by peeling off the PET film is exposed to an ultraviolet irradiation conveyor device (I-Graphics Co., Ltd.) having a high-pressure mercury lamp, and the integrated exposure amount at a wavelength of 365 nm becomes 1000 mJ/cm ² . exposed as Then, the post-exposure photosensitive layer on the glass substrate was scraped off to prepare a 100 mg powdery test sample (hereinafter referred to as sample X). When the scraped post-exposure photosensitive layer was not powdery, it was pulverized before use.

[Measurement of glass transition temperature of photosensitive layer after exposure]
(1) Using 5 to 6 mg of sample X, temperature modulated differential scanning calorimetry was performed under the following conditions.
Apparatus: DSC2500 manufactured by TA Instruments Co., Ltd. (Tzero aluminum pan was used to enclose the sample)
Measurement conditions: nitrogen atmosphere, temperature range -70 to 200°C (5°C/min), temperature modulation condition ±1°C/min (N = 2)))
(2) Next, the temperature (midpoint) at which the baseline shifts in the reversing heat flow (Rev. Heat Flow) was defined as the glass transition temperature (average value of n2). Table 2 shows the measurement results.

[Measurement of moisture content of post-exposure photosensitive layer at 40° C. and 90% RH]
(1) 11 to 12 mg of sample X was weighed in a laboratory at 23° C. and 50% RH (a [mg]).
(2) It was put into the furnace of a heating and expelling device heated to 150 ° C., and the water content was measured for 15 minutes using a Karl Fischer moisture meter (device: Karl Fischer moisture meter manufactured by Hiranuma Sangyo "AQ-2100" ”, and “EV-2000” manufactured by Hiranuma Sangyo Co., Ltd. was used as a heating and expelling device).
(3) From the measured water content, the water content x [mass %] at 23°C and 50% RH was determined by the following formula.
(Moisture content/a) x 100 = x [% by mass]
(4) 11 to 12 mg of sample X was weighed in a laboratory at 23°C and 50% RH (b [mg]).
(5) Sample X was stored in a constant temperature and humidity chamber at 40° C. and 90% RH for 24 hours.
(6) Immediately after taking out from the constant temperature and high humidity chamber, it was immediately put into the furnace of a heating and expelling device heated to 150 ° C., and the water content was measured for 15 minutes using a Karl Fischer moisture meter (device: Karl) A Fischer moisture meter "AQ-2100" manufactured by Hiranuma Sangyo Co., Ltd., and a heating and expelling device "EV-2000" manufactured by Hiranuma Sangyo Co., Ltd. were used).
(7) From the measured water content, the (apparent) water content y [mass %] at 40°C and 90% RH was determined by the following formula.
(Moisture content/b) x 100 = y [% by mass]
(8) Using the above values of x and y, the moisture content at 40° C. and 90% RH was determined by the following equation.
{Moisture content / (dry mass + moisture content)} × 100 [mass%] = [(b × y / 100) / {b × (100-x) / 100 + b × y / 100}] × 100 [mass%] = {y / (100-x + y)} × 100 [mass%]
(9) The above measurements (1) to (8) were performed five times, and the arithmetic average was taken as the moisture content. Table 2 shows the measurement results.

[Production of transfer film]
On a 16 μm thick PET film (manufactured by Toray Industries, 16KS40 (16QS62)) (temporary support), the photosensitive composition of each example or comparative example was applied using a slit-shaped nozzle, and the thickness after drying was the second. The film was adjusted to the thickness shown in the table, coated, and dried at 100° C. for 2 minutes to form a photosensitive layer.
A 16 μm-thick PET film (16KS40 (16QS62) manufactured by Toray Industries, Inc.) (cover film) was press-bonded onto the obtained photosensitive layer to prepare a transfer film of each example and comparative example.

[Evaluation: Corrosion test]
<Preparation of test sample>
(1) The cover film of the prepared transfer film was peeled off to expose the photosensitive layer.
Next, a transfer film was laminated on a copper substrate (copper foil-laminated PET film (manufactured by Geomatec)) such that the copper foil and the exposed photosensitive layer were in contact with each other. Lamination conditions were as follows: lamination temperature: 100° C., line thickness: 3 N/cm, conveying speed: 1 m/min.
(2) Accumulated exposure at a wavelength of 365 nm to the photosensitive layer through a PET film as a temporary support using a proximity type exposure machine (Hitachi High-Tech Electronic Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. was 80 mJ/cm ² .
(3) After exposure, the substrate was allowed to stand in an environment of 25° C. and 50% RH for 30 minutes, after which the PET film as a temporary support was peeled off.
(4) Then, the photosensitive layer exposed by peeling the PET film as a temporary support is subjected to integrated exposure at a wavelength of 365 nm using an ultraviolet irradiation conveyor device (Igraphics Co., Ltd.) having a high-pressure mercury lamp. Exposure was performed so that the dose was 1000 mJ/cm ² .
(5) Then, the copper base material having the photosensitive layer after exposure was used as a test sample, and a corrosion test described later was carried out.

<Corrosion test>
The test sample was placed in an environment of 83° C. and 87% RH, and the color change of the copper was visually observed after a predetermined period of time. The results are shown in Table 2.
(Evaluation criteria)
"A": Copper does not discolor after 1000 hours.
"B": Copper does not discolor after 800 hours, and discolors after 1000 hours.
"C": Copper discolors after 800 hours.

The second table is shown below.

From the results in Table 2, it is clear that the post-exposure photosensitive layers obtained from the photosensitive compositions of the examples are excellent in anticorrosion properties in a moist and heat environment. Therefore, according to the photosensitive compositions of the examples, it is clear that a pattern having excellent corrosion resistance in a moist and hot environment can be formed. In addition, it is clear that the transfer film provided with the photosensitive layer formed from the photosensitive composition of the Examples can also form a pattern excellent in corrosion resistance under a moist and hot environment.
Further, for example, from the comparison of Examples 1 and 2 and the comparison of Examples 3 and 4, according to the photosensitive compositions of Examples, the photosensitive layer formed by the photosensitive composition It can be seen that a pattern can be formed that is excellent in corrosion prevention in a moist and hot environment without depending on the film thickness.
Further, from the comparison of Examples 1 to 12, the photosensitive composition satisfies requirements A1 and A2, and the glass transition temperature in requirement A1 is 100 ° C. or higher, and the glass transition temperature in requirement A2 is 120 ° C. It can be seen that a pattern having excellent corrosion resistance in a moist and hot environment can be formed when the following conditions are satisfied.

The photosensitive composition of Comparative Example did not exhibit the desired effect.

[Example 13]
Using the photosensitive compositions of Examples 1 to 12 described above, pattern formation was performed according to the following procedure.
(1) The cover film of the prepared transfer film was peeled off to expose the photosensitive layer.
Next, a transfer film was laminated on a copper substrate (copper foil-laminated PET film (manufactured by Geomatec)) such that the copper foil and the exposed photosensitive layer were in contact with each other. Lamination conditions were as follows: lamination temperature: 100° C., line thickness: 3 N/cm, conveying speed: 1 m/min.
(2) A line-and-space pattern (line size = 150 µm, line: space = 1) was applied to the photosensitive layer using a proximity type exposure machine (Hitachi High-Tech Electronic Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. : The distance between the exposure mask surface having 1) and the surface of the temporary support is set to 125 μm, and the integrated exposure amount at 365 nm through the PET film as the temporary support is 80 mJ / cm ² Pattern exposure.
(3) After exposure, the substrate was allowed to stand in an environment of 25° C. and 50% RH for 30 minutes, after which the PET film as a temporary support was peeled off.
(4) The exposed photosensitive layer was developed for 45 seconds using a 1% by mass sodium carbonate aqueous solution (liquid temperature: 30° C.) as a developer. After development, the film was rinsed with pure water for 15 seconds and air was blown to remove water, thereby obtaining a pattern.
(5) Next, the entire pattern was exposed using an ultraviolet irradiation conveyor device (I-Graphics Co., Ltd.) having a high-pressure mercury lamp so that the integrated exposure amount at 365 nm was 1000 mJ/cm ² .

It was confirmed that a clear line-and-space pattern was obtained with the photosensitive compositions of Examples 1 to 12 used.

12: Temporary support 14: Photosensitive layer 16: Cover film 100: Transfer film

Claims

A photosensitive composition that satisfies both requirement A1 and requirement B1 shown below.
Requirement A1: The glass transition temperature of the post-exposure photosensitive layer obtained by the following procedure X is 65° C. or higher.
Requirement B1: The moisture content at 40° C. and 90% RH of the post-exposure photosensitive layer obtained by the following procedure X is less than 2.0% by mass.
Procedure X: A laminate having a glass substrate, a photosensitive layer formed from the photosensitive composition, and a resin film in this order is obtained. Next, from the side opposite to the glass substrate side of the laminate, an ultra-high pressure mercury lamp was used to expose the photosensitive layer in the laminate so that the integrated exposure amount at a wavelength of 365 nm was 80 mJ/cm 2 . expose. After exposure, the laminate is left in an environment of 25° C. and 50% RH for 30 minutes, and then the resin film is peeled off. Next, the photosensitive layer is exposed again from the side where the resin film is peeled off using a high-pressure mercury lamp so that the integrated exposure amount at a wavelength of 365 nm is 1000 mJ/cm 2 , After exposure a photosensitive layer is obtained.
2. The photosensitive composition of claim 1, further satisfying requirement A2 below.
Requirement A2: The post-exposure photosensitive layer obtained by the procedure X has a glass transition temperature of 165° C. or lower.
The photosensitive composition according to claim 2, wherein the glass transition temperature in the requirement A2 is 120°C or lower.
The photosensitive composition according to any one of claims 1 to 3, wherein the glass transition temperature in the requirement A1 is 85°C or higher.
A photosensitive composition according to any one of claims 1 to 4, further satisfying requirement B2 below.
Requirement B2: The post-exposure photosensitive layer obtained by procedure X has a moisture content at 40° C. and 90% RH of greater than 0% by mass.
The photosensitive composition according to claim 5, wherein the water content in the requirement B2 is 0.5% by mass or more.
The photosensitive composition according to any one of claims 1 to 6, wherein the glass transition temperature in the requirement A1 is 100°C or higher.
The photosensitive composition contains a compound A having an acid group,
8. The photosensitive composition according to any one of claims 1 to 7, wherein the content of said acid groups in said photosensitive composition is reduced by irradiation with actinic rays or radiation.
The photosensitive composition according to any one of claims 1 to 8, wherein the photosensitive composition satisfies either the following requirements (V01) or the following requirements (W01).
Requirements (V01)
The photosensitive composition contains a compound A having an acid group, and a compound β having a structure that reduces the amount of the acid group contained in the compound A upon exposure to light.
Requirement (W01)
The photosensitive composition contains a compound A having an acid group, and the compound A further contains a structure that reduces the amount of the acid group upon exposure.
In the requirement (V01), the compound β is a compound B having a structure capable of accepting electrons from the acid group contained in the compound A in a photoexcited state,
10. The photosensitive composition according to claim 9, wherein in the requirement (W01), the structure is a structure capable of accepting electrons from the acid group in a photoexcited state.
A compound B that satisfies the requirement (V01) and has a structure in which the compound β is capable of accepting electrons from the acid group contained in the compound A in a photoexcited state;
11. The method according to claim 9 or 10, wherein the total number of the structures capable of accepting electrons contained in the compound B in the photosensitive composition is 1 mol % or more with respect to the total number of acid groups contained in the compound A. A photosensitive composition as described.
The photosensitive composition according to any one of claims 1 to 11, wherein the compound A contains a polymer having an acid group.
The photosensitive composition according to claim 12, wherein the polymer has a polymerizable group.
The photosensitive composition according to any one of claims 1 to 13, wherein the photosensitive composition further contains a polymerizable compound.
The photosensitive composition according to any one of claims 1 to 14, further comprising a photopolymerization initiator.
A transfer film having a temporary support and a photosensitive layer formed from the photosensitive composition according to any one of claims 1 to 15.
A step of bonding the transfer film and the substrate together by bringing the surface of the photosensitive layer in the transfer film according to claim 16 on the side opposite to the temporary support side into contact with the substrate;
patternwise exposing the photosensitive layer;
A pattern forming method comprising, in this order, the step of developing the exposed photosensitive layer with an alkaline developer to form a pattern.
The surface of the photosensitive layer in the transfer film according to claim 16 opposite to the temporary support side is brought into contact with the conductive layer in the substrate having a conductive layer to separate the transfer film and the conductive layer. A step of bonding a substrate having
patternwise exposing the photosensitive layer;
developing the exposed photosensitive layer with an alkaline developer to form a patterned etching resist film;
and a step of etching the conductive layer in a region where the etching resist film is not disposed, in this order.
The surface of the photosensitive layer in the transfer film according to claim 16 opposite to the temporary support side is brought into contact with the conductive layer in the substrate having a conductive layer to separate the transfer film and the conductive layer. A step of bonding a substrate having
patternwise exposing the photosensitive layer;
and developing the exposed photosensitive layer with an alkaline developer to form a patterned protective film or insulating film of the conductive layer, in this order.