JP5641791B2 - Manufacturing method of resin pattern - Google Patents

Description

  The present invention relates to a method for producing a resin pattern, and more specifically, a resin pattern for simultaneously producing resin patterns having different heights by exposing a photosensitive resin layer through a halftone mask or a gray scale mask. It relates to the manufacturing method.

  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 2006-301148 A JP 2010-015025 A JP 2010-049238 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 discloses a technique for manufacturing protrusions and spacers of vertically aligned liquid crystal display elements having different heights using a specific photosensitive composition. In the example of this Patent Document 3, in order to simultaneously manufacture protrusions and spacers having different heights, exposure is performed through masks having different opening widths. If the exposure gap is constant, the exposure amount decreases as the opening width is reduced, so that the degree of cross-linking is reduced. As a result, the flow easily occurs during post-baking, so that a difference in height occurs.
Moreover, in patent document 3, following (1)-(3) is mentioned as another method of forming a protrusion and a spacer.
(1) A method of exposing through a mask having a portion with a large radiation transmittance and a portion with a small radiation transmittance.
(2) A method of exposing a plurality of times using two types of masks having different patterns.
(3) A method of performing both exposure from the upper surface of the coating film and exposure from the back surface of the substrate.

However, the method of exposing through masks having different opening widths has the problem that only resin patterns having different dimensions as well as heights can be formed.
Although the methods (1) to (3) do not have such a problem, the methods (2) and (3) require multiple exposures or exposures from a plurality of directions. It could not be said that it was a simple manufacturing method. Moreover, when the present inventors examined, it was difficult to manufacture simultaneously the resin pattern from which height differs by the method of said (1).

  The present invention has been made in view of such conventional circumstances, and an object thereof is to provide a method for simultaneously and efficiently manufacturing resin patterns having different heights.

  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 specific photopolymerization initiator disclosed in Patent Documents 4 and 5 into the photosensitive resin composition, and the present invention has been completed.

（式中、Ｒ^１ｃ，Ｒ^２ｃはそれぞれ独立に一価の有機基を示し、Ｒ^３ｃはハロゲン原子又は一価の有機基を示し、ｎは０〜４の整数を示す。） That is, in the method for producing a resin pattern according to the present invention, a photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C) is applied on a substrate. A coating process for forming a photosensitive resin layer, an exposure process for exposing the photosensitive resin layer with different exposure amounts according to a desired pattern, and developing the exposed photosensitive resin layer to form a resin pattern. Development process, and the photopolymerization initiator (C) contains a compound represented by the following formula (c-1).

(In formula, R ^<1c >, R < ^2c > shows a monovalent organic group each independently, R < ^3c > shows a halogen atom or a monovalent organic group, and n shows the integer of 0-4.)

  ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing simultaneously and efficiently the resin pattern from which height differs can be provided.

It is a figure which shows the relationship between the transmittance | permeability of the halftone mask in Examples 1-4, and Comparative Examples 1-3, and the film thickness after post-baking. It is a figure which shows the relationship between the transmittance | permeability of the halftone mask in Examples 5-8 and Comparative Examples 4 and 5, and the film thickness after post-baking. It is a figure which shows the relationship between the transmittance | permeability of the halftone mask in Example 15, 16 and Comparative Examples 20 and 21, and the film thickness after post-baking. It is a figure which shows the relationship between the transmittance | permeability of the halftone mask in Examples 17-19, and the film thickness after post-baking.

The method for producing a resin pattern according to the present invention comprises applying a photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C) on a substrate, A coating step for forming a photosensitive resin layer, an exposure step for exposing the photosensitive resin layer with different exposure amounts according to a desired pattern, a development step for developing the exposed photosensitive resin layer to form a resin pattern, Is included.
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 contains an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C). 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)”) is not particularly limited, and alkali-soluble resins conventionally used for forming spacers and the like can be used.

Among such alkali-soluble resins, the structural unit (a1) derived from an unsaturated carboxylic acid, the structural unit (a2) derived from an epoxy group-containing unsaturated compound having no alicyclic group, or an alicyclic ring A resin having a structural unit (a3) derived from an epoxy group-containing unsaturated compound (hereinafter, such a resin is referred to as “(A1) resin”) is preferable.
(A1) The resin preferably further has a structural unit (a4) derived from an alicyclic group-containing unsaturated compound.
(A1) When the resin has a structural unit containing a hydrocarbon-based cyclic group (structural unit derived from the structural unit (a3), (a4), or other cyclic group-containing compound), a development step This is preferable because the margin of this becomes good. Further, it is particularly preferable that the cyclic group is an alicyclic group, since the development process margin is further improved.

  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 An anhydride of these dicarboxylic acids; and the like. 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 ( (Meth) acrylate, (7) epoxyheptyl (meth) acrylate and other (meth) acrylic acid epoxy alkyl esters; α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl And 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 ^1a represents a hydrogen atom or a methyl group, R ^2a represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^3a represents a divalent hydrocarbon having 1 to 10 carbon atoms. Represents a group, and m represents an integer of 0 to 10. R ^2a 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 ^3a 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.

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 ^4a represents a hydrogen atom or a methyl group, R ^5a represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to ⁶ carbon atoms, and R ^6a represents a hydrogen atom or 1 to 5 carbon atoms. Represents an alkyl group. R ^5a 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 ^6a is preferably, for example, a methyl group or an ethyl group.

  Moreover, (A1) resin may have other structural units other than the said structural unit (a1), (a2), (a3), (a4). 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.

  Among these, benzyl (meth) acrylate and styrenes are preferable.

(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.
The proportion of the structural unit (a2) or the structural unit (a3) in the resin (A1) is preferably 20 to 95, more preferably 40 to 90% by mass, and 50 to 75% by mass. % Is more preferable. (A1) When resin contains both a structural unit (a2) and a structural unit (a3), it is preferable that the ratio of a structural unit (a2) is 1-80 mass%, and is 5-60 mass%. Is more preferable, and the proportion of the structural unit (a3) is preferably 5 to 90% by mass, and more preferably 15 to 70% by 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.
Moreover, it is preferable that the ratio of the said structural unit (a4) in (A1) resin is 0-60 mass%, It is more preferable that it is 1-40 mass%, It is that it is 5-30 mass%. Further preferred.
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 hardness of the cured resin pattern and the adhesion to the substrate are made good. be able to.

  (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 the compounds represented by the following formulas (a-1) to (a-3) (reactive compounds) are suitably used in a flask or the like. A reaction mixture is obtained by charging into a reaction vessel and stirring with heating.

（式中、Ｒ^７ａ，Ｒ^８ａはそれぞれ独立して炭素数１〜４のアルキル基を示し、Ｒ^９ａ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 ^7a and R ^8a each independently represents an alkyl group having 1 to 4 carbon atoms, and R ^9a 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^１０ａ，Ｒ^１１ａはそれぞれ独立して炭素数１〜４のアルキル基を示す。）

(In formula, R ^<10a> , R ^<11a > shows a C1-C4 alkyl group each independently.)

（式中、Ｒ^１２ａ，Ｒ^１３ａはそれぞれ独立して炭素数１〜４のアルキル基を示し、Ｒ^１４ａ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 ^12a and R ^13a each independently represent an alkyl group having 1 to 4 carbon atoms, and R ^14a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

  Examples of the compound represented by the formula (a-1) include 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dipropoxyethane, 1,2-dibutoxyethane, diethoxymethane, Dipropoxymethane, dibutoxymethane, 1,1-dimethoxypropane, 1,1-diethoxypropane, 1,1-dipropoxypropane, 1,1-dibutoxypropane, 2,2-dimethoxypropane, 2,2- Examples include diethoxypropane, 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 (a-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 (a-3) include 3,4-dimethoxytoluene, 3,4-diethoxytoluene, 3,4-dipropoxytoluene, 3,4-dibutoxytoluene, 1,2- Examples include 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.

  The content of the component (A) 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.

<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 more polyfunctional monomer is preferable from the viewpoint of increasing the adhesion of the photosensitive resin composition to the substrate and the hardness after curing of the photosensitive resin composition, A polyfunctional monomer having 6 or more functional groups is more preferable. 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)>
The photopolymerization initiator (C) (hereinafter also referred to as “component (C)”) contains a compound represented by the following formula (c-1). This compound has geometric isomers due to oxime double bonds, but these are not distinguished. The compound represented by the following formula (c-1) and the exemplified compound described later represent both mixtures or any one of them, and are not limited to structures showing isomers.

In the formula (c-1), R ^1c and R ^2c each independently represent a monovalent organic group, and R ^3c represents a halogen atom or a monovalent organic group.

As the monovalent organic group represented by R ^1c , R ^2c , and R ^3c , groups represented by R ^4c , OR ^4c , COR ^4c , SR ^4c , NR ^5c R ^6c , and CONR ^5c R ^6c are preferable. R ^4c , R ^5c , and R ^6c each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to 2 carbon atoms. 20 represents a heterocyclic group, and an alkyl group, an aryl group, an arylalkyl group, and a hydrogen atom of the heterocyclic group are further represented by OR ^7c , COR ^7c , SR ^7c , NR ^8c R ^9c , CONR ^8c R ^9c , —NR ^8c. -OR ^9c , -NCOR ^8c -OCOR ^9c , -C (= N-OR ^7c ) -R ^8c , -C (= N-OCOR ^7c ) -R ^8c , CN, halogen atom, -CR ^7c = CR ^8c R ^{9c , -CO-CR 7c = CR 8c} R 9c, which may be substituted with a carboxyl group, or epoxy group. R ^7c , R ^8c and R ^9c are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 2 to 2 carbon atoms. 20 heterocyclic groups are shown.
The alkylene moiety of the substituent represented by R ^4c , R ^5c , R ^6c , R ^7c , R ^8c , R ^9c is an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or a urethane bond. May be interrupted 1 to 5 times. At this time, the linking group to be interrupted may be one type or two or more types. In the case of a group that can be interrupted in succession, two or more may be interrupted in succession. The alkyl part of the substituent may have a branched side chain, may be a cyclic alkyl, and the alkyl terminal of the substituent may be an unsaturated bond.
R ^5c and R ^6c , and R ^8c and R ^9c may be combined to form a ring, and R ^1c may be combined with an adjacent benzene ring to form a ring. Good.

In the above formula (c-1), the alkyl group (including the case where it has a substituent) represented by R ^4c , R ^5c , R ^6c , R ^7c , R ^8c , R ^9c includes a methyl group, an ethyl group, propyl Group, isopropyl group, butyl group, isobutyl group, s-butyl group, tert-butyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tert group -Octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, otadecyl, icosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, vinyl, allyl, Butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, Ropokishiechiru group, pentyloxy ethyl group, octyloxy ethyl, methoxy ethoxy ethyl group, ethoxyethoxyethyl group, propoxy ethoxyethyl group, methoxypropyl group, 2-methoxy-1-methylethyl group and the like.
^Examples of the aryl group represented by R ^4c , R ^5c , R ^6c , R ^7c , R ^8c , and R ^9c (including those having a substituent) include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a chlorophenyl group, Examples thereof include a naphthyl group, an anthryl group, a phenanthrenyl group, a substituted phenyl group substituted with one or more of the above alkyl groups, a substituted biphenylyl group, a substituted naphthyl group, and a substituted anthryl group.
As the arylalkyl group (including the case having a substituent) represented by R ^4c , R ^5c , R ^6c , R ^7c , R ^8c , R ^9c , a benzyl group, a chlorobenzyl group, an α-methylbenzyl group, α, An α-dimethylbenzyl group, a phenylethyl group, a phenylethenyl group and the like can be mentioned.
The heterocyclic groups represented by R ^4c , R ^5c , R ^6c , R ^7c , R ^8c and R ^9c include pyridyl group, pyrimidyl group, furyl group, thienyl group, tetrahydrofuryl group, dioxolanyl group, benzoxazole-2- 5- to 7-membered heterocyclic groups such as yl group, tetrahydropyranyl group, pyrrolidyl group, imidazolidyl group, pyrazolidyl group, thiazolidyl group, isothiazolidyl group, oxazolidyl group, isoxazolidyl group, piperidyl group, piperazyl group, morpholinyl group Is mentioned.
In addition, a ring that R ^5c and R ^6c can form together, a ring that R ^8c and R ^9c together can form, and a ring that R ^1c can form with an adjacent benzene ring. Examples of the ring include 5- to 7-membered rings such as cyclopentane ring, cyclohexane ring, cyclopentine ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring.
R ^4c , R ^5c , R ^6c , R ^7c , R ^8c , R ^9c may be substituted with a halogen atom, and the halogen atom represented by R ^3c includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Is mentioned.

Among these, as R ^1c , an alkyl group having 1 to 20 carbon atoms is preferable, and an ethyl group is particularly preferable. R ^2c is preferably an alkyl group having 1 to 20 carbon atoms, and particularly preferably a methyl group. R ^3c is a halogen atom, a group represented by OR ^4c , and R ^4c is an alkyl group having 1 to 20 carbon atoms which may be interrupted 1 to 5 times by an ether bond, or a complex having 2 to 20 carbon atoms. Preferred is a cyclic group or a group represented by NR ^5c R ^6c and R ^5c , R ^6c is an alkyl group having 1 to 20 carbon atoms which may be interrupted 1 to 5 times by an ether bond, represented by OR ^4c R ^4c is more preferably a group having 1 to 20 carbon atoms which may be interrupted 1 to 5 times by an ether bond, or a heterocyclic group having 2 to 20 carbon atoms.

  In said formula (c-1), n shows the integer of 0-4 and 0 or 1 is preferable.

The compound represented by the above formula (c-1) may be dimerized via R ^2c as represented by the following formula (c-2).

In the formula ^{(c-2), R 1c} , R 3c, n has the same meaning as in the above formula ^{(c-1), R 2c} ' is removing one hydrogen atom from ^{R 2c} in the formula (c-1) A divalent group obtained by

  Preferable specific examples of the compound represented by the formula (c-1) include the following compound No. 1-No. Although 15 compounds are mentioned, it is not limited to these.

  As long as the effect of this invention is show | played, (C) component may contain the other well-known photoinitiator with the compound represented by the said Formula (c-1). Examples of such other photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 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, Non, 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, o-benzoylbenzoic acid Methyl, 2,4-diethylthioxanthone, 2-chlorothio Xanthone, 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'-bisdimethylaminobenzo Enone, 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-phenoxyacetophenone, 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 (trichloro Methyl) -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.

  The ratio of the compound represented by the general formula (c-1) in the component (C) is preferably 80% by mass or more, more preferably 90% by mass or more, and 100% by mass. Is particularly preferred. Moreover, it is preferable that content of the compound represented by the said general formula (c-1) is 0.1-30 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, More preferably, it is 0.5-20 mass parts. By setting it as said range, the resin pattern from which height differs can be manufactured simultaneously and efficiently.

<Colorant (D)>
The photosensitive resin composition used in the present invention may contain a colorant (D) (hereinafter also referred to as “component (D)”) as necessary. Examples of the colorant include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C .. I.) Numbers can be used.

C. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same and only the number is described) 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185;
C. I. Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same, and only the number is described) 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73;
C. I. Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;
C. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 79, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;
C. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same and only the numbers are described), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37;
C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment brown 28;
C. I. Pigment Black 1 and Pigment Black 7.

  Moreover, a black pigment can also be used as a coloring agent. Black pigments include carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides, metal sulfides, metal sulfates, metal carbonates, etc. Is mentioned. As the carbon black, known carbon black such as channel black, furnace black, thermal black, lamp black, and resin-coated carbon black can be used. This resin-coated carbon black has a feature that its conductivity is lower than that of carbon black without resin coating.

  The content of the component (D) is preferably 1 to 40 parts by mass and more preferably 1 to 30 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).

<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.

  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, dipropy (Poly) alkylene glycol monoalkyl ethers such as ethylene 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 glycol Other ethers such as 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. Lactic acid alkyl esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxyacetic acid Ethyl, 2-hydroxy-3-methylbutanoic acid methyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxy Butylpropionate, 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, etc. Aromatic hydrocarbons; amides such as N-methylpyrrolidone, N, N-dimethylformamide, 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 it is 1-60 mass%, and, as for solid content concentration, it is more preferable that it is 20-40 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.
The exposure light preferably contains g-line (436 nm). More specifically, the wavelength is preferably longer than i-line (365 nm), more preferably in the visible light region (380 to 750 nm), and longer than h-line (405 nm) and 450 nm or less. Is more preferable, and g-line (436 nm) is particularly preferable.
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 1-4, Comparative Examples 1-3>
[Preparation of photosensitive resin composition]
Each component shown in Table 1 below is mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / diethylene glycol methyl ethyl ether = 60/40 (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). In Table 1, λ _end represents the wavelength at the end in the absorption spectrum of the photopolymerization initiator.
(A) -1: resin of tricyclodecyl methacrylate: glycidyl methacrylate: methacrylic acid = 9: 71: 20 (mass ratio) (mass average molecular weight 11800)
DPHA: Dipentaerythritol hexaacrylate (C) -1: Compound (C) -2 represented by the following formula (C) -1: Compound (C) -3 represented by the following formula (C) -2: Compound represented by formula (C) -3

[Evaluation of halftone characteristics (1)]
After applying the photosensitive resin composition prepared in Examples 1 to 4 and Comparative Examples 1 to 3 on a 6-inch glass substrate (manufactured by Dow Corning, 1737 glass), 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 5 μm. Next, this photosensitive resin is passed through a halftone mask whose transmittance is 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%. The layer was exposed. For the exposure, a ghi mixed light source was used, and light having a wavelength of h line (405 nm) or less was blocked through a filter. The exposure amount was 50 mJ / cm ² . Next, paddle development was performed at 23 ° C. for 60 seconds using a 0.04% KOH aqueous solution as the developer. After shaking off and drying, the resin layer after development was post-baked on a hot plate at 220 ° C. for 40 minutes, and the film thickness after post-baking was measured. The results are shown in Table 2 and FIG. The unit of numerical values in Table 2 is [μm].

[Evaluation of pencil hardness (1)]
A photosensitive resin layer having a thickness of 5 μm was obtained in the same manner as in the above [Evaluation of halftone characteristics (1)], and then this photosensitive resin layer was exposed through a mask having a transmittance of 100%. However, a ghi mixed light source was used for exposure, and light having a wavelength of h line (405 nm) or less was not blocked. The exposure amount was 50 mJ / cm ² . Next, paddle development was performed at 23 ° C. for 60 seconds using a 0.04% KOH aqueous solution as the developer. After shaking off and drying, the developed resin layer was post-baked on a hot plate at 220 ° C. for 40 minutes. The Mitsubishi pencil uni was pressed against the post-baked resin layer, and it was confirmed by an optical microscope whether the resin layer was damaged. Table 1 shows the pencil hardness immediately before scratching.

As can be seen from Tables 1 and 2 and FIG. 1, in Examples 1 to 4 using the photosensitive resin composition containing the compound represented by the general formula (c-1) as a photopolymerization initiator, a halftone mask The film thickness can be changed almost in proportion to the transmittance of the film, and the margin for the transmittance change is high. The pencil hardness of the cured resin layer was also high.
On the other hand, in Comparative Examples 1 to 3 using a photosensitive resin composition containing a compound not included in the general formula (c-1) as a photopolymerization initiator, the transmittance of the halftone mask is 100%. In particular, in Comparative Example 3, the resin layer was almost dissolved and removed by development.

<Examples 5 to 14 and Comparative Examples 4 to 19>
[Preparation of photosensitive resin composition]
Each component shown in the following Tables 3 and 4 is mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / diethylene glycol methyl ethyl ether = 60/40 (mass ratio) to form a photosensitive resin composition having a solid content concentration of 35 mass%. A product was prepared.

In Tables 3 and 4, each abbreviation indicates the following, and the rest is the same as Table 1. The numerical value in parentheses is the blending amount (part by mass). In Tables 3 and 4, λ _end represents the wavelength at the end in the absorption spectrum of the photopolymerization initiator.
(A) -2: Resin of tricyclodecyl methacrylate: glycidyl methacrylate: 3,4-epoxycyclohexylmethyl methacrylate: methacrylic acid = 9: 35.5: 35.5: 20 (mass ratio) (mass average molecular weight 12000)
(A) -3: Tricyclodecyl methacrylate: 3,4-epoxycyclohexylmethyl methacrylate: Methacrylic acid = 9: 71: 20 (mass ratio) resin (mass average molecular weight 12200)
(A) -4: Resin of benzyl methacrylate: glycidyl methacrylate: methacrylic acid = 9: 71: 20 (mass ratio) (mass average molecular weight 11900)
(A) -5: Resin of styrene: glycidyl methacrylate: methacrylic acid = 9: 71: 20 (mass ratio) (mass average molecular weight 11800)
(A) -6: Resin of cyclohexyl methacrylate: glycidyl methacrylate: methacrylic acid = 9: 71: 20 (mass ratio) (mass average molecular weight 12200)
(A) -7: resin of tricyclodecyl methacrylate: glycidyl methacrylate: methacrylic acid = 13: 71: 16 (mass ratio) (mass average molecular weight 12000)
(A) -8: Resin of tricyclodecyl methacrylate: glycidyl methacrylate: methacrylic acid = 17: 71: 12 (mass ratio) (mass average molecular weight 12100)
OXE02: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime) (“IRGACURE OXE02” manufactured by Ciba Specialty Chemicals)
OXE01: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (“IRGACURE OXE01” manufactured by Ciba Specialty Chemicals)
IR369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (“IRGACURE 369” manufactured by Ciba Specialty Chemicals)
IR907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (“IRGACURE 907” manufactured by Ciba Specialty Chemicals)
Tr-PMS: 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine ("Triazine PMS" manufactured by PANCHIM)
EABF: 4,4′-bisdiethylaminobenzophenone (“EABF” manufactured by Hodogaya Chemical Co., Ltd.)
1,5DON: 1,5-dihydroxynaphthalene

[Evaluation of sensitivity]
Coating, exposure, development, and post-baking were performed under the same conditions as in [Evaluation of pencil hardness (1)]. However, the exposure amount was appropriately adjusted in the range of 30 to 1000 mJ / cm ² . Tables 3 and 4 show “sensitivity” as the minimum exposure amount at which a cured resin layer was obtained after post-baking.

[Evaluation of halftone characteristics (2)]
Except that the exposure amount was the minimum exposure amount at which a cured resin layer was obtained after post-baking in [Sensitivity evaluation], the same as in [Evaluation of half-tone characteristics (1)], after post-baking. The film thickness of the resin layer was measured. The results are shown in Table 5. The unit of numerical values in Table 5 is [μm]. Moreover, the result in Examples 5-8 and Comparative Examples 4 and 5 is shown in FIG.

[Evaluation of pencil hardness (2)]
Pencil hardness was evaluated in the same manner as in [Evaluation of pencil hardness (1)] except that the exposure amount was the minimum exposure amount at which a cured resin layer was obtained after post-baking in [Sensitivity evaluation]. The results are shown in Tables 3 and 4.

As can be seen from Tables 3 to 5 and FIG. 2, in Examples 5 to 14 using the photosensitive resin composition containing the compound represented by the general formula (c-1) as a photopolymerization initiator, an alkali-soluble resin is used. Even in the case where the film thickness is changed variously, the film thickness can be changed substantially in proportion to the transmittance of the halftone mask, and the margin for the transmittance change is high. The pencil hardness of the cured resin layer was also high.
On the other hand, in Comparative Examples 4 to 19 using a photosensitive resin composition containing a compound not included in the general formula (c-1) as a photopolymerization initiator, the transmittance of the halftone mask is 100%. Even so, the resin layer was almost dissolved and removed by development. Moreover, the pencil hardness of the resin layer after hardening was also inferior to Examples 5-14.
Further, from the results of Comparative Examples 18 and 19, it was confirmed that the halftone characteristics are not always good even if the value of λ _end is large.

<Examples 15 and 16, Comparative Examples 20 and 21>
[Preparation of photosensitive resin composition]
The components shown in Table 6 below are mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / diethylene glycol methyl ethyl ether = 60/40 (mass ratio) to obtain a photosensitive resin composition having a solid content concentration of 35 mass%. Prepared.

In Table 6, each abbreviation shows the following, and the rest is the same as Tables 1, 3, and 4. The numerical value in parentheses is the blending amount (part by mass).
CB: Carbon black dispersion (available from Mikuni Dye Co., Ltd.) (carbon black concentration of 20% by mass in 3-methoxybutyl acetate solvent). In addition, the mass part in Table 6 shows the quantity converted only to CB solid content.

[Evaluation of halftone characteristics (3)]
The film thickness of the resin layer after post-baking was measured in the same manner as in [Evaluation of halftone characteristics (1)]. The results are shown in Table 7 and FIG. The unit of numerical values in Table 7 is [μm].

[Evaluation of pencil hardness (3)]
The pencil hardness was evaluated in the same manner as in [Evaluation of pencil hardness (1)]. The results are shown in Table 6.

As can be seen from Tables 6 and 7 and FIG. 3, in Examples 15 and 16 using the photosensitive resin composition containing the compound represented by the general formula (c-1) as a photopolymerization initiator, carbon black was used. Even when it was contained, the film thickness could be changed approximately in proportion to the transmittance of the halftone mask, and the margin of transmittance change was high. The pencil hardness of the cured resin layer was also high.
On the other hand, in Comparative Examples 20 and 21 using a photosensitive resin composition containing a compound not included in the general formula (c-1) as a photopolymerization initiator, the transmittance of the halftone mask is 100%. Even so, the resin layer was almost dissolved and removed by development. Also, the pencil hardness of the cured resin layer was inferior to those of Examples 15 and 16.

<Examples 17 to 19>
[Preparation of photosensitive resin composition]
Each component shown in Table 8 below is mixed and dissolved in a mixed solvent of propylene glycol monomethyl ether acetate / diethylene glycol methyl ethyl ether = 60/40 (mass ratio) to obtain a photosensitive resin composition having a solid content concentration of 35 mass%. Prepared.
In Table 8, each abbreviation is the same as in Tables 1, 3, and 4. The numerical value in parentheses is the blending amount (part by mass).

[Evaluation of halftone characteristics (4)]
The film thickness of the resin layer after post-baking was measured in the same manner as in [Evaluation of halftone characteristics (1)]. The results are shown in Table 9 and FIG. The unit of numerical values in Table 9 is [μm].

[Evaluation of pencil hardness (4)]
The pencil hardness was evaluated in the same manner as in [Evaluation of pencil hardness (1)]. The results are shown in Table 8.

  As can be seen from Tables 8 and 9 and FIG. 4, in Examples 15 to 17 using the photosensitive resin composition containing the compound represented by the general formula (c-1) as a photopolymerization initiator, other light Even when the polymerization initiator was mixed in an amount of 0 to 20%, the film thickness could be changed almost in proportion to the transmittance of the halftone mask, and the margin for changing the transmittance was high. The pencil hardness of the cured resin layer was also high. Furthermore, it was confirmed that the one where the content rate of the compound represented by general formula (c-1) is high is preferable at the point of coexistence with a halftone characteristic and hardening strength.

Claims (6)

A coating step of coating a photosensitive resin composition containing an alkali-soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C) on a substrate to form a photosensitive resin layer;
An exposure step of exposing the photosensitive resin layer with different exposure amounts according to a desired pattern;
Developing the exposed photosensitive resin layer to form a resin pattern, and
The photopolymerization initiator (C) contains a compound represented by the following general formula (c-1) ,
In the exposure step, a resin pattern manufacturing method in which exposure is performed with different exposure amounts through a halftone mask or a gray scale mask .

(In formula, R ^<1c >, R < ^2c > shows a monovalent organic group each independently, R < ^3c > shows a halogen atom or a monovalent organic group, and n shows the integer of 0-4.) Method for producing a resin pattern of claim 1, wherein the exposure light comprises a g-line in the exposure step. The method for producing a resin pattern according to claim 1 or 2 , wherein a ratio of the compound represented by the general formula (c-1) in the photopolymerization initiator (C) is 80% by mass or more. Content of the compound represented by the general formula (c-1) in the photosensitive resin composition is 100 parts by mass in total of the alkali-soluble resin (A) and the photopolymerizable monomer (B). It is 0.1-30 mass parts, The manufacturing method of the resin pattern of any one of Claim 1 to 3 . The alkali-soluble resin (A) is a structural unit (a1) derived from an unsaturated carboxylic acid and a structural unit (a2) derived from an epoxy group-containing unsaturated compound having no alicyclic group or an alicyclic ring 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 formula epoxy group containing unsaturated compound. The method for producing a resin pattern according to claim 5, wherein the alkali-soluble resin (A) further has a structural unit (a4) derived from an alicyclic group-containing unsaturated compound.

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