JP5607346B2 - Photosensitive resin composition, coating film, pattern and display device - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a coating film, a pattern, and a display device.

In recent liquid crystal display panels and the like, the size of a substrate has been increased, and a photosensitive resin composition is usually formed by a spin coating method in order to form a transparent film or pattern such as a coat layer on a substrate surface. The coating is formed by a slit & spin method or the like.
On the other hand, from the viewpoint of improving productivity, supporting large screens, etc., a method for forming a high-quality uniform coating film while reducing the liquid content of the photosensitive resin composition solution has been studied.

From such a background, in order to form an excellent quality coating film, selection of a solvent type is being sought. For example, when a low boiling point solvent is used, the coating film is rapidly dried. On the other hand, at the time of evaporation of the solvent, the microbubbles contained in the coating film forming composition may be bumped. Such bumping causes bubbles to appear on the surface of the coating film, resulting in crater-like defects.
Therefore, conventionally, a high boiling point solvent has been used as a solvent. For example, a photosensitive resin composition containing a high-boiling solvent such as diethylene glycol ethyl methyl ether (boiling point 176 ° C.) and benzyl alcohol (boiling point 205 ° C.) has been proposed (for example, Patent Document 1).

JP, 2007-25645, A Paragraph 46, Table 1

  However, even if the photosensitive resin composition using the above-described solvent is applied to a slit die coating method or the like, which is a typical coating method, a high-quality coating film that does not necessarily cause moisture unevenness or defects cannot be obtained. There was a case.

The present invention provides the following inventions [1] to [8].
[1] A photosensitive resin composition comprising a resin (A), a polymerizable monomer (B), a polymerization initiator (C), a solvent (D), and a surfactant (E),
The solvent (D) is a solvent containing two or more kinds of solvents having a boiling point of 175 ° C. or lower,
The content of the surfactant (E) is 0.0025 to 0.0250% by weight with respect to 100% by weight of the photosensitive resin composition excluding the surfactant,
A photosensitive resin composition having a solid content of 10 to 30% by weight.

[2] The photosensitive resin composition according to [1], wherein the solvent (D) is a solvent containing two or more kinds of solvents having a boiling point of 140 ° C. or higher and 175 ° C. or lower.
[3] The photosensitive resin composition according to [1] or [2], wherein the solvent (D) is a solvent containing an alcohol having 1 to 6 carbon atoms.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the solvent (D) is a solvent containing 3-methoxybutanol.

  [5] The surfactant (E) is at least one selected from the group consisting of silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms [1] to [4] Any photosensitive resin composition of.

[6] A coating film formed using the photosensitive resin composition according to any one of [1] to [5].
[7] A pattern formed using the photosensitive resin composition according to any one of [1] to [5].
[8] A display device comprising at least one selected from the group consisting of the coating film of [6] and the pattern of [7].

According to the photosensitive resin composition of the present invention, it is possible to suppress the occurrence of defects, fogging, and the like due to bumping of the solvent, and to form a uniform and high-quality coating film over the entire coating film.
Moreover, a high quality display device can be obtained by using such a photosensitive resin composition.

  The photosensitive resin composition of the present invention mainly comprises a resin (A), a polymerizable monomer (B), a polymerization initiator (C), a solvent (D), and a surfactant (E).

  The resin (A) used in the photosensitive resin composition of the present invention is not particularly limited, and is preferably alkali-soluble (A1) (hereinafter sometimes referred to as “resin (A1)”), light and heat. (A2) (hereinafter sometimes referred to as “resin (A2)”) exhibiting reactivity due to the action of at least one of the above is more preferable.

  As the resin (A1), at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (A-a) (hereinafter sometimes referred to as “(A-a)”), (A -A) and a copolymerizable monomer (Ab) (excluding (Aa)) (hereinafter sometimes referred to as “(Ab)”), etc. Is done.

Examples of (Aa) include aliphatic unsaturated carboxylic acids and / or aliphatic unsaturated carboxylic acid anhydrides.
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; and anhydrides of these unsaturated dicarboxylic acids;
Unsaturated mono [(meth) acryloyloxy of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Alkyl] esters;
unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid;
5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2. 1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, Such as 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), etc. And bicyclounsaturated compounds containing a carboxy group.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and alkali solubility.
You may use these individually or in combination of 2 or more types.

In the present specification, unless otherwise specified, the exemplified compounds, components, agents and the like can be used alone or in combination of two or more.
Further, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

As (Ab),
(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, dicyclopenta Nyl (meth) acrylate), (meth) acrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate and isoboronyl (meth) acrylate;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate (commonly referred to in the art as dicyclopentanyl acrylate), dicyclopenta Acrylic acid cyclic alkyl esters such as oxyethyl acrylate and isobornyl acrylate;
(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-di (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Chlorounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.

  Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and alkali solubility.

In the resin (A1) obtained by copolymerizing (Aa) and (Ab), the ratio of the structural units derived from each of the resins (A1) is 100 moles in terms of the total number of moles of the structural units constituting the resin (A1). %, The molar fraction is preferably in the following range.
Structural units derived from (Aa); 2 to 40 mol%
Structural units derived from (Ab); 60-98 mol%
Moreover, it is more preferable in the said ratio of the structural unit being the following ranges.
Structural units derived from (Aa); 5-35 mol%
Structural units derived from (Ab); 65-95 mol%
When the composition ratio is in this range, the storage stability, developability and solvent resistance tend to be good.

  Resin (A1) is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the document Can be produced by referring to the cited references described in (the same applies to the resin (A2)).

Specifically, a predetermined amount of units (Aa) and (Ab) constituting the copolymer, a polymerization initiator and a solvent are charged into a reaction vessel, oxygen is replaced by nitrogen, and oxygen is absent. A polymer is obtained by stirring, heating, and keeping the temperature under.
As the polymerization initiator used here, any of those usually used in the art can be used. For example, a polymerization initiator (C) described later can be used.
As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. May be used.
In particular, by using a solvent (D) described later as a solvent during the polymerization, the solution after the reaction can be used as it is, and the production process can be simplified (also in the resin (A2)). The same).

The polystyrene equivalent weight average molecular weight of the resin (A1) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (A1) is in this range, the coating property tends to be good, the film is not easily reduced during development, and the non-pixel part is easily removed during development. is there.
The dispersity (molecular weight distribution) of resin (A1), [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.1 to 6.0, more preferably 1.2 to 4. 0. When the degree of dispersion is within this range, the developability tends to be excellent.

  The content of the resin (A1) that can be used in the photosensitive resin composition of the present invention is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, based on the solid content in the photosensitive resin composition. %. When the content of the resin (A1) is within this range, the solubility in the developer is sufficient, and development residues are hardly generated on the substrate of the non-pixel portion, and the film portion of the pixel portion of the exposed portion is reduced during development. It tends to be difficult, and the non-exposed portion has a good removal property.

Examples of the resin (A2) exhibiting alkali solubility and reactivity due to at least one of light and heat include (A2-1) to (A2-3).
Resin (A2-1) includes (Aa), (Ab), and a monomer (Ac) having a group having a cyclic ether bond having 2 to 4 carbon atoms (hereinafter referred to as “(A- c) ") and the like.
Resin (A2-2) is a copolymer of (Aa) and (Ab), in which a part of the carboxy group derived from (Aa) is replaced with carbon derived from (Ac). Examples thereof include a copolymer obtained by reacting with a group having a cyclic ether bond of 2 to 4.
Examples of the resin (A2-3) include a copolymer of (Aa) and (Ac).

  (Ac) is, for example, at least one group selected from the group consisting of a group having a cyclic ether bond having 2 to 4 carbon atoms (for example, an epoxy group (oxiranyl group), an oxetanyl group and a tetrahydrofuryl group). The polymerizable compound which has. (Ac) is preferably a compound having at least one group selected from the group consisting of groups having a cyclic ether bond having 2 to 4 carbon atoms and having an unsaturated bond. (Ac) is more preferably a compound having at least one group selected from the group consisting of groups having a cyclic ether bond having 2 to 4 carbon atoms and having a (meth) acryloyloxy group. .

  Examples of (Ac) include a monomer having an epoxy group, a monomer having an oxetanyl group, and a monomer having a tetrahydrofuryl group.

The monomer having an epoxy group refers to a polymerizable compound having at least one group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group, for example.
The monomer having an epoxy group is preferably a compound having at least one group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group and having an unsaturated bond.

An aliphatic epoxy group refers to a group having a structure obtained by epoxidizing a chain olefin.
Specific examples of the compound having an aliphatic epoxy group include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and JP-A-7-248625. Examples thereof include compounds represented by the following formula (III).
(In formula (III), R ^{11 to} R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m is an integer of 1 to 5).

  Here, examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, 1-methyl-n-propyl group, 2-methyl- n-propyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n- Examples thereof include a propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group and the like.

  In the present specification, any chemical structural formula varies depending on the number of carbon atoms, but unless otherwise specified, examples of substituents and the like can be similarly applied throughout the present specification. Moreover, the thing which can take both a linear or branched includes both.

  Examples of the compound represented by the formula (III) include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl. -M-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2 , 6-Diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5 -Triglycidyloxymethylstyrene 2,4,6-triglycidyloxymethylstyrene and the like.

Examples of the monomer having an alicyclic epoxy group include a monomer having an aliphatic monocyclic epoxy group, a monomer having an aliphatic polycyclic epoxy group, and the like.
An alicyclic epoxy group refers to a group having a structure obtained by epoxidizing a cyclic olefin.
The aliphatic monocyclic epoxy group refers to a group having a structure obtained by epoxidizing a monocyclic olefin.
The aliphatic polycyclic epoxy group refers to a group having a structure obtained by epoxidizing a polycyclic cyclic olefin.

The monomer having an aliphatic monocyclic epoxy group refers to a polymerizable compound having an epoxy group on the ring of the aliphatic monocyclic compound. The monomer having an aliphatic monocyclic epoxy group is preferably a compound having an epoxy group on the ring of the aliphatic monocyclic compound and having an unsaturated bond. A compound having an epoxy group on the ring and a (meth) acryloyloxy group is more preferable.
Examples of the aliphatic monocyclic compound include cyclopentane, cyclohexane, cycloheptane, cyclooctane, and the like. Especially, a C5-C7 compound is preferable.
Specific examples of the monomer having an aliphatic monocyclic epoxy group include vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3 , 4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), and the like. It is done.

The monomer having an aliphatic polycyclic epoxy group refers to a polymerizable compound having an epoxy group on the ring of the aliphatic polycyclic compound. The monomer having an aliphatic polycyclic epoxy group is preferably a compound having an epoxy group on the ring of the aliphatic polycyclic compound and having an unsaturated bond. A compound having an epoxy group on the ring and a (meth) acryloyloxy group is more preferable.
Examples of the aliphatic polycyclic compound include dicyclopentane, tricyclodecane, norbornane, isonorbornane, bicyclooctane, bicyclononane, bicycloundecane, tricycloundecane, bicyclododecane, and tricyclododecane. Especially, a C8-C12 compound is preferable.

  Examples of the monomer having an aliphatic polycyclic epoxy group include 3,4-epoxynorbornyl acrylate, 3,4-epoxynorbornyl methacrylate, compounds represented by the formula (I), and the formula And at least one compound selected from the group consisting of compounds represented by (II).

In Formula (I) and Formula (II), R ¹ and R ² each independently represent a C 1-4 alkyl group which may be substituted with a hydrogen atom or a hydroxyl group.
X ¹ and X ² each independently represent a C 1-6 alkylene group that may contain a single bond or a hetero atom.

Specific examples of R ¹ and R ² include a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group;
Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy-isopropyl group, And hydroxyl-substituted alkyl groups such as 2-hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group and 4-hydroxy-n-butyl group. It is done.
Among these, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.

Specific examples of X ¹ and X ² include a single bond; an alkylene group such as a methylene group, an ethylene group, and a propylene group;
Examples include heteroatom-containing alkylene groups such as oxyalkylene groups, thioalkylene groups, and iminoalkylene groups. Specific examples include an oxymethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group, an iminomethylene group, an iminoethylene group, and an iminopropylene group.
Of these, a single bond, a methylene group, an ethylene group, an oxymethylene group, and an oxyethylene group are preferable. More preferably, a single bond and an oxyethylene group are mentioned.

As at least one compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II), the compound represented by the following formula (I ′) and the formula (II ′) It is preferably at least one compound selected from the group consisting of compounds represented by
In formula (I ′) and formula (II ′), R ^{1 ′} and R ^{2 ′} have the same meanings as R ¹ and R ² , respectively.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I-11) to Formula (I-15) Is mentioned. More preferably, Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

Specific examples of the compound represented by Formula (II) include compounds represented by Formula (II-1) to Formula (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9), Formula (II-11) to Formula (II-15) Is mentioned.
More preferably, Formula (II-1), Formula (II-7), Formula (II-9), and Formula (II-15) are mentioned.

  At least one compound selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (II) may be used alone or in admixture at any ratio. In the case of mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 to Formula (I): Formula (II). 80:20.

The monomer having an oxetanyl group refers to a polymerizable compound having an oxetanyl group, for example. The monomer having an oxetanyl group is preferably a compound having an oxetanyl group and an unsaturated bond, more preferably a compound having an oxetanyl group and a (meth) acryloyloxy group. .
Specific examples of the monomer having an oxetanyl group include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3- Ethyl-3-acryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane or 3-ethyl-3-acryloyloxy And ethyl oxetane.

The monomer having a tetrahydrofuryl group refers to a polymerizable compound having a tetrahydrofuryl group, for example. The monomer having a tetrahydrofuryl group is preferably a compound having a tetrahydrofuryl group and an unsaturated bond, and having a tetrahydrofuryl group and a (meth) acryloyloxy group. Is more preferable.
Specific examples of the monomer having a tetrahydrofuryl group include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

In resin (A2-1), it is preferable that the ratio of the structural unit derived | led-out from each is a molar fraction with respect to the total mole number of the structural unit which comprises resin (A2-1), and exists in the following ranges.
Structural units derived from (Aa); 2 to 40 mol%
Structural units derived from (Ab); 1 to 65 mol%
Structural units derived from (Ac); 2 to 95 mol%
Moreover, it is more preferable in the said ratio of the structural unit being the following ranges.
Structural units derived from (Aa); 5-35 mol%
Structural units derived from (Ab); 1 to 60 mol%
Structural units derived from (Ac); 5 to 80 mol%
When the composition ratio is in this range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be good.

  Resin (A2-1) can be produced by the same production method as resin (A1) except that (Aa), (Ab) and (Ac) are used.

Resin (A2-2) can be manufactured through a two-step process. For example, the method described in the document “Experimental Methods for Polymer Synthesis” (published by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972), JP-A-2001-89533 It can be produced with reference to the method described in 1.
First, a resin is obtained by the same method as the resin (A1) using a copolymer obtained by copolymerizing (Aa) and (Ab).
In this case, it is preferable that the ratio of the structural units derived from each is in the following range in terms of a mole fraction with respect to the total number of moles of the structural units constituting the copolymer.
Structural units derived from (Aa); 5-50 mol%
Structural units derived from (Ab); 50-95 mol%
Moreover, it is more preferable in the said ratio of the structural unit being the following ranges.
Structural units derived from (Aa); 10 to 45 mol%
Structural units derived from (Ab); 55 to 90 mol%
The polystyrene-reduced weight average molecular weight and molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the obtained resin can be approximately the same as those of the resin (A1).

Next, in order to give reactivity by the action of light and heat, the carboxylic acid and carboxylic acid of (Aa) derived from a copolymer obtained by copolymerizing (Aa) and (Ab) A part of the anhydride is reacted with an epoxy group, oxetanyl group or tetrahydrofuryl group derived from (Ac).
For that purpose, the atmosphere in the flask is subsequently replaced with nitrogen to air, and (A-c), a reaction catalyst, a polymerization inhibitor and the like are placed in the flask, and the reaction is performed, for example, at 60 to 130 ° C. for 1 to 10 hours. to continue.

In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
For example, the number of moles of (Ac) is 5 to 80 mole%, preferably 10 to 75 mole%, more preferably 15 to 70 mole%, based on the number of moles of (Aa). It is. When the composition ratio is within this range, the balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tends to be good.
As the reaction catalyst, for example, those used as a reaction catalyst between a carboxy group and an epoxy group, oxetanyl group or tetrahydrofuryl group are suitable. Specific examples include trisdimethylaminomethylphenol.
The amount of the reaction catalyst used in this case is, for example, about 0.001 to 5% by mass with respect to the total amount of the monomers (Aa) to (Ac).
Examples of the polymerization inhibitor include hydroquinone.
As for the usage-amount of a polymerization inhibitor, about 0.001-5 mass% is illustrated with respect to the total amount of monomer (Aa)-(Ac), for example.

The resin (A2-3) can be produced by the same production method as the resin (A1) except that (Aa) and (Ac) are used.
In resin (A2-3), it is preferable that the ratio of the structural unit derived | led-out from each is a molar fraction with respect to the total mole number of the structural unit which comprises resin (A2-3), and exists in the following ranges.
Structural units derived from (Aa); 5-95 mol%
Structural units derived from (Ac); 5-95 mol%
Moreover, it is more preferable in the said ratio of the structural unit being the following ranges.
Structural units derived from (Aa); 10 to 90 mol%
Structural units derived from (Ac); 10 to 90 mol%
When the composition ratio is in this range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be good.

Examples of the polymerizable monomer (B) contained in the photosensitive resin composition of the present invention include a monofunctional monomer, a bifunctional monomer, or a trifunctional or higher polyfunctional monomer.
Monofunctional monomers include nonylphenyl carbitol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, lauryl (meth) ) Acrylate, stearyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propoxylated nonylphenol (meth) ) Acrylate or N-vinyl pyrrolidone.

  Bifunctional monomers include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, bis (acryloyloxyethyl) ether of bisphenol A, Ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate or 3-methylpenta Diol di (meth) acrylate.

  The trifunctional or higher polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) ) Acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tri Pentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate Rate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, tripentaerythritol hepta (meta ) Acrylate and anhydride caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra ( (Meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) Chryrate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate, caprolactone-modified tripenta Erythritol octa (meth) acrylate, reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride, or caprolactone-modified tripentaerythritol Examples include hepta (meth) acrylate and acid anhydrides.

In the present specification, caprolactone modification means that a caprolactone ring-opening product or a ring-opening polymer is introduced between the alcohol-derived site of the (meth) acrylate compound and the (meth) acryloyloxy group.
In particular, it is preferable to use a bifunctional or higher polyfunctional monomer.

  The content of the polymerizable monomer (B) is preferably 1 to 70% by mass and more preferably 5 to 60% by mass with respect to the total amount of the resin (A) and the polymerizable monomer (B). When the content of the polymerizable monomer (B) is in this range, the sensitivity, the strength of the coating film and the pattern, smoothness, reliability, and mechanical strength tend to be improved.

  The photosensitive resin composition of the present invention may further contain at least one compound (Y) selected from the group consisting of a carboxylic acid anhydride and a compound having at least two carboxy groups. Examples of the latter compound include polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids.

  As the carboxylic acid anhydride, an epoxy resin curing agent made of a commercially available colorless acid anhydride can also be suitably used. Specifically, ADEKA HARDNA-EH-700 (trade name (hereinafter the same), manufactured by ADEKA Corporation), Rikacid-HH, MH-700 (manufactured by Shin Nippon Rika Co., Ltd.), Epikinia 126, YH-306 DX-126 (manufactured by Yuka Shell Epoxy Co., Ltd.).

As the polyvalent carboxylic acid anhydride, for example,
Aliphatic dicarboxylic acids such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, norbornene dicarboxylic acid, and hymic anhydride Anhydride;
Aliphatic polycarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride;
Aromatic polycarboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride;
And ester group-containing acid anhydrides such as ethylene glycol bistrimellitate and glycerin tristrimellitate.
Of these, phthalic anhydride and trimellitic anhydride are preferred because of their high transparency and high resolution.

Examples of the polyvalent carboxylic acid include
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, itaconic acid;
Alicyclic polycarboxylic acids such as hexahydrophthalic acid, 1,2-cyclohexanecarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid;
Examples thereof include aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 1,4,5,8-naphthalene tetracarboxylic acid, and benzophenone tetracarboxylic acid.
Of these, phthalic acid and trimellitic acid are preferred because of their high transparency and high resolution.

  The content of the compound (Y) in the photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass, more preferably relative to the total amount of the binder resin (A) and the polymerizable monomer (B). 1 to 15% by mass. When the compound (Y) is in this range, the resolution and the remaining film rate can be improved.

  Examples of the polymerization initiator (C) contained in the photosensitive resin composition of the present invention include compounds that initiate polymerization by the action of light or heat. For example, a biimidazole compound, an acetophenone compound, a triazine compound, an acyl phosphine oxide compound, or an oxime compound can be used. Of these, biimidazole compounds are particularly preferred because of their excellent sensitivity.

Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4,4. ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4', 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) ) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) bi Imidazole (for example, JP-B-48-38403, JP-A-62-174204, etc.), imidazole compounds in which the phenyl group at the 4,4′5,5′-position is substituted by a carboalkoxy group (for example, -10913 gazette etc.) etc. are mentioned.
Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 Examples include 5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

  Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2. -Methylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylsulfanylphenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -but Non, 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl)- Butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl)- Butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chloro) Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-chloro Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromo Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methoxy) Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-dimethylamino- 1- (4-morpholinophenyl) -butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxybenzyl) -2 -Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromo Of 4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one An oligomer etc. are mentioned.

  Examples of triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl). ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2- Methylphenyl) ete Le] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine

  Examples of the acylphosphine oxide initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Examples of the oxime compound include O-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, a compound represented by the formula (1), a compound represented by the formula (2), and the like.

The polymerization initiator (C) of the photosensitive resin composition of the present invention may contain the following photopolymerization initiator and the like.
Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, thioxanthone compounds, and the like.

  Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxy). Carbonyl) benzophenone and 2,4,6-trimethylbenzophenone.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

  Further, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate or titanocene compound may be used as a photopolymerization initiator.

Further, as a photopolymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in JP-T-2002-544205 can be used.
As a photoinitiator which has the group which can raise | generate the said chain transfer, the photoinitiator of following formula (3)-following formula (8) is mentioned, for example.

In addition, light and / or thermal cationic polymerization initiators can be used.
As the light and / or thermal cationic polymerization initiator, those composed of an onium cation and an anion derived from a Lewis acid can also be used.

  Specific examples of the onium cation include diphenyliodonium, bis (p-tolyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, bis ( p-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (p-octadecyloxyphenyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, triphenylsulfonium, tris (p-tolyl) ) Sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (p-tert-butylphenyl) sulfonium, tris (p-cyano) Enyl) sulfonium, tris (p-chlorophenyl) sulfonium, dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecanoxy) sulfonium, Dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromo Propoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (8-nitrooctyl) Oxy) sulfonium, dimethyl (18-trifluoromethyl octadecanoic oxy) sulfonium, dimethyl (2-hydroxy-isopropoxyphenyl) sulfonium, or dimethyl (tris (trichloromethyl) methyl) sulfonium, and the like.

  Preferred onium cations include bis (p-tolyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium or tris (p-tert-butylphenyl). ) Sulfonium and the like.

Specific examples of the Lewis acid-derived anion include hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, and tetrakis (pentafluorophenyl) borate. Preferred anions derived from Lewis acid include hexafluoroantimonate or tetrakis (pentafluorophenyl) borate.
These onium cations and Lewis acid-derived anions can be arbitrarily combined.

  Specific examples of the cationic polymerization initiator include diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-octylphenyl) iodonium hexa Fluorophosphate, bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium Hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophos , Methyl naphthyl iodonium hexafluorophosphate, ethyl naphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexafluorophosphate, tris (2, 6-dimethylphenyl) sulfonium hexafluorophosphate, tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium Hexafluorophosphate, diethylnaphthyls Honium hexafluorophosphate, dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl (ethoxy) sulfonium hexafluorophosphate, dimethyl (propoxy) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluoro Phosphate, dimethyl (octadecanoxy) sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium Hexafluorophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluorophosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, Dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluorophosphate, dimethyl (tris (trichloromethyl) methyl) Sulfonium hexafluorophosphate;

  Diphenyliodonium hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, bis (p-octylphenyl) iodonium hexafluoroarsenate, bis (p -Octadecylphenyl) iodonium hexafluoroarsenate, bis (p-octyloxyphenyl) iodonium hexafluoroarsenate, bis (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarsenate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, methylnaphthyl iodonium Oxafluoroarsenate, ethyl naphthyl iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (p-tolyl) sulfonium hexafluoroarsenate, tris (p-isopropylphenyl) sulfonium hexafluoroarsenate, tris (2, 6-dimethylphenyl) sulfonium hexafluoroarsenate, tris (p-tert-butylphenyl) sulfonium hexafluoroarsenate, tris (p-cyanophenyl) sulfonium hexafluoroarsenate, tris (p-chlorophenyl) sulfonium hexafluoroarsenate , Dimethylnaphthylsulfonium hexafluoroarsenate, diethylnaphthylsulfonium hexafluoroarsenate Dimethyl (methoxy) sulfonium hexafluoroarsenate, dimethyl (ethoxy) sulfonium hexafluoroarsenate, dimethyl (propoxy) sulfonium hexafluoroarsenate, dimethyl (butoxy) sulfonium hexafluoroarsenate, dimethyl (octyloxy) sulfonium hexafluoroarsenate Dimethyl (octadecanoxy) sulfonium hexafluoroarsenate, dimethyl (isopropoxy) sulfonium hexafluoroarsenate, dimethyl (tert-butoxy) sulfonium hexafluoroarsenate, dimethyl (cyclopentyloxy) sulfonium hexafluoroarsenate, dimethyl (cyclohexyloxy) ) Sulfonium hexafluoroarsenate, dimethyl (Fluoromethoxy) sulfonium hexafluoroarsenate, dimethyl (2-chloroethoxy) sulfonium hexafluoroarsenate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarsenate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroarsenate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroarsenate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroarsenate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroarsenate, dimethyl (tris (trichloromethyl) Methyl) sulfonium hexafluoroarsenate;

  Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, bis (p-octylphenyl) iodonium hexafluoroantimonate, bis (p -Octadecylphenyl) iodonium hexafluoroantimonate, bis (p-octyloxyphenyl) iodonium hexafluoroantimonate, bis (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroantimonate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, methyl naphthalate Tyl iodonium hexafluoroantimonate, ethyl naphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate, tris (p-isopropylphenyl) sulfonium hexafluoroantimonate, tris ( 2,6-dimethylphenyl) sulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium hexafluoroantimonate, tris (p-chlorophenyl) sulfonium hexafluoro Antimonate, dimethyl naphthylsulfonium hexafluoroantimonate, diethyl naphthyl Rufonium hexafluoroantimonate, dimethyl (methoxy) sulfonium hexafluoroantimonate, dimethyl (ethoxy) sulfonium hexafluoroantimonate, dimethyl (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimonate, dimethyl (octyl) Oxy) sulfonium hexafluoroantimonate, dimethyl (octadecanoxy) sulfonium hexafluoroantimonate, dimethyl (isopropoxy) sulfonium hexafluoroantimonate, dimethyl (tert-butoxy) sulfonium hexafluoroantimonate, dimethyl (cyclopentyloxy) sulfonium hexafluoro Antimonate, dimethyl (cyclohexyl) Ruoxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium hexafluoroantimonate, dimethyl (2-chloroethoxy) sulfonium hexafluoroantimonate, dimethyl (3-bromopropoxy) sulfonium hexafluoroantimonate, dimethyl (4-cyano Butoxy) sulfonium hexafluoroantimonate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroantimonate , Dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoro Nchimoneto;

  Diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (p-tolyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-octylphenyl) Iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) Iodonium tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis Pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, methylnaphthyliodonium tetrakis (pentafluorophenyl) borate, ethylnaphthyliodonium tetrakis (pentafluorophenyl) borate, triphenyl Sulfonium tetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-isopropylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (2,6-dimethylphenyl) sulfonium Tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium teto Kiss (pentafluorophenyl) borate, tris (p-cyanophenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, Diethyl naphthylsulfonium tetrakis (pentafluorophenyl) borate, dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (ethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (propoxy) sulfonium tetrakis (pentafluorophenyl) borate, Dimethyl (butoxy) sulfonium tetrakis (pentafluorophenyl) bo Dimethyl (octyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octadecanoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tert-butoxy) Sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclopentyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclohexyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (fluoromethoxy) sulfonium tetrakis (pentafluorophenyl) borate , Dimethyl (2-chloroethoxy) sulfonium tetra (Pentafluorophenyl) borate, dimethyl (3-bromopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (4-cyanobutoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) And methyl) sulfonium tetrakis (pentafluorophenyl) borate.

  Preferably, bis (p-tolyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate , Tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsenate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, bis (p-tert- Butylphenyl) iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (pt-butylphenyl) sulfonate Muhexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, Triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium Tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentafluorophenyl) Yl) borate, tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, and the like.

  More preferably, bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenyl Sulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis ( Pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium Tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, and the like.

The content of the polymerization initiator (C) is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass with respect to the total amount of the resin (A) and the polymerizable monomer (B).
When the total amount of the polymerization initiator (C) is within this range, the photosensitive resin composition becomes highly sensitive, the strength of the coating film or pattern formed using the photosensitive resin composition, and the coating film And the smoothness of the surface of the pattern tends to be good.

Moreover, you may use for the photosensitive resin composition of this invention combining a polymerization initiator adjuvant (C-1) with a polymerization initiator (C) to such an extent that the effect of this invention is not impaired.
Examples of the polymerization initiation aid (C-1) include amine compounds, carboxylic acid compounds, polyfunctional thiol compounds, compounds represented by the formula (IV), compounds represented by the formula (V) or the formula (VI), and the like. Can be mentioned.

  Examples of amine compounds include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylamino. 2-ethylhexyl benzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4′-bis (diethylamino) benzophenone, etc. The aromatic amine compound of these is mentioned.

  Examples of carboxylic acid compounds include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N- Aromatic heteroacetic acids such as phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine or naphthoxyacetic acid can be mentioned.

The polyfunctional thiol compound is a compound having two or more sulfanyl groups in the molecule.
Specific examples of the polyfunctional thiol compound include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and trimethylol. Propane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tris Thiopropionate, pentaerythritol tetrakis (3-mercaptobutyrate) or 1,4-bis (3-mercaptobutyryloxy) butane And the like.
Among these, a compound having two or more sulfanyl groups bonded to a carbon atom of an aliphatic hydrocarbon group is more preferable because the sensitivity of the photosensitive resin composition of the present invention is increased.

The compound represented by the formula (IV) is the following compound.

In formula (IV), the ring represented by X represents an aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom.
Y represents an oxygen atom or a sulfur atom.
R ²¹ represents an alkyl group having 1 to 6 carbon atoms.
R ²² represents an alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom or an aryl group which may be substituted with a halogen atom.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the aromatic ring having 6 to 12 carbon atoms include benzene ring, methylbenzene ring, dimethylbenzene ring, ethylbenzene ring, propylbenzene ring, butylbenzene ring, pentylbenzene ring, hexylbenzene ring, cyclohexylbenzene ring, chlorobenzene ring, and dichlorobenzene. Ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring, phenanthrene ring, chrysene ring, fluoranthene ring, benzo [a] pyrene ring, Examples include benzo [e] pyrene ring, perylene ring, and derivatives thereof. Of these, a benzene ring, a naphthalene ring and the like are preferable.

  Examples of the aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom include a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, a hexylbenzene ring, Examples include cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring, and the like.

  Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2-methyl-n-propyl group, tert- Butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2- Examples include dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group and the like.

  Examples of the alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2- Methyl-n-propyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl- n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group, 1-chloro-n-butyl group, 2-chloro-n- Examples thereof include a butyl group and a 3-chloro-n-butyl group.

  The aryl group which may be substituted with a halogen atom includes a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobromophenyl group, a biphenyl group, a chlorobiphenyl group, a dichlorobiphenyl group, and a bromophenyl group. , Dibromophenyl group, naphthyl group, chloronaphthyl group, dichloronaphthyl group, bromonaphthyl group, dibromonaphthyl group and the like.

As the compound represented by the formula (IV), specifically,
2-benzoylmethylene-3-methyl-naphtho [2,1-d] thiazoline,
2-benzoylmethylene-3-methyl-naphtho [1,2-d] thiazoline,
2-benzoylmethylene-3-methyl-naphtho [2,3-d] thiazoline,
2- (2-naphthoylmethylene) -3-methylbenzothiazoline,
2- (1-naphthoylmethylene) -3-methylbenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-phenylbenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-fluorobenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-fluorobenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-chlorobenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-5-bromobenzothiazoline,
2- (1-naphthoylmethylene) -3-methyl-5-bromobenzothiazoline,
2- (4-biphenoylmethylene) -3-methylbenzothiazoline,
2- (4-biphenoylmethylene) -3-methyl-5-phenylbenzothiazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,
2- (4-biphenoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,
2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,
2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline, 2- Benzoylmethylene-3-methyl-naphtho [2,1-d] oxazoline,
2-benzoylmethylene-3-methyl-naphtho [1,2-d] oxazoline,
2-benzoylmethylene-3-methyl-naphtho [2,3-d] oxazoline,
2- (2-naphthoylmethylene) -3-methylbenzoxazoline,
2- (1-naphthoylmethylene) -3-methylbenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-phenylbenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-fluorobenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-fluorobenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-chlorobenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-5-bromobenzoxazoline,
2- (1-naphthoylmethylene) -3-methyl-5-bromobenzoxazoline,
2- (4-biphenoylmethylene) -3-methylbenzoxazoline,
2- (4-biphenoylmethylene) -3-methyl-5-phenylbenzoxazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,
2- (2-naphthoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline,
2- (4-biphenoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline, 2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline, 2- (P-fluorobenzoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline, and the like. .

Among them, 2- (2-naphthoylmethylene) -3-methylbenzothiazoline represented by formula (9), 2-benzoylmethylene-3-methyl-naphtho represented by formula (10) [1,2-d] Thiazoline and 2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline represented by the formula (11) are preferable.

The compounds represented by formula (V) and formula (VI) are the following compounds.

In Formula (V) and Formula (VI), Ring X ³¹ and Ring X ³² each independently represent an aromatic ring having 6 to 12 carbon atoms. Y ³¹ and Y ³² represent an oxygen atom or a sulfur atom. R ³¹ and R ³² represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.
Carbon atoms contained in these aromatic rings, alkyl groups or aryl groups may be substituted with oxygen atoms, nitrogen atoms or sulfur atoms, and hydrogen atoms contained in these aromatic rings, alkyl groups or aryl groups are substituted with halogen atoms. May be. Moreover, the hydrogen atom contained in the aryl group may be substituted with a hydroxyl group or an alkoxy group. ]

Examples of the hydroxyl group-substituted aryl group include a hydroxyphenyl group and a hydroxynaphthyl group.
As an alkoxy group, a C1-C6 alkoxy group is mentioned, for example. Specifically, methoxy, ethoxy, propoxy, butoxy and the like can be mentioned.
Examples of the alkoxy group-substituted aryl group include methoxyphenyl, ethoxyphenyl, propoxyphenyl, methoxynaphthyl, ethoxynaphthyl, propoxynaphthyl and the like.

As a compound represented by formula (V) or formula (VI), specifically,
Dialkoxynaphthalenes such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene, dibutoxynaphthalene;
Dimethoxyanthracene, diethoxyanthracene, dipropoxyanthracene, diisopropoxyanthracene, dibutoxyanthracene, dipentaoxyanthracene, dihexaoxyanthracene, methoxyethoxyanthracene, methoxypropoxyanthracene, methoxyisopropoxyanthracene, methoxybutoxyanthracene, ethoxypropoxyanthracene Dialkoxyanthracenes such as ethoxyisopropoxyanthracene, ethoxybutoxyanthracene, propoxyisopropoxyanthracene, propoxybutoxyanthracene, isopropoxybutoxyanthracene;
Examples thereof include dialkoxynaphthacenes such as dimethoxynaphthacene, diethoxynaphthacene, dipropoxynaphthacene, diisopropoxynaphthacene and dibutoxynaphthacene.

The content of the polymerization initiation assistant (C-1) is preferably 0.01 to 50% by mass, more preferably 0.1 to 40%, based on the total amount of the resin (A) and the polymerizable monomer (B). % By mass.
In particular, when a polyfunctional thiol compound is used as the polymerization initiation assistant (C-1), the content thereof is preferably 0.5 to 20% by mass, more preferably relative to the polymerization initiator (C). 1 to 15% by mass.
Further, the content of the compound represented by at least one selected from the group consisting of the formula (V) and the formula (VI) is preferably 50 to the content of the polymerization initiation aid (C-1). 100 mass%, More preferably, it is 60-100 mass%, More preferably, it is 65-100 mass%. When the content of these compounds is in this range, when the coating film is formed using the photosensitive resin composition containing the compound, the transparency of the coating film is improved, which is preferable.
When the amount of the polymerization initiation assistant (C-1) is in the above range, the sensitivity of the resulting photosensitive resin composition is further increased, and the developability is improved. The photosensitive resin composition is formed using this photosensitive resin composition. The productivity of the pattern to be improved tends to be improved.

The photosensitive resin composition of the present invention contains a solvent (D). Examples of the solvent (D) include various organic solvents used in the field of photosensitive resin compositions.
Specific examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate;
Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether, propylene glycol ethyl propyl ether, propylene glycol methyl ether propionate, propylene glycol ethyl ether Propylene glycol alkyl ether propionates such as propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate;

Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol, butoxybutyl alcohol;
Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate;
Butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate;
Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether;
Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin;

Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyethyl acetate, hydroxy Butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methylbutane Methyl acetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, propoxy Ethyl acetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2- Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxy Propyl propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3- Methyl toxipropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxy Esters such as butyl propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate;
Cyclic ether groups such as tetrahydrofuran and pyran;
and cyclic esters such as γ-butyrolactone.

The solvent (D) is preferably a solvent containing two or more kinds of solvents having a boiling point of 175 ° C. or lower, and preferably contains a solvent having a boiling point of 140 ° C. or higher and 175 ° C. or lower from the viewpoints of coating properties and drying properties. More preferably, it is a solvent containing two or more solvents having a boiling point of 140 ° C. or higher and 175 ° C. or lower.
Solvents having a boiling point of 140 ° C. or more and 175 ° C. or less include alkylene glycol alkyl ether acetates; alcohols such as methoxybutanol and ethoxybutanol; ketones such as cyclohexanone; ethyl 3-ethoxypropionate, methyl 3-methoxypropionate; Examples thereof include esters such as ethyl 3-ethoxyacetate, butyl 3-methoxyacetate, and butyl 3-ethoxyacetate.
Preferred examples include 3-methoxybutanol, methoxybutyl acetate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate. Of these, 3-methoxybutanol is more preferable.

These solvents (D) may contain a solvent having a boiling point exceeding 175 ° C.
The solvent (D) preferably contains an alcohol having 1 to 6 carbon atoms.
Such an alcohol can be appropriately selected from the solvents described above. Such alcohol preferably has a boiling point of 175 ° C. or lower, but may be a solvent having a boiling point higher than 175 ° C.

  Content of the solvent (D) in the photosensitive resin composition of this invention becomes like this. Preferably it is 60-90 mass% with respect to the photosensitive resin composition, More preferably, it is 65-85 mass%. When the content of the solvent (D) is in this range, the coating property is improved when applied by various coating apparatuses described later. In addition, when the solvent whose boiling point exceeds 175 degreeC is contained, such a solvent has preferable about 30 mass% or less in all the solvents.

  The surfactant (E) in the photosensitive resin composition of the present invention is not particularly limited, and examples thereof include silicone surfactants, fluorine surfactants, silicone surfactants having fluorine atoms, and the like. Can be mentioned. Of these, a silicone-based surfactant having a fluorine atom is preferred. By using such a surfactant (E), generation of fine bubbles contained in the composition can be prevented in combination with other components in the photosensitive resin composition and the content thereof. As a result, bumping at the time of solvent evaporation can be effectively suppressed.

Examples of the silicone surfactant include surfactants having a siloxane bond.
Specifically, Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (made by Momentive Performance Materials Japan GK) Is mentioned.

Examples of the fluorosurfactant include surfactants having a fluorocarbon chain.
Specifically, Florinart (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, R183 (DIC) ), Ftop (registered trademark) EF301, EF303, EF351, EF351, EF352 (manufactured by Mitsubishi Materials Denkasei), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass) Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (both trade names: BM, manufactured by Chemie) and the like.

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned. Preferably, MegaFac (registered trademark) F475 is used.

  The surfactant (E) is 0.0025 to 0.0250% by mass, preferably 0.0025 to 0.0200% by mass, based on 100% by mass of the photosensitive resin composition excluding the surfactant. Preferably it is 0.05-0.0100 mass%. By containing the surfactant in this range, the flatness can be improved, and bumping can be effectively prevented as described above.

In the photosensitive resin composition of the present invention, if necessary, a filler, a polymer compound other than the resin (A), an adhesion promoter, an antioxidant, an ultraviolet absorber, a light stabilizer, an anti-aggregation agent, a chain. You may use together additives, such as a transfer agent.
It is suitable that the photosensitive resin composition of the present invention does not substantially contain colorants such as pigments and dyes. That is, in the photosensitive resin composition of the present invention, the content of the colorant with respect to the whole composition is suitably less than 1% by mass, preferably less than 0.5% by mass.

Examples of the filler include glass, silica, and alumina.
Examples of the polymer compound other than the resin (A) include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Can be mentioned.

  As the adhesion promoter, a silane compound is preferable. Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane , 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

  Antioxidants include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5 -Di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4 , 8,10-Tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-) 5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2′-methylenebis ( -Tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2 , 2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropioate , Pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″ − Mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl -4-methylphenol and the like.

  Examples of ultraviolet absorbers include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H- Benzotriazol-2-yl) phenyl] propionate, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl) Phenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-bis-butyloxyphenyl) -1,3 5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2- (2H-benzo Triazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl)- Examples include 4- (1,1,3,3-tetramethylbutyl) phenol, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like.

  As a light stabilizer, a polymer composed of succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl) ethanol, N, N ′, N ″, N ′ ″ − Tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazin-2-yl) -4,7-diazadecane-1,10- Reaction product of diamine, decandioic acid, bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester and 1,1-dimethylethyl hydroperoxide, bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, 2,4-bis [N-Bu Ru-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine, bis (1, 2,2,6,6-pentamethyl-4-piperidinyl) sebacate or methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate.

Examples of the aggregation inhibitor include sodium polyacrylate.
Examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

The photosensitive resin composition of the present invention preferably has a solid content of about 10 to 30% by mass, more preferably 12 to 28% by mass, and still more preferably 15 to 25% by mass. By setting it as this range, a uniform coating film can be formed without generating defects or mottled unevenness even by various coating methods, particularly the slit method.
Moreover, when the photosensitive resin composition of the present invention is filled in a quartz cell having an optical path length of 1 cm and the transmittance is measured under a measurement wavelength of 400 to 700 nm using a spectrophotometer, the transmittance is 70. % Or more, preferably 80% or more.

  When the photosensitive resin composition of the present invention is used as a coating film, the transmittance of the coating film is preferably 90% or more, and more preferably 95% or more. This transmittance is measured under the conditions of a measurement wavelength of 400 to 700 nm using a spectrophotometer for a coating film having a thickness of 3 μm after heat curing (for example, 100 to 250 ° C., 5 minutes to 3 hours). This is the value when measured. Thereby, the coating film excellent in transparency can be provided.

  The photosensitive resin composition of the present invention is, for example, a substrate such as a substrate such as glass, metal or plastic, a color filter, various insulating or conductive films, a drive circuit, or the like, as described later. A coating film can be formed by applying on the surface. The coating film is preferably dried and cured. Moreover, the obtained coating film can be patterned into a desired shape and used as a pattern. Furthermore, you may form these coating films or patterns as some components, such as a display apparatus.

First, the photosensitive resin composition of this invention is apply | coated on the layer which consists of solid content of the base material or the photosensitive resin composition formed previously.
The coating method is not particularly limited, and for example, it is performed using a coating apparatus such as a spin coater, a slit & spin coater, a slit coater (sometimes referred to as a die coater or a curtain flow coater), an inkjet, a roll coater, or a dip coater. be able to. Among these, from the viewpoint of solubility, prevention of drying, prevention of the generation of foreign substances, etc., it is preferable to use a slit coating method, that is, use a slit & spin coater, a slit coater or the like.

Then, it is preferable to dry or pre-bake to remove volatile components such as a solvent. Thereby, a smooth uncured coating film can be obtained. In particular, drying under reduced pressure is preferable. The reduced-pressure drying here may be performed by removing at least a part of the solvent so that it does not become an obstacle in the subsequent steps, and it is not always necessary to remove all the solvent from the coating film. The drying under reduced pressure is preferably performed in the range of normal pressure to ultimate pressure of 10 to 500 Pa under room temperature (25 ° C.) conditions, more preferably 30 to 400 Pa, and even more preferably 50 to 300 Pa. There is no limitation on the drying time under reduced pressure, and it can be conveniently set in consideration of the film thickness, the size of the substrate, the amount of solvent of the photosensitive resin composition, and the like. Usually, 10 seconds to 60 seconds are preferable. In order to apply such relatively severe vacuum drying conditions, the vacuum rate may be changed in multiple stages until the final ultimate pressure is reached. For example, a smoother uncured film can be obtained by controlling the pressure reduction speed in two stages, that is, the time required from normal pressure to 130 Pa is about 10 seconds and from 130 Pa to 66 Pa is about 10 seconds.
The film thickness of the coating film in this case is not particularly limited, and can be appropriately adjusted depending on the material, use, etc., for example, about 0.1 to 30 μm, preferably about 1 to 20 μm, more preferably 1 to 6 μm. The degree is exemplified.

Further, the obtained uncured coating film is irradiated with light, for example, ultraviolet rays generated from a mercury lamp, a light emitting diode, or the like through a mask for forming a target pattern. The shape of the mask at this time is not particularly limited, and various shapes can be mentioned. Further, the line width and the like can be appropriately adjusted depending on the mask size and the like.
In recent exposure machines, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm is used using a bandpass filter that extracts these wavelength ranges. It is possible to selectively take out and irradiate parallel light uniformly on the entire exposure surface. At this time, an apparatus such as a mask aligner or a stepper may be used to accurately align the mask and the substrate.

Thereafter, a desired pattern shape can be obtained by bringing the coating film into contact with an aqueous alkali solution to dissolve a predetermined portion, for example, an unexposed portion, and developing.
The developing method may be any of a liquid piling method, a dipping method, a spray method, and the like. Further, the substrate may be inclined at an arbitrary angle during development.

The developer used for development is usually an aqueous solution containing an alkaline compound and a surfactant.
The alkaline compound may be either an inorganic or organic alkaline compound.
Inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, Examples include potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate or ammonia.
Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. It is done.
The content of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

Further, the surfactant in the alkali developer may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan Examples include fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.
Anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate. And alkylaryl sulfonates such as
Examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, or quaternary ammonium salts.
The content of the surfactant in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.

  After development, washing may be performed, and post-baking may be performed as necessary. The post-bake is preferably, for example, a temperature range of 150 to 230 ° C. and 10 to 180 minutes.

In particular, the photosensitive resin composition of the present invention is formed by applying the photosensitive resin composition of the present invention on a substrate using a slit coater to form a film, and drying the film formed on the substrate under reduced pressure. Therefore, it is preferably used for producing a coating film.
Moreover, it is preferable to use in order to manufacture a pattern by exposing the obtained coating film through a photomask and developing the exposed coating film.

The coating film or pattern thus obtained is useful as, for example, a photospacer used in a liquid crystal display device or a patternable overcoat. Moreover, a hole can be formed by using the photomask for hole formation at the time of patterning exposure to an uncured coating film, and it is useful as an interlayer insulation film. Furthermore, a transparent film can be formed by performing only the whole surface exposure and heat curing or heat curing without using a photomask when exposing an uncured coating film. This transparent film is useful as an overcoat. Further, it can be used for a display device such as a touch panel. Thereby, it is possible to manufacture a display device having a high-quality coating film or pattern with a high yield.
The photosensitive resin composition of the present invention is a material for forming various films and patterns, such as a transparent film, in particular, a transparent film, a pattern, a photospacer, an overcoat, and an insulating film constituting a part of a color filter. It can be suitably used for forming liquid crystal alignment control protrusions, microlenses, colored patterns combining different film thicknesses, coat layers, and the like. Further, a color filter, an array substrate, or the like provided with these coating films or patterns as a part of its constituent parts, and a display device including these color filters and / or an array substrate, for example, a liquid crystal display device, an organic EL device Etc. can be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. Moreover, in the following Examples and Comparative Examples,% and part representing the content or amount used are based on mass unless otherwise specified.

Synthesis example 1
A 1 liter flask equipped with a reflux condenser, a dropping funnel and a stirrer was flowed with nitrogen at 0.02 L / min to form a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate. And heated to 70 ° C. with stirring.
Next, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) A mixture was prepared by dissolving 240 parts by mass of a mixture of compounds to be mixed (molar ratio = 50: 50) in 140 parts by mass of 3-methoxybutyl acetate.
The obtained solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel.
On the other hand, a solution obtained by dissolving 45 parts by mass of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of 3-methoxybutyl acetate was added to a flask over another 4 hours using another dropping funnel. It was dripped in.
After completion of the dropwise addition of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours, and then cooled to room temperature, and a copolymer having a solid content of 32.3% by mass and an acid value of 35.6 mg-KOH / g ( A resin solution of resin Aa) was obtained. The obtained resin Aa had a weight average molecular weight Mw of 9.1 × 10 ³ and a dispersity of 2.02.

Synthesis example 2
Nitrogen was flowed at 0.02 L / min into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 140 parts by mass of diethylene glycol ethyl methyl ether was added and heated to 70 ° C. with stirring.
Next, 40 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.12.02.6] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) A mixture was prepared by dissolving 360 parts by mass of a compound mixture (molar ratio = 50: 50) in 190 parts by mass of diethylene glycol ethyl methyl ether.
The obtained solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping pump.
On the other hand, a solution prepared by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 240 parts by mass of diethylene glycol ethyl methyl ether was added to a flask over another 5 hours using another dropping pump. It was dripped in.
After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature, and the copolymer (resin Ab) having a solid content of 42.6% by mass and an acid value of 60 mg-KOH / g ) Was obtained. The obtained resin Ab had a weight average molecular weight (Mw) of 8.0 × 10 ³ and a dispersity of 1.91.

About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the said binder polymer, it carried out on condition of the following using GPC method.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
The ratio of the weight-average molecular weight and number-average molecular weight obtained above in terms of polystyrene was defined as the degree of dispersion (Mw / Mn).

Examples 1-8, Comparative Examples 1-3
Each component was mixed with the composition of Table 1, and the photosensitive resin composition was obtained.

In Table 1,
Resin (A) represents a mass part in terms of solid content.
Polymerizable monomer (B); dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerization initiator (C); 2-methyl-2-morpholino (4-methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by Ciba Japan)
Solvent (Da); 3-methoxy-1-butanol (boiling point 161 ° C.)
Solvent (Db); ethyl 3-ethoxypropionate (boiling point 170 ° C.)
Solvent (Dc); 3-methoxybutyl acetate (boiling point 171 ° C.)
Solvent (Dd); Diethylene glycol ethyl methyl ether (boiling point 176 ° C.)
Solvent (De); propylene glycol monomethyl ether acetate (boiling point 146 ° C.)
Solvent (Df); benzyl alcohol (boiling point 205 ° C.)
Solvent (Dg); ethylene glycol monobutyl ether acetate (boiling point 192 ° C.)
Surfactant (E); polyether-modified silicone oil (SH8400 manufactured by Toray Dow Corning Co., Ltd.).
The solvent (D) is mixed so that the solid content of the composition becomes the “solid content (%)” in Table 1. The values of the solvent components (Da) to (Dg) in the solvent (D) D) represents the mass ratio.
The content of the surfactant (E) represents a mass ratio (%) to 100% by mass of the photosensitive resin composition excluding the surfactant.

<Evaluation of bumping and haze unevenness>
The prepared photosensitive resin composition is formed on a 15 cm square ITO film-formed glass substrate so that the film thickness after curing is 3.0 μm by using a slit die coater (Taku Die-100, manufactured by ITOCHU Corporation). The coating was performed under various conditions. Thereafter, the film was dried by reducing the degree of vacuum to 0.5 torr with a vacuum dryer (VCD Microtech Co., Ltd.), and further prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film A.
The obtained coating film A was cooled, the surface was illuminated with a Na lamp, and the coating film surface was visually confirmed.
When the defect resulting from bumping could be confirmed clearly, it was evaluated as “x”, when it was confirmed slightly, “△”, and when almost not confirmed, “◯”.
The symbol X was used when the smear was clearly confirmed, the symbol △ when it was slightly confirmed, and the symbol ◯ when almost not.

<Evaluation of uniformity>
About the obtained coating film A, the film thickness in the measuring point which arranged the distance within 12.5 mm from an end on the matrix at intervals of 12.5 mm was measured. The maximum film thickness, the minimum film thickness, and the average film thickness were obtained and evaluated by the formula (1).
Uniformity (%) = (maximum film thickness × minimum film thickness) / (2 × average film thickness) × 100 (1) If the uniformity is less than 3%, ○, if 3 to 5%, △ 5% or more In the case, it was set as x.

<Evaluation of drying time under reduced pressure>
Conditions such that the film thickness after curing of the prepared composition solution on a 15 cm square ITO film-formed glass substrate becomes 3.0 μm using a slit die coater (Takae Die-100, manufactured by ITOCHU Corporation). It was applied with. Thereafter, the time until the degree of pressure reduction reaches 66 Pa under the conditions of a rotary pump rotation speed of 1800 rpm, a booster pump rotation speed of 3600 rpm, and a room temperature of 25 ° C. (hereinafter referred to as VCD time). Was measured.
A shorter VCD time is advantageous.

  The photosensitive resin composition of the present invention can be applied uniformly over the entire surface of a large area, and the occurrence of defects, fogging, and the like due to bumping of the solvent is suppressed. Moreover, it is possible to form a coating film or a pattern having high resolution and high transmittance. Therefore, it can be suitably used for forming a coating film or a pattern used for a display device, such as an overcoat, a photo spacer, an insulating film, a liquid crystal alignment control protrusion, and a coating layer for adjusting the thickness of a colored pattern.

Claims (8)

A photosensitive resin composition comprising a resin (A), a polymerizable monomer (B), a polymerization initiator (C), a solvent (D) and a surfactant (E),
The resin (A) is a structural unit derived from at least one compound selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II), an unsaturated carboxylic acid and an unsaturated carboxylic acid. A resin having a structural unit derived from at least one compound selected from the group consisting of saturated carboxylic acid anhydrides,
The solvent (D) is a solvent containing two or more kinds of solvents having a boiling point of 175 ° C. or lower,
The content of the surfactant (E) is 0.0025 to 0.0250% by mass with respect to 100% by mass of the photosensitive resin composition excluding the surfactant,
A photosensitive resin composition having a solid content of 10 to 30% by mass.

[In Formula (I) and Formula (II), R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with a hydroxyl group.
X ¹ and X ² each independently represent a C 1-6 alkylene group that may contain a single bond or a hetero atom. ]   The photosensitive resin composition according to claim 1, wherein the solvent (D) is a solvent containing two or more kinds of solvents having a boiling point of 140 ° C. or more and 175 ° C. or less.   The photosensitive resin composition according to claim 1 or 2, wherein the solvent (D) is a solvent containing an alcohol having 1 to 6 carbon atoms.   The photosensitive resin composition according to claim 1, wherein the solvent (D) is a solvent containing 3-methoxybutanol.   The surfactant (E) is at least one selected from the group consisting of a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. Photosensitive resin composition.   The coating film formed using the photosensitive resin composition in any one of Claims 1-5.   The pattern formed using the photosensitive resin composition in any one of Claims 1-5.   A display device comprising at least one selected from the group consisting of the coating film according to claim 6 and the pattern according to claim 7.