JP5922272B2 - Photosensitive resin composition and method for producing coating film - Google Patents

Description

The present invention relates to a photosensitive resin composition and a method for producing a coating film.

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 species is being sought. For example, as a solvent, propylene glycol monomethyl ether acetate, 3-
It is disclosed that a photosensitive resin composition using a mixture of ethoxyethyl propionate, 3-methoxy 1-butanol and 3-methoxybutyl acetate is used (for example,
Patent Document 1).

Japanese Patent Laying-Open No. 2008-181087, paragraph 91

However, when the photosensitive resin composition using the above-described solvent is applied onto a concavo-convex substrate by spin coating, which is a typical application method, radial streaks are formed on the coated surface along the concavo-convex pattern. May occur (hereinafter referred to as “striation”).
In other words, using a conventionally proposed solvent, spin coating method, slit & spin method,
Even when applied to the slit die coating method, etc., the present situation is that a high-quality coating film is not necessarily obtained in all methods.
The present invention has been made in view of the above problems, and a photosensitive resin composition capable of suppressing the occurrence of striation and forming a uniform and high-quality coating film throughout the coating film and the same. An object is to provide a display device or the like.

The photosensitive resin composition of the present invention includes a resin (A), a polymerizable compound (B), a polymerization initiator (C), and a solvent (D).
One of the features of the solvent (D) is that it contains a solvent represented by the formula (D1).
R ¹ —O— (A—O) _n —R ² (D1)
(In Formula (D1), R ¹ and R ² each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms. A represents a linear or branched carbon number of 1; Represents an alkylene group of .about.3.
Represents an integer of 2 or 3. A plurality of A may be the same or different. )

In such a photosensitive resin composition, the solvent (D) has two or more different formulas (D1
It is preferable that the solvent represented by this is included.
Further, the solvent (D) contains diethylene glycol ethyl methyl ether or the solvent (D
) Preferably contains 10 to 90% by mass of diethylene glycol ethyl methyl ether based on the total amount of the solvent.
Furthermore, the solvent (D) is a solvent containing at least one solvent selected from the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether, or the solvent (D) is diethylene glycol butyl methyl with respect to the total amount of the solvent. It is preferable to contain 10 to 50% by mass of at least one solvent selected from the group consisting of ether and triethylene glycol dimethyl ether.
Furthermore, the solvent (D) is a solvent containing diethylene glycol ethyl methyl ether and at least one solvent selected from the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether, or diethylene glycol ethyl with respect to the total amount of the solvent. It is preferable to contain 60 to 100% by mass of methyl ether and at least one solvent selected from the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether.

Moreover, it is one of the characteristics that the coating film of this invention is formed using the photosensitive resin composition mentioned above.
Furthermore, the pattern of the present invention is formed using the above-described photosensitive resin composition.
The display device of the present invention is at least one selected from the group consisting of the above-mentioned coating film and pattern.
One of the characteristics is that it contains seeds.

According to the photosensitive resin composition of the present invention, the occurrence of striation can be suppressed, and a uniform and high quality coating film can be formed over the entire coating film.
Further, by using this photosensitive resin composition, it is possible to obtain a high-quality display device or the like.

The photosensitive resin composition of the present invention comprises a resin (A), a polymerizable compound (B), a polymerization initiator (C), and a solvent (D). In addition, in this specification, the compound illustrated as each component can be used individually or in combination unless there is particular notice.

As the resin (A) used in the photosensitive resin composition of the present invention, a resin (A1) having alkali solubility, a resin (A2) having reactivity due to alkali solubility and at least one of light and heat. And the like.

As the resin (A1) having alkali solubility, at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to as “(a)”), ( Examples thereof include a copolymer of a) and a copolymerizable monomer (c) (hereinafter sometimes referred to as “(c)”).

As (a), specifically, for example, acrylic acid, methacrylic acid, crotonic acid, o-
, M-, p-vinylbenzoic acid and other unsaturated monocarboxylic acids;
Saturated dicarboxylic acids such as 1,4-cyclohexene dicarboxylic acid and methyl-5-norbornene-2,3-dicarboxylic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid;
Anhydrides of these unsaturated dicarboxylic acids;

Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of copolymerization reactivity and alkali solubility.

(C) includes methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (
(Meth) acrylic acid alkyl esters such as (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 It is said to be 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 (referred to in the art as dicyclopentanyl acrylate), dicyclopentaoxyethyl acrylate, isobornyl acrylate, etc. Acrylic acid cyclic alkyl esters;
(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-carboxybicyclo [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 Ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [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-carboxy-5-methylbicyclo [2.2
. 1] Hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-
2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy -6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), 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 Bicyclo unsaturated compounds such as 2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide,
N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide, etc. Dicarbonylimide derivatives of

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride,
Examples include 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.
(A) and (c) can be used alone or in combination.
In this specification, (meth) acrylate means acrylate and / or methacrylate.

In the copolymer obtained by copolymerizing (a) and (c), the ratio of the constituent components derived from each is 100 mol% in terms of the total number of moles of the constituent components constituting the copolymer. Sometimes it is preferred that the molar fraction is in the following range:
Structural units derived from (a); 2 to 40 mol%
Structural unit derived from (c); 60 to 98 mol%

Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (a); 5-35 mol%
Structural unit derived from (c); 65 to 95 mol%
When the composition ratio is in the above range, storage stability, developability, and solvent resistance tend to be good.

The resin (A1) having alkali solubility is, for example, the document “Experimental Method for Polymer Synthesis”.
It can be produced with reference to the method described in (Takayuki Otsu Publishing Co., Ltd., Chemical Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the cited references described in the literature.

Specifically, a predetermined amount of units (a) and (c) constituting the copolymer, a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and the oxygen is replaced with nitrogen, so that oxygen is not present. Then, a method of stirring, heating and keeping warm is exemplified. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those usually used in the field can be used. For example, a polymerization initiator and a solvent 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 in this polymerization, the solution after the reaction can be used as it is, and the production process can be simplified (
The same applies to the resin (A2) hereinafter).

The polystyrene-reduced weight average molecular weight of the alkali-soluble resin (A1) is:
Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000. If the weight-average molecular weight of the resin (A1) having alkali solubility is in the above range, the coating property tends to be good, the film is not easily reduced during development, and the non-pixel portion can be removed during development. Tends to be good, which is preferable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A1) having alkali solubility is preferably 1.1 to 6.0, more preferably 1.2 to 4. 0
It is. The molecular weight distribution in the above range is preferable because it tends to be excellent in developability.

Resin (A1) having alkali solubility that can be used in the photosensitive resin composition of the present invention
The content of is a mass fraction with respect to the solid content in the photosensitive resin composition, preferably 5 to 90 mass%, more preferably 10 to 70 mass%. When the content of the resin (A1) having alkali solubility is in the above range, the solubility in the developer is sufficient, development residue is hardly generated on the non-pixel portion of the substrate, and the exposed portion is developed during development. It is preferable that the film thickness of the pixel portion is less likely to occur, and that the non-exposed portion tends to be easily removed.

Resin having alkali solubility and reactivity by the action of at least one of light and heat (
As A2)
Resin (A2-1): a copolymer of (a), (c), and a compound (b) having a cyclic ether structure having 2 to 4 carbon atoms (hereinafter sometimes referred to as “(b)”),
Resin (A2-2): a copolymer obtained by reacting (b) with a copolymer of (a) and (c),
Resin (A2-3): The copolymer of (a) and (b) etc. are mentioned.

(B) refers to a polymerizable compound having at least one structure selected from the group consisting of, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, an epoxy group, an oxetanyl group, and a tetrahydrofuryl group). (B) is preferably a compound having at least one structure selected from the group consisting of cyclic ether structures having 2 to 4 carbon atoms and having an ethylenic carbon-carbon unsaturated bond. It is more preferable that the compound has at least one structure selected from the group consisting of -4 cyclic ether structures and has an acryloyl group or a methacryloyl group.

Examples of (b) include a monomer (b1) having an epoxy group (hereinafter sometimes referred to as “(b1)”), a monomer (b2) having an oxetanyl group (hereinafter referred to as “(b2)”) And a monomer having a tetrahydrofuryl group.

(B1) refers to, for example, a polymerizable compound having at least one structure selected from the group consisting of an aliphatic epoxy structure and an alicyclic epoxy structure. The monomer having an epoxy group is a compound having at least one structure selected from the group consisting of an aliphatic epoxy structure and an alicyclic epoxy structure, and having an ethylenic carbon-carbon unsaturated bond. And at least 1 selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group
More preferably, it is a compound having a seed structure and having an acryloyl group or a methacryloyl group.

（式中、Ｒ^１１〜Ｒ^１３は、それぞれ独立に水素原子または炭素原子数１〜１０のアルキ
ル基であり、ｍは１〜５の整数である。）。 The aliphatic epoxy structure refers to a structure obtained by epoxidizing a chain olefin.
Specific examples of the compound (b1) having an aliphatic epoxy structure and having an ethylenic carbon-carbon unsaturated bond include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β -Ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, compounds represented by the following formulas described in JP-A-7-248625, and the like.

(In formula, R < ¹¹ > -R < ¹³ > is a hydrogen atom or a C1-C10 alkyl group each independently, and m is an integer of 1-5.).

Examples of the compound represented by the above formula include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α
-Methyl-o-vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethyl Styrene, 2,5-
Diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,
3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, 2,4, Examples include 6-triglycidyloxymethylstyrene.

The alicyclic epoxy structure refers to a structure obtained by epoxidizing a cyclic olefin.
Among (b1) in (A2), it has an alicyclic epoxy structure and has an ethylenic carbon-
Examples of the compound having a carbon unsaturated bond 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-epoxy Cyclohexylmethyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.) or at least one selected from the group consisting of a compound represented by Formula (I) and a compound represented by Formula (II) Compounds.

[In Formula (I) and Formula (II), R and R ′ each independently represents a C 1-4 alkyl group which may be substituted with a hydrogen atom or a hydroxy group.
X and X ′ are each independently a single bond, C _1-6 alkylene group, oxy-C _1-6 alkylene, thio-C _1-6 alkylene or imino-C _1-6 alkylene group, C _1-6 alkylene. The group -oxy, _{C1-6alkylene-} thio or _{C1-6alkylene-} imino group is represented. ]

Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
As the hydroxyalkyl group, a hydroxymethyl group, a 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, 2-hydroxy-isopropyl group, 1-hydroxy-n -Butyl group, 2-hydroxy-n-butyl group,
A 3-hydroxy-n-butyl group, a 4-hydroxy-n-butyl group, etc. are mentioned.
The substituents R and R ′ are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, 1
-Hydroxyethyl group and 2-hydroxyethyl group are mentioned, more preferably a hydrogen atom,
A methyl group is mentioned.

Examples of the alkylene group include a methylene group, an ethylene group, and a propylene group.
Examples of the oxyalkylene group include an oxymethylene group, an oxyethylene group, and an oxypropylene group.
Examples of the thioalkylene group include a thiomethylene group, a thioethylene group, and a thiopropylene group.
Examples of the iminoalkylene group include an iminomethylene group, an iminoethylene group, and an iminopropylene group.

Examples of the alkyleneoxy group include a methyleneoxy group, an ethyleneoxy group, and a propyleneoxy group.
Examples of the alkylenethio group include a methylenethio group, an ethylenethio group, and a propylenethio group.
Examples of the alkyleneimino group include a methyleneimino group, an ethyleneimino group, and a propyleneimino group.
The substituents X and X ′ are preferably a single bond, a methylene group, an ethylene group, an oxymethylene group and an oxyethylene group, more preferably a single bond and an oxyethylene group.

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), and formula (I-11) to formula (I-15). More preferably, the formula (I
-1), formula (I-7), formula (I-9), and formula (I-15).

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)-Formula (II-15) are 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) can be used alone. They can also be mixed in any ratio. When mixing, the mixing ratio is a molar ratio, preferably the formula (
I): In the formula (II), it is 5:95 to 95: 5, more preferably 10:90 to 90:10, and particularly preferably 20:80 to 80:20.

Examples of the compound having an oxetanyl group (b2) and an unsaturated bond in the copolymers (A2-1) and (A2-2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl -3-acryloxymethyl oxetane, 3-ethyl-3-methacryloxymethyl oxetane, 3-ethyl-3-acryloxymethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl Examples include oxetane, 3-ethyl-3-methacryloxyethyl oxetane, and 3-ethyl-3-acryloxyethyl oxetane.

In the copolymer (A2-1), the ratio of the constituent components derived from each of the copolymer (A2-1)
A molar fraction with respect to the total number of moles of the constituent components constituting A2-1) is preferably in the following range.
Structural units derived from (a); 2 to 40 mol%
Structural units derived from (c); 1 to 65 mol%
Structural units derived from (b1) or (b2); 2-95 mol%

Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (a); 5-35 mol%
Structural units derived from (c); 1 to 60 mol%
Structural units derived from (b1) or (b2); 5 to 80 mol%
When the composition ratio is in the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be good.

The resin (A2-1) having alkali solubility is disclosed in, for example, the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu Publishing Co., Ltd., Chemical Dojin Co., Ltd. First Edition, First Edition, issued March 1, 1972) ) With reference to the method described in (1) and the cited references described in the document.

Specifically, a predetermined amount of a compound that leads to the units (a), (c) and (b1) or (b2) constituting the copolymer, a polymerization initiator and a solvent are charged into a reaction vessel, and oxygen is added with nitrogen. By substituting, there may be mentioned a method of stirring, heating and keeping warm in the absence of oxygen.

Resin (A2-2) can be manufactured through a two-step process, for example. In this case as well, the method described in the above-mentioned document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu Publishing Co., Ltd., Chemical Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972), JP-A-2001-2001 It can be produced with reference to the method described in JP 89533.

First, as a first step, a copolymer (that is, a resin having alkali solubility) is obtained in the same manner as in the method for producing the alkali-soluble resin (A1) described above.
In this case, similar to the above, it can be continuously used in various forms. Moreover, it is suitable to make it the polystyrene equivalent weight average molecular weight and molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] similar to the above.
However, it is preferable that the ratio of the component derived from each of (a) and (c) is in the following range in terms of a mole fraction with respect to the total number of moles of the component constituting the copolymer.
Structural units derived from (a); 5 to 50 mol%
Structural unit derived from (c); 50 to 95 mol%
Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (a); 10 to 45 mol%
Structural unit derived from (c); 55 to 90 mol%

Next, as a second step, a part of the carboxylic acid and carboxylic acid anhydride (a) derived from the obtained copolymer is replaced with the epoxy group or oxetanyl group derived from the aforementioned (b1) or (b2). React with.
Specifically, following the above, the atmosphere in the flask is replaced from nitrogen to air, and the components (
For example, trisdimethylaminomethylphenol is used as a monomer (a) as a reaction catalyst of 5 to 80 mol% of component (b1) or (b2), a carboxy group and an epoxy group or oxetanyl group with respect to the number of moles of a). ) To 0.005% on a mass basis with respect to the total amount of (c)
And as a polymerization inhibitor, for example, hydroquinone is put into a flask at 0.001 to 5% by mass based on the total amount of monomers (a) to (c), and at 60 to 130 ° C. for 1 to 10 hours. Continue the reaction. Thereby, resin (A2-2) can be obtained. 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.
In this case, the number of moles of (b1) or (b2) is 10 to 10 with respect to the number of moles of (a).
It is preferable to set it as 75 mol%, More preferably, it is 15-70 mol%. By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity to become favorable.

In the resin (A2-3), the ratio of the constituent components derived from each may be in the following range in terms of mole fraction with respect to the total number of moles of the constituent components constituting the alkali-soluble resin (A2-3). preferable.
Structural units derived from (a); 5-95 mol%
Structural units derived from (b1) or (b2); 5-95 mol%
Moreover, it is more preferable in the ratio of the said structural component being the following ranges.
Structural units derived from (a); 10 to 90 mol%
Structural units derived from (b1) or (b2); 10-90 mol%
When the composition ratio is in the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be good.

Resin (A2-3) is, for example, a method described in the document “Experimental Method of Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) It can manufacture with reference to the cited reference etc. which were described in the said literature.
Specifically, a predetermined amount of a compound that leads to the units (a) and (b1) or (b2) constituting the copolymer, a polymerization initiator and a solvent are charged into a reaction vessel, and oxygen is substituted with nitrogen. Thus, a polymer can be obtained by stirring, heating and heat-retaining in the absence of oxygen. In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and took out as solid (powder) by methods, such as reprecipitation. Things may be used.

The polymerizable compound (B) contained in the photosensitive fat composition of the present invention is not particularly limited as long as it has polymerizability, and examples thereof include a monofunctional monomer, a bifunctional monomer, a trifunctional or higher polyfunctional monomer, and the like. The

Monofunctional monomers include nonylphenyl carbitol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) (Meth) acrylates such as acrylate, caprolactone (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propoxylated nonylphenol (meth) acrylate;
Styrene, α-, o-, m-, p-methylstyrene, p-methoxystyrene, p-tert
Styrenes such as butoxystyrene and chloromethylstyrene;
Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, Tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, dicyclopentanyl (meth) acrylate, ( (Meth) acrylic acid isobornyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, (meth) acrylic acid dicyclohexyl, (meth) acrylic acid adamantyl, (meth)
Allyl acrylate, Promethyl (meth) acrylate, Phenyl (meth) acrylate, Naphtyl (meth) acrylate, Anthracenyl (meth) acrylate, Cyclopentyl (meth) acrylate, Furyl (meth) acrylate, (Meth) acrylic Tetrahydrofuryl acid, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate,
Perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-i-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, etc. (Meth) acrylic acid alkyl ester, (meth)
Cycloalkyl acrylate or aryl (meth) acrylate;

(Meth) acrylic acid hydroxyalkyl esters such as (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl;
Vinyl compounds such as (meth) acrylic acid amide, (meth) acrylic acid anilide, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, N-vinylpyrrolidone, vinyl acetate;
Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;

Glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, α-
n-propylglycidyl (meth) acrylate, α-n-butylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxyheptyl (
Examples thereof include glycidyl compounds such as (meth) acrylate, α-ethyl-6,7-epoxyheptyl (meth) acrylate, allyl glycidyl ether, and vinyl glycidyl ether.

Specific examples of the bifunctional monomer 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 (meta ) Acrylate, ethoxylated neopentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, and the like.

Examples of the trifunctional or higher polyfunctional monomer 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, tripentaerythritol penta (meth)
Acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, dipentaerythritol penta ( Reaction product of (meth) acrylate and acid anhydride, tripentaerythritol hepta (meth) 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 Sex dipentaerythritol penta (meth) acrylate,
Caprolactone-modified dipentaerythritol hexa (meth) acrylate, 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 tripentaerythritol octa (meth) acrylate, reaction product of caprolactone modified pentaerythritol tri (meth) acrylate and acid anhydride, caprolactone modified dipentaerythritol penta (meth) acrylate and acid anhydride Reaction product, caprolactone-modified tripentaerythritol hepta (
And meth) acrylates and acid anhydrides. Among these, a bifunctional or higher functional monomer is preferably used.

Content of a polymeric compound (B) is a mass fraction with respect to the total amount of resin (A) and polymeric compound (B), Preferably it is 1-70 mass%, More preferably, it is 5-60 mass%. is there. When the content of the polymerizable compound (B) is in the above range, the sensitivity, the strength and smoothness of the coating film and the pattern, the reliability, and the mechanical strength tend to be good, which is preferable.

The polymerization initiator (C) contained in the photosensitive resin composition of the present invention is not particularly limited as long as it is a compound that initiates polymerization by the action of light or heat, and a known polymerization initiator may be used. it can.
As the polymerization initiator (C), for example, biimidazole compounds, acetophenone compounds, triazine compounds, acylphosphine oxide compounds, and oxime compounds are preferable. Moreover, you may use the light and / or thermal cationic polymerization initiator (For example, what is comprised from the onium cation and the anion derived from a Lewis acid) described in Unexamined-Japanese-Patent No. 2008-181087. Of these, biimidazole compounds are more preferred because of their excellent sensitivity.

Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,
4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (for example, JP-A-6-7
See 5372, JP-A-6-75373, and the like. ), 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) biimidazole (for example, Japanese Patent Publication No. 48-384)
See No. 03, JP-A 62-174204, and the like. ), An imidazole compound in which the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group (for example, see JP-A-7-10913). Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (
2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2
, 2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl]. -2-Methylpropane-1-
ON, 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-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methyl Benzyl) -2-dimethylamino-1- (4
-Morpholinophenyl) -butanone, 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-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) -2-
Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2- Dimethylamino-1- (4-morpholinophenyl) -butanone, 2
-(3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2 -(2-methoxybenzyl) -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-4-methoxybenzyl) -2-dimethylamino-1- (4 -Morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- [4
-(1-methylvinyl) phenyl] propan-1-one oligomer and the like.

Examples of the triazine compound 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) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5
-Triazine etc. are mentioned.

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

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

In addition, it is preferable to use a polymerization initiation assistant (C-1) together with the polymerization initiator (C) described above. Examples of the polymerization initiation assistant (C-1) include compounds represented by the formula (V).

［式（Ｖ）中、Ｘで示される点線はハロゲン原子で置換されていてもよい炭素数６〜１
２の芳香環を表す。
Ｙは、酸素原子、硫黄原子を表す。
Ｒ^３は、炭素数１〜６のアルキル基を表す。
Ｒ^４は、ハロゲン原子で置換されていてもよい炭素数１〜１２のアルキル基またはハロ
ゲン原子で置換されていてもよいアリール基を表す。］

[In the formula (V), the dotted line represented by X represents a carbon number of 6 to 1 which may be substituted with a halogen atom.
2 aromatic rings are represented.
Y represents an oxygen atom or a sulfur atom.
R ³ represents an alkyl group having 1 to 6 carbon atoms.
R ⁴ 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 a benzene ring and a naphthalene ring.

Examples of the aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom include a benzene ring,
Methylbenzene ring, dimethylbenzene ring, ethylbenzene ring, propylbenzene ring, butylbenzene ring, pentylbenzene ring, hexylbenzene ring, cyclohexylbenzene ring,
Examples include 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, t
ert-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, Examples include 2-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- A butyl group, 3-chloro-n-butyl group, etc. are mentioned.

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.
In the present specification, any chemical structural formula varies depending on the number of carbon atoms, but the above examples are applied to each substituent unless otherwise specified. Moreover, the thing which can take both a linear or branched includes any of them.

As the compound represented by the formula (V), 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.

Of these, 2- (2-naphthoylmethylene) -3- represented by the formula (V-1) is preferable.
Methylbenzothiazoline, 2-benzoylmethylene-3-methyl-naphtho [1,2-d] thiazoline represented by formula (V-2) and 2- (4-biphenoylmethylene) represented by formula (V-3) -3-Methyl-naphtho [1,2-d] thiazoline.

Since the photosensitive resin composition obtained by using these compounds becomes highly sensitive, it is preferable to form a coating film or pattern using this because the productivity of the coating film or pattern is improved.
The compound represented by the formula (V) is preferable because it does not sublime due to the heat at the time of post-baking of the coating film, and discolors due to the action of at least one of light and heat to improve transparency.

Further, as the polymerization initiation aid (C-1), a compound represented by at least one selected from the group consisting of formula (VI) and formula (VII) may be used.

[In Formula (VI) and Formula (VII), Ring X ¹ and Ring X ² each independently represent an aromatic or heterocyclic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom.
Y ¹ and Y ² represent an oxygen atom or a sulfur atom.
R ⁵ and R ⁶ represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. These alkyl group and aryl group are a halogen atom, a hydroxy group or a carbon number of 1-6.
It may be substituted with an alkoxy group.

Examples of the aromatic ring or heterocyclic ring that 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, and a cyclohexylbenzene ring. , Chlorobenzene ring, 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, benzo [e] pyrene ring, perylene ring and derivatives thereof.

Examples of the hydroxy group-substituted alkyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group.
Examples of the hydroxy group-substituted aryl group include a hydroxyphenyl group and a hydroxynaphthyl group.
Examples of the alkoxy-substituted alkyl group include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a butoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, and a propoxybutyl group.
Examples of the alkoxy-substituted aryl group include a methoxyphenyl group and an ethoxynaphthyl group.

Specifically, the compounds represented by formula (VI) and formula (VII) are:
Dialkoxynaphthalenes such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene, dibutoxynaphthalene, etc. Dimethoxyanthracene, diethoxyanthracene, dipropoxyanthracene, diisopropoxyanthracene, dibutoxyanthracene, dipentaoxyanthracene, Dihexoxyoxyanthracene, methoxyethoxyanthracene, methoxypropoxyanthracene, methoxyisopropoxyanthracene, methoxybutoxyanthracene, ethoxypropoxyanthracene, ethoxyisopropoxyanthracene, ethoxybutoxyanthracene, propoxyisopropoxyanthracene, propoxybutoxyanthracene, isopropoxybutoxyanthracene, etc. Dialkoxyanthracenes Examples include dialkoxynaphthacenes such as dimethoxynaphthacene, diethoxynaphthacene, dipropoxynaphthacene, diisopropoxynaphthacene, and dibutoxynaphthacene.

Moreover, you may use a photoinitiator as a polymerization initiator (C) mentioned above.
Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, thioxanthone compounds, anthracene compounds, and the like.
Examples of the benzoin compound 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-butyl). Peroxycarbonyl)
Examples include benzophenone and 2,4,6-trimethylbenzophenone.

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

Examples of the anthracene compound include 9,10-dimethoxyanthracene,
2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene,
Examples include 2-ethyl-9,10-diethoxyanthracene.

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

Moreover, as a photopolymerization initiator having a group capable of causing chain transfer, JP-T-2002-5442
You may use the photoinitiator described in the 05 gazette.
Examples of the photopolymerization initiator having a group capable of causing chain transfer include the following formula (1):
(6) The photoinitiator of (6) is mentioned.

The photopolymerization initiator having a group capable of causing chain transfer can also be used as a component constituting the resin (A).

It is preferable to use a polymerization initiation assistant (C-2) together with the polymerization initiator described above.
Examples of the polymerization initiation assistant (C-2) include amine compounds and carboxylic acid compounds.
Examples of amine compounds include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, 4-
Ethyl dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) Aromatic amine compounds such as benzophenone (common name: Michler's ketone) and 4,4′-bis (diethylamino) benzophenone are exemplified.

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, naphthoxyacetic acid and the like can be mentioned.

Content of a polymerization initiator (C) is a mass fraction with respect to the total amount of resin (A) and polymeric compound (B), Preferably it is 0.1-40 mass%, More preferably, it is 1-30 mass. %.
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 this photosensitive resin composition, The smoothness on the surface tends to be good, which is preferable.

The amount of the polymerization initiation aid (C-1) and / or (C-2) used is a mass fraction with respect to the total amount of the resin (A) and the polymerizable compound (B), preferably 0.01. It is -50 mass%, More preferably, it is 0.1-40 mass%.
When the amount of the polymerization initiation assistant (C-1) and / or (C-2) is within this range, the sensitivity of the resulting photosensitive resin composition is further increased, and the photosensitive resin composition is formed using this photosensitive resin composition. This is preferable because the productivity of the patterned substrate tends to be improved.

In particular, when a compound represented by the formula (V) is used, its content is determined depending on the polymerization initiation assistant (C
-1) content is 50% by mass to 100% by mass, and further 60% by mass to 100% by mass.
In particular, the content is preferably 65% by mass to 100% by mass. When the content of the compound represented by the formula (V) is in this range, when the coating film is formed using the photosensitive resin composition containing the compound, the transparency of the coating film becomes favorable.

Moreover, the photosensitive resin composition of this invention may contain the polyfunctional thiol compound (T) further. This polyfunctional thiol compound (T) is a compound having two or more sulfanyl groups in the molecule. Especially, when using the compound which has two or more sulfanyl groups couple | bonded with the carbon atom of two or more aliphatic hydrocarbon groups, since the sensitivity of the photosensitive resin composition of this invention becomes high, it is preferable.

Specific examples of the polyfunctional thiol compound (T) include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, and ethylene glycol bisthioglycolate. , Trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, tris Hydroxyethyltristhiopropionate, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-
And mercaptobutyryloxy) butane.
Content of a polyfunctional thiol compound (T) is a mass fraction with respect to a polymerization initiator (C), Preferably it is 0.5-100 mass%, More preferably, it is 1-90 mass%. Moreover, content of a polyfunctional thiol compound is a mass fraction with respect to the total amount of binder resin (A) and a photopolymerizable compound (C), Preferably it is 0.1-20 mass%, More preferably, it is 1-. 10% by mass.
When the content of the polyfunctional thiol compound (T) is within this range, the sensitivity becomes high and the developability tends to be good, which is preferable.

The solvent (D) used in the photosensitive resin composition of the present invention is a resin (A) or a polymerizable compound (B
) And the polymerization initiator (C) are suitably dissolved and do not react with each component.
Further, the solvent (D) is at least the formula (D1)
R ¹ —O— (A—O) _n —R ² (D1)
(In the formula (D1),
R ¹ and R ² each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms.
A represents a linear or branched alkylene group having 1 to 3 carbon atoms.
n represents an integer of 2 or 3. A plurality of A may be the same or different. )
The solvent represented by these is included.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methyl-n-propyl group, a 2-methyl-n-propyl group, and a tert-butyl group. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a methylethylene group.

Specific examples of the compound of the formula (D1) include
Di- or trimethylene glycol dimethyl ether,
Di- or triethylene glycol dimethyl ether,
Di- or tripropylene glycol dimethyl ether,
Di- or trimethylene glycol methyl ethyl ether,
Di- or triethylene glycol methyl ethyl ether,
Di- or tripropylene glycol methyl ethyl ether,
Di- or trimethylene glycol methyl propyl ether,
Di- or triethylene glycol methyl propyl ether,
Di- or tripropylene glycol methyl propyl ether,
Di- or trimethylene glycol methyl butyl ether,
Di- or triethylene glycol methyl butyl ether,
Di- or tripropylene glycol methyl butyl ether,
Di- or trimethylene glycol diethyl ether,
Di- or triethylene glycol diethyl ether,
Di- or tripropylene glycol diethyl ether,
Di- or trimethylene glycol ethyl propyl ether,
Di- or triethylene glycol ethyl propyl ether,
Di- or tripropylene glycol ethyl propyl ether,
Di- or trimethylene glycol ethyl butyl ether,
Di- or triethylene glycol ethyl butyl ether,
Di- or tripropylene glycol ethyl butyl ether,
Di- or trimethylene glycol dipropyl ether,
Di- or triethylene glycol dipropyl ether,
Di- or tripropylene glycol dipropyl ether,
Di- or trimethylene glycol propyl butyl ether,
Di- or triethylene glycol propyl butyl ether,
Di- or tripropylene glycol propyl butyl ether,
Di- or trimethylene glycol dibutyl ether,
Di- or triethylene glycol dibutyl ether,
Examples thereof include di- or tripropylene glycol dibutyl ether.

Of these, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether and the like are preferable.
Furthermore, it is preferable to use a combination of two or more solvents of the formula (D1). By using these solvents in combination, ensuring compatibility with each component of the photosensitive resin composition, various coating methods, particularly when applied on the concavo-convex substrate by spin coating,
The striation can be effectively prevented.

The solvent of the formula (D1) is preferably contained at 50 to 100% by mass, more preferably 70 to 100% by mass, and 90 to 100% by mass with respect to the total amount of the solvent. It is particularly preferred. When the content of the solvent of the formula (D1) is within this range, a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater or a curtain flow coater), an inkjet, a roll coater, a dip coater, etc. In these various coating apparatuses, good coating properties can be expected.
In particular, when the solvent (D) contains diethylene glycol ethyl methyl ether, it is suitable that diethylene glycol ethyl methyl ether is contained in an amount of 10 to 100% by mass with respect to the total amount of the solvent, 10 to 90% by mass, and further 30 -90 mass% is preferable.
Further, when the solvent (D) contains diethylene glycol butyl methyl ether and / or triethylene glycol dimethyl ether, diethylene glycol butyl methyl ether and / or triethylene glycol dimethyl ether is contained at 0 to 50% by mass with respect to the total amount of the solvent. It is suitable and it is preferable to contain at 10-50 mass%.
Further, those containing diethylene glycol ethyl methyl ether and at least one solvent selected from the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether are preferred.
In this case, it may contain 50 to 100% by mass of diethylene glycol ethyl methyl ether and at least one solvent selected from the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether with respect to the total amount of the solvent. It is suitable, 60-100 mass%, Furthermore, 70-100 mass% is preferable.
By setting this range, striation can be more effectively prevented, particularly in the spin coating method.

The solvent (D) is preferably composed of only solvents other than those described above, but may contain other solvents.
Examples thereof include alcohols such as monoalcohols and polyhydric alcohols.
Such alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether,
Examples include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, methyl lactate, ethyl lactate, 2-methyl methyl lactate, diacetone alcohol, 3-methoxybutanol, and glycerin. It is done. Of these, 3-methoxybutanol is preferable.

The alcohol is suitably contained in an amount of 0 to 50% by mass, 10 to 50% by mass, further 10 to 45% by mass, and 10 to 40% by mass with respect to the total amount of the solvent (D).
By containing the alcohol within this range, the solubility of the resin and the like can be sufficiently obtained, and the uniformity of the obtained coating film can be achieved by adjusting to an appropriate viscosity. In addition, when applying the photosensitive resin composition using a slit die coater, it is possible to prevent the nozzle tip from being dried, to suppress the deposition of foreign matter due to the dried product, and to ensure that vertical streaks due to the foreign matter are generated. Can be prevented.

And ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl 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;

Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone;

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, 3
-Butyl hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, propoxyacetic acid Methyl, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate Butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate,
-Butyl ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate,
Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3 -Butyl ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3
Esters such as methyl butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate;
Cyclic ethers such as tetrahydrofuran and pyran;
It may contain cyclic esters such as γ-butyrolactone.

Among the above solvents, an organic solvent having a boiling point of 100 ° C. to 200 ° C. is preferable from the viewpoints of coating properties and drying properties. Among them, alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate are exemplified, and propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, 3
-Ethyl ethoxypropionate, methyl 3-methoxypropionate and the like are suitable.

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, for example, a mass fraction of less than 1% by mass, preferably less than 0.5% by mass.
For example, the photosensitive resin composition of the present invention does not substantially contain the following colorant used in the art.
Pigment by Color Index (published by The Society of Dyers and Colorists)
ment), specifically,
C. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 2
4, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128,
137, 138, 139, 147, 148, 150, 153, 154, 166, 173,
Yellow pigments such as 194, 214;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55
59, 61, 64, 65, 71, 73 orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 16
6, 168, 176, 177, 180, 192, 209, 215, 216, 224, 24
Red pigments such as 2, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7 and 36;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. Black pigments such as CI Pigment Black 1 and 7.

If necessary, the photosensitive resin composition of the present invention includes a filler, other polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, a light stabilizer, a chain transfer agent, and the like. Various additives may be used in combination.

Examples of the filler include glass, silica, and alumina.
Examples of other polymer compounds include curable resins such as epoxy resins and maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether,
Examples thereof include thermoplastic resins such as polyfluoroalkyl acrylate, polyester, and polyurethane.

The surfactant may be any of silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, and amphoteric surfactants. Specifically, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, 3
Commercial surfactants can be used in addition to secondary amine-modified polyurethanes and polyethyleneimines. For example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (Mitsubishi Materials Electronics Chemicals Co., Ltd.), MegaFac (DIC)
Manufactured by), FLORARD (manufactured by Sumitomo 3M), Surflon (manufactured by AGC Seimi Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by CIBA), Ajisper P
B821 (Ajinomoto Co., Inc. product) etc. are mentioned.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

Examples of the antioxidant 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-
Butyl dibenz [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 (6-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′-thiodipropionate, pentaerythrityltetrakis (3-lauryl thiopropionate),
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-te
Examples thereof include rt-butyl-4-methylphenol.

Examples of the ultraviolet absorber 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-dimethyl) Phenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-
Hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -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-benzotriazol-2-yl) -4
, 6-Bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3 , 3
-Tetramethylbutyl) phenol, 2- (3-tert-butyl-2-hydroxy-5)
-Methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.

Examples of the light stabilizer include 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-diamine, decandioic acid, reaction of bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester with 1,1-dimethylethyl hydroperoxide Product, bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[
[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, 2,4-bis [N-butyl-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 , Methyl (1,2,2,6,6-pentamethyl-4-piperidinyl)
Sebacate etc. are mentioned.

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 is, for example, as described later, a substrate such as a substrate made of glass, metal, plastic, etc., a color filter, various insulating films or conductive films, a drive circuit, etc. By applying on top, it can be formed as a coating film. The coating is
It is preferably dried and cured. Moreover, the obtained coating film can be patterned into a desired shape and used as a pattern. Furthermore, these coating films and / or patterns may be formed and used as a part of components such as a display device.

In addition, when the curable 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 average transmittance is It is 70% or more, preferably 75% or more. Thereby, a transparent pattern and coating film can be formed in the visible light region.

First, the photosensitive resin composition of this invention is apply | coated on a base material.
As described above, the coating can be performed using various coating apparatuses such as a spin coater, a slit & spin coater, a slit coater, an ink jet, a roll coater, and a dip coater. Among these, from the viewpoint of solubility, prevention of drying, prevention of the generation of foreign matters, etc., it is preferable to perform application by spin coating, that is, application using a slit & spin coater, spin coater, or the like.

It is then suitable to dry and / or pre-bake to remove volatile components such as solvents. Thereby, a smooth uncured coating film can be obtained.
The film thickness of the coating film in this case is not particularly limited, and can be appropriately adjusted depending on the material used, application, etc. For example, about 1 to 6 μm is exemplified.

Furthermore, the obtained uncured coating film is irradiated with light, for example, ultraviolet rays generated from a mercury lamp or a light emitting diode, 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, the coating film is brought into contact with an alkaline aqueous solution to dissolve a predetermined portion, for example, an unexposed portion,
By developing, the target pattern shape can be obtained.
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.
Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, Examples thereof include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.

Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Is mentioned.
The concentration of these inorganic and organic alkaline compounds in the alkaline developer is preferably 0. 0.
It is 01-10 mass%, More preferably, it is 0.03-5 mass%.

The surfactant may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Examples include ethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

Examples of the anionic surfactant 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 dodecyl sodium sulfate. And alkylaryl sulfonates such as sodium naphthalene sulfonate.

Examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
The concentration of the surfactant in the alkali developer is preferably in the range of 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and still 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 suitable for a temperature range of 150 to 230 ° C. and 10 to 180 minutes, for example.

The curable resin composition of the present invention has a measurement wavelength of 400 to 700 n using a spectrophotometer for a coating having a thickness of 3 μm after heat curing (for example, 150 to 250 ° C., 0.1 to 3 hours).
When the transmittance is measured under the condition of m, the transmittance is 90% or more, preferably 95% or more. Thereby, a transparent pattern and coating film can be formed in the visible light region.

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, when performing exposure to the uncured coating film, by using only the entire surface exposure and heat curing or heat curing without using a photomask,
A transparent film can be formed. 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, for example,
Transparent films, especially transparent films that form part of color filters, patterns, photo spacers, overcoats, insulating films, liquid crystal alignment control projections, micro lenses, colored patterns combining different film thicknesses, coat layers, etc. Therefore, it can be used suitably. 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,
It can be used for liquid crystal display devices, organic EL devices, and the like.

Hereinafter, although the photosensitive resin composition of this invention is demonstrated in detail by an Example, 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
In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, and 140 parts of diethylene glycol ethyl methyl ether was added,
Heat to 70 ° C. with stirring. Next, 40 parts 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) The compound is dissolved in 360 parts of a 50:50 molar ratio) and 190 parts of diethylene glycol ethyl methyl ether to prepare a solution. This solution is heated to 70 ° C. over 4 hours using a dropping pump. It was dripped in the flask kept warm.

On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 240 parts of diethylene glycol ethyl methyl ether was dropped into the flask over another 5 hours using another dropping pump. did. After completion of dropping of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours, and then cooled to room temperature to have a solid content of 42.6% and an acid value of 60 mg-KO.
A solution of H / g copolymer (resin Aa) was obtained. The weight average molecular weight of the obtained resin Aa (Mw
) Was 8000, and the dispersity was 1.91.

Synthesis example 2
In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, 0.02 L / nitrogen was added.
The mixture was poured in minutes to form a nitrogen atmosphere, 305 parts of diethylene glycol ethyl methyl ether was added, and the mixture was heated to 70 ° C. with stirring. Next, 60 parts 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) 240 parts of a compound with a molar ratio of 50:50)
A solution was prepared by dissolving in 140 parts of diethylene glycol ethyl methyl ether, and this 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 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of diethylene glycol ethyl methyl ether was dropped into the flask using another dropping funnel over 4 hours. did. After the 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 to obtain a solid content of 32.6% and an acid value of 110 mg-K.
A solution of a copolymer (resin Ab) of OH / g (in terms of solid content) was obtained. The obtained resin Ab had a weight average molecular weight Mw of 13,600 and a dispersity of 2.49.

Synthesis example 3
Into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, and 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added. Heat to 70 ° C. with stirring. Next, 60 parts 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) The molar ratio of the compound is 50: 5
0 part) 240 parts was dissolved in 140 parts of 3-methoxybutyl acetate to prepare a solution, and this solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel.

On the other hand, 3 parts of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) 3 parts
-The solution melt | dissolved in 225 parts of methoxybutyl acetate was dripped in the flask over 4 hours using another dropping funnel. 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. The solid content was 32.6% and the acid value was 110 mg-KOH / g (solid content conversion). A solution of coalescence (resin Ac) was obtained. Weight average molecular weight M of the obtained resin Ac
w was 13,400 and the degree of dispersion was 2.50.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resins Aa to Ac were measured under the following conditions using the 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 the number average molecular weight in terms of polystyrene obtained above is calculated as the dispersity (M
w / Mn).

Examples 1 to 10, Comparative Example 1
The composition of Table 1 was mixed and the photosensitive resin compositions 1-11 were obtained.

Each component in Table 1 is as follows.
Polymerizable compound (B); dipentaerythritol hexaacrylate (KAYARAD)
DPHA; Nippon Kayaku Co., Ltd.)
Polymerization initiator Ca; 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (B-CIM; manufactured by Hodogaya Chemical Co., Ltd.)
Initiating aid C2a; 9,10-dibutoxyanthracene (DBA; manufactured by Kawasaki Kasei Co., Ltd.)
Initiating aid C2b; pentaerythritol tetrakis (3-sulfanylpropionate) (PEMP; manufactured by SC Organic Chemical Co., Ltd.)
Initiating aid C2c; 2- (2-naphthoylmethylene) -3-methylbenzothiazoline Solvent Da; Diethylene glycol ethyl methyl ether Solvent Db; Diethylene glycol butyl methyl ether Solvent Dc; Triethylene glycol dimethyl ether Solvent Dd; Propylene glycol monomethyl ether acetate Solvent De; 3-ethoxyethyl propionate solvent Df; 3-methoxy 1-butanol solvent Dg; 3-methoxybutyl acetate solvent Dh; dipropylene glycol dimethyl ether additive 1; polyether-modified silicone oil (Toray Dow Corning Co., Ltd.) SH
8400)
Additive 2; IRGANOX 3114 (Ciba Japan)

<Striation evaluation>
Each component shown in Table 2 was mixed in the ratio shown in Table 2 to obtain a colored photosensitive resin composition 1.

A 4-inch silicon substrate was sequentially washed with a neutral detergent, water and alcohol and then dried. On this silicon substrate, the colored photosensitive resin composition 1 is exposed to an exposure amount of 100 mJ / cm ² (3
65 nm) and spin-coated so that the film thickness after development, washing with water and post-baking becomes 3.0 μm. Next, it was pre-baked at 90 ° C. for 3 minutes in a clean oven. After cooling, the distance between the substrate coated with the colored photosensitive resin composition 1 and the photomask made of quartz glass is 100.
Using an exposure device (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp), the light was irradiated with an exposure amount of 100 mJ / cm ² (based on 365 nm) in an air atmosphere.
In addition, the irradiation to the colored photosensitive resin composition at this time used the radiated light from an ultrahigh pressure mercury lamp through the optical filter (UV-35; Asahi Techno Glass Co., Ltd.). In addition, a photomask in which a pattern (having a square light-transmitting portion with one side of 10 mm and a space between the squares of 100 mm) was formed on the same plane was used as the photomask.

After the light irradiation, the coating film was immersed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23 ° C. for 80 seconds to develop, washed with water, and 220 in an oven. 2 at ℃
Post-baking was performed for 0 minutes to prepare a silicon substrate having a 10 mm square colored pattern.
Examples 1 to 10 and Comparative Example 1 were applied to a silicon substrate having a colored pattern of 10 mm square.
The photosensitive resin composition was applied using a spin coater under conditions such that the film thickness after curing was 2.0 μm. Thereafter, the degree of vacuum was reduced to 1. with a vacuum dryer (VCD Microtech Co., Ltd.)
It was dried under reduced pressure to 0 torr. Next, place it on a hot plate set at 95 ° C, and then 2
Pre-baked for minutes to form a coating. After cooling, the surface of the film was illuminated with a Na lamp, and the surface of the coating film was visually confirmed.

As a result, about Examples 1-10, striation was hardly confirmed along the coloring pattern. The results are shown in Table 3.
Here, the striation means a radial unevenness derived from the step of the colored pattern.

<Average transmittance of photosensitive resin composition>
About the photosensitive resin composition 1, an ultraviolet-visible spectrophotometer (V-650DS; JASCO Corporation)
Manufactured) (quartz cell, optical path length: 1 cm), average transmittance at 400 to 700 nm (
%). The results are shown in Table 3.

<Average transmittance of coating film>
The same operation as described above was performed except that no photomask was used at the time of light irradiation, and a coating film was prepared so that the film thickness after post-baking became 2.0 μm. Wavelength 400-7 of the prepared coating film
The average transmittance (%) at 00 nm was measured using a microspectrophotometer (OSP-SP200; OLY
MPUS). The results are shown in Table 3.

As described above, when the coating film is formed using the photosensitive resin composition of the present invention, the occurrence of striation is suppressed even when the coating film is formed on a relatively thick film, and is uniform and smooth throughout the coating film. And a high-quality coating film can be formed.
In addition, the coating drying time can be shortened and productivity can be improved, while the tip of the slit nozzle can be prevented from being dried, and the generation of foreign matters due to drying, mixing into the coating film and vertical stripes can be prevented. Can be prevented.
Further, the solubility of the resin and various components is good, and the storage stability can be improved.
By forming a coating film or a pattern using such a photosensitive resin composition and manufacturing a display device using them, it is possible to improve the yield.

According to the photosensitive resin composition of the present invention, the occurrence of striation can be suppressed, and a uniform and high quality coating film can be formed over the entire coating film.
Further, by using this photosensitive resin composition, it is possible to obtain a high-quality display device or the like.

Claims (5)

Resin (A), polymerizable compound (B), polymerization initiator (C) and solvent (D),
The solvent (D) is a photosensitive resin composition comprising at least one solvent selected from the group consisting of diethylene glycol ethyl methyl ether and diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether.   The photosensitive resin composition according to claim 1, wherein the solvent (D) is a solvent containing 10 to 90% by mass of diethylene glycol ethyl methyl ether based on the total amount of the solvent.   The solvent (D) is a solvent containing 10 to 50% by mass of at least one solvent selected from the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether with respect to the total amount of the solvent. Photosensitive resin composition.   The solvent (D) is a solvent containing 60 to 100% by mass of diethylene glycol ethyl methyl ether and at least one solvent selected from the group consisting of diethylene glycol butyl methyl ether and triethylene glycol dimethyl ether with respect to the total amount of the solvent. The photosensitive resin composition as described in any one of Claims 1-3. A coating film is formed using the photosensitive resin composition as described in any one of Claims 1-4, The manufacturing method of the coating film characterized by the above-mentioned .