JP2011215270A - Method for producing resin pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a resin pattern by which resin patterns having different heights are simultaneously produced while keeping fracture strength effective.SOLUTION: The method for producing a resin pattern includes: a coating step of coating a top of a substrate with a photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light absorber (D) which absorbs light in a specific wavelength region, to thereby form a photosensitive resin layer; an exposure step of exposing the photosensitive resin layer with different exposure intensities according to desired patterns; and a development step of developing the exposed photosensitive resin layer to thereby form resin patterns.

Description

  The present invention relates to a method for producing a resin pattern, and more particularly, to a method for producing a resin pattern in which resin patterns having different heights are produced simultaneously by exposing a photosensitive resin layer through a halftone mask or a gray scale mask. .

  In a liquid crystal panel of a liquid crystal display device, since a liquid crystal material is sandwiched between two transparent substrates such as a glass substrate, a spacer may be formed between the two substrates so that the liquid crystal material can be filled. is necessary.

  Conventionally, in order to form a spacer, a method in which bead particles serving as a spacer are dispersed over the entire surface of the substrate has been adopted. However, the beads are also adhered to the pixel display portion, and the image contrast and display image quality are deteriorated. was there. Therefore, in recent years, various methods for forming this spacer with a photosensitive resin composition have been proposed (see Patent Documents 1 and 2, etc.). In this method, a photosensitive resin composition is applied onto a substrate, exposed through a predetermined mask, and then developed to form a dot-like spacer. A predetermined portion other than a pixel display portion Only the spacer can be formed.

JP 2006-184841 A JP 2006-308961 A JP 2008-145986 A

  By the way, this spacer may be provided not on the color filter side but on the array substrate side. However, since there are steps in the array substrate, it is necessary to make the height of the spacers different in order to keep the distance between the substrates constant.

  Here, Patent Document 3 includes a photocurable resin composition containing an alkali-soluble resin, a polymerizable monomer, a photopolymerization initiator, and a radical quencher, and liquid crystal alignment protrusions having different heights and A technique for simultaneously forming spacers is disclosed. However, when the present inventors formed spacers having different heights using this photocurable resin composition, it was found that the rate of change in height due to changing the exposure amount was small. Further, the height change ratio is improved by increasing the amount of radical deactivator added. On the other hand, it has also been found that the breaking strength of the formed spacer is lowered.

  The present invention has been made in view of such conventional circumstances, and an object of the present invention is to provide a resin pattern manufacturing method for simultaneously manufacturing resin patterns having different heights while maintaining good fracture strength. .

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by incorporating a light absorbent that absorbs light in a specific wavelength region into the photosensitive resin composition, and the present invention has been completed.

  That is, the resin pattern manufacturing method according to the present invention includes an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light absorber that absorbs light in a specific wavelength region ( A coating step of coating a photosensitive resin composition containing D) on a substrate to form a photosensitive resin layer, and an exposure step of exposing the photosensitive resin layer with different exposure amounts according to a desired pattern; A development step of developing the exposed photosensitive resin layer to form a resin pattern.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the resin pattern which manufactures simultaneously the resin pattern from which height differs while maintaining favorable fracture strength can be provided.

It is a figure which shows the relationship between the exposure amount in Examples 1-3 and Comparative Examples 1-4, and the film thickness after post-baking.

The method for producing a resin pattern according to the present invention includes an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light absorber (D) that absorbs light in a specific wavelength region. A photosensitive resin composition containing a coating on a substrate to form a photosensitive resin layer, an exposure step of exposing the photosensitive resin layer with a different exposure amount according to a desired pattern, and exposure A development step of developing the photosensitive resin layer to form a resin pattern.
Below, the photosensitive resin composition used by this invention is demonstrated first, Then, the manufacturing method of the resin pattern using this photosensitive resin composition is demonstrated.

≪Photosensitive resin composition≫
The photosensitive resin composition used in the present invention comprises an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light absorber (D) that absorbs light in a specific wavelength region. ). Hereinafter, each component contained in the photosensitive resin composition will be described.

<Alkali-soluble resin (A)>
An alkali-soluble resin is a resin film having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate) and a resin film having a thickness of 1 μm is formed on a substrate, and 2.38% by mass of tetramethylammonium hydroxide ( TMAH) When dissolved in an aqueous solution for 1 minute, it means that the film thickness is dissolved by 0.01 μm or more.
The alkali-soluble resin (A) (hereinafter also referred to as “component (A)”) contained in the photosensitive resin composition is not particularly limited, and alkali-soluble resins conventionally used for forming spacers and the like. Can be used.

  Among such alkali-soluble resins, a structural unit (a1) derived from an unsaturated carboxylic acid, a structural unit (a2) derived from an epoxy group-containing unsaturated compound having no alicyclic group, and fat A resin having a structural unit (a3) derived from a cyclic epoxy group-containing unsaturated compound (hereinafter, such a resin is referred to as “(A1) resin”), or the structural unit (a1) and the structure A resin having a unit (a2) and a structural unit (a4) derived from an alicyclic group-containing unsaturated compound (hereinafter, such a resin is referred to as “(A2) resin”) is preferable. Hereinafter, each case will be described in order.

((A1) resin)
(A1) The resin has at least the structural unit (a1), the structural unit (a2), and the structural unit (a3).

  Examples of the unsaturated carboxylic acid for deriving the structural unit (a1) include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; And anhydrides of these dicarboxylic acids. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. These unsaturated carboxylic acids can be used alone or in combination of two or more.

  Examples of the epoxy group-containing unsaturated compound having no alicyclic group for deriving the structural unit (a2) include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meta ) (Meth) acrylic acid epoxy alkyl esters such as acrylate and 6,7-epoxyheptyl (meth) acrylate; glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-alkylacrylic acid epoxy alkyl esters such as α-ethylacrylic acid 6,7-epoxyheptyl; and the like. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate are preferable from the viewpoint of copolymerization reactivity and the strength of the cured resin. These epoxy group-containing unsaturated compounds having no alicyclic group can be used alone or in combination of two or more.

The alicyclic epoxy group-containing unsaturated compound for deriving the structural unit (a3) is not particularly limited as long as it is an unsaturated compound having an alicyclic epoxy group. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.
Specifically, examples of the alicyclic epoxy group-containing unsaturated compound include compounds represented by the following formulas (a3-1) to (a3-15). Among these, in order to moderate developability, the compounds represented by the following formulas (a3-1) to (a3-5) are preferable, and the following formulas (a3-1) to (a3-3) are preferable. The compounds represented are more preferred.

In the above formula, R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ¹³ represents a divalent hydrocarbon having 1 to 10 carbon atoms. Represents a group, and n represents an integer of 0 to 10. R ¹² is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. Examples of R ¹³ include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph is A phenylene group) is preferred.

  In addition, the resin (A1) may have a structural unit (a4) which will be described later, and has a structural unit other than the structural units (a1), (a2), (a3), and (a4). It may be. Examples of the compound for deriving other structural units include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds can be used alone or in combination of two or more.

  As (meth) acrylic acid esters, linear or branched chain such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate, etc. Alkyl (meth) acrylates; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (Meth) acrylate; etc. are mentioned.

  (Meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, N -Methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.

  Examples of the allyl compound include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Can be mentioned.

  As vinyl ethers, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether , Alkyl vinyl ethers such as diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichloropheny And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.

  Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl vinyl. Examples include enyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

  Styrenes include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy Alkyl styrene such as methyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Styrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

(A1) The proportion of the structural unit (a1) in the resin is preferably 5 to 60% by mass, and more preferably 10 to 40% by mass.
Further, the total of the proportion of the structural unit (a2) and the proportion of the structural unit (a3) in the resin (A1) is preferably 20 to 95, and more preferably 40 to 90 mass%. . Among these, it is preferable that the ratio of the said structural unit (a2) is 1-95 mass%, and it is more preferable that it is 5-80 mass%. Moreover, it is preferable that the ratio of the said structural unit (a3) is 5-95 mass%, and it is more preferable that it is 15-80 mass%. By setting the proportion of the structural unit (a3) in the above range, the developability can be made moderate, and the relative dielectric constant after curing can be lowered.
In addition, the proportion of the structural unit (a4) in the (A1) resin is preferably 0 to 60% by mass, and more preferably 1 to 40% by mass.
Moreover, it is preferable that the ratio of the said other structural unit in (A1) resin is 0-30 mass%, and it is more preferable that it is 1-20 mass%.
By making the proportion of each structural unit in the above range, the developability of the photosensitive resin composition is made moderate, and the shape and breaking strength of the cured resin pattern and the adhesion to the substrate are good. can do.

  (A1) The mass average molecular weight of the resin (Mw: measured value in terms of styrene by gel permeation chromatography (GPC). The same applies in this specification) is preferably 2000 to 50000, and preferably 5000 to 30000. More preferred. By setting it as the above range, the film forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

  When the (A1) resin has structural units other than the structural units (a1), (a2), and (a3), the (A1) resin can be produced by a known radical polymerization method. That is, it can be produced by dissolving each compound for deriving each structural unit and a known radical polymerization initiator in a polymerization solvent, followed by heating and stirring.

On the other hand, when the resin (A1) does not have a structural unit other than the structural units (a1), (a2), and (a3), the carboxyl group and the structural unit of the structural unit (a1) and the structural unit ( The epoxy groups of a2) and (a3) may react and gel.
Therefore, in such a case, first, an unsaturated carboxylic acid and a specific reactive compound are reacted to obtain a reaction mixture (reaction step), and then this reaction mixture does not have an alicyclic group. (A1) Resin is manufactured by copolymerizing an epoxy group-containing unsaturated compound and an alicyclic epoxy group-containing unsaturated compound (polymerization step). If necessary, purification and washing may be performed last (purification step).

  First, in the reaction step, an unsaturated carboxylic acid and at least one compound selected from compounds (reactive compounds) represented by the following formulas (1) to (3) are placed in a suitable reaction vessel such as a flask. The reaction mixture is obtained by charging and heating and stirring.

（式中、Ｒ^１及びＲ^２はそれぞれ独立して炭素数１〜４のアルキル基を示し、Ｒ^３は酸素原子を含んでいてもよい炭素数１〜４の直鎖状又は分岐鎖状の炭化水素基を示す。）

(Wherein R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, and R ³ is a linear or branched chain having 1 to 4 carbon atoms which may contain an oxygen atom. Indicates a hydrocarbon group.)

（式中、Ｒ^４及びＲ^５はそれぞれ独立して炭素数１〜４のアルキル基を示す。）

(In the formula, R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 4 carbon atoms.)

（式中、Ｒ^６及びＲ^７はそれぞれ独立して炭素数１〜４のアルキル基を示し、Ｒ^８は水素原子又は炭素数１〜４のアルキル基を示す。）

(In the formula, R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 4 carbon atoms, and R ⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

  Examples of the compound represented by the formula (1) include 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dipropoxyethane, 1,2-dibutoxyethane, diethoxymethane, and dipropoxy. Methane, dibutoxymethane, 1,1-dimethoxypropane, 1,1-diethoxypropane, 1,1-dipropoxypropane, 1,1-dibutoxypropane, 2,2-dimethoxypropane, 2,2-diethoxy Examples include propane, 2,2-dipropoxypropane, 2,2-dibutoxypropane, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether.

  Examples of the compound represented by the above formula (2) include 2,5-dimethoxytetrahydrofuran, 2,5-diethoxytetrahydrofuran, 2,5-dipropoxytetrahydrofuran, 2,5-dibutoxytetrahydrofuran and the like.

  Examples of the compound represented by the above formula (3) include 3,4-dimethoxytoluene, 3,4-diethoxytoluene, 3,4-dipropoxytoluene, 3,4-dibutoxytoluene, 1,2-dimethoxybenzene. 1,2-diethoxybenzene, 1,2-dipropoxybenzene, 1,2-dibutoxybenzene and the like.

  Among these reactive compounds, diethoxymethane, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, 2,5 in terms of reactivity with unsaturated carboxylic acid. -Dimethoxytetrahydrofuran, 1,1-diethoxypropane, and 2,2-diethoxypropane are preferred. These reactive compounds can be used alone or in combination of two or more.

  The molar ratio of the unsaturated carboxylic acid and the reactive compound is not particularly limited, but is preferably 1: 0.5 to 1: 3, and more preferably 1: 0.8 to 1: 2. The reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C. The reaction time is preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours.

  Next, in the polymerization step, the reaction mixture obtained in the reaction step, the epoxy group-containing unsaturated compound having no alicyclic group, and the alicyclic epoxy group-containing unsaturated compound together with a known radical polymerization initiator are used as a polymerization solvent. Then, the polymer is obtained by stirring with heating.

  Finally, in the purification step, the residue is removed by washing with, for example, a poor solvent.

  (A1) The content of the resin is preferably 40 to 85% by mass and more preferably 45 to 75% by mass with respect to the solid content of the photosensitive resin composition used in the present invention.

((A2) resin)
(A2) The resin has at least the structural unit (a1), the structural unit (a2), and the structural unit (a4). The compounds for deriving the structural units (a1) and (a2) are the same as in the case of the (A1) resin, and thus the description thereof is omitted. (A2) The resin may have other structural units other than the structural units (a1), (a2), and (a4). As said other structural unit, the structural unit similar to the other structural unit in (A1) resin is mentioned.

The alicyclic group-containing unsaturated compound for deriving the structural unit (a4) is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.
Specifically, examples of the alicyclic group-containing unsaturated compound include compounds represented by the following formulas (a4-1) to (a4-7). Among these, in order to moderate developability, compounds represented by the following formulas (a4-3) to (a4-8) are preferable, and in the following formulas (a4-3) and (a4-4) The compounds represented are more preferred.

In the above formula, R ²¹ represents a hydrogen atom or a methyl group, R ²² represents a single bond or a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ²³ represents a hydrogen atom or 1 to 5 carbon atoms. Represents an alkyl group. R ²² is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group. R ²³ is preferably, for example, a methyl group or an ethyl group.

(A2) The proportion of the structural unit (a1) in the resin is preferably 5 to 60% by mass, and more preferably 10 to 40% by mass.
Moreover, it is preferable that the ratio of the said structural unit (a2) in (A2) resin is 20-95 mass%, and it is more preferable that it is 30-90 mass%.
Further, the proportion of the structural unit (a4) in the (A2) resin is preferably 1 to 60% by mass, and more preferably 5 to 40% by mass. By setting the proportion of the structural unit (a4) within the above range, the developability can be made moderate and the relative dielectric constant after curing can be lowered.
Moreover, it is preferable that the ratio of the said other structural unit in (A2) resin is 0-60 mass%, and it is more preferable that it is 1-40 mass%.
By making the proportion of each structural unit in the above range, the developability of the photosensitive resin composition is made moderate, and the shape and breaking strength of the cured resin pattern and the adhesion to the substrate are good. can do.

  (A2) The mass average molecular weight of the resin is preferably 2000 to 50000, and more preferably 5000 to 30000. By setting it as the above range, the film forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

  (A2) The resin can be produced by a known radical polymerization method. That is, it can be produced by dissolving each compound for deriving each structural unit and a known radical polymerization initiator in a polymerization solvent, followed by heating and stirring.

  The content of (A2) resin is preferably 40 to 85 mass%, more preferably 45 to 75 mass%, based on the solid content of the photosensitive resin composition used in the present invention.

<Photopolymerizable monomer (B)>
As the photopolymerizable monomer (B) (hereinafter also referred to as “component (B)”), a monomer having an ethylenically unsaturated group can be preferably used. Monomers having an ethylenically unsaturated group include monofunctional monomers and polyfunctional monomers.

  Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone or in combination of two or more.

  On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meta Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (Meth) acrylate, urethane (meth) acrylate (that is, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate and 2-bidoxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene Examples thereof include polyfunctional monomers such as ethers, polyhydric alcohols and N-methylol (meth) acrylamide condensates, and triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more.

  Among these monomers having an ethylenically unsaturated group, a trifunctional or higher polyfunctional monomer is preferable from the viewpoint of increasing the adhesion of the photosensitive resin composition to the substrate and the breaking strength after curing of the photosensitive resin composition. More preferred are polyfunctional monomers having 6 or more functional groups. Among them, dipentaerythritol hexaacrylate (DPHA) is particularly preferable from the viewpoint of increasing the rate of change in the film thickness of the resin pattern when the exposure amount is changed. When DPHA and another monomer are used in combination, the ratio of DPHA is preferably 90% by mass or more in the photopolymerizable monomer.

  The amount of the component (B) is preferably such that the mass ratio of the component (A) to the component (B) is 50:50 to 80:20, and more preferably 60:40 to 70:30. By setting it as said range, the ratio of the film thickness change of the resin pattern when changing exposure amount can be enlarged.

<Photopolymerization initiator (C)>
It does not specifically limit as a photoinitiator (C) (henceforth "(C) component"), A conventionally well-known photoinitiator can be used.

  Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl- 4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4 -Dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone , 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone , Octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidar, 2-mercaptobenzoxazole, 2-mercapto Benzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzopheno 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether Benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4- Enoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5 -Bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- ( Furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4 Diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl)- s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3- Bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, and the like. Among these, it is particularly preferable in terms of sensitivity to use an oxime-based photopolymerization initiator. These photopolymerization initiators can be used alone or in combination of two or more.

  (C) It is preferable that content of a component is 0.5-30 mass% with respect to solid content of the photosensitive resin composition, and it is more preferable that it is 1-20 mass%. By setting it as the above range, sufficient heat resistance and chemical resistance can be obtained, film forming ability can be improved, and curing failure can be suppressed.

<Light absorber (D)>
The light absorber (D) (hereinafter, also referred to as “component (D)”) is not particularly limited, and any one that can absorb exposure light can be used, and in particular, a wavelength of 200 to 450 nm. Those that absorb the light in the region are preferred.

  Specific examples of the light absorber include α-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, anthracene Naphthalene derivatives such as 9,10-dihydroxyanthracene or anthracene or derivatives thereof; azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes Triazine dyes, dyes such as p- aminobenzoic acid dyes; and the like. Among these, it is preferable to use a naphthalene derivative. These light absorbers can be used alone or in combination of two or more.

  The content of the component (D) is preferably 0.01 to 10 parts by mass, and 0.05 to 7 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). More preferably, it is 0.1-5 mass parts. By setting it as said range, the ratio of the film thickness change of the resin pattern when changing an exposure amount can be enlarged, keeping the fracture strength after hardening favorable.

<Organic solvent (S)>
The photosensitive resin composition used in the present invention preferably contains an organic solvent (S) (hereinafter also referred to as “component (S)”) for improving coating properties and adjusting viscosity.

  Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene glycol monomethyl ether, (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene (Poly) alkylene glycol monoalkyl ether acetates such as glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate Diethylene Other ethers such as recall dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Alkyl 2-lactic acid esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3- Methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-butyrate Other esters such as -propyl, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; toluene, xylene Aromatic hydrocarbons such as N-methylpyrrolidone, N, N-dimethylformamide, amides such as N, N-dimethylacetamide, and the like. Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers described above, alkyl lactate esters, and other esters described above are preferable, alkylene glycol monoalkyl ether acetates described above. Other ethers and other esters described above are more preferred. These solvents can be used alone or in combination of two or more.

  The content of the component (S) is not particularly limited, and is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating film thickness. The viscosity of the photosensitive resin composition is preferably 5 to 500 cp, more preferably 10 to 50 cp, and still more preferably 20 to 30 cp. Moreover, it is preferable that solid content concentration is 5-100 mass%, and it is more preferable that it is 20-50 mass%.

<Other ingredients>
The photosensitive resin composition used in the present invention may contain additives such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, and an antifoaming agent as necessary. Any additive can be used as the additive. Examples of the surfactant include anionic, cationic, and nonionic compounds, examples of the adhesion improver include conventionally known silane coupling agents, and examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone mono Examples of the antifoaming agent include silicone-based and fluorine-based compounds.

<Method for preparing photosensitive resin composition>
In the photosensitive resin composition used in the present invention, the above components are mixed (dispersed and kneaded) with a stirrer such as a three-roll mill, a ball mill, or a sand mill, and if necessary, filtered with a filter such as a 5 μm membrane filter. Can be prepared.

≪Resin pattern manufacturing method≫
The method for producing a resin pattern according to the present invention includes a coating step of coating the photosensitive resin composition on a substrate to form a photosensitive resin layer, and an exposure amount that varies the photosensitive resin layer depending on a desired pattern. And an exposure step of developing the exposed photosensitive resin layer to form a resin pattern.

  First, the photosensitive resin composition is formed on a substrate by using a contact transfer type coating device such as a roll coater, reverse coater, bar coater or the like, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater. The photosensitive resin layer is formed by applying and drying to remove the solvent.

Next, the photosensitive resin layer is exposed with different exposure amounts according to a desired pattern. In order to perform exposure with different exposure amounts according to a desired pattern, exposure may be performed through a halftone mask or a gray scale mask. For the exposure, a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. In particular, it is preferable to use i-line (365 nm) as exposure light. The amount of exposure varies depending on the composition of the photosensitive resin composition, but is preferably about 25 to 300 mJ / cm ² , for example.

  Next, the exposed photosensitive resin layer is developed with a developer to form a resin pattern. The developing method is not particularly limited, and an immersion method, a paddle method, a spray method, or the like can be used. Specific examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

  The developed resin pattern is post-baked and cured by heating. The post-baking temperature is preferably 150 to 250 ° C. In this way, resin patterns having different heights can be manufactured simultaneously.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

<Examples 1-3, Comparative Examples 1-4>
[Preparation of photosensitive resin composition]
The components shown in Table 1 below are mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / diethylene glycol methyl ethyl ether = 50/50 (mass ratio) to obtain a photosensitive resin composition having a solid content concentration of 35 mass%. Prepared.

In Table 1, each abbreviation indicates the following, and the numerical value in parentheses is the blending amount (part by mass).
(A) -1: Resin of benzyl methacrylate: tricyclodecyl methacrylate: glycidyl methacrylate: methacrylic acid = 15: 20: 35: 30 (mass ratio) (mass average molecular weight 13000)
(A) -2: Resin of benzyl methacrylate: tricyclodecyl methacrylate: glycidyl methacrylate: methacrylic acid = 10: 20: 40: 30 (mass ratio) (mass average molecular weight 13000)
DPHA: dipentaerythritol hexaacrylate OXE-02: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime) (Ciba Specialty Chemicals) "IRGACURE OXE02")
1,5DON: 1,5-dihydroxynaphthalene α-NPOH: α-naphthol HNBA: hydroxynitrobenzaldehyde

[Evaluation of halftone characteristics (1)]
After applying the photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 4 on a 6-inch glass substrate (1737 glass manufactured by Dow Corning), conditions of 80 ° C. and 10 minutes are applied. And dried on a hot plate to obtain a photosensitive resin layer having a thickness of 3.5 μm. Next, the photosensitive resin layer was exposed with a ghi mixed light source through a band-pass filter that transmits only i-line. The exposure amount was 25, 50, 75, 100, 200 mJ / cm ² . Next, paddle development was performed at 23 ° C. for 60 seconds using a 0.5% tetramethylammonium hydroxide aqueous solution as a developer. Thereafter, post-baking was performed on a hot plate at 100 ° C. for 10 minutes, then at 220 ° C. for 40 minutes, and the film thickness after post-baking was measured.
And the halftone characteristic (HT characteristic) of the photosensitive resin composition was evaluated on the following evaluation criteria. The results are shown in Table 1 below and FIG.
◎: In the cases of the 200 mJ / cm ² exposure 25 mJ / cm ^2, the film thickness difference after post-baking is 1.5μm or more ○: the case where the exposure dose 25 mJ / cm ² and 200 mJ / cm ² The film thickness difference after post-baking is 1 μm or more and less than 1.5 μm. Δ: The film thickness difference after post-baking is 0.5 μm or more and less than 1 μm between the exposure amount of 25 mJ / cm ² and 200 mJ / cm ^2. X: The film thickness difference after post-baking is less than 0.5 μm between the exposure amount of 25 mJ / cm ² and 200 mJ / cm ^2.

[Evaluation of fracture strength (1)]
A dot-shaped resin pattern was formed in the same manner as in [Evaluation of halftone characteristics (1)] except that the photosensitive resin layer was exposed through a 9 μm diameter mask at an exposure amount of 200 mJ / cm ² .
Then, pressurization was performed at an additional speed of 14.2 mN / sec, the force required until the pattern was broken was examined, and the breaking strength of the resin pattern was evaluated according to the following evaluation criteria. The results are shown in Table 1 below.
◎: The force required to be destroyed is 200 mN or more ○: The force required to be destroyed is 100 mN or more and less than 200 mN ×: The force required to be destroyed is less than 100 mN

As can be seen from Table 1 and FIG. 1, when a photosensitive resin composition containing a light absorber was used, the film thickness greatly changed according to the exposure amount, and the halftone characteristics were good. (Examples 1-3). Moreover, the breaking strength of the formed resin pattern was also good.
On the other hand, when a photosensitive resin composition containing a radical deactivator is used instead of the light absorber, the film thickness changes even if the amount of the radical deactivator is increased to 2.5 parts by mass. Was less than 0.5 μm, and the halftone characteristics were poor (Comparative Examples 1 and 2). When the amount of the radical deactivator was increased to 10 parts by mass, the change in the film thickness was improved to 0.5 μm or more and less than 1 μm.
In addition, when the photosensitive resin composition which contains neither a light absorber nor a radical quencher was used, the film thickness change was less than 0.5 micrometer and the halftone characteristic was bad (comparative example 4).

<Examples 4 to 9>
[Preparation of photosensitive resin composition]
The components shown in Table 2 below are mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / diethylene glycol methyl ethyl ether = 50/50 (mass ratio) to obtain a photosensitive resin composition having a solid content concentration of 35 mass%. Prepared.
In Table 2, each abbreviation is the same as in Table 1 above. Moreover, the numerical value in a parenthesis is a compounding quantity (mass part).

[Evaluation of halftone characteristics (2)]
After applying the photosensitive resin composition prepared in Examples 4 to 9 on a 6-inch glass substrate (1737 glass manufactured by Dow Corning), it was dried on a hot plate at 80 ° C. for 10 minutes. A photosensitive resin layer having a thickness of 3.5 μm was obtained. Next, the photosensitive resin layer was exposed with a ghi mixed light source through a band-pass filter that transmits only i-line. The exposure amount was 25, 50, 75, 100, 200 mJ / cm ² .
Subsequently, paddle development was performed at 23 ° C. using a 0.5% tetramethylammonium hydroxide aqueous solution as a developer. The development time was BP × about 1.5 (seconds) on the basis of the time until the unexposed area was completely dissolved (BP: break point). However, because the development time cannot be set to less than 20 seconds due to the convenience of the apparatus for measuring BP, those whose BP did not reach 20 seconds are described as “less than 20 seconds” in Table 2, and the development time is 30 Seconds. The reason why the development time is about 1.5 times that of BP is that halftone characteristics are considered to be better. A guideline for optimum development time is in the range of BP × (1.3 to 2.0) seconds.
Thereafter, post-baking was performed on a hot plate at 100 ° C. for 10 minutes, then at 220 ° C. for 40 minutes, and the film thickness after post-baking was measured.
And the halftone characteristic (HT characteristic) of the photosensitive resin composition was evaluated on the same evaluation criteria as Example 1. The results are shown in Table 2 below.

[Evaluation of fracture strength (2)]
A dot-like resin pattern was formed in the same manner as in [Evaluation of halftone characteristics (2)] except that the photosensitive resin layer was exposed through a 9 μm diameter mask at an exposure amount of 200 mJ / cm ² .
And the fracture strength of the resin pattern was evaluated according to the same evaluation criteria as in Example 1 and the like. The results are shown in Table 2 below.

  As can be seen from Table 2, when any of the photosensitive resin compositions was used, the film thickness greatly changed according to the exposure amount, and the halftone characteristics were good (Examples 4 to 9). . In particular, when the mass ratio of the alkali-soluble resin to the photopolymerizable monomer is 50:50 to 80:20, the change in film thickness is 1 μm or more (Examples 5 to 8), and among these, the mass ratio is In the case of 60:40 to 70:30, the film thickness change was 1.5 μm or more, which was even better (Examples 6 and 7). Moreover, even when any photosensitive resin composition was used, the breaking strength of the formed resin pattern was good.

<Examples 10 to 15>
[Preparation of photosensitive resin composition]
The components shown in Table 3 below are mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / diethylene glycol methyl ethyl ether = 50/50 (mass ratio) to obtain a photosensitive resin composition having a solid content concentration of 35 mass%. Prepared.

In Table 3, each abbreviation indicates the following. Other abbreviations are the same as in Table 1 above. Moreover, the numerical value in a parenthesis is a compounding quantity (mass part).
(A) -3: Resin of benzyl methacrylate: tricyclodecyl methacrylate: glycidyl methacrylate: methacrylic acid = 15: 20: 40: 25 (mass ratio) (mass average molecular weight 13000)
(A) -4: Resin of tricyclodecyl methacrylate: glycidyl methacrylate: 3,4-epoxycyclohexylmethyl methacrylate: methacrylic acid = 9: 35.5: 35.5: 20 (mass ratio) (mass average molecular weight 13000)
CN9006: Aliphatic urethane acrylate ("CN9006" manufactured by Sartomer)

[Evaluation of halftone characteristics (3)]
After applying the photosensitive resin composition prepared in Examples 10 to 15 above on a 6-inch glass substrate (manufactured by Dow Corning, 1737 glass), it was dried on a hot plate at 80 ° C. for 10 minutes. A photosensitive resin layer having a thickness of 3.5 μm was obtained. Next, the photosensitive resin layer was exposed with a ghi mixed light source through a band-pass filter that transmits only i-line. The exposure amount was 25, 50, 75, 100, 200 mJ / cm ² . Subsequently, paddle development was performed at 23 ° C. using a 0.5% tetramethylammonium hydroxide aqueous solution as a developer. The development time was BP × about 1.5 (seconds) on the basis of the time until the unexposed area was completely dissolved (BP: break point). Thereafter, post-baking was performed on a hot plate at 100 ° C. for 10 minutes, then at 220 ° C. for 40 minutes, and the film thickness after post-baking was measured.
And the halftone characteristic (HT characteristic) of the photosensitive resin composition was evaluated on the same evaluation criteria as Example 1. The results are shown in Table 3 below.

[Evaluation of fracture strength (3)]
A dot-like resin pattern was formed in the same manner as in [Evaluation of halftone characteristics (3)] except that the photosensitive resin layer was exposed through a 9 μm diameter mask at an exposure amount of 200 mJ / cm ² .
And the fracture strength of the resin pattern was evaluated according to the same evaluation criteria as in Example 1 and the like. The results are shown in Table 3 below.

As can be seen from Table 2, when any photosensitive resin composition was used, the film thickness greatly changed according to the exposure amount, and the halftone characteristics were good (Examples 10 to 15). . In particular, when the ratio of DPHA in the photopolymerizable monomer was 90% or more, the change in film thickness was 1 μm or more (Examples 11 to 15).
Moreover, when any photosensitive resin composition was used, the breaking strength of the formed resin pattern was good, but the resin of (A) -4 having a particularly high proportion of structural units having an epoxy group was used. When used, the fracture strength was remarkably high.

Claims (7)

A photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerizable monomer (B), a photopolymerization initiator (C), and a light absorber (D) that absorbs light in a specific wavelength region is formed on a substrate. Coating process to form a photosensitive resin layer,
An exposure step of exposing the photosensitive resin layer with different exposure amounts according to a desired pattern;
A development step of developing the exposed photosensitive resin layer to form a resin pattern.   The method for producing a resin pattern according to claim 1, wherein in the exposure step, exposure is performed with different exposure amounts through a halftone mask or a gray scale mask.   The method for producing a resin pattern according to claim 1 or 2, wherein the light absorber (D) absorbs light in a wavelength region of 200 to 450 nm.   Content of the said light absorber (D) in the said photosensitive resin composition is 0.01-10 mass with respect to a total of 100 mass parts of the said alkali-soluble resin (A) and the said photopolymerizable monomer (B). The method for producing a resin pattern according to claim 1, wherein the resin pattern is a part.   The alkali-soluble resin (A) is a structural unit (a1) derived from an unsaturated carboxylic acid, a structural unit (a2) derived from an epoxy group-containing unsaturated compound having no alicyclic group, The manufacturing method of the resin pattern of any one of Claim 1 to 4 which has a structural unit (a3) induced | guided | derived from a cyclic epoxy group containing unsaturated compound.   The alkali-soluble resin (A) is a structural unit (a1) derived from an unsaturated carboxylic acid, a structural unit (a2) derived from an epoxy group-containing unsaturated compound having no alicyclic group, The manufacturing method of the resin pattern of any one of Claim 1 to 4 which has a structural unit (a4) induced | guided | derived from a cyclic group containing unsaturated compound.   The method for producing a resin pattern according to any one of claims 1 to 6, wherein a mass ratio of the alkali-soluble resin (A) and the photopolymerizable monomer (B) is 50:50 to 80:20.

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