CN116356321A

CN116356321A - Method for manufacturing vapor deposition mask

Info

Publication number: CN116356321A
Application number: CN202211681072.8A
Authority: CN
Inventors: 石坂壮二; 藤本进二
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2021-12-27
Filing date: 2022-12-26
Publication date: 2023-06-30
Also published as: TW202330959A

Abstract

The invention provides a method for manufacturing a vapor deposition mask with excellent resolution. The method for manufacturing the vapor deposition mask sequentially comprises the following steps: preparing a metal layer having a 1 st surface and a 2 nd surface at a position opposite to the 1 st surface; attaching a photosensitive transfer material including a dummy support and a transfer layer to the metal layer, and disposing the transfer layer and the dummy support in this order on the 1 st surface of the metal layer; peeling the pseudo support; pattern exposure is carried out on the transfer printing layer; developing the transfer layer to form a resist pattern; etching the metal layer not covered by the resist pattern to form a through hole extending from the 1 st surface of the metal layer to the 2 nd surface of the metal layer; and removing the resist pattern.

Description

Method for manufacturing vapor deposition mask

Technical Field

The present invention relates to a method for manufacturing an evaporation mask.

Background

The vapor deposition method using the vapor deposition mask is used for manufacturing, for example, an OLED (Organic Light Emitting Diode: organic light emitting diode). The vapor deposition mask is used as a master of a pattern formed by a vapor deposition method. As a typical example of the vapor deposition method, a vacuum vapor deposition method is known. For example, in a vacuum vapor deposition method using a vapor deposition mask having through holes, a substance vaporized from a vaporization source is attached to an object through the through holes of the vapor deposition mask disposed on the object, thereby forming a pattern.

Patent document 1 discloses a metal mask base material comprising a metal surface having a resist disposed thereon, wherein the three-dimensional surface roughness Sa of the surface is 0.11 μm or less and the three-dimensional surface roughness Sz of the surface is 3.17 μm or less.

Patent document 1: japanese patent application laid-open No. 2021-73377

An increase in resolution (e.g., a minimization of pattern size) of a pattern formed using an evaporation mask, for example, can contribute to an increase in pixel density in a display device including an OLED. However, in the vapor deposition mask disclosed in patent document 1, the size of the even small hole portions 5a is 150 μm×50 μm, and therefore, it is considered that the vapor deposition mask is not suitable for the resolution improvement of the pattern.

Disclosure of Invention

An object of an embodiment of the present invention is to provide a method for manufacturing a vapor deposition mask having excellent resolution.

The present invention includes the following means.

< 1 > a method for producing an evaporation mask, comprising the following steps in order: preparing a metal layer having a 1 st surface and a 2 nd surface at a position opposite to the 1 st surface; attaching a photosensitive transfer material including a dummy support and a transfer layer to the metal layer, and disposing the transfer layer and the dummy support in this order on the 1 st surface of the metal layer; peeling the pseudo support; pattern exposure is carried out on the transfer printing layer; developing the transfer layer to form a resist pattern; etching the metal layer not covered by the resist pattern to form a through hole extending from the 1 st surface of the metal layer to the 2 nd surface of the metal layer; and removing the resist pattern.

< 2 > the method for producing an evaporation mask according to < 1 >, wherein,

the roughness Rmax of the 1 st surface of the metal layer is 0.5-5.0 μm.

< 3 > the method for producing an evaporation mask according to < 1 > or < 2 >, wherein,

the etching solution used in the etching treatment contains ferric chloride.

A method for producing an evaporation mask according to any one of < 1 > to < 3 >, wherein,

the solubility of the resist pattern in an aqueous solution containing 40 mass% ferric chloride at 45 ℃ is 1 [ mu ] m/min or less.

A method for producing an evaporation mask according to any one of < 1 > to < 4 >, wherein,

the transfer layer has a melt viscosity of 1.0X10 at 25 DEG C ⁵ Pa·s～1.0×10 ⁸ Pa·s。

A method for producing an evaporation mask according to any one of < 1 > to < 5 >, wherein,

the transfer layer has an intermediate layer and a photosensitive resin layer in this order from the dummy support side.

A method for producing an evaporation mask according to any one of < 1 > to < 6 >, wherein,

the transfer layer includes a buffer layer, an intermediate layer, and a photosensitive resin layer in this order from the dummy support side.

< 8 > the method for producing an evaporation mask according to < 6 > or < 7 >, wherein,

The intermediate layer contains a water-soluble resin.

< 9 > the method for producing an evaporation mask according to < 8 >, wherein,

the water-soluble resin contains polyvinyl alcohol.

A method for producing a vapor deposition mask according to < 8 > or < 9 > wherein,

the water-soluble resin contains polyvinylpyrrolidone.

A method for producing an evaporation mask according to any one of < 8 > to < 10 >, wherein,

the water-soluble resin contains a hydroxyalkyl cellulose compound.

< 12 > the method for producing an evaporation mask according to < 11 >, wherein,

the hydroxyalkyl cellulose compound is hydroxypropyl cellulose.

A method for producing an evaporation mask according to any one of < 7 > to < 12 >, wherein,

the buffer layer includes an alkali-soluble resin.

A method for producing an evaporation mask according to any one of < 1 > to < 13 >,

a light-shielding mask is used for the pattern exposure, and the distance between the transfer layer and the light-shielding mask is 50 μm or less.

A method for producing an evaporation mask according to any one of < 1 > to < 14 >, wherein,

a light shielding mask is used for the pattern exposure, and a distance between the metal layer and the light shielding mask during the pattern exposure is 50 μm or less.

A method for producing an evaporation mask according to any one of < 1 > to < 15 >, wherein,

the surface energy of the surface of the transfer layer on the pseudo-support side was 68.0mJ/m ² The following is given.

A method for producing an evaporation mask according to any one of < 1 > to < 16 >, wherein,

the photosensitive transfer material includes, in order, the dummy support, the transfer layer, and a protective film, wherein the photosensitive resin layer in the transfer layer is in contact with the protective film, and the surface of the protective film opposite to the surface in contact with the photosensitive resin layer has an arithmetic average roughness Ra of more than 0.05 [ mu ] m.

the photosensitive transfer material includes, in order, the dummy support, the transfer layer, and a protective film, wherein the photosensitive resin layer in the transfer layer is in contact with the protective film, and the protective film is a polypropylene film.

A method for producing an evaporation mask according to < 19 > and < 18 >, wherein,

the polypropylene film has an arithmetic average roughness Ra of 0.05 [ mu ] m or less on a surface thereof in contact with the photosensitive resin layer.

Effects of the invention

According to an embodiment of the present invention, there is provided a method for manufacturing a vapor deposition mask having excellent resolution.

Drawings

Fig. 1 is a schematic plan view showing an embodiment of a vapor deposition mask manufactured by the method for manufacturing a vapor deposition mask according to the present invention.

Fig. 2 is a schematic plan view showing enlarged through holes of the vapor deposition mask shown in fig. 1.

Fig. 3 is a schematic cross-sectional view showing enlarged through holes of the vapor deposition mask shown in fig. 1.

Fig. 4 is a schematic cross-sectional view showing a method for manufacturing a vapor deposition mask according to one embodiment.

Symbol description

10-metal layer, 10F-1 st side of metal layer, 10 FA-formed on the 1 st side of metal layer openings, 10H-through holes, 10R-2 nd side of metal layer, 10 RA-formed on the 2 nd side of metal layer openings, 20-transfer layer, 21-resist pattern, 100-evaporation mask.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited by the following embodiments. The following embodiments may be appropriately modified within the scope of the object of the present invention.

When the embodiments of the present invention are described with reference to the drawings, the description of the constituent elements and symbols repeated in the drawings may be omitted. The constituent elements denoted by the same reference numerals in the drawings refer to the same constituent elements. The ratio of the dimensions in the drawings does not necessarily represent the ratio of the actual dimensions.

In the present invention, the numerical range indicated by "to" means a range including the numerical value before "to" as a lower limit value and including the numerical value after "to" as an upper limit value. In the numerical ranges described in stages in the present invention, the upper limit or the lower limit described in a certain numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. In the numerical ranges described in the present invention, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value described in the examples.

In the present invention, "(meth) acrylic" means acrylic, methacrylic, or both acrylic and methacrylic.

In the present invention, "(meth) acrylate" means acrylate, methacrylate, or both acrylate and methacrylate.

In the present invention, "(meth) acryl" means two of acryl, methacryl, or acryl and methacryl.

In the present invention, the amounts of the respective components in the composition, when a plurality of substances corresponding to the respective components are present in the composition, refer to the total amount of the corresponding plurality of substances present in the composition unless otherwise specified.

In the present invention, the term "process" includes not only an independent process but also a process which cannot be clearly distinguished from other processes when the intended purpose can be achieved.

In the present invention, the unsubstituted and substituted groups (radicals) include groups (radicals) having no substituent and groups (radicals) having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (i.e., an unsubstituted alkyl group) but also an alkyl group having a substituent (i.e., a substituted alkyl group).

In the present invention, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam. The light used for exposure generally includes an open spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and activation rays (active energy rays) such as electron beams.

The chemical structural formula in the present invention is sometimes described in a simplified structural formula in which a hydrogen atom is omitted.

In the present invention, "mass%" means the same as "wt%", and "part by mass" means the same as "part by weight".

In the present invention, a combination of 2 or more preferred modes is a more preferred mode.

In the present invention, "transparent" means that the average transmittance of visible light having a wavelength of 400nm to 700nm is 80% or more, preferably 90% or more.

In the present invention, the average transmittance of visible light is a value measured by a spectrophotometer, and can be measured by, for example, a spectrophotometer U-3310 manufactured by Hitachi, ltd.

Unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are molecular weights converted by using a Gel Permeation Chromatography (GPC) analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both manufactured by tosohorporation, trade names), and detecting them by using a solvent THF (tetrahydrofuran), a differential refractometer, and using polystyrene as a standard substance.

In the present invention, unless otherwise specified, the content of the metal element is a value measured using an inductively coupled plasma (ICP: inductively Coupled Plasma) spectroscopic analysis device.

In the present invention, unless otherwise specified, the refractive index is a value measured at a wavelength of 550nm using an ellipsometer.

In the present invention, unless specified otherwise, the hue is a value measured using a color difference meter (CR-221, minolta Co., ltd.).

In the present invention, "alkali-soluble" means that the solubility of 100g of a 1 mass% aqueous solution of sodium carbonate having a liquid temperature of 22 ℃ is 0.1g or more.

In the present invention, "water-soluble" means that the solubility of 100g of water at pH7.0 at a liquid temperature of 22℃is 0.1g or more.

In the present invention, "solid component" means all components except a solvent.

Method for producing vapor deposition mask

The method for manufacturing the vapor deposition mask according to the present invention comprises the following steps in order: preparing a metal layer having a 1 st surface and a 2 nd surface at a position opposite to the 1 st surface (hereinafter, also referred to as a "preparation process"); bonding a photosensitive transfer material including a dummy support and a transfer layer to the metal layer, and disposing the transfer layer and the dummy support in this order on the 1 st surface of the metal layer (hereinafter, also referred to as a "bonding step"); peeling the pseudo support (hereinafter, also referred to as a "pseudo support peeling step"); pattern exposure (hereinafter, also referred to as an "exposure process") is performed on the transfer layer; developing the transfer layer to form a resist pattern (hereinafter, also referred to as a "developing step"); forming a through hole extending from the 1 st surface of the metal layer to the 2 nd surface of the metal layer by performing an etching process on the metal layer not covered with the resist pattern (hereinafter, also referred to as an "etching process"); and removing the resist pattern (hereinafter, also referred to as "removal process").

The vapor deposition mask manufacturing method according to the present invention can suppress diffusion of exposure light at the time of pattern exposure by peeling off the dummy support and exposing the dummy support, and can provide a vapor deposition mask manufacturing method excellent in resolution.

The details of each step in the vapor deposition mask manufacturing method according to the present invention will be described below.

(preparation step)

In the preparation step, a metal layer having a 1 st surface and a 2 nd surface at a position opposite to the 1 st surface is prepared. The metal layer may be a known metal substrate (including commercially available). The metal layer may be produced by a known method (for example, casting, forging, sputtering, and plating).

The structure of the metal layer may be a single-layer structure or a multi-layer structure. Examples of the metal element contained in the metal layer include Cu, ni, fe, cr, mn and Co. Part or all of the metal layer may be an alloy. Examples of the alloy include Ni-Co alloy and Fe-Ni alloy. The metal layer preferably contains at least one metal element selected from the group consisting of Cu, ni, fe, cr, mn and Co, more preferably contains at least one metal element selected from the group consisting of Cu, fe, and Ni, further preferably contains Fe, and particularly preferably contains Fe and Ni. The metal layer may contain an element other than a metal element. Examples of the element other than the metal element include B, C, N, O, P, S and Cl. The metal layer may be a metal substrate.

Among these, the metal in the metal layer may preferably be nickel, a ni—co alloy, an fe—ni alloy, copper, or the like, and is preferably an alloy containing 30 mass% or more and 45 mass% or less of nickel, and more preferably an invar alloy which is a metal mainly composed of an alloy of 36 mass% nickel and 64 mass% iron. When the metal in the metal layer is invar, the thermal expansion coefficient of the metal pattern is, for example, 1.2X10 ^-6 about/DEG C.

Further, as the metal in the metal layer, for example, an fe—ni—co alloy (for example, super invar alloy) may be cited.

From the viewpoints of adhesion and resolution, the roughness Rmax of the 1 st surface of the metal layer is preferably 0.5 μm to 5.0 μm, more preferably 0.60 μm to 4.0 μm, and particularly preferably 0.75 μm to 3.0 μm.

The roughness Rmax of the 2 nd surface of the metal layer may be 0.5 μm to 5.0 μm. The roughness Rmax of the 1 st face of the metal layer may be the same as or different from the roughness Rmax of the 2 nd face of the metal layer.

In the present invention, the roughness Rmax of the target surface was measured using a three-dimensional optical profiler (New View7300, manufactured by Zygo corporation). First, the surface profile of the object surface is obtained. As the assay/analysis software, microscope Application of MetroPro ver8.3.2 was used. Next, a Surface Map screen is displayed using measurement/analysis software, and histogram data is obtained in the Surface Map screen. The roughness Rmax of the object surface is obtained from the obtained histogram data. The roughness Rmax of the target surface corresponds to the maximum height of the roughness curve at the reference length.

In the preparation step, the metal layer may be prepared in a state of being disposed on the substrate. In other words, in the preparation step, a laminate including a base material and a metal layer having a 2 nd surface facing the base material and a 1 st surface located opposite to the 2 nd surface in this order may be prepared. Examples of the component of the substrate include glass and polymer. Examples of the polymer include polyimide, cycloolefin polymer, polyethylene, polypropylene, polyethylene terephthalate, cellulose triacetate, polystyrene and polycarbonate. The base material is preferably a glass substrate or a resin film, and more preferably a resin film. Examples of the resin film include polyimide films, cycloolefin polymer films, polyethylene films, polypropylene films, polyethylene terephthalate films, cellulose triacetate films, polystyrene films, and polycarbonate films.

The average thickness of the metal layer is preferably 10 μm to 500 μm, more preferably 20 μm to 400 μm, and even more preferably 20 μm to 300 μm from the viewpoint of resolution of the through holes. The average thickness of the metal layer was calculated by arithmetic average of thicknesses at 5 points measured in cross-sectional observation using a Scanning Electron Microscope (SEM).

(bonding step)

In the bonding step, a photosensitive transfer material including a dummy support and a transfer layer is bonded to a metal layer, and the transfer layer and the dummy support are sequentially disposed on the 1 st surface of the metal layer.

In addition, a preferable mode of the photosensitive transfer material will be described later.

The photosensitive transfer material and the metal layer can be bonded by a known method. In the bonding step, the photosensitive transfer material is preferably pressure-bonded to the metal layer. For example, it is preferable to bond the photosensitive transfer material and the metal layer by superposing the photosensitive transfer material and the metal layer and applying pressure and heat by a mechanism such as a roller. In the lamination step, a known laminator, such as a laminator, a vacuum laminator, and an automatic cutting laminator, which can improve productivity, can be used. The lamination temperature is preferably, for example, 70℃to 130 ℃. When the photosensitive transfer material includes a protective film, a bonding process is performed after the protective film is removed.

(pressurizing step)

After the photosensitive transfer material is bonded to the metal layer, a pressurizing step may be performed. For example, a laminate obtained by bonding the photosensitive transfer material and the metal layer may be pressurized. The pressed laminate is preferably a laminate including a metal layer, a transfer layer, and a dummy support in this order. The pressed laminate may be a laminate including a metal layer and a transfer layer in this order. For example, if the dummy support is peeled off after the bonding step, a laminate including a metal layer and a transfer layer in this order can be formed. In the pressurizing step, the laminate obtained by bonding the photosensitive transfer material and the metal layer may be subjected to pressurizing treatment with an autoclave. For example, the pressure treatment can be performed at 50℃for 60 minutes under 0.5 MPa. By subjecting the laminate to the pressure treatment, the adhesion between the transfer layer and the metal layer can be improved, and the following property of the transfer layer to the irregularities on the metal layer surface can be improved. The pressurizing step is preferably performed before the exposing step.

(pseudo support peeling step)

The method for manufacturing a vapor deposition mask according to the present invention includes a dummy support peeling step of peeling the dummy support between the dummy support and the transfer layer.

The peeling method of the pseudo support is not particularly limited, and the same mechanism as the cover film peeling mechanism described in paragraphs 0161 to 0162 of japanese patent application laid-open No. 2010-072589 can be used.

(Exposure Process)

In the exposure step, the transfer layer is subjected to pattern exposure. The term "pattern-exposing the transfer layer" means that an exposed portion and a non-exposed portion are formed in the transfer layer by irradiating light to the transfer layer. The positional relationship between the exposed portion and the non-exposed portion can be determined, for example, according to the shape of the target resist pattern.

The light for pattern-exposing the transfer layer is preferably irradiated to the transfer layer in a direction from the transfer layer toward the metal layer. The light for pattern-exposing the transfer layer preferably includes at least one wavelength selected from the group consisting of 365nm and 405 nm.

Examples of the light source include an ultra-high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode: light emitting diode).

The exposure is preferably 5mJ/cm ² ～200mJ/cm ² More preferably 10mJ/cm ² ～100mJ/cm ² 。

Examples of the exposure method include a contact exposure method and a noncontact exposure method. As the contact exposure method, for example, a method using a photomask is mentioned. Examples of the non-contact exposure method include a proximity (proximity) exposure method, a lens-based or mirror-based projection exposure method, and a direct exposure method using an exposure laser. In projection exposure by a lens system or a mirror system, an exposure machine having an appropriate lens aperture Number (NA) can be used according to a required resolution and a required focal depth. In the direct exposure method, the transfer layer may be directly drawn, or the transfer layer may be subjected to reduced projection exposure via a lens. The exposure process may be performed under atmospheric pressure, reduced pressure, or vacuum. The exposure step may be performed by interposing a liquid such as water between the light source and the transfer layer.

The exposure step is performed after the dummy support is peeled off. In the exposure step using the photomask, the transfer layer may be pattern-exposed in a state where the photomask is brought into contact with the transfer layer, or the transfer layer may be pattern-exposed in a state where the photomask is not brought into contact with the transfer layer but is brought close to the transfer layer. When the pattern exposure is performed on the transfer layer via the dummy support, the dummy support is preferably peeled off after the exposure process and before the development process.

Among them, the exposure step preferably uses a photomask, and as the photomask, a light-shielding mask is preferable.

When a light-shielding mask is used for the pattern exposure in the exposure step, the distance between the transfer layer and the light-shielding mask is preferably 50 μm or less, more preferably 0 μm to 25 μm, still more preferably 0 μm to 10 μm, and particularly preferably 0 μm, in terms of resolution, i.e., the photosensitive transfer material is exposed by being brought into contact with the light-shielding mask.

When a light shielding mask is used for the pattern exposure in the exposure step, the distance between the metal layer and the light shielding mask at the time of the pattern exposure is preferably 50 μm or less, more preferably 1 μm to 30 μm, still more preferably 2 μm to 20 μm, and particularly preferably 2 μm to 10 μm from the viewpoint of resolution.

(developing step)

In the development step, the transfer layer is subjected to a development process to form a resist pattern. The resolution of the resist pattern formed by the development process is considered to affect the resolution of the through-holes formed by the etching process described later, and further, the resolution of the through-holes affects the resolution of the pattern formed using the vapor deposition mask.

The resist pattern is formed by removing the exposed or unexposed portions of the transfer layer. When the transfer layer includes a negative-type photosensitive resin layer, the non-exposed portion of the transfer layer is usually removed by a development process, and a resist pattern is formed from the exposed portion of the transfer layer. When the transfer layer includes a positive-working photosensitive resin layer, the exposed portion of the transfer layer is usually removed by a developer, and a resist pattern is formed from the non-exposed portion of the transfer layer.

The development treatment is performed using a developer, for example. As the developer, for example, a known developer (for example, a developer described in japanese patent application laid-open No. 5-72724) is cited. As the developer, an aqueous alkali developer containing a compound having pka=7 to 13 at a concentration of 0.05mol/L to 5mol/L is preferable. Examples of the alkali compound contained in the aqueous alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyl trimethylammonium hydroxide). The developer may contain a water-soluble organic solvent. The developer may contain a surfactant. Examples of the preferable developer include the developer described in paragraph 0194 of International publication No. 2015/093271.

The temperature of the developer is preferably 20 to 40 ℃.

Examples of the development method include spin-coating immersion development (puddle development), spray development (shower development), spray and spin development, and immersion development. The shower development is a development method in which a developer is sprayed onto an object. A preferable development method is, for example, the development method described in paragraph 0195 of international publication No. 2015/093271.

The developer and residue remaining after the developing step are preferably removed by a known method. Examples of the method for removing the developer and the residue include a shower treatment and an air knife treatment. In the shower treatment, a liquid such as water and a cleaning agent is sprayed onto an object. Residues can also be removed using a brush.

(etching step)

In the etching step, the metal layer not covered with the resist pattern is subjected to etching treatment to form a through hole extending from the 1 st surface of the metal layer to the 2 nd surface of the metal layer.

The etching treatment may be a known method. Examples of the etching process include wet etching and dry etching (e.g., plasma etching). Examples of the etching treatment include the methods described in paragraphs 0209 to 0210 of Japanese patent application laid-open No. 2017-120435 and the methods described in paragraphs 0048 to 0054 of Japanese patent application laid-open No. 2010-152155.

The etching process is preferably wet etching. In wet etching, an etching liquid is generally used. The type of the etching liquid may be selected from acidic or alkaline etching liquids depending on the object to be etched. Examples of the acidic etching solution include an aqueous solution containing at least one acidic component selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid. The acidic etching solution may be, for example, a mixed aqueous solution of the acidic component and at least one salt selected from the group consisting of ferric chloride, ammonium fluoride and potassium permanganate. The acidic component may be a component obtained by combining a plurality of acidic components. Examples of the alkaline etching liquid include an aqueous solution containing at least one alkali component selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, an organic amine, and a salt of an organic amine (e.g., tetramethyl ammonium hydroxide). The alkaline etching solution may be, for example, a mixed aqueous solution of the above-mentioned alkali component and a salt (for example, potassium permanganate). The alkali component may be a component obtained by combining a plurality of alkali components.

Among them, from the viewpoint of further exhibiting the effects of the present invention, the etching solution used in the etching treatment preferably contains ferric chloride.

The solubility of the resist pattern in an aqueous solution containing 40 mass% ferric chloride at 45℃is preferably 1 μm/min or less, more preferably 0.5 μm/min or less. The lower limit value is 0 μm/min.

The metal layer in the vapor deposition mask manufactured by the method for manufacturing a vapor deposition mask according to the present invention has a through hole extending from the 1 st surface to the 2 nd surface. The metal layer may have a plurality of through holes. The depth of the through hole corresponds to the thickness of the metal layer. The through-holes are typically defined by the inner surface of the metal layer. The through hole may be defined by 1 or 2 or more faces. The surface defining the through hole as seen in a plan view may be a straight line or a curved line. The number, shape, and arrangement of the through holes are determined, for example, according to the target pattern. The through hole extending from the 1 st surface to the 2 nd surface is opened in the 1 st surface, and the opening is formed in the 2 nd surface. The diameter of the opening formed in the 1 st surface corresponds to the diameter of the through hole in the 1 st surface described later, and the diameter of the opening formed in the 2 nd surface corresponds to the diameter of the through hole in the 2 nd surface described later. Examples of the shape of the through hole (specifically, the opening) as seen in a plan view include a circle, an ellipse, and a quadrangle. The shape of the through hole as seen in a plan view is preferably a quadrangle, more preferably a square or rectangle. When the shape of the through hole as seen in a plan view is a polygon (for example, a quadrangle), a part or all of the corners of the polygon may be rounded.

The average diameter of the through holes in the 2 nd plane of the metal layer (hereinafter, sometimes referred to as "average diameter of the through holes D2") is smaller than the average diameter of the through holes in the 1 st plane of the metal layer (hereinafter, sometimes referred to as "average diameter of the through holes D1"). In other words, the average diameter D1 of the through holes is larger than the average diameter D2 of the through holes. For example, if the average diameter D1 of the through-holes is larger than the average diameter D2 of the through-holes, the substances that reach the 1 st surface of the metal layer from the vaporization source easily enter the through-holes from the openings formed in the 1 st surface of the metal layer. As a result, for example, productivity and pattern accuracy are improved. The ratio of the average diameter D2 of the through holes to the average diameter D1 of the through holes (i.e., D2/D1) is preferably 0.8 or less, more preferably 0.4 or less, and still more preferably 0.3 or less. From the viewpoint of higher resolution of the pattern, the ratio of the average diameter D2 of the through holes to the average diameter D1 of the through holes (i.e., D2/D1) is preferably 0.01 or more, more preferably 0.1 or more, and still more preferably 0.15 or more.

The average diameter of the through holes (i.e., the average diameter D2 of the through holes) in the 2 nd surface of the metal layer is 25 μm or less. If the average diameter D2 of the through holes is 25 μm or less, the pattern can be formed with high resolution. From the viewpoint of higher resolution of the pattern, the average diameter D2 of the through holes is preferably 25 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less. The lower limit of the average diameter D2 of the through holes is not limited. The average diameter D2 of the through holes may be 5 μm, 1 μm or 0.1. Mu.m.

The average diameter D1 of the through holes is not limited as long as the relationship of "average diameter D2 of through holes" < "average diameter D1 of through holes" is satisfied. The average diameter D1 of the through holes is preferably 15 μm to 100 μm, more preferably 20 μm to 50 μm, and even more preferably 20 μm to 30 μm from the viewpoint of improving the resolution of the pattern. The lower limit of the average diameter D1 of the through holes may be 8 μm or 10 μm.

In the present invention, the average diameter of the through holes is calculated by arithmetic average of the diameters of 10 through holes measured from an image obtained using a Scanning Electron Microscope (SEM). In the present invention, the diameter of the through-hole is defined by the maximum value of a straight line connecting any 2 points on the outline of the through-hole (specifically, the opening) as seen in a plan view. Since the average diameter D2 of the through holes is smaller than the average diameter D1 of the through holes, the outline of the opening formed on the 2 nd surface of the metal layer may be observed inside the outline of the opening formed on the 1 st surface of the metal layer when the 1 st surface of the metal layer is viewed in plan. The average diameter D1 of the through holes and the average diameter D2 of the through holes can be calculated from the observation as described above.

The diameter of the through-holes may be continuously or discontinuously changed in the direction from the 1 st surface toward the 2 nd surface as long as the relationship of "the average diameter of through-holes D2" < "the average diameter of through-holes D1" is satisfied. The diameter of the through hole preferably gradually decreases in a direction from the 1 st surface toward the 2 nd surface.

(removal step)

In the removal step, the resist pattern is removed. As the removal method, for example, a method of removing a resist pattern using chemical treatment is cited. A method of removing the resist pattern using a removing liquid is preferable.

Examples of the removing liquid include removing liquids containing an inorganic base component or an organic base component and water, dimethyl sulfoxide, N-methylpyrrolidone, or a mixed solvent thereof. Examples of the inorganic alkali component include sodium hydroxide and potassium hydroxide. Examples of the organic base component include a primary amine compound, a secondary amine compound, a tertiary amine compound, and a quaternary ammonium salt compound.

The resist pattern may be removed by immersing the laminate including the resist pattern in a removing liquid. The temperature of the removing liquid is preferably 30 to 80 ℃, more preferably 50 to 80 ℃. The dipping time is preferably 1 to 30 minutes. In the impregnation method, the removing liquid may be stirred.

The resist pattern can be removed by, for example, a spray method, a shower method, or a spin-on immersion method using a removing liquid.

(other procedure)

The method for manufacturing a vapor deposition mask according to the present invention may further include other steps as necessary. When the metal layer of the vapor deposition mask is formed on the substrate, the method for manufacturing the vapor deposition mask according to the present invention may include a step of removing the substrate.

A method of manufacturing the vapor deposition mask will be described with reference to fig. 4. Fig. 4 is a schematic cross-sectional view showing a method for manufacturing a vapor deposition mask according to one embodiment. As shown in fig. 4 (a), a metal layer 10 having a 1 st surface 10F and a 2 nd surface 10R located opposite to the 1 st surface 10F is prepared. As shown in fig. 4 b, a photosensitive transfer material (not shown) is bonded to the metal layer 10, and the transfer layer 20 is disposed on the 1 st surface 10F of the metal layer 10. The transfer layer 20 has an average thickness of 50 μm or less. As shown in fig. 4 (c), the transfer layer 20 is subjected to pattern exposure, and then the transfer layer 20 is subjected to development treatment, thereby forming a resist pattern 21. As shown in fig. 4 (d), the metal layer 10 not covered with the resist pattern 21 is subjected to etching treatment to form the through hole 10H. During the etching process, it is considered that isotropic etching (i.e., etching performed in a direction orthogonal to the depth direction of the metal layer 10 in addition to etching performed in the depth direction of the metal layer 10) occurs to form the through-hole 10H having a cross-sectional shape as shown in fig. 4 (d). As shown in fig. 4 (e), the resist pattern 21 is removed to obtain the vapor deposition mask 100. The through-hole 10H formed in the metal layer 10 extends from the 1 st surface 10F of the metal layer 10 to the 2 nd surface 10R of the metal layer 10. The through hole 10H forms an opening 10FA in the 1 st surface 10F of the metal layer 10, and forms an opening 10RA in the 2 nd surface 10R of the metal layer 10.

The vapor deposition mask manufactured by the method for manufacturing a vapor deposition mask according to the present invention may include constituent elements other than the metal layer as necessary. As a constituent element other than the metal layer, for example, a frame is cited. The frame body can enhance the vapor deposition mask or improve the operability of the vapor deposition mask. The frame may be disposed around the through hole in a plan view or may be disposed on the outer periphery of the metal layer in a plan view. Examples of the component of the frame include metals. Examples of the metal include Fe-Ni alloy (for example, invar alloy) and Fe-Ni-Co alloy (for example, super invar alloy).

The structure of the vapor deposition mask manufactured by the method for manufacturing a vapor deposition mask according to the present invention will be described with reference to fig. 1, 2, and 3. Fig. 1 is a schematic plan view showing an embodiment of a vapor deposition mask. Fig. 2 is a schematic plan view showing enlarged through holes of the vapor deposition mask shown in fig. 1. Fig. 3 is a schematic cross-sectional view showing enlarged through holes of the vapor deposition mask shown in fig. 1. The vapor deposition mask 100 includes a metal layer 10 having a 1 st surface 10F, a 2 nd surface 10R located opposite to the 1 st surface 10F, and a through hole 10H. The 1 st side of the metal layer 10 is facing the viewer looking at fig. 1 and 2. The 1 st surface 10F of the metal layer 10 and the 2 nd surface 10R of the metal layer face in mutually opposite directions. As shown in fig. 1 and 2, the through-holes 10H are defined by a lattice-like pattern formed by the metal layer 10, and the through-holes 10H have a quadrangular shape in plan view. In fig. 2, the reason why the contour line of the through hole 10H is doubly observed is that the contour line of the opening (specifically, the opening 10RA in fig. 3) formed in the 2 nd surface 10R of the metal layer 10 is observed inside the contour line of the opening (specifically, the opening 10FA in fig. 3) formed in the 1 st surface 10F of the metal layer 10. As shown in fig. 3, the through hole 10H extends from the 1 st surface 10F of the metal layer 10 to the 2 nd surface 10R of the metal layer 10. The through hole 10H forms an opening 10FA in the 1 st surface 10F of the metal layer 10, and forms an opening 10RA in the 2 nd surface 10R of the metal layer 10. The through hole 10H is defined by the inner surface of the metal layer 10, and the inner surface of the metal layer 10 defining the through hole 10H is curved. The average diameter of the through holes 10H in the 2 nd face 10R of the metal layer 10 is smaller than the average diameter of the through holes 10H in the 1 st face 10F of the metal layer 10. The diameter of the through hole 10H gradually decreases in the direction from the 1 st surface 10F toward the 2 nd surface 10R.

The vapor deposition mask manufactured by the method for manufacturing a vapor deposition mask according to the present invention is preferably applied to a method for manufacturing a pattern using a vapor deposition method. In the vapor deposition method, the vapor deposition mask is preferably disposed on the object so that the 2 nd surface of the metal layer faces the object. If the 2 nd surface of the metal layer faces the object, the substance reaching the 1 st surface of the metal layer from the vaporization source easily enters the through-hole. The substance introduced into the through-hole moves in the through-hole along the direction from the 1 st surface to the 2 nd surface of the metal layer, and adheres to the object. The substance passing through the through-holes is deposited on the object to form a pattern. Examples of the object to be patterned include a glass substrate and a resin film. The type of the vapor deposition method, the conditions of the vapor deposition method, and the type of the vapor deposited material can be determined, for example, based on the target pattern. Preferred examples of the vapor deposition method include a vacuum vapor deposition method. A preferred application of the vapor deposition mask manufactured by the method for manufacturing a vapor deposition mask according to the present invention is, for example, a method for manufacturing an OLED.

(photosensitive transfer Material)

The photosensitive transfer material used in the method for manufacturing a vapor deposition mask according to the present invention preferably includes a dummy support and a transfer layer, and preferably includes, in order, the dummy support, the transfer layer including at least a photosensitive resin layer, and a protective film.

The photosensitive resin layer in the transfer layer is preferably in contact with the protective film.

The photosensitive transfer material used in the present invention may have other layers between the dummy support and the photosensitive resin layer, between the photosensitive resin layer and the protective film, and the like.

The photosensitive transfer material used in the present invention preferably has an intermediate layer and a photosensitive resin layer in this order from the pseudo support side.

The photosensitive transfer material used in the present invention is preferably a roll-shaped photosensitive transfer material from the viewpoint of further exhibiting the effects of the present invention.

In the photosensitive transfer material used in the method for producing a vapor deposition mask according to the present invention, the melt viscosity of the transfer layer at 25 ℃ is preferably 5.0x10 from the viewpoints of adhesion and resolution ⁴ Pa·s～5.0×10 ⁸ Pa.s, more preferably 1.0X10 ⁵ Pa·s～1.0×10 ⁸ Pa.s, particularly preferably 5.0X10 ⁵ Pa·s～1.0×10 ⁷ Pa·s。

In the present invention, the "melt viscosity of the transfer layer" is defined by the melt viscosity of a layer located at a position farthest from the pseudo support among 1 or 2 or more layers constituting the transfer layer. For example, when the transfer layer has a multilayer structure, the melt viscosity of a layer located at a position farthest from the pseudo support among the plurality of layers included in the transfer layer is referred to as "melt viscosity of the transfer layer", and when the transfer layer has a single-layer structure, the melt viscosity of a single transfer layer is referred to as "melt viscosity of the transfer layer". The melt viscosity of the transfer layer is adjusted, for example, according to the composition of the transfer layer. The melt viscosity of the transfer layer is adjusted, for example, according to the kind of the polymer, the kind of the polymerizable compound, the ratio of the content of the polymerizable compound to the content of the polymer, and the kind of the additive. For example, if the ratio of the content of the polymerizable compound to the content of the polymer is large, the melt viscosity becomes small, and if the ratio of the content of the polymerizable compound to the content of the polymer is small, the melt viscosity becomes large.

In the present invention, melt viscosity was measured using a rheometer (e.g., rheometer DHR-2 manufactured by TA Instruments Co.), a parallel plate of 20mm phi, and a Peltier plate (Gap: about 0.5 mm) under the following conditions. The melt viscosity specified in the present invention is a melt viscosity at 25 ℃.

(1) Temperature: 20-125 DEG C

(2) Heating rate: 5 ℃/min

(3) Frequency: 1Hz

(4) Strain: 0.5%

In the photosensitive transfer material used in the method for producing a vapor deposition mask according to the present invention, the surface energy of the surface of the transfer layer on the pseudo support side is preferably 75.0mJ/m from the viewpoints of adhesion and resolution ² Hereinafter, more preferably 68.0mJ/m ² Hereinafter, it is more preferably 50.0mJ/m ² ～68.0mJ/m ² Particularly preferably 55.0mJ/m ² ～65.0mJ/m ² 。

In the present invention, the value of the surface energy (unit: mJ/m of the surface on the pseudo-support side of the transfer layer ² ) Calculated using the following method.

On the measurement surface of the transfer layer, the contact angles of two solutions, i.e., pure water and diiodomethane at 3 points, were measured by a contact angle meter CA-A (Kyowa Interface Science co., ltd.) at room temperature at 23 ℃ and a relative humidity of 50% to 60%, and the average value was used as the contact angle. Using the contact angle of the two solutions obtained, the dispersion gamma was calculated by geometric mean method based on Owens-Wendt ^d Polar force gamma ^p And a surface energy γ (=γ) as the sum of the dispersion force and the polar force ^d +γ ^p )。

A specific calculation method is shown. The meaning of each symbol is as follows. When gamma is _SL When the tension is at the interface between the solid and the liquid, the following expression (1) holds.

γ _SL : surface free energy of film surface and known solution

γ _S : surface free energy of film surface

γ _L : surface free energy of known solutions

γ _S ^d : dispersing force component of surface free energy of film surface

γ _S ^p : polar force component of surface free energy of film surface

γ _L ^d : dispersing force component of surface free energy of known solution

γ _L ^p : polar force component of surface free energy of known solutions

γ _SL ＝γ _S +γ _L -2(γ _S ^d ·γ _L ^d ) ^1/2 -2(γ _S ^p ·γ _L ^p ) ^1/2 … … (1)

The state when the smooth solid surface is in contact with the droplet at the contact angle (θ) is expressed by the following formula (Young's formula).

γ _S ＝γ _SL +γ _L cos theta … …%2)

When these expressions (1) and (2) are combined, the following expression is obtained.

(γ _s ^d ·γ _L ^d ) ^1/2 +(γ _s ^p ·γ _L ^p ) ^1/2 (＝γ _L (1+cos θ)/2 … … type (3)

In practice, the contact angle (θ) of two solutions of pure water and diiodomethane, the surface energy γ of the known solution _L Each component (gamma) _L ^d 、γ _L ^p ) Substituting the formula (3) to solve simultaneous equations.

As a result, the surface energy (. Gamma.) of the measured surface of the transfer layer was calculated _S )。

The method of adjusting the surface energy value of the surface of the transfer layer on the side opposite to the dummy support within the above range is not particularly limited, and examples thereof include a method of forming a layer such as an intermediate layer containing a water-soluble resin on the surface.

An example of a method for using the photosensitive transfer material of the present invention is shown below, but the present invention is not limited thereto.

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

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

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

(4) "pseudo support/buffer layer/intermediate layer/photosensitive resin layer/protective film"

In each of the above structures, the photosensitive resin layer may be a positive photosensitive resin layer or a negative photosensitive resin layer, and is preferably a negative photosensitive resin layer. The photosensitive resin layer is also preferably a colored resin layer.

Among them, the photosensitive transfer material is preferably, for example, the structures (2) to (4) described above, more preferably the structures (3) or (4) described above, and particularly preferably the structure (3) described above.

In the case where the photosensitive transfer material has a structure in which the photosensitive resin layer further has another layer on the side opposite to the dummy support side, the total thickness of the other layers disposed on the side opposite to the dummy support side of the photosensitive resin layer is preferably 0.1% to 30%, more preferably 0.1% to 20%, with respect to the layer thickness of the photosensitive resin layer.

Hereinafter, a photosensitive transfer material used in the present invention will be described by taking a specific example of an embodiment.

The following describes the respective elements constituting the photosensitive transfer material.

[ pseudo-supporting body ]

The photosensitive transfer material used in the present invention has a pseudo support.

The dummy support is a support that supports a laminate including a transfer layer and is peelable.

The dummy support may have light transmittance. In the present specification, "light-transmitting" means that the transmittance of light of a wavelength used for pattern exposure is 50% or more.

The transmittance of light of a wavelength (more preferably, 365 nm) used for pattern exposure of the dummy support is preferably 60% or more, more preferably 70% or more.

The transmittance of the layer included in the photosensitive transfer material was a ratio of the intensity of the emitted light emitted through the layer when the light was incident in a direction perpendicular to the main surface of the layer (thickness direction) to the intensity of the incident light, and was measured using MCPD Series manufactured by Otsuka Electronics co.

Examples of the material constituting the pseudo-support include a glass substrate, a resin film, and paper, and from the viewpoints of strength, flexibility, and light transmittance, the resin film is preferable.

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

The thickness (layer thickness) of the dummy support is not particularly limited, and may be selected according to the material from the viewpoints of strength as a support, flexibility required for adhesion to the circuit wiring forming substrate, and light transmittance required in the initial exposure step.

The thickness of the pseudo-support is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 50 μm, still more preferably in the range of 10 μm to 20 μm, and particularly preferably in the range of 10 μm to 16 μm, from the viewpoints of ease of handling and versatility.

Further, from the viewpoints of defect suppression, resolution, and linearity of the resist pattern, the thickness of the dummy support is preferably 50 μm or less, more preferably 25 μm or less, further preferably 20 μm or less, and particularly preferably 16 μm or less.

Further, in the film used as the pseudo-support, it is preferable that the film is free from deformation such as wrinkles, scratches, defects, and the like.

From the viewpoint of imparting handleability, a layer (lubricant layer) containing fine particles may be provided on the surface of the pseudo support. The lubricant layer may be provided on one side or both sides of the pseudo-support. The diameter of the particles contained in the lubricant layer can be, for example, 0.05 μm to 0.8 μm. The thickness of the lubricant layer can be, for example, 0.05 μm to 1.0 μm.

From the viewpoints of conveyability, defect suppression of resist pattern, and resolution, the arithmetic average roughness Ra of the surface of the dummy support on the side opposite to the photosensitive resin layer side is preferably equal to or greater than the arithmetic average roughness Ra of the surface of the dummy support on the photosensitive resin layer side.

The arithmetic average roughness Ra of the surface of the dummy support on the side opposite to the photosensitive resin layer side is preferably 100nm or less, more preferably 50nm or less, still more preferably 20nm or less, and particularly preferably 10nm or less from the viewpoints of conveyability, defect suppression of resist pattern, and resolution.

The arithmetic average roughness Ra of the surface of the dummy support on the photosensitive resin layer side is preferably 100nm or less, more preferably 50nm or less, further preferably 20nm or less, and particularly preferably 10nm or less, from the viewpoints of releasability of the dummy support, defect suppression of the resist pattern, and resolution.

Further, from the viewpoints of conveyability, defect suppression property of resist pattern and resolution, the arithmetic average roughness Ra of the surface of the dummy support on the side opposite to the photosensitive resin layer side is preferably 0nm to 10nm, more preferably 0nm to 5nm.

The arithmetic average roughness Ra of the surface of the pseudo support or the protective film in the present invention is set to a value measured by the following method.

The surface profile of the film was obtained by measuring the surface of the pseudo support or the protective film using a three-dimensional optical profiler (New View7300, manufactured by Zygo corporation) under the following conditions.

As the assay/analysis software, microscope Application of MetroPro ver8.3.2 was used. Then, the Surface Map screen is displayed by the analysis software, and histogram data is obtained in the Surface Map screen. An arithmetic average roughness was calculated from the obtained histogram data to obtain an Ra value of the surface of the pseudo support or protective film.

When the pseudo support or the protective film is bonded to the photosensitive resin layer or the like, the pseudo support or the protective film may be peeled off from the photosensitive resin layer, and the Ra value of the peeled surface may be measured.

When the wound laminate is conveyed again by a roll-to-roll method, the peeling force of the pseudo support, specifically, the peeling force between the pseudo support and the photosensitive resin layer or the buffer layer is preferably 0.5mN/mm or more, more preferably 0.5mN/mm to 2.0mN/mm, from the viewpoint of peeling inhibition of the pseudo support due to adhesion of the laminate to the laminate stacked up and down.

The peel force of the pseudo support in the present invention is measured as follows.

A copper layer having a thickness of 200nm was formed on a polyethylene terephthalate (PET) film having a thickness of 100 μm by a sputtering method, thereby producing a PET substrate with a copper layer.

The protective film was peeled off from the photosensitive transfer material thus produced, and laminated on the PET substrate with a copper layer under lamination conditions of a lamination roller temperature of 100℃and a line pressure of 0.6MPa and a line speed (lamination speed) of 1.0 m/min. Next, after the adhesive tape (PRINTACK manufactured by Nitto Denko Corporation) was attached to the surface of the pseudo-support, a laminate having at least the pseudo-support and the photosensitive resin layer on the PET substrate with the copper layer was cut into 70mm×10mm, and a sample was produced. The PET substrate side of the sample was fixed to a sample stage.

The tape was stretched at 5.5 mm/sec in a direction of 180 degrees using a tensile compression tester (IMADA seismakusho co., ltd., SV-55) to peel between the photosensitive resin layer or the buffer layer and the pseudo support, and the force (peeling force) or adhesion force required for peeling was measured.

Preferable modes of the pseudo-support are described in, for example, paragraphs 0017 to 0018 of Japanese patent application laid-open No. 2014-85643, paragraphs 0019 to 0026 of Japanese patent application laid-open No. 2016-27363, paragraphs 0041 to 0057 of International publication No. 2012/081680, paragraphs 0029 to 0040 of International publication No. 2018/179370, and paragraphs 0012 to 0032 of Japanese patent application laid-open No. 2019-101405, the contents of which are incorporated into the present specification.

[ photosensitive resin layer ]

The photosensitive transfer material used in the present invention has a photosensitive resin layer.

The photosensitive resin layer may be a positive photosensitive resin layer or a negative photosensitive resin layer, and is preferably a negative photosensitive resin layer.

The negative photosensitive resin layer preferably contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator, and more preferably contains an alkali-soluble resin based on the total mass of the photosensitive resin layer: 10 to 90 mass percent; olefinically unsaturated compounds: 5 to 70 mass percent; photopolymerization initiator: 0.01 to 20 mass%.

The positive photosensitive resin layer is not limited, and a known positive photosensitive resin layer can be used. The positive photosensitive resin layer preferably contains an acid-decomposable resin, that is, a polymer having a structural unit of an acid group protected by an acid-decomposable group, and a photoacid generator. The positive photosensitive resin layer preferably contains a resin having a structural unit having a phenolic hydroxyl group and a quinone diazide compound.

The positive photosensitive resin layer is more preferably a chemically amplified positive photosensitive resin layer containing a polymer having a structural unit having an acid group protected by an acid-decomposable group and a photoacid generator.

The components are described in order below. When simply referred to as a "photosensitive resin layer", the term "photosensitive resin layer" refers to both a positive photosensitive resin layer and a negative photosensitive resin layer.

Polymerizable Compound

The negative photosensitive resin layer preferably contains a polymerizable compound. In the present specification, the term "polymerizable compound" refers to a compound different from the alkali-soluble resin, which is polymerized by the action of a photopolymerization initiator described later.

The polymerizable group of the polymerizable compound is not particularly limited as long as it is a group involved in polymerization reaction, and examples thereof include a group having an ethylenically unsaturated group such as a vinyl group, an acryl group, a methacryl group, a styryl group, and a maleimide group; and a group having a cationically polymerizable group such as an epoxy group and an oxetanyl group.

The polymerizable group is preferably a group having an ethylenically unsaturated group, and more preferably an acryl group or a methacryl group.

The polymerizable compound preferably contains an ethylenically unsaturated compound, and more preferably contains a (meth) acrylate compound.

From the viewpoints of resolution and pattern formation, the photosensitive resin layer preferably contains a polymerizable compound having 2 or more functions (polyfunctional polymerizable compound), and more preferably contains a polymerizable compound having 3 or more functions.

The polymerizable compound having 2 or more functions herein means a compound having 2 or more polymerizable groups in one molecule.

In addition, from the viewpoint of excellent resolution and releasability, the number of polymerizable groups in one molecule of the polymerizable compound is preferably 6 or less.

From the viewpoint of more excellent balance of photosensitivity, resolution and releasability of the photosensitive resin layer, the negative photosensitive resin layer preferably contains a 2-functional or 3-functional ethylenically unsaturated compound, more preferably contains a 2-functional ethylenically unsaturated compound.

From the viewpoint of excellent releasability, the content of the 2-functional or 3-functional ethylenically unsaturated compound in the negative photosensitive resin layer is preferably 60 mass% or more, more preferably more than 70 mass%, and still more preferably 90 mass% or more relative to the total content of the ethylenically unsaturated compounds. The upper limit is not particularly limited and may be 100 mass%. That is, all of the ethylenically unsaturated compounds contained in the negative photosensitive resin layer may be 2-functional ethylenically unsaturated compounds.

From the viewpoints of resolution and pattern formation, the negative photosensitive resin layer preferably contains a polymerizable compound having a polyalkylene oxide structure, and more preferably contains a polymerizable compound having a polyethylene oxide structure.

The polymerizable compound having a polyalkylene oxide structure may preferably be polyalkylene glycol di (meth) acrylate or the like, which will be described later.

Olefinically unsaturated compounds B-

The negative photosensitive resin layer preferably contains an ethylenically unsaturated compound B having an aromatic ring and 2 ethylenically unsaturated groups. The ethylenically unsaturated compound B is a 2-functional ethylenically unsaturated compound having 1 or more aromatic rings in one molecule among the ethylenically unsaturated compounds.

In the negative photosensitive resin layer, the mass ratio of the content of the ethylenically unsaturated compound B to the content of the ethylenically unsaturated compound is preferably 40 mass% or more, more preferably 50 mass% or more, still more preferably 55 mass% or more, and particularly preferably 60 mass% or more, from the viewpoint of more excellent resolution. The upper limit is not particularly limited, but from the viewpoint of releasability, it is preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and particularly preferably 85% by mass or less.

Examples of the aromatic ring of the ethylenically unsaturated compound B include aromatic hydrocarbon rings such as benzene ring, naphthalene ring and anthracene ring, aromatic heterocyclic rings such as thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring and pyridine ring, and condensed rings thereof, and aromatic hydrocarbon rings are preferable, and benzene ring is more preferable. The aromatic ring may have a substituent.

The ethylenically unsaturated compound B may have only 1 aromatic ring or may have 2 or more aromatic rings.

The ethylenically unsaturated compound B preferably has a bisphenol structure from the viewpoint of improving resolution by suppressing swelling of the negative photosensitive resin layer by the developer.

Examples of the bisphenol structure include bisphenol a structure derived from bisphenol a (2, 2-bis (4-hydroxyphenyl) propane), bisphenol F structure derived from bisphenol F (2, 2-bis (4-hydroxyphenyl) methane), and bisphenol B structure derived from bisphenol B (2, 2-bis (4-hydroxyphenyl) butane), and bisphenol a structure is preferable.

Examples of the ethylenically unsaturated compound B having a bisphenol structure include compounds having a bisphenol structure and 2 polymerizable groups (preferably, (meth) acryloyl groups) bonded to both ends of the bisphenol structure.

The bisphenol structure may be directly bonded to 2 polymerizable groups at both ends, or may be bonded via 1 or more alkyleneoxy groups. The alkyleneoxy group added to both ends of the bisphenol structure is preferably ethyleneoxy group or propyleneoxy group, and more preferably ethyleneoxy group. The number of alkylene oxide groups added to the bisphenol structure is not particularly limited, but is preferably 4 to 16, more preferably 6 to 14 per 1 molecule.

The olefinically unsaturated compound B having a bisphenol structure is described in paragraphs 0072 to 0080 of Japanese patent application laid-open No. 2016-224162, the contents of which are incorporated into the present specification.

As the ethylenically unsaturated compound B, a 2-functional ethylenically unsaturated compound having a bisphenol a structure is preferable, and 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane is more preferable.

Examples of the 2, 2-bis (4- ((meth) acryloxypolyalkoxy) phenyl) propane include 2, 2-bis (4- (methacryloxydiethoxy) phenyl) propane (manufactured by FA-324M,Hitachi ChemicaL Co, ltd.), 2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane (BPE-500, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydodecaethoxy tetrapropoxy) phenyl) propane (manufactured by FA-3200MY,Hitachi Chemical Co, ltd.), 2-bis (4- (methacryloxypentaethoxy) phenyl) propane (BPE-1300, shin-Nakamura Chemical co, manufactured by ltd.), 2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, shin-Nakamura Chemical co), and manufactured by ltd.10-b.10, and also, the use of the same.

As the ethylenically unsaturated compound B, a compound represented by the following formula (Bis) can be used.

[ chemical formula 1]

In the formula (Bis), R ₁ R is R ₂ Each independently represents a hydrogen atom or a methyl group, A is C ₂ H ₄ B is C ₃ H ₆ ，n ₁ N is as follows ₃ Are each independently an integer of 1 to 39, and n ₁ +n ₃ Is an integer of 2 to 40, n ₂ N is as follows ₄ Each independently is an integer of 0 to 29, and n ₂ +n ₄ The repeating units of- (A-O) -and- (B-O) -may be arranged randomly or in blocks, and are integers of 0 to 30. Also, in the case of the block, any one of- (A-O) -and- (B-O) -may be on the bisphenol structure side.

In one aspect, n ₁ +n ₂ +n ₃ +n ₄ Preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and still more preferably an integer of 4 to 12. And n is ₂ +n ₄ Preferably an integer of 0 to 10, more preferably an integer of 0 to 4, still more preferably an integer of 0 to 2Number, particularly preferably 0.

The ethylenically unsaturated compound B may be used singly or in combination of two or more.

From the viewpoint of more excellent resolution, the content of the ethylenically unsaturated compound B in the negative photosensitive resin layer is preferably 10 mass% or more, more preferably 20 mass% or more, relative to the total mass of the negative photosensitive resin layer. The upper limit is not particularly limited, but is preferably 70 mass% or less, more preferably 60 mass% or less, from the viewpoints of transferability and edge melting (a phenomenon in which components in the negative photosensitive resin layer bleed out from the end portion of the photosensitive transfer material).

The negative photosensitive resin layer may contain an ethylenically unsaturated compound other than the ethylenically unsaturated compound B.

The ethylenically unsaturated compounds other than the ethylenically unsaturated compound B are not particularly limited, and can be appropriately selected from known compounds. Examples thereof include compounds having 1 ethylenically unsaturated group in one molecule (monofunctional ethylenically unsaturated compounds), 2-functional ethylenically unsaturated compounds having no aromatic ring, and ethylenically unsaturated compounds having 3 or more functions.

Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate.

Examples of the 2-functional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.

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

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

Examples of urethane di (meth) acrylate include propylene oxide modified urethane di (meth) acrylate and ethylene oxide and propylene oxide modified urethane di (meth) acrylate. Examples of the commercial products include 8UX-015A (Taisei Fine Chemical Co., ltd.), UA-32P (Shin-Nakamura Chemical Co., ltd.), and UA-1100H (Shin-Nakamura Chemical Co., ltd.).

Examples of the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, isocyanuric acid tri (meth) acrylate, glycerol tri (meth) acrylate, and alkylene oxide modified products thereof.

Wherein, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate. In one embodiment, the negative photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound B and an ethylenically unsaturated compound having 3 or more functions, and more preferably contains the above-mentioned ethylenically unsaturated compound B and an ethylenically unsaturated compound having two or more 3 or more functions. In this case, the mass ratio of the ethylenically unsaturated compound B to the ethylenically unsaturated compound having 3 or more functions is preferably (total mass of the ethylenically unsaturated compounds B): (total mass of the ethylenically unsaturated compounds having 3 or more functions) =1:1 to 5:1, more preferably 1.2:1 to 4:1, still more preferably 1.5:1 to 3:1.

In one embodiment, the negative photosensitive resin layer preferably contains the above-mentioned ethylenically unsaturated compound B and two or more 3-functional ethylenically unsaturated compounds.

Examples of the alkylene oxide modified product of the ethylenically unsaturated compound having 3 or more functions include caprolactone-modified (meth) acrylate compounds (such as KAYARAD (registered trademark) DPCA-20, shin-Nakamura Chemical co, a-9300-1CL, manufactured by ltd), alkylene oxide-modified (meth) acrylate compounds (such as KAYARAD RP-1040, shin-Nakamura Chemical co, ATM-35E and a-9300, DAICEL-ALLNEX ltd, manufactured by Nippon Kayaku co, ltd), ethoxylated glycerol triacrylate (such as Shin-Nakamura Chemical co, a-GLY-9E, manufactured by shinix (registered trademark) T0-2349 (such as toagoeico, ltd), ARONIX M-520 (manufactured by toagoeico), manufactured by toagoeico, manufactured by artix).

Further, as the ethylenically unsaturated compound other than the ethylenically unsaturated compound B, the ethylenically unsaturated compounds having an acid group described in paragraphs 0025 to 0030 of japanese unexamined patent publication No. 2004-239942 can be used.

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

Further, from the viewpoint of curability and resolution, the ethylenically unsaturated compound in the negative photosensitive resin layer preferably contains a (meth) acrylic compound.

Further, from the viewpoints of curability, resolution, and linearity, it is more preferable that the ethylenically unsaturated compound in the negative-type photosensitive resin layer contains a (meth) acrylic compound, and the content of the acrylic compound is 60 mass% or less relative to the total mass of the (meth) acrylic compounds contained in the negative-type photosensitive resin layer.

The molecular weight (weight average molecular weight (Mw) when having a distribution) of the ethylenically unsaturated compound containing the ethylenically unsaturated compound B is preferably 200 to 3,000, more preferably 280 to 2,200, and further preferably 300 to 2,200.

The ethylenically unsaturated compound may be used singly or in combination of two or more.

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

Photopolymerization initiator

The negative photosensitive resin layer preferably contains a photopolymerization initiator.

The photopolymerization initiator is a compound that initiates polymerization of an ethylenically unsaturated compound by exposure to activating light such as ultraviolet light, visible light, or X-ray. The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

Examples of the photopolymerization initiator include a photo radical polymerization initiator and a photo cation polymerization initiator.

Among them, the negative photosensitive resin layer is preferably a photo radical polymerization initiator from the viewpoints of resolution and pattern formation.

Examples of the photo-radical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α -aminoalkylbenzophenone structure, a photopolymerization initiator having an α -hydroxyalkylbenzophenone structure, a photopolymerization initiator having an acylphosphine oxide structure, a photopolymerization initiator having an N-phenylglycine structure, and a bisimidazole compound.

Examples of the photo radical polymerization initiator include those described in paragraphs 0031 to 0042 of Japanese patent application laid-open No. 2011-95716 and paragraphs 0064 to 0081 of Japanese patent application laid-open No. 2015-14783.

Examples of the photo radical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, (p, p ' -dimethoxybenzyl) anisyl ester, TAZ-110 (trade name: midori Kagaku Co., ltd.), benzophenone, TAZ-111 (trade name: midori Kagaku Co., ltd.), irgacure OXE01, OXE02, OXE03, OXE04 (manufactured by BASF corporation), omnirad651 and 369 (trade name: IGM Resins B.V. Co., ltd.), and 2,2' -bis (2-chlorophenyl) -4,4', 5' -tetraphenyl-1, 2' -bisimidazole (Tokyo Chemical Industry Co., ltd.).

Examples of the commercially available photo radical polymerization initiator include 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, manufactured by BASF corporation), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetoxime) (trade name: IRGACURE OXE-02, manufactured by BASF corporation), IRGACURE OXE-03 (manufactured by BASF corporation), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butanone (trade name: omnirad 379EG,IGM Resins B.V. Manufactured by Omnirad.), 2-methyl-1- (4-methylthiophenyl) -2-morpholinylpropane-1-one (trade name: omni 907,IGMResins B.V. Manufactured by Omnii), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropoyl) benzyl ] phenyl } -2-methylpropane-1-one (trade name: omnif) 127,IGM Resins B.V 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 (trade name: omnirad 369,IGM Resins B.V. Manufactured), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: omnirad 1173,IGM Resins B.V. Manufactured), 1-hydroxycyclohexylphenyl ketone (trade name: omnirad 184,IGM Resins B.V. Manufactured), 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: omnirad651,IGM Resins B.V. Manufactured), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (trade name: omnirad TPO H, manufactured by IGM Resins B.V. manufactured), bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: omnirad 819,IGM Resins B.V. Manufactured), oxime esters photo-polymerization initiators (trade name: lunar 6, DK. Manufactured by SH Japan K. Manufactured), 2 '-bis (2-chlorophenyl) -4,4',5 '-tetraphenylimidazole (2- (2-diphenyl) -dimeric imidazole (trade name: 2, 4-diphenyl imidazole (manufactured by Omnirad651,IGM Resins B.V. Manufactured by Omnirad. Manufactured) 4, 5' -tetraphenyl imidazole (trade name: 2, 4-diphenyl imidazole B. Manufactured by Happtzm. 4, 4-tsche).

The photo cation polymerization initiator (photoacid generator) is a compound that generates an acid upon receiving activating light. The photo cation polymerization initiator is preferably a compound which generates an acid in response to an activating light having a wavelength of 300nm or more, preferably 300nm to 450nm, but the chemical structure thereof is not limited. The photo-cation polymerization initiator which does not directly induce an activating light having a wavelength of 300nm or more may be preferably used in combination with a sensitizer as long as it is a compound which generates an acid by inducing an activating light having a wavelength of 300nm or more when used in combination with a sensitizer.

The photo-cation polymerization initiator is preferably a photo-cation polymerization initiator that generates an acid having a pKa of 4 or less, more preferably a photo-cation polymerization initiator that generates an acid having a pKa of 3 or less, and particularly preferably a photo-cation polymerization initiator that generates an acid having a pKa of 2 or less. The lower limit of pKa is not particularly limited, but is preferably-10.0 or more, for example.

Examples of the photo-cationic polymerization initiator include an ionic photo-cationic polymerization initiator and a nonionic photo-cationic polymerization initiator.

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

As the ionic photo-cation polymerization initiator, the ionic photo-cation polymerization initiator described in paragraphs 0114 to 0133 of Japanese unexamined patent publication No. 2014-85643 can be used.

Examples of the nonionic photo-cationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds and oxime sulfonate compounds. As the trichloromethyl-s-triazines, diazomethane compounds and imide sulfonate compounds, those described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494 can be used. Further, as the oxime sulfonate compound, the compounds described in paragraphs 0084 to 0088 of International publication No. 2018/179640 can be used.

The negative photosensitive resin layer may contain one kind of photopolymerization initiator alone or two or more kinds thereof.

The content of the photopolymerization initiator in the negative-type photosensitive resin layer is not particularly limited, but is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and further preferably 1.0 mass% or more relative to the total mass of the photosensitive resin layer. The upper limit is not particularly limited, but is preferably 10 mass% or less, more preferably 5 mass% or less, relative to the total mass of the negative photosensitive resin layer.

Alkali-soluble resin

The negative photosensitive resin layer preferably contains an alkali-soluble resin.

In the present specification, "alkali-soluble" means that the solubility of the aqueous solution of sodium carbonate in 1% by mass at a liquid temperature of 22 ℃ is 0.1g or more in 100 g.

The alkali-soluble resin is not particularly limited, and for example, a known alkali-soluble resin used for etching resists (etching resists) can be preferably used.

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

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

Among them, the alkali-soluble resin is preferably a polymer a described later.

Polymer A-

As the alkali-soluble resin, polymer a is preferably contained.

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

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

The acid value is the mass [ mg ] of potassium hydroxide required for neutralizing 1g of the sample, and in this specification, the unit is referred to as mgKOH/g. The acid value can be calculated, for example, from the average acid group content in the compound.

The acid value of the polymer a may be adjusted by the kind of the structural unit constituting the polymer a and the content of the structural unit containing an acid group.

The weight average molecular weight of polymer a is preferably 5,000 ～ 500,000. From the viewpoint of improving the resolution and the developability, the weight average molecular weight is preferably 500,000 or less. The weight average molecular weight is more preferably 100,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film such as edge meltability and chipping property, the weight average molecular weight is preferably 5,000 or more. The weight average molecular weight is more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more. The edge meltability means the easiness of the photosensitive resin layer to overflow from the end surface of the roll when the photosensitive transfer material is wound into a roll. The chipping property refers to the ease of scattering of chips when cutting an unexposed film with a cutter. If the chips adhere to the upper surface of the photosensitive resin layer or the like, the chips are transferred to a mask in a subsequent exposure step or the like, which causes defective products. The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, still more preferably 1.0 to 3.0. In the present invention, the molecular weight is a value measured using gel permeation chromatography. And the dispersity is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight/number average molecular weight).

From the viewpoint of suppressing deterioration of line width thickness and resolution at the time of focus position deviation at the time of exposure, the negative photosensitive resin layer preferably contains a monomer component having an aromatic hydrocarbon group as the polymer a. Examples of such an aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content of the monomer component having an aromatic hydrocarbon group in the polymer a is preferably 20 mass% or more, more preferably 30 mass% or more, still more preferably 40 mass% or more, particularly preferably 45 mass% or more, and most preferably 50 mass% or more, based on the total mass of all the monomer components. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 85% by mass or less. The content of the monomer component having an aromatic hydrocarbon group in the case of containing a plurality of polymers a was determined as a weight average value.

Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methyl styrene, vinyl toluene, t-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, and the like). Among them, monomers having an aralkyl group or styrene are preferable. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer a is styrene, the content of the styrene monomer component is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, still more preferably 30 to 40% by mass, and particularly preferably 30 to 35% by mass, based on the total mass of all the monomer components.

Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group), a substituted or unsubstituted benzyl group, and the like, and a substituted or unsubstituted benzyl group is preferable.

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

Examples of the monomer having a benzyl group include (meth) acrylic acid esters having a benzyl group, for example, benzyl (meth) acrylate, chlorobenzyl (meth) acrylate, and the like; vinyl monomers having a benzyl group such as vinylbenzyl chloride, vinylbenzyl alcohol, and the like. Among them, benzyl (meth) acrylate is preferable. In one embodiment, when the monomer component having an aromatic hydrocarbon group in the polymer a is benzyl (meth) acrylate, the content of the benzyl (meth) acrylate monomer component is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, still more preferably 70 to 90% by mass, and particularly preferably 75 to 90% by mass, based on the total mass of all the monomer components.

The polymer a containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one first monomer described later and/or at least one second monomer described later.

The polymer a containing no monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one first monomer described later, more preferably by copolymerizing at least one first monomer with at least one second monomer described later.

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

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

The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all the monomer components. The copolymerization ratio is preferably 10 mass% or more, more preferably 15 mass% or more, and still more preferably 20 mass% or more from the viewpoint of exhibiting good developability, controlling edge meltability, and the like. The copolymerization ratio is preferably 50 mass% or less from the viewpoint of high resolution of the resist pattern and the shape of the skirt portion, and more preferably 35 mass% or less, further preferably 30 mass% or less, particularly preferably 27 mass% or less from the viewpoint of chemical resistance of the resist pattern.

The second monomer is a monomer that is non-acidic and has at least 1 polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth) acrylonitrile, etc. Among them, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate are preferable, and methyl (meth) acrylate is more preferable.

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

From the viewpoint of suppressing deterioration of line width thickness or resolution when the focus position is deviated at the time of exposure, it is preferable to contain a monomer having an aralkyl group and/or styrene as a monomer. For example, a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, or the like is preferable.

In one embodiment, the polymer a preferably contains 25 to 40 mass% of a monomer component having an aromatic hydrocarbon group, 20 to 35 mass% of a first monomer component, and 30 to 45 mass% of a second monomer component. In another embodiment, the polymer preferably contains 70 to 90 mass% of the monomer component having an aromatic hydrocarbon group and 10 to 25 mass% of the first monomer component.

The polymer a may have any one of a linear structure, a branched structure, and an alicyclic structure in a side chain. The branched structure or alicyclic structure can be introduced into the side chain of the polymer a by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain. The group having an alicyclic structure may be monocyclic or polycyclic.

Specific examples of the monomer having a group having a branched structure in a side chain include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isopentyl (meth) acrylate, tert-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate, and tert-octyl (meth) acrylate. Among these, isopropyl (meth) acrylate, isobutyl (meth) acrylate or tert-butyl methacrylate is preferable, and isopropyl methacrylate or tert-butyl methacrylate is more preferable.

Examples of the monomer having a group having an alicyclic structure in a side chain include a monomer having a monocyclic aliphatic hydrocarbon group and a monomer having a polycyclic aliphatic hydrocarbon group, and examples thereof include (meth) acrylic esters having an alicyclic hydrocarbon group having 5 to 20 carbon atoms (the number of carbon atoms). More specific examples thereof include (bicyclo [2.2.1] heptyl-2) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 3-methyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyl adamantyl (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl (meth) acrylate, 3,5, 8-triethyl-1-adamantyl (meth) acrylate, 3, 5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4, 7-methanoindene (meth) acrylate, 3, 5-triethyl-1-adamantyl (meth) acrylate, 7-octahydro-indene (meth) acrylate, 1-menthyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-hydroxy-1-adamantyl (meth) acrylate, octahydro-4, 7-bridged (meth) acrylate, and (meth) acrylate 3-hydroxy-2, 6-trimethyl-bicyclo [3.1.1] heptyl (meth) acrylate, 3, 7-trimethyl-4-hydroxy-bicyclo [4.1.0] heptyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, fenchyl (meth) acrylate, 2, 5-trimethylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. Among these (meth) acrylic esters, cyclohexyl (meth) acrylate, (norbornyl) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fenchyl (meth) acrylate, 1-menthyl (meth) acrylate or tricyclodecane (meth) acrylate is preferable, and cyclohexyl (meth) acrylate, (norbornyl) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate or tricyclodecane (meth) acrylate is particularly preferable.

The polymer a may be used alone, or two or more kinds may be used in combination. When two or more kinds of the polymers are used in combination, it is preferable to use two kinds of the polymers a containing the monomer component having an aromatic hydrocarbon group in combination or to use the polymer a containing the monomer component having an aromatic hydrocarbon group in combination with the polymer a not containing the monomer component having an aromatic hydrocarbon group. In the latter case, the ratio of the polymer a containing the monomer component having an aromatic hydrocarbon group to be used is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total amount of the polymer a.

The polymer a is preferably synthesized by adding a proper amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting one or more monomers described in the above description with a solvent such as acetone, methyl ethyl ketone or isopropyl alcohol, and heating and stirring the mixture. In some cases, synthesis may be performed while dropping a part of the mixture into the reaction solution. After the completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As the synthesis method, in addition to the solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

The glass transition temperature Tg of the polymer A is preferably 30℃or more and 135℃or less. By using the polymer a having a Tg of 135 ℃ or less in the photosensitive resin layer, deterioration of line width thickness and resolution at the time of focus position deviation at the time of exposure can be suppressed. From this viewpoint, the Tg of the polymer A is more preferably 130℃or lower, still more preferably 120℃or lower, and particularly preferably 110℃or lower. Further, from the viewpoint of improving the edge melting resistance, it is preferable to use the polymer a having Tg of 30 ℃ or higher. From this viewpoint, the Tg of the polymer A is more preferably 40℃or higher, still more preferably 50℃or higher, particularly preferably 60℃or higher, and most preferably 70℃or higher.

Further, from the viewpoints of sensitivity and resolution, the photosensitive resin layer (preferably, a negative photosensitive resin layer) preferably contains a polymer having a crosslinkable group, and more preferably contains a polymer having a crosslinkable group as an alkali-soluble resin.

The polymer having a crosslinkable group is preferably a polymer having a polymerizable group, more preferably a polymer having an ethylenically unsaturated group, further preferably an acrylic resin having an ethylenically unsaturated group, and particularly preferably an acrylic resin having a structural unit having an ethylenically unsaturated group, from the viewpoints of developability, sensitivity and resolution.

The polymerizable group is not particularly limited as long as it is a group involved in polymerization reaction, and examples thereof include a group having an ethylenically unsaturated group such as a vinyl group, an acryl group, a methacryl group, a styryl group, and a maleimide group; and a group having a cationically polymerizable group such as an epoxy group and an oxetanyl group.

The polymer a having a crosslinkable group is preferably one having a crosslinkable group from the viewpoints of developability, sensitivity and resolution.

The negative photosensitive resin layer may contain a resin other than the alkali-soluble resin.

Examples of the resin other than the alkali-soluble resin include acrylic resins, styrene-acrylic copolymers (copolymers having a styrene content of 40 mass% or more), polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethylenimines, polyallylamines, and polyalkylene glycols.

The alkali-soluble resin may be used singly or two or more kinds may be used in combination.

The proportion of the alkali-soluble resin to the total mass of the negative photosensitive resin layer is preferably in the range of 10 to 90 mass%, more preferably 30 to 70 mass%, and even more preferably 40 to 60 mass%. From the viewpoint of controlling the development time, the proportion of the alkali-soluble resin to the negative photosensitive resin layer is preferably 90 mass% or less. On the other hand, from the viewpoint of improving the edge melting resistance, the proportion of the alkali-soluble resin to the negative photosensitive resin layer is preferably 10 mass% or more.

Compounds having unshared electron pairs

The photosensitive resin layer preferably contains a compound having an unshared electron pair from the viewpoint of adhesion to the conductive layer.

The compound having an unshared electron pair is preferably a compound containing at least a nitrogen atom, an oxygen atom, or a sulfur atom, more preferably a heterocyclic compound, a thiol compound, or a disulfide compound, still more preferably a heterocyclic compound, and particularly preferably a nitrogen-containing heterocyclic compound, from the viewpoint of adhesion to the conductive layer.

The heterocycle of the heterocyclic compound may be a single ring or a multi-ring.

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

Examples of the heterocyclic compound include preferably a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodamine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, and a pyrimidine compound. Among the above, from the viewpoint of adhesion to the conductive layer, the heterocyclic compound is preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodamine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds, more preferably at least one compound selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, thiazole compounds, benzothiazole compounds, benzimidazole compounds, and benzoxazole compounds, and still more preferably at least one compound selected from the group consisting of triazole compounds and tetrazole compounds, and particularly preferably triazole compounds.

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

[ chemical formula 2]

[ chemical formula 3]

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

[ chemical formula 4]

[ chemical formula 5]

As thiadiazole compounds, the following compounds can be exemplified.

[ chemical formula 6]

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

[ chemical formula 7]

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

[ chemical formula 8]

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

[ chemical formula 9]

As benzothiazole compounds, the following compounds can be exemplified.

[ chemical formula 10]

As benzimidazole compounds, the following compounds can be exemplified.

[ chemical formula 11]

[ chemical formula 12]

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

[ chemical formula 13]

The thiol compound may preferably be an aliphatic thiol compound.

As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (i.e., an aliphatic thiol compound having 2 or more functions) can be preferably used.

Examples of the polyfunctional aliphatic thiol compound include trimethylolpropane tris (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutanoyloxy) butane, pentaerythritol tetrakis (3-mercaptobutanoate), 1,3, 5-tris (3-mercaptobutanoyloxy) ethyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, trimethylolethane tris (3-mercaptobutanoate), tris [ (3-mercaptopropionyloxy) ethyl ] isocyanurate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), ethylene glycol dithiopropionate, 1, 4-bis (3-mercaptobutanoyloxy) butane, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 6-hexamethylenedithiol, 2' - (ethylenedithiol), and mesoethyl (3-mercaptosuccinic acid).

Examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β -mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

Examples of the disulfide compound include 2- (4 '-morpholinodithio) benzothiazole, 2' -benzothiazolyl disulfide, bis (2-benzoamidophenyl) disulfide, 1-thiobis (2-naphthol), bis (2, 4, 5-trichlorophenyl) disulfide, 4 '-dithiomorpholine, tetraethylthiuram disulfide, dibenzyl disulfide, bis (2, 4-dinitrophenyl) disulfide, 4' -diaminodiphenyl disulfide, diallyl disulfide, di-t-butyl disulfide, bis (6-hydroxy-2-naphthyl) disulfide, dicyclohexyldisulfide, o-isobutyrylthioamine disulfide, and diphenyl disulfide.

The molecular weight of the compound having an unshared electron pair is preferably less than 1,000, more preferably 50 to 500, even more preferably 50 to 200, and particularly preferably 50 to 115, from the viewpoint of adhesion to the conductive layer.

The photosensitive resin layer may contain one kind of compound having an unshared electron pair alone or two or more kinds thereof.

From the viewpoint of adhesion to the conductive layer, the content of the compound having an unshared electron pair is preferably 0.01 to 20 mass%, more preferably 0.1 to 10 mass%, even more preferably 0.3 to 8 mass%, and particularly preferably 0.5 to 5 mass% relative to the total mass of the photosensitive resin layer.

Pigment

The photosensitive resin layer preferably contains a dye, and more preferably contains a dye having a maximum absorption wavelength of 450nm or more in a wavelength range of 400nm to 780nm at the time of color development and a maximum absorption wavelength that changes by an acid, an alkali or a radical (also simply referred to as "dye N") from the viewpoints of visibility of an exposed portion and a non-exposed portion, pattern visibility after development, and resolution. When the dye N is contained, although the detailed mechanism is not clear, the adhesion to the adjacent layers (for example, the pseudo support and the 1 st resin layer) is improved, and the resolution is further excellent.

In the present specification, the "change in maximum absorption wavelength of the dye by an acid, an alkali or a radical" may refer to any one of a method in which the dye in a developed state is decolorized by an acid, an alkali or a radical, a method in which the dye in a decolorized state is developed by an acid, an alkali or a radical, and a method in which the dye in a developed state is changed to a developed state of another hue.

Specifically, the dye N may be a compound that changes color from a decolored state by exposure, or may be a compound that changes color from a decolored state by exposure. In this case, the coloring matter may be a coloring matter which changes the state of color development or decoloration by generating an acid, an alkali or a radical in the photosensitive resin layer by exposure and causing these to act, or may be a coloring matter which changes the state of color development or decoloration by changing the state (for example, pH) in the photosensitive resin layer by an acid, an alkali or a radical. The coloring matter may be a coloring matter which is not exposed to light but is directly subjected to an acid, an alkali or a radical as a stimulus to change the state of color development or decoloration.

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

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

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

Examples of the coloring mechanism of the dye N in the present invention include a system in which a radical, an acid, or a base generated from a radical polymerization initiator, a photo cation polymerization initiator (photoacid generator), or a photobase generator after adding a radical polymerization initiator, a photo cation polymerization initiator, or a photobase generator to a photosensitive resin layer and exposing the mixture to light, and then developing the color from the radical, the acid, or the base generated from the radical polymerization initiator, the photo cation polymerization initiator, or the photobase generator.

The maximum absorption wavelength in the wavelength range of 400nm to 780nm at the time of color development of the dye N is preferably 550nm or more, more preferably 550nm to 700nm, and even more preferably 550nm to 650nm, from the viewpoint of visibility of the exposed portion and the non-exposed portion.

The maximum absorption wavelength of pigment N was measured by using a spectrophotometer in the atmospheric environment: UV3100 (manufactured by Shimadzu Corporation) was obtained by measuring the transmission spectrum of a solution containing pigment N (liquid temperature 25 ℃) in the range of 400nm to 780nm, and detecting the wavelength (maximum absorption wavelength) at which the intensity of light becomes the minimum in the above wavelength range.

Examples of the coloring matter which is developed or decolored by exposure to light include colorless compounds.

Examples of the coloring matter to be decolorized by exposure to light include colorless compounds, diarylmethane-based coloring matters, oxazine-based coloring matters, xanthene-based coloring matters, iminonaphthoquinone-based coloring matters, azomethine-based coloring matters, and anthraquinone-based coloring matters.

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

Examples of the colorless compound include a colorless compound having a triarylmethane skeleton (triarylmethane-based dye), a colorless compound having a spiropyran skeleton (spiropyran-based dye), a colorless compound having a fluoran skeleton (fluoran-based dye), a colorless compound having a diarylmethane skeleton (diarylmethane-based dye), a colorless compound having a rhodamine lactam skeleton (rhodamine lactam dye), a colorless compound having an indolyl phthalide lactone skeleton (indolyl phthalide-based dye), and a colorless compound having a colorless gold amine skeleton (colorless gold amine-based dye).

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

The colorless compound preferably has a lactone ring, a sultone ring (sultone ring), or a sultone ring from the viewpoint of visibility of an exposed portion and a non-exposed portion. Thus, the lactone ring, sultone ring or sultone ring of the colorless compound can be reacted with a radical generated by a photo radical polymerization initiator or an acid generated by a photo cation polymerization initiator to change the colorless compound to a closed state to decolorize the colorless compound, or to change the colorless compound to an open state to develop the colorless compound. As the colorless compound, a compound having a lactone ring, a sultone ring, or a sultone ring, which develops color by free radical or acid ring opening, is preferable, and a compound having a lactone ring, which develops color by free radical or acid ring opening is more preferable.

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

Specific examples of dyes among the dyes include brilliant green (brilliant green), ethyl violet, methyl green, crystal violet, basic fuchsin (basic fuchsin), methyl violet 2B, quinaldine red (quinaldine red), rose bengal (rose bengal), meter yellow (metandil yellow), thymol sulfophthalein (thymol sulfonphthalein), xylenol (xylenol) blue, methyl orange, para-methyl red, congo red, benzored purpurin (benzopurline) 4B, alpha-naphthyl red, nile blue (nile blue) 2B, nile blue a, methyl violet, malachite green (malachite green), parapsine red (paramfuchsin), victorian pure blue (victoria pure blue) -naphthalene sulfonate, victorian pure blue BOH (Hodogaya Chemical co., ltd, manufactured), oil blue #603 (Orient Chemical Industries co., ltd, manufactured), oil pink #312 (0 rient Chemical Industries Co, ltd, manufactured), oil red 5B (Orient Chemical Industries co., ltd, manufactured), oil scarlet (oil scarlet) #308 (Orient Chemical Industries co., ltd, manufactured), oil red OG (Orient Chemical Industries co., ltd, manufactured), oil red RR (Orient Chemical Industries co., ltd, manufactured), oil green #502 (Orient Chemical Industries co., ltd, manufactured), shi Bilong red (spilon red) BEH special (Hodogaya Chemical co., ltd, manufactured), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, gold amine, 4-p-diethylaminophenyl iminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearyl amino-4-p-N, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-beta-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone.

Specific examples of the colorless compound among the dye N include p, p', p "-hexamethyltriphenylmethane (colorless crystal violet), pergascript Blue SRB (Ciba-Geigy Co.), crystal violet lactone, malachite green lactone, benzoyl colorless methylene blue, 2- (N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) amino fluoran, 2-anilino-3-methyl-6- (N-ethyl-p-toluidinyl) fluoran, 3, 6-dimethoxy fluoran, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilino fluoran, 3- (N, N-diethylamino) -6-methyl-7-dimethylanilino fluoran, 3- (N, N-diethylamino) -6-methyl-7-methylanilino fluoran, 3- (N, N-diethylamino) -6-chloro-7-methyl-7- (N, N-dibenzylamino) fluoran, 3- (N-cyclohexyl-N-methylamino) -6-methyl-7-anilino fluoran, 3- (N, N-diethylamino) -4-ethyl-anilino-fluoran, 3- (N, N-diethylamino) -7-chlorofluoran, 3- (N, N-diethylamino) -7-benzylaminofluoran, 3- (N, N-diethylamino) -7, 8-benzofluoran, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluoran, 3- (N, N-dibutylamino) -6-methyl-7-dimethylanilino fluoran, 3-piperidinyl-6-methyl-7-anilinofluoran, 3-pyrrolidinyl-6-methyl-7-anilinofluoran, 3-bis (1-ethyl-2-methylindol-3-yl) phthalide, 3-bis (1-N-butyl-2-methylindol-3-yl) phthalide, 3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-aza-phthalide, 3- (4-ethyl-2-methylindol-3-yl) phthalide, 3- (3-ethyl-2-methylindol-3-yl) phthalide, 6 '-bis (diphenylamino) spiroisobenzofuran-1 (3H), 9' - [9H ] xanthen-3-one.

From the viewpoints of visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution, the dye N is preferably a dye whose maximum absorption wavelength is changed by a radical, and more preferably a dye which develops color by a radical.

As pigment N, preference is given to leuco crystal violet, crystal violet lactone, brilliant green or Victoria pure blue-naphthalene sulfonate.

The pigment may be used singly or in combination of two or more.

The content of the dye is preferably 0.1 mass% or more, more preferably 0.1 mass% to 10 mass%, even more preferably 0.1 mass% to 5 mass%, and particularly preferably 0.1 mass% to 1 mass% relative to the total mass of the photosensitive resin layer, from the viewpoints of visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution.

The content of the dye N is preferably 0.1 mass% or more, more preferably 0.1 mass% to 10 mass%, even more preferably 0.1 mass% to 5 mass%, and particularly preferably 0.1 mass% to 1 mass% based on the total mass of the photosensitive resin layer, from the viewpoints of visibility of the exposed portion and the non-exposed portion, pattern visibility after development, and resolution.

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

Two solutions were prepared in which 0.001g or 0.01g of pigment was dissolved in 100mL of methyl ethyl ketone. To each of the obtained solutions, a photo radical polymerization initiator (trade name, irgacure OXE01, manufactured by BASF Japan ltd.) was added, and 365nm light was irradiated, whereby radicals were generated and all pigments were brought into a color development state. Thereafter, the absorbance of each solution having a liquid temperature of 25℃was measured using a spectrophotometer (manufactured by UV3100, shimadzu Corporation) under atmospheric conditions, and a calibration curve was prepared.

Next, absorbance of the solution in which all the pigments were developed was measured by the same method as described above except that 3g of the photosensitive resin layer was dissolved in methyl ethyl ketone instead of the pigments. The content of the pigment contained in the photosensitive resin layer was calculated from the absorbance of the obtained solution containing the photosensitive resin layer based on the calibration curve.

Heat-crosslinkable Compound

The photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film. In the present specification, a thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as a polymerizable compound but is treated as a thermally crosslinkable compound.

Examples of the thermally crosslinkable compound include methylol compounds and blocked isocyanate compounds. Among them, blocked isocyanate compounds are preferable from the viewpoints of the strength of the obtained cured film and the adhesiveness of the obtained uncured film.

Since the blocked isocyanate compound reacts with the hydroxyl group and the carboxyl group, for example, when the resin and/or the polymerizable compound has at least one of the hydroxyl group and the carboxyl group, the hydrophilicity of the film formed is reduced, and the function of the film obtained by curing the photosensitive resin layer as a protective film tends to be enhanced.

The blocked isocyanate compound means a "compound having a structure in which an isocyanate group of an isocyanate is protected (so-called mask) with a blocking agent".

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

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

As the differential scanning calorimeter, for example, a differential scanning calorimeter manufactured by Seiko Instruments inc (model: DSC 6200) can be preferably used. However, the differential scanning calorimeter is not limited thereto.

Examples of the blocking agent having a dissociation temperature of 100℃to 160℃include active methylene compounds [ malonic acid diesters (dimethyl malonate, diethyl malonate, di-N-butyl malonate, di-2-ethylhexyl malonate, etc. ] ], oxime compounds (formaldehyde oxime, aldoxime, acetone oxime, methyl ethyl ketoxime, cyclohexanone oxime, etc. ] having a structure represented by-C (=N-OH) -, in the molecule).

Among these, the blocking agent having a dissociation temperature of 100 to 160 ℃ preferably contains an oxime compound, for example, from the viewpoint of storage stability.

For example, the blocked isocyanate compound preferably has an isocyanurate structure from the viewpoints of improving brittleness of the film, improving adhesion to a transfer object, and the like.

The blocked isocyanate compound having an isocyanurate structure is obtained, for example, by isocyanating hexamethylene diisocyanate to protect it.

Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure in which an oxime compound is used as a blocking agent is preferable from the viewpoint of easily setting a dissociation temperature within a preferable range and easily reducing development residues as compared with a compound having no oxime structure.

The blocked isocyanate compound may have a polymerizable group.

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

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

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

As the blocked isocyanate compound, commercially available ones can be used.

Examples of the commercially available blocked isocyanate compounds include Karenz (registered trademark) AOI-BM, karenz (registered trademark) MOI-BP, etc. (manufactured by SHOWA DENKO K.K. above), and blocked Duranate series (manufactured by Duranate (registered trademark) TPA-B8OE, duranate (registered trademark) WT32-B75P, etc., asahi Kasei Chemicals Corporation).

As the blocked isocyanate compound, a compound having the following structure can be used.

[ chemical formula 14]

The thermally crosslinkable compound may be used singly or in combination of two or more.

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

Polymer having structural unit having acid group protected by acid-decomposable group

The positive photosensitive resin layer preferably contains a polymer (hereinafter, sometimes referred to as "polymer X") having a structural unit (hereinafter, sometimes referred to as "structural unit a") having an acid group protected by an acid-decomposable group. The positive photosensitive resin layer may contain one polymer X alone or two or more polymers X.

In the polymer X, the acid group protected by the acid-decomposable group is converted into an acid group through deprotection reaction by the action of a catalytic amount of an acidic substance (for example, acid) generated by exposure. By generating an acid group in the polymer X, the solubility of the positive photosensitive resin layer in the developer increases.

The polymer X is preferably an addition-polymerizable polymer, more preferably a polymer having a structural unit derived from (meth) acrylic acid or an ester thereof.

Structural units having acid groups protected by acid-decomposable groups

The polymer X preferably has a structural unit (structural unit a) having an acid group protected by an acid-decomposable group. The polymer X has the structural unit a, so that the sensitivity of the positive photosensitive resin layer can be improved.

The acid group is not limited, and a known acid group can be used. The acid group is preferably a carboxyl group or a phenolic hydroxyl group.

Examples of the acid-decomposable group include a group which is relatively easily decomposed by an acid and a group which is relatively hardly decomposed by an acid. Examples of the group relatively easily decomposed by an acid include acetal protecting groups (for example, 1-alkoxyalkyl groups, tetrahydropyranyl groups, and tetrahydrofuranyl groups). Examples of the group which is relatively hard to decompose by an acid include a tertiary alkyl group (for example, a tertiary butyl group) and a tertiary alkoxycarbonyl group (for example, a tertiary butoxycarbonyl group). Among the above, the acid-decomposable group is preferably an acetal-type protecting group.

The molecular weight of the acid-decomposable group is preferably 300 or less from the viewpoint of suppressing variation in line width of the resist pattern.

From the viewpoints of sensitivity and resolution, the structural unit a is preferably a structural unit represented by the following formula A1, a structural unit represented by the formula A2, or a structural unit represented by the formula A3, and more preferably a structural unit represented by the formula A3. The structural unit represented by formula A3 is a structural unit having a carboxyl group protected by an acetal acid-decomposable group.

[ chemical formula 15]

In the formula A1, R ¹¹ R is R ¹² Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ¹¹ R is R ¹² At least one of which is alkyl or aryl, R ¹³ Represents alkyl or aryl, R ¹¹ Or R is ¹² And R is R ¹³ Can be linked to form a cyclic ether, R ¹⁴ Represents a hydrogen atom or a methyl group, X ¹ Represents a single bond or a divalent linking group, R ¹⁵ Represents a substituent, and n represents an integer of 0 to 4.

In the formula A2, R ²¹ R is R ²² Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ²¹ R is R ²² At least one of which is alkyl or aryl, R ²³ Represents alkyl or aryl, R ²¹ Or R is ²² And R is R ²³ Can be linked to form a cyclic ether, R ²⁴ Each independently represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.

In the formula A3, R ³¹ R is R ³² Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ³¹ R is R ³² At least one of which is alkyl or aryl, R ³³ Represents alkyl or aryl, R ³¹ Or R is ³² And R is R ³³ Can be linked to form a cyclic ether, R ³⁴ Represents a hydrogen atom or a methyl group, X ⁰ Represents a single bond or arylene.

In the formula A3, when R ³¹ Or R is ³² When alkyl is preferred, the number of carbon atoms is 1 to 10.

In the formula A3, when R ³¹ Or R is ³² When aryl is preferred, phenyl is preferred.

In the formula A3, R ³¹ R is R ³² Each independently is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula A3, R ³³ The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

In the formula A3, R ³¹ ～R ³³ The alkyl group and the aryl group may have a substituent.

In formula A3, R is preferably ³¹ Or R is ³² And R is R ³³ To form a cyclic ether. The number of ring members of the cyclic ether is preferably 5 or 6, more preferably 5.

In the formula A3, X ⁰ Preferably a single bond. Arylene groups may have substituents.

In formula A3, R is from the viewpoint of being able to further lower the glass transition temperature (Tg) of polymer X ³⁴ Preferably a hydrogen atom.

R in formula A3 ³⁴ The content of the structural unit which is a hydrogen atom is preferably 20 mass% or more with respect to the total mass of the structural unit a contained in the polymer X. R in formula A3 in structural unit A ³⁴ The content of the structural unit which is a hydrogen atom can be used according to ¹³ C-Nuclear magnetic resonance Spectrometry (NMR) measurement the intensity ratio of the peak intensities calculated by the conventional method was confirmed.

As a preferable embodiment of the formulae A1 to A3, paragraphs 0044 to 0058 of international publication No. 2018/179640 can be referred to.

In the formulae A1 to A3, the acid-decomposable group is preferably a group having a cyclic structure, more preferably a group having a tetrahydrofuran ring structure or a tetrahydropyran ring structure, further preferably a group having a tetrahydrofuran ring structure, and particularly preferably a tetrahydrofuranyl group, from the viewpoint of sensitivity.

The polymer X may have a single structural unit a or may have two or more structural units a.

The content of structural units A relative to the polymerThe total mass of X is preferably 10 to 70% by mass, more preferably 15 to 50% by mass, and particularly preferably 20 to 40% by mass. By the content of the structural unit a being within the above range, the resolution is further improved. When the polymer X contains two or more structural units a, the content of the structural units a described above represents the total content of the two or more structural units a. The content of the structural unit A can be used according to ¹³ The C-NMR measurement was confirmed by the intensity ratio of the peak intensities calculated by a conventional method.

Structural units having acid groups

The polymer X may have a structural unit (hereinafter, also referred to as "structural unit B") having an acid group.

The structural unit B is a structural unit having an acid group not protected by an acid-decomposable group, that is, an acid group not having a protecting group. By having the structural unit B in the polymer X, sensitivity at the time of pattern formation becomes good. Further, since the developer is easily dissolved in an alkaline developer in a development step after exposure, the development time can be shortened.

The acid group in the structural unit B means a proton dissociable group having a pKa of 12 or less. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, more preferably 6 or less. Further, the pKa of the acid group is preferably-5 or more.

Examples of the acid group include a carboxyl group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonylimide group. The acid group is preferably a carboxyl group or a phenolic hydroxyl group, more preferably a carboxyl group.

The polymer X may have a single structural unit B or may have two or more structural units B.

The content of the structural unit B is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass relative to the total mass of the polymer X. By the content of the structural unit B being within the above range, resolution becomes better. When the polymer X has two or more structural units B, the content of the structural units B described above represents the total content of the two or more structural units B. The content of structural unit B canAccording to the utilization ¹³ The C-NMR measurement was confirmed by the intensity ratio of the peak intensities calculated by a conventional method.

Other structural units

The polymer X preferably has other structural units (hereinafter, sometimes referred to as "structural unit C") than the structural units a and B described above. By adjusting at least one of the kind and the content of the structural unit C, various characteristics of the polymer X can be adjusted. By having the structural unit C in the polymer X, the glass transition temperature, acid value and hydrophilicity and hydrophobicity of the polymer X can be easily adjusted.

Examples of the monomer forming the structural unit C include styrenes, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, aryl (meth) acrylates, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated dicarboxylic anhydrides.

From the viewpoint of adhesion to a substrate, the monomer forming the structural unit C is preferably an alkyl (meth) acrylate, more preferably an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

Examples of the structural unit C include structural units derived from styrene, α -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, or ethylene glycol monoacetoacetate mono (meth) acrylate. The structural unit C may be a structural unit derived from a compound described in paragraphs 0021 to 0024 of Japanese unexamined patent publication No. 2004-264623.

From the viewpoint of resolution, the structural unit C preferably contains a structural unit having a basic group. Examples of the basic group include a group having a nitrogen atom. Examples of the group having a nitrogen atom include an aliphatic amino group, an aromatic amino group, and a nitrogen-containing heteroaromatic group. The basic group is preferably an aliphatic amino group.

The aliphatic amino group may be any of a primary amino group, a secondary amino group and a tertiary amino group, but from the viewpoint of resolution, a secondary amino group or a tertiary amino group is preferable.

As the monomer forming the structural unit having a basic group, examples thereof include 1,2, 6-pentamethyl-4-piperidine methacrylate, 2- (dimethylamino) ethyl methacrylate, 2, 6-tetramethyl-4-piperidine acrylate, 2, 6-tetramethyl-4-piperidine methacrylate, 2, 6-tetramethyl-4-piperidine acrylate 2- (diethylamino) ethyl methacrylate, 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate N- (3-diethylamino) propyl methacrylate, N- (3-diethylamino) propyl acrylate, 2- (diisopropylamino) ethyl methacrylate, 2-morpholinoethyl acrylate, N- [3- (dimethylamino) propyl ] acrylamide, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole and 1-vinyl-1, 2, 4-triazole. Among the above, 1,2, 6-pentamethyl-4-piperidyl methacrylate is preferred.

Further, as the structural unit C, a structural unit having an aromatic ring or a structural unit having an aliphatic ring skeleton is preferable from the viewpoint of improving electrical characteristics. Examples of the monomer forming these structural units include styrene, α -methylstyrene, dicyclopentanyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate. Among the above, cyclohexyl (meth) acrylate is preferable.

The polymer X may have a single structural unit C or may have two or more structural units C.

The content of the structural unit C is preferably 90 mass% or less, more preferably 85 mass% or less, and particularly preferably 80 mass% or less, relative to the total mass of the polymer X. The content of the structural unit C is preferably 10 mass% or more, more preferably 20 mass% or more, relative to the total mass of the polymer X. The content of the structural unit C in the above range further improves resolution and adhesion to the substrate. When the polymer X has two or more structural units C, the content of the structural units C described above represents the total content of the two or more structural units C. The content of the structural unit C can be used according to ¹³ The C-NMR measurement was confirmed by the intensity ratio of the peak intensities calculated by a conventional method.

Preferred examples of the polymer X are shown below. However, the polymer X is not limited to the following examples. In order to obtain preferable physical properties, the ratio of each structural unit and the weight average molecular weight in the polymer X shown below may be appropriately selected.

[ chemical formula 16]

Glass transition temperature-

The glass transition temperature (Tg) of the polymer X is preferably 90℃or lower, more preferably 20℃to 60℃and particularly preferably 30℃to 50 ℃. When the positive photosensitive resin layer is formed using a transfer material described later, the transferability of the positive photosensitive resin layer can be improved by the glass transition temperature of the polymer X falling within the above range.

As a method for adjusting Tg of the polymer X within the above range, for example, a method using FOX formula can be cited. According to the FOX formula, for example, the Tg of the target polymer X can be adjusted according to the Tg of the homopolymer of each structural unit and the mass fraction of each structural unit in the target polymer X.

Hereinafter, a copolymer having a first structural unit and a second structural unit will be described as an example of the FOX formula.

When the glass transition temperature of the homopolymer of the first structural unit is Tgl, the mass fraction of the first structural unit in the copolymer is W1, the glass transition temperature of the homopolymer of the second structural unit is Tg2, and the mass fraction of the second structural unit in the copolymer is W2, the glass transition temperature Tg0 (unit: K) of the copolymer having the first structural unit and the second structural unit can be estimated according to the following formula.

FOX formula: 1/Tg 0= (W1/Tgl) + (W2/Tg 2)

The Tg of the polymer can also be adjusted by adjusting the weight average molecular weight of the polymer.

Acid number-

From the viewpoint of resolution, the acid value of the polymer X is preferably 0mgKOH/g to 50mgKOH/g, more preferably 0mgKOH/g to 20mgKOH/g, particularly preferably 0mgKOH/g to 10mgKOH/g.

The acid number of the polymer represents the mass of potassium hydroxide required to neutralize the acidic component in every 1g of the polymer. Specific measurement methods are described below. First, a measurement sample is dissolved in a mixed solvent containing tetrahydrofuran and water (volume ratio: tetrahydrofuran/water=9/1). The resulting solution was subjected to neutralization titration with a 0.1mol/L aqueous sodium hydroxide solution AT 25℃using a potential difference titration apparatus (for example, trade name: AT-510,KYOTO ELECTRONICS MANUFACTURING CO, manufactured by LTD.). The acid value was calculated by the following equation with the inflection point of the titration pH curve as the titration end point.

A＝56.11×Vs×0.1×f/w

A: acid value (mgKOH/g)

Vs: the amount of 0.1mol/L aqueous sodium hydroxide solution (mL) required for titration

f: titration amount of 0.1mol/L sodium hydroxide aqueous solution

w: the mass (g) of the sample was measured (solid content conversion)

Weight average molecular weight-

The weight average molecular weight (Mw) of the polymer X is preferably 60,000 or less in terms of polystyrene. When the positive photosensitive resin layer is formed using a transfer material described later, the positive photosensitive resin layer can be transferred at a low temperature (for example, 130 ℃ or lower) by the weight average molecular weight of the polymer X being 60,000 or lower.

The weight average molecular weight of the polymer X is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.

The ratio (dispersity) of the number average molecular weight to the weight average molecular weight of the polymer X is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

The weight average molecular weight of the polymer X was measured by GPC (gel permeation chromatography). As the measuring device, various commercially available devices can be used. Hereinafter, a method for measuring the weight average molecular weight of the polymer X by GPC will be specifically described.

As the measurement device, HLC (registered trademark) -8220GPC (manufactured by TOSOH CORPORATION) was used.

As the column, a column in which 1 column was connected in series to TSKgel (registered trademark) Super HZM-M (manufactured by 4.6 mmID. Times. 15cm,TOSOH CORPORATION), super HZ4000 (manufactured by 4.6 mmID. Times. 15cm,TOSOH CORPORATION), super HZ3000 (manufactured by 4.6 mmID. Times. 15cm,TOSOH CORPORATION), and Super HZ2000 (manufactured by 4.6 mmID. Times. 15cm,TOSOH CORPORATION) was used.

As eluent THF (tetrahydrofuran) was used.

The measurement conditions were set to 0.2 mass% for the sample concentration, 0.35mL/min for the flow rate, 10. Mu.L for the sample injection amount, and 40℃for the measurement temperature.

As the detector, a differential Refractive Index (RI) detector is used.

The calibration curve was prepared using a "standard sample TSK standard, polystyrene" manufactured by TOSOH CORPORATION: any of the 7 samples "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500" and "A-1000" were prepared.

Content-

From the viewpoint of high resolution, the content of the polymer X is preferably 50 to 99.9 mass%, more preferably 70 to 98 mass%, relative to the total mass of the positive photosensitive resin layer.

Manufacturing method-

The method for producing the polymer X is not limited, and a known method can be used. For example, the polymer X can be produced by polymerizing a monomer for forming the structural unit a, and if necessary, a monomer for forming the structural unit B and a monomer for forming the structural unit C in an organic solvent using a polymerization initiator. The polymer X can also be produced by a so-called polymer reaction.

Other polymers

When the positive photosensitive resin layer includes a polymer having a structural unit having an acid group protected by an acid-decomposable group, the positive photosensitive resin layer may include a polymer not having a structural unit having an acid group protected by an acid-decomposable group (hereinafter, sometimes referred to as "other polymer") in addition to a polymer having a structural unit having an acid group protected by an acid-decomposable group.

Examples of the other polymer include polyhydroxystyrene. Examples of commercial products of polyhydroxystyrene include SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA P and SMA 3840F, TOAGOSEI C0. manufactured by Sartomer Company, inc., ARUFON UC-3000 manufactured by LTD. ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920 and ARUFON UC-3080 manufactured by BASF corporation and Joncryl 690, joncryl 678, joncryl 67 and Joncryl 586 manufactured by BASF corporation.

The positive photosensitive resin layer may contain one kind of other polymer alone or two or more kinds of other polymers.

When the positive photosensitive resin layer contains another polymer, the content of the other polymer is preferably 50 mass% or less, more preferably 30 mass% or less, and particularly preferably 20 mass% or less, relative to the total mass of the polymer components.

In the present invention, the "polymer component" refers to a general term for all polymers contained in the positive photosensitive resin layer. For example, when the positive photosensitive resin layer contains the polymer X and other polymers, the polymer X and other polymers are collectively referred to as "polymer components". Further, the compound corresponding to the crosslinking agent, dispersant and surfactant described later is not included in the polymer component even if it is a polymer compound.

The content of the polymer component is preferably 50 to 99.9 mass%, more preferably 70 to 98 mass%, based on the total mass of the positive photosensitive resin layer.

Alkali-soluble resin (Positive type)

The positive photosensitive resin layer preferably contains an alkali-soluble resin, more preferably contains an alkali-soluble resin and a quinone diazide compound, and particularly preferably contains a resin having a structural unit having a phenolic hydroxyl group and a quinone diazide compound.

Examples of the alkali-soluble resin include resins having a hydroxyl group, a carboxyl group, or a sulfonic acid group in the main chain or a side chain. Examples of the alkali-soluble resin include polyamide resins, polyhydroxystyrenes, polyhydroxystyrene derivatives, styrene-maleic anhydride copolymers, polyvinyl hydroxybenzoates, carboxyl group-containing (meth) acrylic resins, and novolak resins. Preferable alkali-soluble resins include, for example, polycondensates of m-/p-cresol and formaldehyde, and polycondensates of phenol, cresol and formaldehyde.

The alkali-soluble resin may have a phenolic hydroxyl group (-Ar-OH) and a carboxyl group (-CO) ₂ H) Sulfonic acid group (-SO) ₃ H) Phosphate group (-OPO) ₃ H) Sulfonamide (-SO) ₂ NH-R) or substituted sulfonamide acid groups (e.g., reactive imide groups, -SO) ₂ NHCOR、-SO ₂ NHSO ₂ R and-CONHSO ₂ R). Here, ar represents a 2-valent aryl group which may have a substituent, and R represents a hydrocarbon group which may have a substituent.

The novolak resin is obtained, for example, by condensing a phenolic compound with an aldehyde compound in the presence of an acid catalyst. Examples of the phenolic compound include o-, m-or p-cresol, 2,5-, 3, 5-or 3, 4-xylenol (xylenol), 2,3, 5-trimethylphenol, 2-t-butyl-5-methylphenol and t-butylhydroquinone. Examples of the aldehyde compound include aliphatic aldehydes (for example, formaldehyde, acetaldehyde, and glyoxal (glyoxyl)) and aromatic aldehydes (for example, benzaldehyde and Liu Quan (salicylaldehyde)). Examples of the acid catalyst include inorganic acids (e.g., hydrochloric acid, sulfuric acid, and phosphoric acid), organic acids (e.g., oxalic acid, acetic acid, and p-toluenesulfonic acid), and divalent metal salts (e.g., zinc acetate). The condensation reaction can be carried out according to conventional methods. The condensation reaction is carried out, for example, at a temperature in the range of 60 to 120℃for 2 to 30 hours. The condensation reaction may be carried out in a suitable solvent.

Among them, as the alkali-soluble resin, a resin having a structural unit having a phenolic hydroxyl group, such as a novolak resin, is preferable.

From the viewpoint of pattern formability, the weight average molecular weight of the alkali-soluble resin is preferably 5.0X10 ² ～2.0×10 ⁵ . The number average molecular weight of the alkali-soluble resin is preferably 2.0X10 from the viewpoint of pattern formability ² ～1.0×10 ⁵ 。

For example, a polycondensate of phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as a substituent, such as a polycondensate of tert-butylphenol and formaldehyde and a polycondensate of octylphenol and formaldehyde described in U.S. Pat. No. 4123279, may be used together. A condensate of phenol and formaldehyde having an alkyl group having 3 to 8 carbon atoms as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin described in U.S. Pat. No. 4123279, may be used in combination.

The positive photosensitive resin layer may contain one kind or two or more kinds of alkali-soluble resins alone.

The content of the alkali-soluble resin is preferably 30 to 99.9 mass%, more preferably 40 to 99.5 mass%, and particularly preferably 70 to 99 mass% relative to the total mass of the positive photosensitive resin layer.

Photoacid generator

The positive photosensitive resin layer preferably contains a photoacid generator as a photosensitive compound. Photoacid generators are compounds that are capable of generating an acid upon irradiation with activating light (e.g., ultraviolet, extreme ultraviolet, X-rays, and electron beams).

The photoacid generator is preferably a compound that generates an acid by inducing an activating light having a wavelength of 300nm or more, preferably 300nm to 450 nm. The photoacid generator that does not directly induce an activating light having a wavelength of 300nm or more can be preferably used in combination with a sensitizer as long as it is a compound that generates an acid by being used in combination with a sensitizer and inducing an activating light having a wavelength of 300nm or more.

The photoacid generator is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and particularly preferably a photoacid generator that generates an acid having a pKa of 2 or less. The lower limit of the pKa of the acid derived from the photoacid generator is not limited. The pKa of the acid derived from the photoacid generator is, for example, preferably-10.0 or more.

Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.

Examples of the ionic photoacid generator include onium salt compounds. Examples of the onium salt compound include a diaryliodonium salt compound, a triarylsulfonium salt compound, and a quaternary ammonium salt compound. The ionic photoacid generator is preferably an onium salt compound, and particularly preferably at least one of a triarylsulfonium salt compound and a diaryliodonium salt compound.

As the ionic photoacid generator, the ionic photoacid generators described in paragraphs 0114 to 0133 of jp 2014-85643 a can also be preferably used.

Examples of the nonionic photoacid generator include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. The nonionic photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion to a substrate.

Specific examples of the trichloromethyl-s-triazine compound, the diazomethane compound and the imide sulfonate compound include those described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494.

As the oxime sulfonate compound, those described in paragraphs 0084 to 0088 of International publication No. 2018/179640 can be preferably used.

From the viewpoints of sensitivity and resolution, the photoacid generator is preferably at least one compound selected from the group consisting of an onium salt compound and an oxime sulfonate compound, and more preferably an oxime sulfonate compound.

Preferable examples of the photoacid generator include photoacid generators having the following structures.

[ chemical formula 17]

Examples of the photoacid generator having absorption at a wavelength of 405nm include ADEKA ARKLS (registered trademark) SP-601 (manufactured by ADEKA CORPORATION).

From the viewpoints of heat resistance and dimensional stability, the positive photosensitive resin layer preferably contains a quinone diazide compound as an acid generator (preferably a photoacid generator).

The quinone diazide compound can be synthesized, for example, by subjecting a compound having a phenolic hydroxyl group and quinone diazide sulfonyl halide to a condensation reaction in the presence of a dehalogenation agent.

Examples of the quinone diazide compound include 1, 2-benzoquinone diazide-4-sulfonate, 1, 2-naphthoquinone diazide-5-sulfonate, 1, 2-naphthoquinone diazide-6-sulfonate, 2, 1-naphthoquinone diazide-4-sulfonate, 2, 1-naphthoquinone diazide-5-sulfonate, 2, 1-naphthoquinone diazide-6-sulfonate, sulfonate of other quinone diazide derivatives, 1, 2-benzoquinone diazide-4-sulfonyl chloride, 1, 2-naphthoquinone diazide-5-sulfonyl chloride, l, 2-naphthoquinone diazide-6-sulfonyl chloride, 2, 1-naphthoquinone diazide-4-sulfonyl chloride, 2, 1-naphthoquinone diazide-5-sulfonyl chloride and 2, 1-naphthoquinone diazide-6-sulfonyl chloride.

The positive photosensitive resin layer may contain one photoacid generator alone or two or more photoacid generators.

The content of the photoacid generator is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, relative to the total mass of the positive photosensitive resin layer, from the viewpoints of sensitivity and resolution.

Other ingredients

The photosensitive resin layer may have a component other than the above.

Surfactant-containing compositions

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

Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants, and nonionic surfactants are preferable.

Examples of the surfactant include surfactants described in paragraphs 0017 and 0060 to 0071 of JP-A-2009-237362, respectively, in JP-A-4502784.

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

Commercial products of fluorine-based surfactants, examples of the materials include MEGAFACE (trade name) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP.MFS-330, MFS-578, MFS-579, MFS-586, MFS-587, R-41-LM, R-01, R-40-LM, RS-43, TF-1956, RS-90, R-94 RS-72-K, DS-21 (manufactured by DIC Corporation, supra), fluorad (trade name) FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited, supra), surflon (trade name) S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc., supra), polyFox (trade name) PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc, supra), ftergent 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 212M, 250, 209F, 222F, 208G, 710LA, 710FS, 730LM, 650AC, 681, 683 (manufactured by neos corporation above), and the like.

The fluorine-based surfactant may preferably be an acrylic compound having a molecular structure including a functional group containing a fluorine atom, and the fluorine atom may be volatilized by cutting a functional group portion containing a fluorine atom when heat is applied. Examples of such a fluorine-based surfactant include the MEGAFACE (trade name) DS series (chemical industry daily report (2016, 2, 22 days), daily-use industry news (2016, 2, 23 days)) manufactured by DIC Corporation, and for example, MEGAFACE (trade name) DS-21.

The fluorine-based surfactant is preferably a polymer of a vinyl ether compound containing a fluorine atom and a hydrophilic vinyl ether compound, the vinyl ether compound containing a fluorinated alkyl group or a fluorinated alkylene ether group.

Fluorine-based surfactants can also use capped polymers. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound containing a structural unit derived from a (meth) acrylate compound having a fluorine atom and a structural unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups).

The fluorine-based surfactant may be a fluoropolymer having an ethylenically unsaturated group in a side chain. Examples of the "MEGAFACE" include MEGAFACE (trade name) RS-101, RS-102, RS-718K, RS-72-K (manufactured by DIC Corporation).

Examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerin propoxylate, glycerin 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 (trade name) L10, L31, L61, L62, 10R5, 17R2, 25R2 (trade name) manufactured by Chemical F company, etc.), tetronic (trade name) 304, 701, 704, 901, 904, 150R1 (trade name) manufactured by BASF company, solsponse (trade name) 20000 (manufactured by Lubrizol Japan limit. Above), NCW-101, NCW-1001, NCW-1002 (trade name) manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN (trade name) D-6112, D-5712-W, D (trade name) manufactured by Chemical F company, etc., tetronic (trade name) 304, 701, 704, 901, 904, 150R1 (trade name) manufactured by BASF (trade name) 20000 (trade name) manufactured by Lubrizol Japan Limid. Manufactured by BASF, etc., and desk (trade name) 400, ln..

In recent years, since compounds having a linear perfluoroalkyl group having 7 or more carbon atoms have serious concerns about environmental suitability, surfactants using alternative materials of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) are preferred.

Examples of the silicone surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminal ends.

Specific examples of silicone surfactants include DOWSIL (trade name) 8032ADDITIVE, toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH8400 (manufactured by Ltd. Above Dow Corning Toray 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 Sin-Etsu Chemical Co., ltd., above), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by KK.above Momentive Performance Materials c), KF-307, X-22-4515, KF-6004, KF-6001, and BYK.BY.BY.330.

The photosensitive resin layer may contain one kind of surfactant alone or two or more kinds thereof.

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

Additive-

The photosensitive resin layer may contain a known additive as required in addition to the above components.

Examples of the additive include a polymerization inhibitor, a sensitizer, a plasticizer, an alkoxysilane compound, and a solvent. The photosensitive resin layer may contain one kind of each additive alone or two or more kinds thereof.

Examples of the additives include metal oxide particles, antioxidants, dispersants, acid-proliferation agents, development accelerators, conductive fibers, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic anti-settling agents. A preferred embodiment of these additives is described in paragraphs 0165 to 0184 of japanese unexamined patent publication No. 2014-85643, respectively, which are incorporated herein by reference.

The photosensitive resin layer may contain a polymerization inhibitor. As the polymerization inhibitor, a radical polymerization inhibitor is preferable.

Examples of the polymerization inhibitor include thermal polymerization inhibitors described in paragraph 0018 of Japanese patent No. 4502784. Among them, phenothiazine, phenoxazine or 4-methoxyphenol is preferable. Examples of the other polymerization inhibitor include naphthylamine, cuprous chloride, N-nitrosophenyl hydroxylamine aluminum salt, and diphenylnitrosoamine. In order not to impair the sensitivity of the photosensitive resin composition, an N-nitrosophenyl hydroxylamine aluminum salt is preferably used as a polymerization inhibitor.

The content of the polymerization inhibitor is preferably 0.01 to 3 mass%, more preferably 0.05 to 1 mass%, relative to the total mass of the photosensitive resin layer. The content is preferably 0.01 mass% or more from the viewpoint of imparting storage stability to the photosensitive resin composition. On the other hand, from the viewpoint of maintaining sensitivity, the content is preferably 3 mass% or less.

The photosensitive resin layer may contain a sensitizer.

The sensitizer is not particularly limited, and known sensitizers, dyes and pigments can be used. Examples of the sensitizer include a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, a coumarin compound, a xanthone (xanthone) compound, a thioxanthone (thioxanthone) compound, an acridone compound, an oxazole compound, a benzoxazole compound, a thiazole compound, a benzothiazole compound, a triazole compound (for example, 1,2, 4-triazole), a stilbene compound, a triazine compound, a thiophene compound, a naphthalimide compound, a triarylamine compound, and an aminoacridine compound.

The photosensitive resin layer may contain one kind of sensitizer alone or two or more kinds thereof.

When the photosensitive resin layer contains a sensitizer, the content of the sensitizer can be appropriately selected according to the purpose, but from the viewpoint of improving the sensitivity to a light source and improving the curing speed by balancing the polymerization speed and chain transfer, it is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% with respect to the total mass of the photosensitive resin layer.

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

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

The photosensitive resin layer (preferably, a positive photosensitive resin layer) may contain an alkoxysilane compound.

Examples of alkoxysilane compounds include gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trialkoxysilane, gamma-glycidoxypropyl alkyl dialkoxysilane, gamma-methacryloxypropyl trialkoxysilane, gamma-methacryloxypropyl alkyl dialkoxysilane, gamma-chloropropyl trialkoxysilane, gamma-mercaptopropyl trialkoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl trialkoxysilane and vinyl trialkoxysilane.

Among the above, the alkoxysilane compound is preferably a trialkoxysilane compound, more preferably γ -glycidoxypropyl trialkoxysilane or γ -methacryloxypropyl trialkoxysilane, further preferably γ -glycidoxypropyl trialkoxysilane, and particularly preferably 3-glycidoxypropyl trimethoxysilane.

The photosensitive resin layer may contain one alkoxysilane compound alone or two or more alkoxysilane compounds.

The content of the alkoxysilane compound is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and particularly preferably 1.0 to 30% by mass relative to the total mass of the photosensitive resin layer, from the viewpoints of adhesion to a substrate and etching resistance.

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

Impurity etc

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

Specific examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among them, the halide ion, sodium ion and potassium ion are easily mixed in the form of impurities, and therefore, the following contents are preferable.

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

The method of setting the impurity in the above range includes selecting a raw material of the composition having a small impurity content, preventing the impurity from being mixed in and cleaning and removing the impurity in the production of the photosensitive resin layer. In this way, the impurity amount can be set within the above range.

The impurities can be quantified by a known method such as ICP (Inductively Coupled Plasma: inductively coupled plasma) emission spectrometry, atomic absorption spectrometry, or ion chromatography.

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

The lower limit may be 10ppb or more or 100ppb or more relative to the total mass of the photosensitive resin layer on a mass basis. These compounds can be suppressed in content by the same method as the impurities of the above metals. Further, the quantitative determination can be performed by a known measurement method.

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

Residual monomer

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

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

From the viewpoints of patterning properties and reliability, the residual monomer of each structural unit of the alkali-soluble resin is preferably 3,000 mass ppm or less, more preferably 600 mass ppm or less, and still more preferably 100 mass ppm or less, relative to the total mass of the photosensitive resin layer. The lower limit is not particularly limited, but is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more.

The residual monomer amount of the monomer in synthesizing the alkali-soluble resin by the polymer reaction is also preferably set within the above range. For example, when synthesizing an alkali-soluble resin by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably set within the above range.

The amount of the residual monomer can be measured by a known method such as liquid chromatography or gas chromatography.

Physical Properties and the like

The layer thickness of the photosensitive resin layer is preferably 0.1 μm to 300. Mu.m, more preferably 0.2 μm to 100. Mu.m, still more preferably 0.5 μm to 50. Mu.m, still more preferably 0.5 μm to 15. Mu.m, particularly preferably 0.5 μm to 10. Mu.m, and most preferably 0.5 μm to 8. Mu.m. This improves the developability of the photosensitive resin layer, and can improve resolution.

Further, the layer thickness (thickness) of the photosensitive resin layer is preferably 10 μm or less, more preferably 5.0 μm or less, further preferably 0.5 μm to 4.0 μm, and particularly preferably 0.5 μm to 3.0 μm from the viewpoint of further exhibiting the resolution and the effect in the present invention.

The layer thickness of each layer included in the photosensitive transfer material was measured by observing a cross section of the photosensitive transfer material in a direction perpendicular to the main surface by a scanning electron microscope (SEM: scanning Electron Microscope), measuring the thickness of each layer at 10 points or more from the obtained observation image, and calculating an average value thereof.

Further, from the viewpoint of further excellent adhesion, the light transmittance of the photosensitive resin layer at 365nm is preferably 10% or more, more preferably 30% or more, and still more preferably 50% or more. The upper limit is not particularly limited, but is preferably 99.9% or less.

Forming method

The method for forming the photosensitive resin layer is not particularly limited as long as the layer containing the above components can be formed.

As a method for forming the photosensitive resin layer, for example, when the photosensitive resin layer is a negative type photosensitive resin layer, there is a method in which a photosensitive resin composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, a solvent, and the like is prepared, the photosensitive resin composition is applied to the surface of a pseudo support or the like, and a coating film of the photosensitive resin composition is dried.

Examples of the photosensitive resin composition used for forming the photosensitive resin layer include a composition containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, any of the above components, and a solvent.

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

Solvent-

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

Examples of the solvent include alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (methanol, ethanol, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbon solvents (toluene, etc.), aprotic polar solvents (N, N-dimethylformamide, etc.), cyclic ether solvents (tetrahydrofuran, etc.), ester solvents, amide solvents, lactone solvents, and mixed solvents containing two or more of these solvents.

When the photosensitive transfer material including the dummy support, the buffer layer, the intermediate layer, the photosensitive resin layer, and the protective film is produced, the photosensitive resin composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. Among these, a mixed solvent containing at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent is more preferable, and a mixed solvent containing at least three selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent and a cyclic ether solvent is further preferable.

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

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

As the solvent, a solvent described in paragraphs 0092 to 0094 of international publication No. 2018/179640 and a solvent described in paragraph 0014 of japanese patent application laid-open No. 2018-177889, which are incorporated herein by reference, can be used.

The photosensitive resin composition may contain one kind of solvent alone or two or more kinds thereof.

The content of the solvent in coating the photosensitive resin composition is preferably 50 to 1 part by mass, 900 parts by mass, and more preferably 100 to 900 parts by mass, based on 100 parts by mass of the total solid content in the photosensitive resin composition.

The method for producing the photosensitive resin composition is not particularly limited, and examples thereof include a method in which a solution in which each component is dissolved in the above-mentioned solvent is prepared in advance, and the obtained solution is mixed at a predetermined ratio to produce the photosensitive resin composition.

From the viewpoint of particle removability, the photosensitive resin composition is preferably filtered using a filter before forming the photosensitive resin layer, more preferably filtered using a filter having a pore size of 0.2 μm to 10 μm, even more preferably filtered using a filter having a pore size of 0.2 μm to 7 μm, and particularly preferably filtered using a filter having a pore size of 0.2 μm to 5 μm.

The material and shape of the filter are not particularly limited, and known materials and shapes can be used.

The filtration is preferably performed 1 or more times, and more preferably performed several times.

The method of applying the photosensitive resin composition is not particularly limited, and may be applied by a known method. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.

The photosensitive resin layer can be formed by applying a photosensitive resin composition to a protective film described later and drying the same.

In the photosensitive transfer material of the present invention, it is preferable that another layer is provided between the dummy support and the photosensitive resin layer from the viewpoints of resolution and releasability of the dummy support.

Examples of the other layer include an intermediate layer, a buffer layer, and a protective film.

Among them, the transfer layer is preferably provided with an intermediate layer, and more preferably with a buffer layer and an intermediate layer.

[ intermediate layer ]

When the photosensitive transfer material has a buffer layer described later between the dummy support and the photosensitive resin layer, it is preferable to have an intermediate layer between the buffer layer and the photosensitive resin layer. According to the intermediate layer, mixing of components at the time of forming a plurality of layers and at the time of storage can be suppressed.

The intermediate layer is preferably a water-soluble layer from the viewpoints of developability and suppression of mixing of components at the time of coating a plurality of layers and at the time of storage after coating. In the present invention, "water-soluble" means that the solubility of 100g of water at pH7.0 at a liquid temperature of 22℃is 0.1g or more.

Examples of the intermediate layer include an oxygen barrier layer having an oxygen barrier function described as a "separation layer" in JP-A-5-72724. By using the intermediate layer as the oxygen barrier layer, the sensitivity at the time of exposure is improved, and the time load of the exposure machine is reduced, as a result, the productivity is improved. The oxygen barrier layer used as the intermediate layer may be appropriately selected from known layers. The oxygen barrier layer used as the intermediate layer is preferably an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution (1 mass% aqueous solution of sodium carbonate at 22 ℃).

Further, the intermediate layer preferably contains an inorganic layered compound from the viewpoints of oxygen barrier property, resolution and pattern formation property.

Examples of the inorganic layered compound include mica compounds such as natural mica and synthetic mica, and particles having a thin plate-like shape, and the formula: 3MgO.4SiOH ₂ Talc, with mica, montmorillonite, saponite, hectorite, zirconium phosphate, etc. represented by O.

Examples of the mica compound include the formula: a (B, C) _2-5 D ₄ O ₁₀ (OH，F，O) ₂ Wherein A is any one of K, na and Ca, B and C are any one of Fe (II), fe (III) and Mn, al, mg, VOne, D is Si or Al. Mica groups such as natural mica and synthetic mica are shown.

Among the mica groups, natural mica may be muscovite, sodium mica, phlogopite, biotite, or lepidolite. As synthetic mica, fluorophlogopite KMg may be mentioned ₃ (AlSi ₃ O ₁₀ )F ₂ Potassium tetrasilicon mica KMg _2.5 Si ₄ O ₁₀ )F ₂ Equal non-swelling mica and Na tetrasilicium mica NaMg _2.5 (Si ₄ O ₁₀ )F ₂ Na or Li-carrying mica (Na, li) Mg ₂ Li(Si ₄ O ₁₀ )F ₂ Na or Li hectorite (Na, li) of montmorillonite type _1/8 Mg _2/5 Li _1/8 (Si ₄ O ₁₀ )F ₂ And swellable mica. In addition, synthetic montmorillonite (smeite) is also useful.

The shape of the inorganic lamellar compound is preferable from the viewpoint of controlling diffusion, and the smaller the thickness, the more preferable the planar size is as long as the smoothness of the coated surface or the transmittance of the activation light is not hindered. Therefore, the aspect ratio is preferably 20 or more, more preferably 100 or more, and particularly preferably 200 or more. The aspect ratio is a ratio of the long diameter to the thickness of the particles, and can be measured, for example, from a projection obtained from a microscopic photograph of the particles. The larger the aspect ratio, the greater the effect obtained.

The average long diameter of the particle size of the inorganic layered compound is preferably 0.3 μm to 20. Mu.m, more preferably 0.5 μm to 10. Mu.m, and particularly preferably 1 μm to 5. Mu.m. The average thickness of the particles is preferably 0.1 μm or less, more preferably 0.05 μm or less, and particularly preferably 0.01 μm or less. Specifically, for example, in the case of swellable synthetic mica as a representative compound, it is preferable that the thickness is about 1nm to 50nm and the surface size (long diameter) is about 1 μm to 20 μm.

The content of the inorganic layered compound is preferably 0.1 to 50% by mass, more preferably 1 to 20% by mass, relative to the total mass of the intermediate layer, from the viewpoints of oxygen barrier property, resolution and pattern formation.

The intermediate layer preferably comprises a resin. Examples of the resin contained in the intermediate layer include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, and polyamide resins, and copolymers thereof. The resin contained in the intermediate layer is preferably a water-soluble resin.

From the viewpoint of suppressing mixing of components between the plurality of layers, the resin contained in the intermediate layer is preferably a resin different from either the polymer a contained in the negative photosensitive resin layer or the thermoplastic resin (alkali-soluble resin) contained in the buffer layer.

Further, the intermediate layer preferably contains a water-soluble compound, more preferably contains a water-soluble resin, from the viewpoints of oxygen barrier property, developability, resolution and pattern formation property.

The water-soluble compound is not particularly limited, but is preferably at least one compound selected from the group consisting of water-soluble cellulose derivatives, polyols, oxide adducts of polyols, polyethers, phenol derivatives and amide compounds, more preferably at least one water-soluble resin selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl cellulose and hydroxypropyl methylcellulose, from the viewpoints of oxygen barrier property, developability, resolution and pattern formation.

Examples of the water-soluble resin include water-soluble cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide resins, (meth) acrylate resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof.

Among them, from the viewpoints of oxygen barrier property, development property, resolution and pattern formation property, the water-soluble resin preferably contains polyvinyl alcohol, more preferably contains polyvinyl alcohol and a water-soluble cellulose derivative, further preferably contains polyvinyl alcohol and hydroxypropyl cellulose, and particularly preferably contains polyvinyl alcohol, polyvinylpyrrolidone and hydroxypropyl cellulose.

The degree of hydrolysis of polyvinyl alcohol is not particularly limited, but is preferably 73mol% to 99mol% from the viewpoints of oxygen barrier property, developability, resolution and pattern formation property.

Further, from the viewpoints of oxygen barrier property, developability, resolution and pattern formation property, the polyvinyl alcohol preferably contains ethylene as a monomer unit.

The content of the polyvinyl alcohol is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and particularly preferably 50 to 75% by mass relative to the total mass of the intermediate layer, from the viewpoints of oxygen-blocking property, developability, defect-suppressing property, resolution, and sensitivity of the resulting resist pattern.

The water-soluble resin preferably contains a water-soluble cellulose derivative, more preferably contains a hydroxyalkyl cellulose compound, and particularly preferably contains hydroxypropyl cellulose, from the viewpoints of oxygen barrier property, developability, defect inhibition property, resolution, and sensitivity of the resulting resist pattern.

The content of the hydroxypropyl cellulose is preferably 0.005 to 20 mass%, more preferably 0.01 to 10 mass%, even more preferably 0.1 to 5 mass%, and particularly preferably 0.5 to 3 mass% with respect to the total mass of the intermediate layer, from the viewpoints of oxygen-blocking property, developability, defect-suppressing property, resolution, and sensitivity of the resulting resist pattern.

The water-soluble resin preferably contains polyvinylpyrrolidone from the viewpoints of oxygen barrier property, developability, defect suppression property, resolution, and sensitivity of the resulting resist pattern.

The content of polyvinylpyrrolidone is preferably 1 to 60% by mass, more preferably 10 to 50% by mass, even more preferably 20 to 45% by mass, and particularly preferably 25 to 40% by mass, relative to the total mass of the intermediate layer, from the viewpoints of oxygen-blocking property, developability, defect-suppressing property, resolution, and sensitivity of the resulting resist pattern.

The intermediate layer may contain a single resin or two or more resins.

The content of the water-soluble compound in the intermediate layer is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass, relative to the total mass of the intermediate layer, from the viewpoints of oxygen barrier property and suppression of mixing of components at the time of coating the multilayer and at the time of storage after coating.

And, the intermediate layer may contain additives as needed. Examples of the additive include surfactants.

The thickness of the intermediate layer is not limited. The average thickness of the intermediate layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. When the thickness of the intermediate layer is within the above range, the mixing of the components at the time of forming a plurality of layers and at the time of storage can be suppressed without deteriorating the oxygen barrier property, and the increase in the removal time of the intermediate layer at the time of development can be suppressed.

The method for forming the intermediate layer is not limited as long as it is a method capable of forming a layer containing the above-described components. Examples of the method for forming the intermediate layer include a method of coating the intermediate layer composition on the surface of the buffer layer or the photosensitive resin layer and then drying the coating film of the intermediate layer composition.

Examples of the intermediate layer composition include a composition containing a resin and optional additives. In order to adjust the viscosity of the intermediate layer composition to facilitate formation of the intermediate layer, the intermediate layer composition preferably contains a solvent. The solvent is not limited as long as it is a solvent capable of dissolving or dispersing the resin. The solvent is preferably at least one selected from the group consisting of water and water-miscible organic solvents, more preferably water or a mixed solvent of water and water-miscible organic solvents.

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

[ buffer layer ]

The photosensitive transfer material used in the present invention may have a buffer layer. The photosensitive transfer material preferably has a buffer layer between the dummy support and the photosensitive resin layer or the intermediate layer. This is because, since the photosensitive transfer material has the buffer layer between the dummy support and the photosensitive resin layer or the intermediate layer, the following property to the adherend is improved, and the mixing of bubbles between the adherend and the photosensitive transfer material is suppressed, and as a result, the adhesion between layers is improved.

The buffer layer preferably contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator.

As the alkali-soluble resin, the polymerizable compound, and the photopolymerization initiator used for the buffer layer, the alkali-soluble resin, the polymerizable compound, and the photopolymerization initiator used for the photosensitive resin layer can be preferably used.

Examples of the alkali-soluble resin include acrylic resins, polystyrene resins, styrene-acrylic copolymers, polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, polyester resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.

The alkali-soluble resin is preferably an acrylic resin from the viewpoints of developability and adhesion to the layer adjacent to the buffer layer. Here, the "acrylic resin" refers to a resin having at least one selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide.

In the acrylic resin, the ratio of the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is preferably 50 mass% or more relative to the total mass of the acrylic resin. In the acrylic resin, the ratio of the total content of the structural units derived from (meth) acrylic acid and the structural units derived from (meth) acrylic acid ester is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the total mass of the acrylic resin.

Also, the alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phosphonic acid group, and a carboxyl group is preferable.

From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60mgKOH/g or more, more preferably an acrylic resin containing a carboxyl group having an acid value of 60mgKOH/g or more. The upper limit of the acid value is not limited. The acid value of the alkali-soluble resin is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less.

The acrylic resin having an acid value of 60mgKOH/g or more and containing a carboxyl group is not limited, and can be appropriately selected from known resins. Examples of the carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more include carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more among the polymers described in paragraph 0025 of JP 2011-95716, carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more among the polymers described in paragraphs 0033 to 0052 of JP 2010-237589, and carboxyl group-containing acrylic resins having an acid value of 60mgKOH/g or more among the binder polymers described in paragraphs 0053 to 0068 of JP 2016-224162.

The content of the structural unit having a carboxyl group in the acrylic resin having a carboxyl group is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 12 to 30% by mass, based on the total mass of the acrylic resin having a carboxyl group.

The alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth) acrylic acid from the viewpoints of developability and adhesion to a layer adjacent to the buffer layer.

The alkali-soluble resin may have a reactive group. The reactive group may be, for example, a group capable of addition polymerization. Examples of the reactive group include an ethylenically unsaturated group, a polycondensable group (e.g., a hydroxyl group and a carboxyl group), and a polyaddition reactive group (e.g., an epoxy group and a (blocked) isocyanate group).

The alkali-soluble resin preferably has a weight average molecular weight (Mw) of 1,000 or more, more preferably 1 to 10 tens of thousands, particularly preferably 2 to 5 tens of thousands.

The buffer layer may contain a single alkali-soluble resin or two or more alkali-soluble resins.

The content ratio of the alkali-soluble resin is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, further preferably 40 to 80% by mass, and particularly preferably 50 to 70% by mass relative to the total mass of the buffer layer, from the viewpoints of developability and adhesion of the layer adjacent to the buffer layer.

The buffer layer preferably contains a dye (hereinafter, sometimes referred to as "dye B") having a maximum absorption wavelength of 450nm or more in the wavelength range of 400nm to 780nm at the time of color development and a maximum absorption wavelength that changes by an acid, a base, or a radical. The preferred embodiment of the dye B is the same as that of the dye N described above, except for the point described below.

From the viewpoints of visibility of the exposed portion, visibility and resolution of the non-exposed portion, the dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical, and more preferably a dye whose maximum absorption wavelength is changed by an acid.

From the viewpoints of visibility of an exposed portion, visibility and resolution of a non-exposed portion, the buffer layer preferably contains a dye whose maximum absorption wavelength is changed by an acid as a dye B and contains a compound that generates an acid by light described later.

The buffer layer may contain a single pigment B or two or more pigments B.

The content of the dye B is preferably 0.2 mass% or more, more preferably 0.2 mass% to 6 mass%, even more preferably 0.2 mass% to 5 mass%, and particularly preferably 0.25 mass% to 3.0 mass% relative to the total mass of the buffer layer, from the viewpoints of visibility of the exposed portion and visibility of the non-exposed portion.

The content ratio of the dye B herein refers to the content ratio of the dye when all the dye B contained in the buffer layer is in a color development state. Hereinafter, a method for quantifying the content ratio of the dye B will be described by taking a dye that develops color by a radical as an example. Two solutions were prepared in which pigment (0.001 g) and pigment (0.01 g) were dissolved in methyl ethyl ketone (100 mL). After IRGACURE OXE-01 (BASF corporation) was added as a photo radical polymerization initiator to each of the obtained solutions, a radical was generated by irradiation with 365nm light, and all the pigments were brought into a color-developed state. Next, the absorbance of each solution having a liquid temperature of 25 ℃ was measured using a spectrophotometer (UV 3100, shimadzu Corporation) under atmospheric conditions, and a calibration curve was prepared. Next, absorbance of the solution in which all the pigments were developed was measured by the same method as described above except that the buffer layer (0.1 g) was dissolved in methyl ethyl ketone instead of the pigments. The amount of the dye contained in the buffer layer was calculated from the absorbance of the obtained buffer layer-containing solution based on the calibration curve.

The buffer layer may contain a compound that generates an acid, a base, or a radical by light (hereinafter, sometimes referred to as "compound C"). The compound C is preferably a compound which generates an acid, a base or a radical upon exposure to activating light (for example, ultraviolet rays and visible rays). Examples of the compound C include a known photoacid generator, a photoacid generator, and a photoradical polymerization initiator (photoradical generator). Compound C is preferably a photoacid generator.

From the viewpoint of resolution, the buffer layer preferably contains a photoacid generator. The photo-acid generator may be a photo-cation polymerization initiator which may be contained in the photosensitive resin layer, and the same is preferable except for the point described below.

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

The photoacid generator is also preferably one having the following structure.

[ chemical formula 18]

The buffer layer may comprise a photobase generator. Examples of the photobase generator include 2-nitrobenzyl cyclohexyl carbamate, triphenylmethanol, O-carbamoyl hydroxyamide, O-carbamoyl oxime, [ [ (2, 6-dinitrobenzyl) oxy ] carbonyl ] cyclohexylamine, bis [ [ (2-nitrobenzyl) oxy ] carbonyl ] hexane-1, 6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N-mono (2-nitrobenzyloxycarbonyl) pyrrolidine, hexamine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2, 6-dimethyl-3, 5-diacetyl-4- (2-nitrophenyl) -1, 4-dihydropyridine, 2, 6-dimethyl-3, 5-diacetyl-4- (2, 4-dinitrophenyl) -1, 4-dihydropyridine.

The buffer layer may include a photo radical polymerization initiator. The photo radical polymerization initiator may be, for example, a photo radical polymerization initiator that may be contained in the photosensitive resin layer, and the same is preferable.

The buffer layer may contain a single one or two or more compounds C.

The content ratio of the compound C is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass% with respect to the total mass of the buffer layer, from the viewpoints of visibility of the exposed portion, visibility of the non-exposed portion, and resolution.

The buffer layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to the layer adjacent to the buffer layer, and developability.

The molecular weight of the plasticizer (molecular weight of the oligomer or polymer means weight average molecular weight (Mw). Hereinafter, the same applies in this paragraph) is preferably smaller than that of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.

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

From the viewpoints of resolution and storage stability, the plasticizer preferably contains a (meth) acrylate compound. From the viewpoints of compatibility, resolution, and adhesion to a layer adjacent to the buffer layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.

Examples of the (meth) acrylate compound used as the plasticizer include the (meth) acrylate compounds described in the above-mentioned ethylenically unsaturated compounds. When the buffer layer and the photosensitive resin layer are disposed in direct contact in the photosensitive transfer material, the buffer layer and the photosensitive resin layer preferably each contain the same (meth) acrylate compound. This is because the buffer layer and the photosensitive resin layer each contain the same (meth) acrylate compound, so that the diffusion of components between layers is suppressed and the storage stability is improved.

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

In one embodiment, the (meth) acrylate compound used as the plasticizer is preferably a (meth) acrylate compound having 2 or more (meth) acryloyl groups in one molecule from the viewpoints of resolution, adhesion to a layer adjacent to the buffer layer, and developability.

In a certain embodiment, the (meth) acrylate compound used as the plasticizer is preferably a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound.

The buffer layer may contain a single plasticizer or two or more plasticizers.

The content ratio of the plasticizer is preferably 1 to 70% by mass, more preferably 10 to 60% by mass, and particularly preferably 20 to 50% by mass, relative to the total mass of the buffer layer, from the viewpoints of resolution, adhesion to the layer adjacent to the buffer layer, and developability.

From the viewpoint of uniformity of thickness, the buffer layer preferably contains a surfactant. The surfactant may be, for example, a surfactant that may be contained in the photosensitive resin layer, and the same preferable embodiment is also adopted.

The buffer layer may contain a single kind or two or more kinds of surfactants.

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

The buffer layer may comprise a sensitizer. Examples of the sensitizer include those that can be contained in the negative photosensitive resin layer.

The buffer layer may comprise a single sensitizer or two or more sensitizers.

The content ratio of the sensitizer is preferably 0.01 to 5 mass%, more preferably 0.05 to 1 mass% relative to the total mass of the buffer layer, from the viewpoint of improving the sensitivity to the light source, the visibility of the exposed portion, and the visibility of the non-exposed portion.

The buffer layer may contain known additives as required in addition to the above components.

The buffer layer is described in paragraphs 0189 to 0193 of Japanese patent application laid-open No. 2014-85643. The contents of the above publications are incorporated by reference into the present specification.

The thickness of the buffer layer is not limited. The average thickness of the buffer layer is preferably 1 μm or more, more preferably 2 μm or more, from the viewpoint of adhesion to the layer adjacent to the buffer layer. The upper limit of the average thickness of the buffer layer is not limited. The average thickness of the buffer layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less from the viewpoints of developability and resolution.

The method for forming the buffer layer is not limited as long as the layer containing the above components can be formed. Examples of the method for forming the buffer layer include a method of applying a buffer layer forming composition to the surface of a dummy support and drying a coating film of the buffer layer forming composition.

Examples of the composition for forming a buffer layer include compositions containing the above components. In order to adjust the viscosity of the composition for forming a buffer layer to facilitate formation of a buffer layer, the composition for forming a buffer layer preferably contains a solvent.

The solvent contained in the composition for forming a buffer layer is not limited as long as it is a solvent capable of dissolving or dispersing the components contained in the buffer layer. The solvent may be any solvent that the photosensitive resin composition may contain, and the same is preferable.

The buffer layer forming composition may contain one or two or more solvents alone.

The content ratio of the solvent in the composition for forming a buffer layer is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, relative to 100 parts by mass of the total solid content in the composition for forming a buffer layer.

The composition for forming a buffer layer and the buffer layer may be prepared according to the method for preparing a photosensitive resin composition and the method for forming a negative photosensitive resin layer described above. For example, a buffer layer can be formed by preparing a buffer layer-forming composition by preparing a solution in which each component contained in the buffer layer is dissolved in a solvent in advance and mixing the obtained solutions in a predetermined ratio, then applying the obtained buffer layer-forming composition to the surface of the pseudo support, and drying a coating film of the buffer layer-forming composition. Further, after the photosensitive resin layer is formed on the protective film, a buffer layer may be formed on the surface of the photosensitive resin layer.

[ protective film ]

The photosensitive transfer material preferably has a protective film.

In addition, the protective film is not included in the transfer layer.

The photosensitive resin layer is preferably in direct contact with the protective film.

As a material constituting the protective film, a resin film and paper are exemplified, and from the viewpoint of strength and flexibility, a resin film is preferable.

Examples of the resin film include a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, polyethylene film, polypropylene film or polyethylene terephthalate film is preferable, and polypropylene film is more preferable from the viewpoints of transport property, antistatic property, strength and flexibility.

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

From the viewpoints of conveyability, defect suppression of resist pattern, and resolution, the arithmetic average roughness Ra of the surface of the protective film on the side opposite to the photosensitive resin layer side is preferably equal to or less than the arithmetic average roughness Ra of the surface of the protective film on the photosensitive resin layer side, and more preferably less than the arithmetic average roughness Ra of the surface of the protective film on the photosensitive resin layer side.

The arithmetic average roughness Ra of the surface of the protective film on the side opposite to the photosensitive resin layer side is preferably 300nm or less, more preferably 100nm or less, and particularly preferably 80nm or less from the viewpoints of transportation and windability.

Further, from the viewpoints of conveyability and antistatic properties, the arithmetic average roughness Ra of the surface of the protective film on the side opposite to the photosensitive resin layer side is preferably greater than 20nm (0.02 μm), more preferably greater than 50nm (0.05 μm).

Further, from the viewpoint of more excellent resolution, the arithmetic average roughness Ra of the surface of the protective film on the photosensitive resin layer side is preferably 300nm (0.3 μm) or less, more preferably 100nm (0.1 μm) or less, still more preferably 70nm (0.07 μm) or less, and particularly preferably 50nm (0.05 μm) or less. This is considered to be because the Ra value of the surface of the protective film is in the above range, and the uniformity of the layer thickness of the photosensitive resin layer and the resist pattern formed is improved.

The lower limit of the Ra value of the surface of the protective film is not particularly limited, but both surfaces are each preferably 1nm or more, more preferably 10nm or more, particularly preferably 20nm or more.

Also, the peeling force of the protective film is preferably smaller than that of the dummy support.

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

The contrast enhancement layer is described in paragraph 0134 of International publication No. 2018/179640. Further, other layers are described in paragraphs 0194 to 0196 of Japanese patent application laid-open No. 2014-85643. The contents of these publications are incorporated into the present specification.

The total thickness of the photosensitive transfer material is preferably 5 μm to 55. Mu.m, more preferably 10 μm to 50. Mu.m, particularly preferably 20 μm to 40. Mu.m. The total thickness of the photosensitive transfer material was measured by a method according to the method for measuring the thickness of each layer described above.

From the viewpoint of further exhibiting the effects of the present invention, the total thickness of each layer of the photosensitive transfer material other than the dummy support and the protective film is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

Further, from the viewpoint of further exhibiting the effects of the present invention, the total thickness of the photosensitive resin layer, the intermediate layer, and the buffer layer in the photosensitive transfer material is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, and particularly preferably 2 μm or more and 8 μm or less.

[ method for producing photosensitive transfer Material ]

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

As a method for producing the photosensitive transfer material, for example, a method including the steps of: a step of forming an intermediate layer by coating the intermediate layer composition on the surface of the pseudo support and then drying a coating film of the intermediate layer composition; and a step of forming a photosensitive resin layer by applying a photosensitive resin composition to the surface of the intermediate layer and then drying the coating film of the photosensitive resin composition.

The photosensitive transfer material is produced by pressing a protective film against the photosensitive resin layer of the laminate produced by the above-described production method.

As a method for producing the photosensitive transfer material used in the present invention, it is preferable to produce a photosensitive transfer material comprising a dummy support, an intermediate layer, a photosensitive resin layer, and a protective film by including a step of providing the protective film so as to be in contact with a surface of the photosensitive resin layer on the side opposite to the dummy support side.

After the photosensitive transfer material is produced by the above-described production method, the photosensitive transfer material can be produced and stored in a roll form by winding the photosensitive transfer material. The photosensitive transfer material in the roll form can be directly supplied to a step of bonding a substrate in a roll-to-roll manner described later.

The photosensitive transfer material used in the present invention can be preferably used for various applications requiring precise micromachining based on photolithography. After patterning the photosensitive resin layer, the photosensitive resin layer may be etched as a coating film, or electroforming mainly including electroplating may be performed. The cured film obtained by patterning can be used as a permanent film, for example, an interlayer insulating film, a wiring protective film having an index matching layer, or the like. The photosensitive transfer material used in the present invention can be preferably used for various wiring formation applications of semiconductor packages, printed boards, sensor boards, conductive films such as touch panels, electromagnetic wave shielding materials, and film heaters, liquid crystal sealing materials, and formation of structures in the micro-mechanical or micro-electronic fields.

The photosensitive transfer material used in the present invention may preferably be one in which the photosensitive resin layer is a colored resin layer containing a pigment.

The use of the colored resin layer is suitable for, for example, the use of a colored pixel or a black matrix such as a color filter used for a Liquid Crystal Display (LCD) and a solid-state imaging device (for example, a CCD (charge-coupled device) and a CMOS (complementary metal oxide semiconductor: complementary metal oxide semiconductor)) in addition to the above.

The same applies to the coloring resin layer except for the pigment.

Pigment >, pigment

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

In recent years, a cover glass (cover glass) in which a black frame-like light shielding layer is formed on a rear surface peripheral edge portion of a transparent glass substrate or the like is sometimes mounted on a liquid crystal display window included in an electronic device in order to protect the liquid crystal display window. In order to form such a light shielding layer, a colored resin layer can be used.

The pigment may be appropriately selected according to a desired hue, and may be selected from black pigments, white pigments, and color pigments other than black and white. Among them, when forming a black-based pattern, a black pigment is preferably selected as the pigment.

As the black pigment, a known black pigment (organic pigment, inorganic pigment, or the like) can be appropriately selected as long as the effect in the present invention is not impaired. Among them, carbon black, titanium oxide, titanium carbide, iron oxide, graphite, and the like are preferable as the black pigment from the viewpoint of optical density, and carbon black is particularly preferable. As the carbon black, carbon black having at least a part of the surface coated with a resin is preferable from the viewpoint of surface resistance.

From the viewpoint of dispersion stability, the particle diameter of the black pigment is preferably 0.001 μm to 0.1 μm, more preferably 0.01 μm to 0.08 μm in terms of the number average particle diameter.

The particle diameter is an average value obtained by obtaining the particle diameter of any 100 particles from a photographic image of pigment particles taken by an electron microscope, taking into consideration the diameter of a circle having the same area as the area of the pigment particles, and averaging the obtained 100 particle diameters.

As the pigment other than the black pigment, the white pigment described in paragraphs 0015 and 0114 of japanese patent application laid-open publication No. 2005-007765 can be used as the white pigment. Specifically, among the white pigments, titanium oxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, or barium sulfate is preferable as the inorganic pigment, titanium oxide or zinc oxide is more preferable, and titanium oxide is further preferable. The inorganic pigment is preferably rutile-type or anatase-type titanium oxide, and particularly preferably rutile-type titanium oxide.

The surface of titanium oxide may be treated with silica, alumina, titania, zirconia, or an organic substance, or may be treated with two or more kinds of treatments. Thus, the catalyst activity of titanium oxide is suppressed, and heat resistance, gloss reducing property and the like are improved.

From the viewpoint of reducing the thickness of the heated photosensitive resin layer, at least one of an alumina treatment and a zirconia treatment is preferable as the surface treatment of the surface of titanium oxide, and both of the alumina treatment and the zirconia treatment are more preferable.

In addition, when the photosensitive resin layer is a colored resin layer, it is preferable that the photosensitive resin layer further contains a color pigment other than a black pigment and a white pigment from the viewpoint of transferability. When the color pigment is contained, the particle diameter of the color pigment is preferably 0.1 μm or less, more preferably 0.08 μm or less, from the viewpoint of more excellent dispersibility.

As the Color pigment, there is used, examples thereof include Victoria pure blue B0 (Color Index) (hereinafter, C.I.) 42595, auramine (C.I.41000), fat black HB (C.I.26150), mononet yellow GT (C.I. pigment yellow 12), permanent yellow GR (C.I. pigment yellow 17), permanent yellow HR (C.I. pigment yellow 83), permanent carmine (permanent carmine) FBB (C.I. pigment Red 146), herta Bam red ESB (C.I. pigment Violet 19), permanent red (permanent red) FBH (C.I. pigment Red 11) Fastel pink (pastel pink) B sepura (C.I. pigment Red 81), monte Law fast blue (monastral fast blue) (C.I. pigment blue 15), monte fast black B (C.I. pigment Black 1), carbon, C.I. pigment Red 97, C.I. pigment Red 122, C.I. pigment Red 149, C.I. pigment Red 168, C.I. pigment Red 177, C.I. pigment Red 180, C.I. pigment Red 192, C.I. pigment Red 215, C.I. pigment Green 7, C.I. pigment blue 15:1, C.I. pigment blue 15:4, C.I. pigment blue 22, C.I. pigment blue 60, C.I. pigment blue 64, C.I. pigment Violet 23, and the like. Among them, c.i. pigment red 177 is preferred.

When the photosensitive resin layer contains a pigment, the content of the pigment is preferably more than 3 mass% and 40 mass% or less, more preferably more than 3 mass% and 35 mass% or less, further preferably more than 5 mass% and 35 mass% or less, and particularly preferably 10 mass% or more and 35 mass% or less, relative to the total mass of the photosensitive resin layer.

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

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

The dispersion liquid may be prepared by adding a mixture obtained by mixing a black pigment and a pigment dispersant in advance to an organic solvent (vehicle) and dispersing it with a dispersing machine. The pigment dispersant may be selected according to the pigment and the solvent, and for example, a commercially available dispersant can be used. The vehicle means a medium part for dispersing the pigment when the pigment dispersion is formed, and is a liquid state and includes a binder component for holding the black pigment in a dispersed state and a solvent component (organic solvent) for dissolving and diluting the binder component.

The dispersing machine is not particularly limited, and examples thereof include known dispersing machines such as kneaders, roll mills, attritors, super mills, dissolvers, homomixers, sand mills, and the like. Further, the fine grinding may be performed by mechanical grinding by friction. For the disperser and the fine pulverization, a description of "pigment dictionary" (manufactured by kubang, first edition, kuku shop, 2000, page 438, page 310) can be referred to.

Examples

The present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples. In the following description, "%" means "% by mass" and "parts" means "parts by mass" unless otherwise specified.

< manufacturing of pseudo-supporting body 1 >

A pseudo support comprising a polyester film having a thickness of 16 μm and a particle-containing layer having a thickness of 40nm was produced by the following procedure.

(particle-containing layer-forming composition 1)

The components were mixed in the following manner to obtain a particle-containing layer-forming composition 1. After the particle-containing layer forming composition 1 was prepared, filtration was performed using a 6 μm filter (F20, manufactured by MAHLE Japan ltd.) and, subsequently, membrane degassing was performed using 2×6Radial Flow Super Phobic (Polypore co., manufactured by ltd.).

Acrylic polymer (AS-563A,Daicel FineChem Ltd. Manufactured, solid content 27.5 mass%): 167 parts by mass

Nonionic surfactant (narobacty CL95, sanyo Chemical Industries, ltd. Manufactured, solid content 100 mass%): 0.7 part by mass

Anionic surfactant (manufactured by RAPISOL a-90,NOF CORPORATION), diluted with water to a solid content of 1 mass%): 114.4 parts by mass

Barceicose wax dispersion (Selosol 524,CHUKYO YUSHI CO, manufactured by LTD., solid content 30 mass%): 7 parts by mass

Carbodiimide compound (CARBODILITE V-02-L2, nisshinbo Chemical Inc. manufactured, diluted with water to a solid content of 10% by mass): 20.9 parts by mass

Matting agent (SNOWTEX XL, nissan Chemical Corporation, 40 mass% solids, average particle size 50 nm): 2.8 parts by mass

Water: 690.2 parts by mass

(extrusion molding)

The pellets of polyethylene terephthalate containing the citric acid chelate organic titanium complex described in Japanese patent publication No. 5575671 as a polymerization catalyst were dried to a water content of 50ppm or less, then charged into a hopper of a single-shaft kneading extruder having a diameter of 30mm, and melted and extruded at 280 ℃. After passing the melt through a strainer (pore size: 2 μm), the melt was extruded from a die onto a cooling roll at 25℃to obtain an unstretched film. In addition, the extruded melt was brought into close contact with a cooling roll using an electrostatic application method.

(stretching and coating)

The cured unstretched film was successively biaxially stretched by the following method to obtain a pseudo support comprising a polyester film having a thickness of 16 μm and a particle-containing layer having a thickness of 40 nm.

(a) Stretching in the longitudinal direction

The unstretched film was stretched in the machine direction (conveying direction) by passing it between 2 pairs of nip rolls having different peripheral speeds. The preheating temperature was 75 ℃, the stretching temperature was 90 ℃, the stretching ratio was 3.4 times, and the stretching speed was 1300%/sec.

(b) Coating

The particle-containing layer-forming composition 1 was applied to one side of the longitudinally stretched film by a bar coater so that the thickness became 40nm after film formation.

(c) Transverse stretching

The film subjected to the above longitudinal stretching and coating was subjected to transverse stretching using a tenter under the following conditions.

Preheating temperature: 110 DEG C

Stretching temperature: 120 DEG C

Stretching multiplying power: 4.2 times

Stretching speed: 50%/second

(Heat setting and thermal relaxation)

The biaxially stretched film after the completion of the longitudinal stretching and the transverse stretching was heat-set under the following conditions.

Heat setting temperature: 227 DEG C

Heat setting time: 6 seconds

After heat setting, the width of the tenter was reduced, and thermal relaxation was performed under the following conditions.

Thermal relaxation temperature: 190 DEG C

Thermal relaxation rate: 4%

(coiling)

After heat setting and thermal relaxation, both ends were trimmed, and the ends were extrusion-worked (knurled) to a width of 10mm, and then wound up at a tension of 40 kg/m. The width was 1.5m, and the roll length was 6300m. The resulting film roll was set as a dummy support 1. The haze value of the pseudo support 1 is 0.2. The haze value was measured as a total haze value using a haze meter (NIPPON DENSHOKU INDUSTRIES co., ltd. Manufactured by NDH 2000). The heat shrinkage rate by heating at 150℃for 30 minutes was 1.0% on the MD (conveying direction, machine Direetion) side and 0.2% on the TD (direction perpendicular to the conveying direction, transverse Direction) side. The film thickness of the particle-containing layer was measured from the cross-sectional TEM photograph and found to be 40nm. The average particle diameter of the particles contained in the particle-containing layer was measured by the above method using a Transmission Electron Microscope (TEM) type HT-7700 manufactured by Hitachi High-Technologies, and the result was 50nm.

Example 1 >

(production of photosensitive transfer Material)

The photosensitive transfer material including the dummy support 1, the intermediate layer, the photosensitive resin layer, and the protective film in this order was produced in the following order. The photosensitive resin layer is a negative photosensitive resin layer.

A composition B containing the components described in the column "middle layer" of table 1 was prepared. After coating the composition B on the pseudo-support 1 using a slit nozzle, the composition B was dried at 90 ℃ for 2 minutes, thereby forming an intermediate layer. The layer thicknesses of the intermediate layers are set forth in table 1.

A composition C containing the components described in the column of "photosensitive resin layer" in table 1 was prepared. After the composition C was applied to the intermediate layer using a slit nozzle, the composition C was dried at 80 ℃ for 2 minutes, thereby forming a photosensitive resin layer. The layer thicknesses of the photosensitive resin layers are shown in table 1.

Finally, a protective film (16KS40,TORAY INDUSTRIES,INC. Manufactured, thickness: 16 μm) was provided on the photosensitive resin layer to obtain a photosensitive transfer material 2.

Subsequently, an evaporation mask was manufactured by using the obtained photosensitive transfer material 2 in the following order.

As the metal layer having the 1 st surface and the 2 nd surface at a position opposite to the 1 st surface, an invar substrate was prepared. The 1 st and 2 nd faces face each other in opposite directions. The roughness Rmax of the 1 st surface of the invar substrate was 0.80. Mu.m. The roughness Rmax of the 2 nd surface of the invar substrate was 0.90 μm. The average thickness of the invar substrate was 50 μm.

The protective film is peeled from the transfer layer. Using a roll laminator, a photosensitive transfer material was bonded to an invar substrate at a temperature of 100 ℃, a line pressure of 0.5MPa, and a line speed (lamination speed) of 4 m/min, and a transfer layer (i.e., a photosensitive resin layer and an intermediate layer) and a dummy support 1 were sequentially disposed on the 1 st surface of the invar substrate. The 1 st surface of the invar substrate is in contact with the photosensitive resin layer.

After the dummy support 1 is peeled off from the transfer layer, the exposure mask is brought into close contact with the exposed surface of the transfer layer. The exposure mask has a plurality of square light shielding portions. The size of each light shielding portion varies in 1 μm unit in a range of 2 μm long by 2 μm wide to 100 μm long by 100 μm wide. The transfer layer was irradiated with light using a high-pressure mercury lamp exposure machine (MAP-1200L,Japan Science Engineering Co, manufactured by ltd., dominant wavelength: 365 nm). The exposure amount is adjusted to the exposure amount of the pattern shape of the photomask to be reproduced by the resist pattern shape obtained after development.

A resist pattern was obtained by developing a resist pattern using a 1.0 mass% aqueous sodium carbonate solution at 28 ℃. Specifically, in the development, air knife treatment was further performed by performing a 30-second shower treatment with pure water after performing an air knife treatment to remove the developer.

An etching treatment was performed on the invar alloy layer not covered with the resist pattern using an etching solution containing ferric chloride at 45 ℃ for 60 seconds to form a through hole in the invar alloy substrate. The through hole extends from the 1 st surface of the invar alloy substrate toward the 2 nd surface of the invar alloy substrate. The resist pattern was removed using a 4 mass% sodium hydroxide solution to obtain an evaporation mask. In the vapor deposition mask obtained, the average diameter of the through holes in the 1 st surface of the invar substrate was 20.0 μm, and the average diameter of the through holes in the 2 nd surface of the invar substrate was 7.0 μm.

Examples 2 to 30 and comparative examples 1 and 2 >, respectively

In the production of the photosensitive transfer material, a vapor deposition mask was produced in the procedure of example 1 except that the configuration of the transfer layer was changed as shown in tables 1 to 7.

Examples 31 to 34 and comparative example 3 >, respectively

In the production of the photosensitive transfer material, a vapor deposition mask was produced in the procedure of example 1, except that the configuration of the transfer layer was changed as shown in tables 8 to 9.

< evaluation >

The following items were evaluated using the photosensitive transfer materials or vapor deposition masks manufactured in examples and comparative examples.

(resolution)

In the obtained vapor deposition mask, the obtained hole pattern was observed with an optical microscope, and the smallest pattern size among the pattern sizes resolved by the size of the vapor deposition mask was used as resolution. The smaller the minimum pattern size of resolution, the more excellent the resolution. In addition, regarding the pattern size, the smallest diameter among the openings (10 RA in fig. 3) formed on the 2 nd surface of the metal layer was measured.

(laminating Property)

After the photosensitive transfer material obtained by laminating the metal substrate having a surface roughness Rmax of 0.5 μm to 5.0 μm was observed by an optical microscope from the pseudo support side of the laminated laminate, 25mm was observed ² The number of bubbles in the area of (2).

A: less than 10

B: more than 10 and less than 20

C: more than 20

(pseudo support peelability)

After the obtained photosensitive transfer material was laminated on the metal substrate, the dummy support was peeled off at an angle of 180 degrees, and then the surfaces of the dummy support and the transfer material were visually confirmed and evaluated according to the following evaluation criteria.

A: can smoothly peel off the pseudo support

B: although the pseudo support can be peeled off, the peeling is performed with a sound

C: peeling of the intermediate layer, cracking of the pseudo support, and cohesive failure occur when the pseudo support is peeled off.

(mask non-adhesiveness)

When the dummy support is peeled from the laminate obtained in the above, in which the transfer layer and the dummy support are sequentially disposed on the 1 st surface of the invar substrate, and the exposure mask is brought into direct contact with the transfer layer to perform exposure, it is determined whether or not the transfer layer is adhered to the exposure mask.

A: the transfer layer not being attached to the exposure mask

B: the transfer layer was not adhered to the exposure mask, but was sounded when peeled off

C: the transfer layer is attached to the mask (although the exposure mask can be peeled off, peeling of the transfer layer occurs)

The evaluation results are summarized in tables 5 to 7 and 9.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

The following abbreviations shown in tables 1 to 4 and 8 have the following meanings, respectively.

"M/B": ratio of total mass of polymerizable compound to total mass of polymer

"PVA": polyvinyl alcohol, KURARAY co., ltd

"PVP": polyvinylpyrrolidone, NIPPON SHOKUBIAI CO., LTD. Manufactured K-30

"HPMC": hydroxypropyl cellulose, shin-Etsu Chemical Co., ltd. METOLOSE 60SH-03

"F-444": MEGAFACE F-444 from DIC Corporation, fluorine-based surfactant

"BYK-345": silicone-based surfactant manufactured by BYK Japan K.K

"BYK-348": silicone-based surfactant manufactured by BYK Japan K.K

"EXP.S-506": silicone-based surfactant manufactured by DIC Corporation

"MeOH": methanol

"Compound B1": benzyl methacrylate (BzMA)/methacrylic acid (MAA)/Acrylic Acid (AA) =78/14.5/7.5 (mass ratio), mw:12,500, acid number: 187mgKOH/g, glass transition temperature: 75 ℃, solid components: 30 mass%

"Compound B2": styrene (St)/Methyl Methacrylate (MMA)/methacrylic acid (MAA)/glycidyl methacrylate (GMA-MAA) =47.7/1.3/19/32, mw:20,000, acid number: 124mgKOH/g, glass transition temperature: 76 ℃, solid components: 30 mass%

The term "glycidyl methacrylate" refers to a structural unit obtained by reacting an epoxy group of glycidyl methacrylate with a carboxyl group of a structural unit derived from methacrylic acid.

"Compound B3": styrene (St)/Methyl Methacrylate (MMA)/methacrylic acid (MAA) =52/19/29, mw:50,000, acid number: 148mgKOH/g, glass transition temperature: 131 ℃, solid components: 30 mass%

"Compound B4": styrene (St)/Methyl Methacrylate (MMA)/methacrylic acid (MAA) =45/19/36, mw:47,000, acid number: 183mgKOH/g, glass transition temperature: 122 ℃, solid components: 30 mass%

"Compound B5": styrene (St)/Methyl Methacrylate (MMA)/methacrylic acid (MAA) =57/11/32, mw:49,000, acid number: 163mgKOH/g, glass transition temperature: 140 ℃, solid components: 30 mass%

"BPE-500": ethoxylated bisphenol A dimethacrylate (average 10 molar equivalents of ethoxylate), shin-Nakamura Chemical Co., ltd. Manufactured NK Ester BPE-500

"BPE-100": ethoxylated bisphenol A dimethacrylate (average 2.6 molar equivalents of ethoxylate), shin-Nakamura Chemical Co., ltd. Manufactured NK Ester BPE-100

"ARONIX M-270": polypropylene glycol diacrylate, TOAGOSEI co., ltd. ARONIX M-270 manufactured by ARONIX

"A-DCP": tricyclodecane dimethanol diacrylate (Shin-Nakamura Chemical Co., ltd.)

"8UX-015A": taisei Fine Chemical Co., ltd

"TO-2349": ARONIX TO-2349 (TOAGOSEI CO., LTD.)

"B-IMD": (2- (2-chlorophenyl) -4, 5-diphenylimidazole dimer, KUROGANE KASEI co., ltd. B-CIM

"EAB-F": 4,4' -bis (diethylamino) benzophenone obtained from Sanyo tracking co., ltd

"phenothiazine": FUJIFILM Wako Pure Chemical Corporation manufacture

"feitinone 1% mek solution": methyl ethyl ketone solution containing 1 mass% of phenanthridone

"Compound A": N-phenylcarbamoylmethyl-N-carboxymethylaniline, manufactured by FUJIFILM Wako Pure Chemical Corporation

"LCV": colorless crystal violet, pigment developed by free radical, tokyo Chemical Industry co., ltd. Manufactured

"CBT-1": carboxybenzotriazole, JOHOKU CHEMICAL co., ltd. Manufactured CBT-1

"F-552": MEGAFACE F-552 manufactured by DIC Corporation, a fluorine-based surfactant, solid content: 30 mass% (methyl ethyl ketone solution)

"EXP.S-315": silicone-based surfactant manufactured by DIC Corporation

"EXP.S-503-2": silicone-based surfactant manufactured by DIC Corporation

"KP-124": silicone-based surfactant, shin-Etsu Chemical co., ltd

"MMPGAc": 1-methoxy-2-propyl acetate

"MFG": 1-methoxy-2-propanol

"MEK": methyl ethyl ketone [ Table 5]

TABLE 6

TABLE 7

TABLE 8

TABLE 9

Tables 5 to 7 and 9 show that the vapor deposition mask manufactured by the vapor deposition mask manufacturing method of the example has better resolution than the vapor deposition mask manufactured by the vapor deposition mask manufacturing method of the comparative example.

Examples 101 to 106

In the production method of the photosensitive transfer material, a photosensitive transfer material was produced in the same manner as in example 1 except that the protective film was changed to a polypropylene film (any one of protective films 1 to 6 and ALPHAN E-200C, ALPHAN FG-201 and ALPHAN ER-440) described in Table 10 below, and the photosensitive resin layer was changed to the photosensitive resin layer of example 20.

In the production method of the photosensitive transfer material, a photosensitive transfer material was produced in the same manner as in example 1 except that the protective film was changed to a polypropylene film (any one of protective films 1 to 6 and ALPHAN E-200C, ALPHAN FG-201 and ALPHAN ER-440) described in Table 10 below, and the photosensitive resin layer was changed to the photosensitive resin layer of example 31.

ALPHAN is OPP film manufactured by Oji F-Tex Co., ltd.

The photosensitive transfer material obtained was evaluated as follows.

Transport properties: when the photosensitive transfer material was conveyed in a roll-to-roll manner, it was visually confirmed that wrinkles, distortions, and the like did not occur in the photosensitive transfer material.

Antistatic properties: when the cover film was peeled off from the photosensitive transfer material, the charge amount was measured by an electrostatic meter (electrostatic meter SK series manufactured by KEYENCE CORPORATION). When the charge amount is small, the antistatic property is more excellent.

The details of the protective films 1 to 6 and ALPHAN E-200C, ALPHAN FG-201 and ALPHAN ER-440 used are shown in Table 10 below.

TABLE 10

TABLE 11

TABLE 12

The photosensitive transfer materials of examples 101 to 118 using a polypropylene film for the protective film were each a material having more excellent conveyability and antistatic properties.

Examples 201 to 207

A photosensitive transfer material was produced in the same manner as in example 1, except that the protective film was changed to the polypropylene film (protective film 3) described in table 13, and the photosensitive resin layers were changed to the photosensitive resin layers of examples 24 to 30, respectively, in the production method of the photosensitive transfer material.

The photosensitive transfer material obtained was evaluated as follows.

The details of the protective film 3 used are shown in table 10.

TABLE 13

The photosensitive transfer materials of examples 201 to 207, in which polypropylene films were used for the protective films, were more excellent in the conveyability and antistatic properties of the photosensitive transfer materials, respectively.

Claims

1. A method for manufacturing an evaporation mask sequentially comprises the following steps:

preparing a metal layer having a 1 st surface and a 2 nd surface at a position opposite to the 1 st surface;

attaching a photosensitive transfer material including a dummy support and a transfer layer to the metal layer, and disposing the transfer layer and the dummy support in this order on the 1 st surface of the metal layer;

peeling the pseudo support;

pattern exposure is carried out on the transfer printing layer;

developing the transfer layer to form a resist pattern;

etching the metal layer not covered by the resist pattern to form a through hole extending from the 1 st surface of the metal layer to the 2 nd surface of the metal layer; and

And removing the resist pattern.

2. The method for manufacturing an evaporation mask according to claim 1, wherein,

the roughness Rmax of the 1 st surface of the metal layer is 0.5-5.0 μm.

3. The method for manufacturing an evaporation mask according to claim 1 or 2, wherein,

The etching solution used in the etching treatment contains ferric chloride.

4. The method for manufacturing an evaporation mask according to claim 1 or 2, wherein,

5. The method for manufacturing an evaporation mask according to claim 1 or 2, wherein,

the transfer layer had a melt viscosity of 1.0X10 at 25 DEG C ⁵ Pa·s～1.0×10 ⁸ Pa·s。

6. The method for manufacturing an evaporation mask according to claim 1, wherein,

7. The method for manufacturing an evaporation mask according to claim 1, wherein,

the transfer layer has a buffer layer, an intermediate layer, and a photosensitive resin layer in this order from the dummy support side.

8. The method for manufacturing an evaporation mask according to claim 6 or 7, wherein,

the intermediate layer includes a water-soluble resin.

9. The method for manufacturing an evaporation mask according to claim 8, wherein,

the water-soluble resin comprises polyvinyl alcohol.

10. The method for manufacturing an evaporation mask according to claim 8, wherein,

the water-soluble resin comprises polyvinylpyrrolidone.

11. The method for manufacturing an evaporation mask according to claim 8, wherein,

the water-soluble resin comprises a hydroxyalkyl cellulose compound.

12. The method for manufacturing an evaporation mask according to claim 11, wherein,

the hydroxyalkyl cellulose compound is hydroxypropyl cellulose.

13. The method for manufacturing an evaporation mask according to claim 7, wherein,

the buffer layer includes an alkali-soluble resin.

14. The method for manufacturing an evaporation mask according to claim 1 or 2, wherein,

a shadow mask is used in the pattern exposure,

the distance between the transfer layer and the light shielding mask is less than 50 μm.

15. The method for manufacturing an evaporation mask according to claim 1 or 2, wherein,

a shadow mask is used in the pattern exposure,

the distance between the metal layer and the light shielding mask during pattern exposure is less than 50 μm.

16. The method for manufacturing an evaporation mask according to claim 1 or 2, wherein,

the surface energy of the pseudo-support side surface of the transfer layer was 68.0mJ/m ² The following is given.

17. The method for manufacturing an evaporation mask according to claim l or 2, wherein,

the photosensitive transfer material comprises the dummy support, the transfer layer and a protective film in this order,

The photosensitive resin layer in the transfer layer is in contact with the protective film,

the surface of the protective film opposite to the surface in contact with the photosensitive resin layer has an arithmetic average roughness Ra of more than 0.05 [ mu ] m.

18. The method for manufacturing an evaporation mask according to claim 1 or 2, wherein,

the protective film is a polypropylene film.

19. The method for manufacturing an evaporation mask according to claim 18, wherein,

the polypropylene film has an arithmetic average roughness Ra of 0.05 [ mu ] m or less on a surface in contact with the photosensitive resin layer.