KR102021613B1 - Photosensitive resin composition - Google Patents

Abstract

Photosensitive resin composition containing (A), (B) and (C):
(A) Structural unit derived from the structural unit derived from 1 or more types chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond. And a structural unit derived from a monomer having a siloxane structure and an ethylenically unsaturated bond, wherein the content of the structural unit derived from the monomer having a siloxane structure and an ethylenically unsaturated bond is added to all structural units of the copolymer. Copolymer which is 0.01 mass% or more and 5 mass% or less with respect to;
(B) a polymerizable compound having no silicon atom;
(C) polymerization initiator.

Description

Photosensitive resin composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive resin composition.

In recent liquid crystal display panels and the like, members such as photospacers, overcoats and inkjet partitions are used, and resin members and cured films formed of photosensitive resin compositions are used as these members.

As such a photosensitive resin composition, the photosensitive resin composition containing the copolymer of methacrylic acid and 3, 4- epoxy cyclocyclo [5.2.1.0 ^2.6 ] decyl acrylate as a resin is known (JP2009-139932-A), for example.

When using the resin pattern formed from the photosensitive resin composition as a photospacer, the resin pattern is requested | required of the mechanical characteristic, ie, flexibility which returns to an original shape, when weighting is removed. This mechanical characteristic is represented by the recovery rate which is the ratio of the displacement amount (elastic displacement amount) returning to the original shape when this is removed, with respect to the displacement amount (total displacement amount) when a load is applied to the photospacer.

The recovery rate of the resin pattern obtained from the said photosensitive resin composition conventionally known was not necessarily fully satisfying.

The present invention includes the following inventions.

[1] A photosensitive resin composition comprising the following (A), (B) and (C).

(A) Structural unit derived from the structural unit derived from 1 or more types chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond. And a copolymer comprising a structural unit derived from a monomer having a siloxane structure and an ethylenically unsaturated bond,

Copolymer whose content of the structural unit derived from the monomer which has a siloxane structure and ethylenically unsaturated bond is 0.01 mass% or more and 5 mass% or less with respect to the total structural units of the said copolymer.

(B) a polymerizable compound having no silicon atom

(C) polymerization initiator

[2] The photosensitive resin composition according to [1], wherein the weight average molecular weight of the monomer having a siloxane structure and an ethylenically unsaturated bond is 300 to 50000.

[3] A resin pattern formed from the photosensitive resin composition according to [1] or [2].

[4] A display device comprising the resin pattern according to [3].

[5] Structural units derived from at least one structural unit selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and monomers having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond And a copolymer comprising a structural unit derived from a monomer having a polysiloxane structure and an ethylenically unsaturated bond,

The copolymer whose content of the structural unit derived from the monomer which has a polysiloxane structure and an ethylenically unsaturated bond is 0.01 mass% or more and 5 mass% or less with respect to the total structural units of the said copolymer.

According to the photosensitive resin composition of this invention, since the recovery rate at the time of removing the applied load is high, the resin pattern formed from this photosensitive resin composition is excellent in mechanical characteristics.

In this specification, the compound illustrated as each component can be used individually or in combination of multiple types unless there is particular notice.

The photosensitive resin composition of this invention contains following (A), (B) and (C).

(A) Structural unit derived from the structural unit derived from 1 or more types chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond. And a copolymer comprising a structural unit derived from a monomer having a siloxane structure and an ethylenically unsaturated bond,

Copolymer whose content of the structural unit derived from the monomer which has a siloxane structure and ethylenically unsaturated bond is 0.01 mass% or more and 5 mass% or less with respect to all the structural units of the said copolymer (henceforth "resin (A)" may be called. )

(B) Polymeric compound which does not have a silicon atom (hereinafter may be called "polymerizable compound (B)")

(C) Polymerization initiator (hereinafter may be referred to as "polymerization initiator (C)")

Moreover, it is preferable that the photosensitive resin composition of this invention contains 1 or more types chosen from the group which consists of a solvent (E) and surfactant (H).

Moreover, the photosensitive resin composition of this invention may contain 1 or more types chosen from the group which consists of a thiol compound (T), antioxidant (F), and a polymerization start adjuvant (C1).

<Resin>

Resin (A) is a structural unit derived from 1 or more types (it may be called "(a)" hereafter) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and C2-C4 cyclic | annular form Structural units derived from an ether structure and a monomer having an ethylenically unsaturated bond (hereinafter referred to as "(b)") and a monomer having a siloxane structure and an ethylenically unsaturated bond (hereinafter referred to as "(x)") Structural units derived from the above). The copolymer may further have a structural unit copolymerizable with (a) and derived from a monomer different from (b) and (x) (hereinafter sometimes referred to as "(c)").

As resin (A), resin [K1] and resin [K2] are mentioned, for example.

Resin [K1]: A copolymer consisting of a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from (x);

Resin [K2]: A copolymer consisting of a structural unit derived from (a), a structural unit derived from (b), a structural unit derived from (x), and a structural unit derived from (c).

Resin (A) is a copolymer in which (a), (b) and (x) and (c) were copolymerized as needed.

Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic 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 and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic 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 Bicyclo unsaturated compounds containing carboxyl groups, such as [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride Unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

Unsaturated mono [(meth) acryloyloxyalkyl of a divalent or higher polyhydric carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl] and monophthalate [2- (meth) acryloyloxyethyl] ] Esters;

and unsaturated acrylates containing a hydroxy group and a carboxyl group in a molecule such as α- (hydroxymethyl) acrylic acid.

Among these, (meth) acrylic acid, maleic anhydride, etc. are preferable at the point of copolymerization reactivity and the solubility of resin to aqueous alkali solution, and (meth) acrylic acid is more preferable.

In addition, in this specification, "(meth) acryloyl" shows 1 or more types chosen from the group which consists of acryloyl and methacryloyl. Notation, such as "(meth) acrylic acid" and "(meth) acrylate", has the same meaning.

Examples of the cyclic ether structure having 2 to 4 carbon atoms (b) include an oxirane ring, an oxetane ring and a tetrahydrofuran ring. As for (b), the monomer which has a C2-C4 cyclic ether and a (meth) acryloyloxy group is preferable.

As (b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)") and a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter "( b2) ”and a monomer (b3) (hereinafter sometimes referred to as“ (b3) ”) having a tetrahydrofuryl group and an ethylenically unsaturated bond.

As (b1), the monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") and the alicyclic unsaturated hydrocarbon which have a structure where the linear or branched aliphatic unsaturated hydrocarbon was epoxidized are epoxidized, for example. And monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure that is used.

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and o-vinyl benzyl. Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α -Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxy Methyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene, etc. Can be.

(b1-2) include, for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane [eg, ceoxide 2000; Daicel Corporation], 3, 4- epoxycyclohexylmethyl (meth) acrylate [for example, cyclomer A400; Daicel Corporation], 3, 4- epoxycyclohexyl methyl (meth) acrylate [For example, cyclomer M100; Daicel Co., Ltd.], the monomer represented by following formula (I), the monomer represented by general formula (II), etc. are mentioned.

[In the said Formula (I) and Formula (II), R <^b1> and R <^b2> represent a hydrogen atom or a C1-C4 alkyl group, and the hydrogen atom contained in this alkyl group may be substituted by the hydroxy group.

X ^b1 and X ^b2 represent a single bond, -R ^b3- , * -R ^b3 -O-, * -R ^b3 -S- or * -R ^b3 -NH-.

R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents the number of bonds with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group and the like.

As an alkyl group in which the hydrogen atom was substituted by hydroxy, it is a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy A hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

As R ^b1 and R ^b2 , Preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and 2-hydroxyethyl group are mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group and hexane-1 And a 6-diyl group.

X ^b1 and X ^b2 are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, and more preferably a single bond, *- CH ₂ CH ₂ —O— (* indicates the number of bonds with O).

As a monomer represented by general formula (I), the monomer etc. which are represented by either of the following general formula (I-1)-general formula (I-15) are mentioned. Among them, the formulas (I-1), (I-3), (I-5), (I-7), (I-9) or (I-11) to (I-15) The monomer represented by is preferable, and the monomer represented by general formula (I-1), general formula (I-7), general formula (I-9), or general formula (I-15) is more preferable.

As a monomer represented by general formula (II), the monomer etc. which are represented by either of the following general formula (II-1)-general formula (II-15) are mentioned. Among them, the formulas (II-1), (II-3), (II-5), (II-7), (II-9) or (II-11) to (II-15) The monomer represented by is preferable, and the monomer represented by general formula (II-1), general formula (II-7), general formula (II-9), or general formula (II-15) is more preferable.

The monomer represented by general formula (I) and the monomer represented by general formula (II) may be used independently, respectively, and may use together the monomer represented by general formula (I) and the monomer represented by general formula (II) together. When using these together, the content rate of the monomer represented by general formula (I) and the monomer represented by general formula (II) is based on molar basis, Preferably it is 5: 95-95: 5, More preferably, it is 10: 90-90. : 10, More preferably, it is 20: 80-80: 20.

As (b2), the monomer which has an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3 -Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryl Royloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, etc. are mentioned.

As (b3), the monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Yukikagaku Kogyo Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), it is preferable that it is (b1) from the point which can improve reliability, such as heat resistance of a resin pattern and cured film obtained, chemical-resistance, etc. more. Moreover, (b1-2) is more preferable at the point which is excellent in the storage stability of the photosensitive resin composition.

The siloxane structure of (x) is a structure represented by following General formula (x1), for example.

[In the formula (x1), A ¹ and A ² independently represent a monovalent organic group.]

As monovalent organic group, a monovalent hydrocarbon group is mentioned, for example. Monovalent hydrocarbon group, Preferably it is a C1-C10 monovalent aliphatic hydrocarbon group, a C3-C10 monovalent alicyclic hydrocarbon group, and a C6-C10 monovalent aromatic hydrocarbon group, More preferably, it is C1-C4. It is an alkyl group or a C6-C10 monovalent aromatic hydrocarbon group, More preferably, it is a methyl group or a phenyl group.

The ethylenically unsaturated bond of (x) is preferably a (meth) acryl group.

As (x), the monomer represented by general formula (x2) is mentioned, for example.

[In the formula (x2), Q ¹ represents a hydrogen atom or a methyl group.

L ¹ represents-(CH ₂ ) _r- , -O- (CH ₂ ) _r -or -C (= O) -O- (CH ₂ ) _r -and at least one -CH ₂ -contained in these groups. May be substituted with a hetero atom.

r represents the integer of 0-8.

A ^{3 to} A ¹¹ each independently represent an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

s, t and u each independently represent an integer of 0 to 200.]

Examples of the aliphatic hydrocarbon group for A ^{3 to} A ¹¹ include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, octyl group and dodecyl group.

The aryl group of A ³ ~A ¹¹ there may be mentioned such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, a biphenyl group and a naphthyl group.

As an aralkyl group of A <^3> -A <^11> , a benzyl group and a phenylethyl group are mentioned, for example.

As a monomer represented by general formula (x2), the monomer represented by the following general formula (x3) and the monomer represented by general formula (x4) are preferable, and the monomer represented by general formula (x3) is more preferable.

[In the formulas (x3) and (x4), Q ² and Q ³ represent a hydrogen atom or a methyl group.

A ¹² represents an aliphatic hydrocarbon group having 1 to ¹² carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.

v represents the integer of 0-200.

w and y each independently represent an integer of 0 to 30.]

Examples of A ¹² include the same groups as A ^{3 to} A ^11, and are preferably methyl or phenyl.

v preferably represents an integer of 0 to 100.

Examples of (x) include (trimethylsilylmethyl) methacrylate, (phenyldimethylsilyl) methyl methacrylate, tert-butyldimethylvinylsilane, allyldimethylsilane, allyltrimethylsilane, triphenylvinylsilane, trimethylsilylmethacrylate, Vinyldiethylmethylsilane, vinyltris (trimethylsiloxy) silane, vinyltrimethylsilane, vinylmethylbis (trimethylsiloxy) silane, phenyldimethylvinylsilane, phenylmethylvinylsilane and monomers represented by the following formulas. In the following formulae, Q ⁴ represents a hydrogen atom or a methyl group, and z represents 2 to 200.

As (x), for example, silaplane FM-0711 (weight average molecular weight (hereinafter may be referred to as "Mw"): 1000, monomer represented by the formula (x3-2), Q ⁴ = methyl group), silaplane FM -0721 (Mw: 5000, monomer represented by the formula (x3-2), Q ⁴ = methyl group), silaplane FM-0725 (Mw: 10000, monomer represented by the formula (x3-2), Q ⁴ = methyl group ), Silaplane FM-0701 (Mw: 420, monomer represented by formula (x3-1), Q ⁴ = methyl group), silaplane FM-0701T (Mw: 420, represented by formula (x4-2) Monomer, Q ⁴ = methyl group (all manufactured by JNC Corporation), X-22-2475 (Mw: 420, monomer represented by formula (x3-1), Q ⁴ = methyl group), X-22-174DX (Mw 4600, monomer represented by formula (x3-2), Q ⁴ = methyl group), X-24-8201 (Mw: 2100), X-22-2426 (Mw: 12000, represented by formula (x3-2) Monomer, Q ⁴ = methyl group), X-22-2404 (Mw: 420, monomer represented by the formula (x4-2), Q ⁴ = methyl group), X-22-2406 (all manufactured by Shin-Etsu Chemical Co., Ltd.) You may use a commercial item, such as a tank.

The weight average molecular weight of (x) becomes like this. Preferably it is 300-50000, More preferably, it is 350-7000, More preferably, it is 2000-6000. When the weight average molecular weight of (x) is in the said range, there exists a tendency for the mechanical characteristic of a resin pattern, and the contact angle with water and an organic solvent to become high.

As (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclo Hexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art, it is commonly known as "dicyclopentanyl (meth) acrylate." , May be referred to as "tricyclodecyl (meth) acrylate", tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in the technical field, the common name is "dicyclophene" Tenyl (meth) acrylate), dicyclopentanyl jade Cethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naph (Meth) acrylic acid esters such as methyl (meth) acrylate and benzyl (meth) acrylate;

Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;

Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybi Cyclo [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-methyl Bicyclo [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-phenoxy Cycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bi Ratios of s (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Cyclo unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl Dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide And vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferable in terms of copolymerization reactivity and heat resistance.

In resin (A), content of the structural unit derived from (x) is 0.01 mass% or more and 5 mass% or less with respect to all the structural units of resin (A), Preferably they are 0.01 mass% or more and 3 mass% or less. More preferably, they are 0.02 mass% or more and 1 mass% or less.

The ratio of the structural unit derived from each monomer in resin [K1] is with respect to the whole structural unit which comprises resin [K1],

structural unit derived from (a); 5 to 60 mol%

structural unit derived from (b); 40-98 mol%

structural unit derived from (x); 0.01-5 mol% is preferable,

structural unit derived from (a); 10-50 mol%

structural unit derived from (b); 50 to 90 mol%

structural unit derived from (x); 0.01-3 mol% is more preferable.

If the ratio of the structural unit which comprises resin [K1] exists in the said range, the image development speed | rate at the time of resin pattern formation is high, and the obtained resin pattern is excellent in a mechanical characteristic, a contact angle with water and an organic solvent, and adhesiveness with a board | substrate. Do.

Resin [K1] is, for example, the method described in the literature "Experimental method of polymer synthesis" [Oct Takayuki Otsu Chemical Co., Ltd. First Edition First Edition March 1, 1972] and the citations described in this document. It can manufacture by reference.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are put in a reaction vessel, and the method of heating and keeping warm while stirring to form a deoxygen atmosphere by, for example, replacing oxygen with nitrogen, is mentioned. Can be. In addition, the polymerization initiator, solvent, etc. which are used here are not specifically limited, What is normally used in the said field | area can be used. For example, an azo compound [2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.] and an organic peroxide (benzoyl peroxide etc.) are mentioned as a polymerization initiator. As a solvent, what is necessary is just to melt | dissolve each monomer, and the solvent mentioned later used for the photosensitive resin composition of this invention, etc. are mentioned.

In addition, the obtained resin may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was extracted as solid (powder) by methods, such as reprecipitation. In particular, by using the solvent used for the photosensitive resin composition of this invention as a polymerization solvent, since the solution after reaction can be used as it is for manufacture of the photosensitive resin composition, the manufacturing process of the photosensitive resin composition can be simplified.

In resin [K2], the ratio of the structural unit derived from each is in the all the structural units which comprise resin [K2],

structural unit derived from (a); 2-40 mol%

structural unit derived from (b); 2 to 96 mol%

structural unit derived from (c); 1 to 65 mol%

structural unit derived from (x); It is preferable that it is 0.01-5 mol%,

structural unit derived from (a); 5 to 35 mol%

structural unit derived from (b); 5 to 80 mol%

structural unit derived from (c); 1 to 60 mol%

structural unit derived from (x); It is more preferable that it is 0.01-3 mol%.

If the ratio of the structural unit of resin [K2] is in the said range, the image development speed | rate at the time of resin pattern formation is high, and the resin pattern obtained is excellent in a mechanical characteristic, a contact angle with water and an organic solvent, and adhesiveness with a board | substrate.

Resin [K2] can be manufactured by the method similar to resin [K1].

Examples of the combination of the monomers constituting the resin [K1] include (meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / formula (x3-2). Monomer represented by (meth) acrylic acid / 3,4-epoxycyclohexylmethyl (meth) acrylate / formula (x3-2), (meth) acrylic acid / glycidyl (meth) acrylate / formula ( monomer represented by x3-2), (meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / monomer represented by formula (x4-2) , Monomer represented by (meth) acrylic acid / 3,4-epoxycyclohexylmethyl (meth) acrylate / formula (x4-2), (meth) acrylic acid / glycidyl (meth) acrylate / formula (x4-2) Monomer represented by), (meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / formula (x3-1) Monomer, (meth) acrylic acid / 3,4-epoxycyclohexylmethyl (meth) acrylate / monomer represented by formula (x3-1), (meth) acrylic acid / glycidyl (meth) acrylate / formula (x3 The monomer etc. represented by -1) are mentioned, Especially, (meth) acrylic acid / [The monomer represented by General formula (I-1) and / or The monomer represented by General formula (II-1)] / Chemical formula (x3- Monomer represented by 2), (meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / monomer represented by formula (x3-1), and ( Preferred are methacrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / monomer represented by formula (x4-2).

Examples of the combination of the monomers constituting the resin [K2] include (meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / formula (x3-2). Monomer / styrene, (meth) acrylic acid / glycidyl (meth) acryl represented by monomer / styrene, (meth) acrylic acid / 3,4-epoxycyclohexylmethyl (meth) acrylate / formula (x3-2) Monomer / styrene represented by rate / formula (x3-2), (meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / formula (x4- Monomer / styrene represented by 2), (meth) acrylic acid / 3,4-epoxycyclohexylmethyl (meth) acrylate / monomer / styrene represented by formula (x4-2), (meth) acrylic acid / glycidyl ( Monomer / styrene represented by meth) acrylate / formula (x4-2), (meth) acrylic acid / [monomer represented by formula (I-1) and / or chemical formula Monomer represented by (II-1)] / monomer represented by formula (x3-1) / styrene, (meth) acrylic acid / 3,4-epoxycyclohexylmethyl (meth) acrylate / formula (x3-1) Monomer / styrene represented by (meth) acrylic acid / glycidyl (meth) acrylate / monomer represented by formula (x3-1) / (meth) acrylic acid / [monomer represented by formula (I-1) and / Or monomer represented by the formula (II-1)] / monomer represented by the formula (x3-2) / N-cyclohexyl maleimide, (meth) acrylic acid / 3,4-epoxycyclohexyl methyl (meth) acrylate Monomer / N-cyclohexylmaleimide represented by the formula (x3-2), (meth) acrylic acid / glycidyl (meth) acrylate / monomer / N-cyclohexyl maleimide represented by the formula (x3-2) , (Meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / monomer represented by formula (x3-1) / N- Lohexylmaleimide, (meth) acrylic acid / 3,4-epoxycyclohexylmethyl (meth) acrylate / monomer represented by formula (x3-1) / N-cyclohexylmaleimide, (meth) acrylic acid / glycidyl Monomer / N-cyclohexylmaleimide represented by (meth) acrylate / formula (x3-1), (meth) acrylic acid / [monomer represented by formula (I-1) and / or formula (II-1) Monomer / N-cyclohexylmaleimide, (meth) acrylic acid / 3,4-epoxycyclohexylmethyl (meth) acrylate / formula (x4-2) Monomer / N-cyclohexyl maleimide to be represented, (meth) acrylic acid / glycidyl (meth) acrylate / monomer / N-cyclohexyl maleimide represented by formula (x4-2), etc. may be mentioned. (Meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / formula (x3-2) Is represented by monomer / N-cyclohexylmaleimide, (meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / formula (x3-1) Monomer / N-cyclohexylmaleimide and (meth) acrylic acid / [monomer represented by formula (I-1) and / or monomer represented by formula (II-1)] / monomer represented by formula (x4-2) / N-cyclohexylmaleimide is preferred.

The weight average molecular weight of polystyrene conversion of resin (A) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-20,000. When the weight average molecular weight of resin (A) exists in the said range, there exists a tendency for the applicability | paintability of the photosensitive resin composition to become favorable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (A) becomes like this. Preferably it is 1.1-6.0, More preferably, it is 1.2-4.0. When molecular weight distribution exists in the said range, a resin pattern and a cured film tend to be excellent in chemical resistance.

The acid value of resin (A) becomes like this. Preferably it is 30 mg-KOH / g or more and 180 mg-KOH / g or less, More preferably, it is 40 mg-KOH / g or more and 150 mg-KOH / g or less. The acid value is a value measured as the amount of potassium hydroxide required to neutralize 1 g of the resin (mg), and can be obtained by titration using an aqueous potassium hydroxide solution. When the acid value of resin (A) is in the said range, developability at the time of resin pattern preparation, a resin pattern, and a cured film tend to be excellent in adhesiveness with a board | substrate.

Content of resin (A) becomes like this. Preferably it is 30-90 mass%, More preferably, it is 35-80 mass% with respect to solid content of the photosensitive resin composition of this invention, More preferably, it is 40-70 mass%. When content of resin (A) exists in the said range, there exists a tendency which is excellent in the heat resistance of a resin pattern and a cured film, and excellent in adhesiveness with a board | substrate and chemical-resistance. Here, solid content of the photosensitive resin composition means the quantity remove | excluding content of a solvent (E) from the total amount of the photosensitive resin composition of this invention.

The photosensitive resin composition of this invention may contain resin different from resin (A). As resin different from resin (A), for example,

Resin [K1 ']: A copolymer consisting of a structural unit derived from (a) and a structural unit derived from (b);

Resin [K2 ']: A copolymer consisting of a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from (c);

Resin [K3]: A copolymer consisting of a structural unit derived from (a) and a structural unit derived from (c)

Can be mentioned.

<Polymeric Compound (B)>

A polymerizable compound (B) is a compound which can superpose | polymerize with the active radical which generate | occur | produced from the polymerization initiator (C), For example, it is a compound etc. which have a polymerizable ethylenically unsaturated bond, Preferably it is a (meth) acrylic acid ester compound. .

As a polymeric compound (B) which has one ethylenically unsaturated bond, the same thing as the compound mentioned as said (a), (b), and (c) is mentioned, Especially, (meth) acrylic acid ester is preferable.

Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, and 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 neopentylglycol di (meth) acrylate, ethoxylated neopentylglycol di (meth) Acrylate, 3-methylpentanediol di (meth) acrylate, and the like.

Examples of the polymerizable compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylic. 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, tripentaerythritolhepta (meth) acrylate, tripentaerythritol octa (Meth) acrylate, reactant of pentaerythritol tri (meth) acrylate with acid anhydride, di Reaction product of taerythritol penta (meth) acrylate with acid anhydride, tripentaerythritolhepta (meth) acrylate and acid anhydride caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylic acid Latex, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, capro Lactone-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 tripentaerythritolhepta (meth) a Relate, Caprolactone-modified tripentaerythritol octa (meth) acrylate, Caprolactone-modified pentaerythritol tri (meth) acrylate and reactants of acid anhydride, Caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride And reactant, caprolactone-modified tripentaerythritol hepta (meth) acrylate, acid anhydride, and the like.

Especially, the polymeric compound which has three or more ethylenically unsaturated bonds is preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 to 1,500 or less.

Content of a polymeric compound (B) becomes like this. Preferably it is 5-95 mass%, More preferably, it is 20-80 mass% with respect to the total amount of resin (A) and a polymeric compound (B). When content of a polymeric compound (B) exists in the said range, there exists a tendency for the sensitivity at the time of resin pattern preparation, the intensity | strength, smoothness, and reliability of the resin pattern and cured film obtained to become favorable.

<Polymerization Initiator (C)>

The polymerization initiator (C) is not particularly limited as long as it is a compound capable of generating an active radical, an acid, or the like by the action of light or heat and can initiate polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (C) include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds, and biimidazole compounds.

The O-acyl oxime compound is a compound having a partial structure represented by the following general formula (d1). Hereinafter, * represents a bond number.

Examples of the O-acyl oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3- Dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl ) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- And the like] -3-cyclopentylpropane-1-one-2-imine. You may use commercially available products, such as Ilgacure (registered trademark) OXE01, OXE02 (above BASF Corporation make), and N-1919 (ADEKA Corporation make).

The alkylphenone compound is a compound having a partial structure represented by the following general formula (d2) or a partial structure represented by the general formula (d3). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4- Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1 -On etc. can be mentioned. You may use commercially available products, such as Ilgacure (trademark) 369, 907, and 379 (above, BASF Corporation make). In addition, a polymerization initiator having a group capable of causing chain transfer described in JP2002-544205-A may be used.

Examples of the compound having a partial structure represented by the general formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2-hydroxy Oligomers of hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, (alpha)-diethoxy acetophenone, benzyl dimethyl ketal, etc. are mentioned.

In terms of sensitivity, as the alkylphenone compound, a compound having a partial structure represented by the general formula (d2) is preferable.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloro Rhomethyl) -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 (trichloromethyl)- 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc. are mentioned as said acylphosphine oxide compound. You may use a commercial item, such as Ilgacure (trademark) 819 (made by BASF Corporation).

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 eg JPH06-75372-A, JPH06-75373-A, etc.), 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 (see, eg, JPS48-38403-B, JPS62-174204-A, etc.), the phenyl group at the 4,4'5,5'-position already substituted by a carboalkoxy group And a dazole compound (see, for example, JP 7-10913-A and the like).

Moreover, as a polymerization initiator, Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization start adjuvant (C1) (especially amines) mentioned later.

As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4- Acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodium p-toluenesulfonate, diphenyliodine Onium salts such as nium hexafluoro antimonate, nitrobenzyl tosylates, benzointosylates and the like.

As a polymerization initiator (C), the polymerization initiator containing 1 or more types chosen from the group which consists of an alkyl phenone compound, a triazine compound, an acyl phosphine oxide compound, an O-acyl oxime compound, and a biimidazole compound is preferable, The polymerization initiator containing a diazole compound is more preferable. If it is these polymerization initiators, it is highly sensitive and there exists a tendency for the transmittance | permeability in a visible light region to become high.

Content of a polymerization initiator (C) becomes like this. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total content of resin (A) and a polymeric compound (B), More preferably, it is 0.5-15 mass parts, Preferably it is 1-8 mass parts. When content of a polymerization initiator (C) exists in the said range, since it exists in the tendency to become high sensitivity and shorten an exposure time, productivity improves and there exists a tendency for the visible light transmittance of the resin pattern obtained to be high.

<Polymerization start preparation (C1)>

The polymerization initiation assistant (C1) is used together with the polymerization initiator (C) and is a compound or sensitizer used to promote the polymerization of a compound (eg, a polymerizable compound (B)) in which polymerization is initiated by the polymerization initiator (C). to be.

As a polymerization start adjuvant (C1), a thiazoline compound, an amine compound, an alkoxy anthracene compound, a thioxanthone compound, and a carboxylic acid compound are mentioned, for example.

Examples of the thiazolin compound include compounds represented by the following general formulas (III-1) to (III-3), compounds described in JP2008-65319-A, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethyl Aminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4, 4'-bis (ethylmethylamino) benzophenone etc. are mentioned, Especially, 4,4'-bis (diethylamino) benzophenone is preferable. You may use a commercial item, such as EAB-F (made by Hodogaya Kagaku Kogyo Co., Ltd.).

Examples of the alkoxy anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10- Dibutoxy anthracene, 2-ethyl-9, 10- dibutoxy anthracene, etc. are mentioned.

As said thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxide Citioxanthone etc. are mentioned.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, Chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthylthioacetic acid, N-naphthyl glycine, naphthoxy acetic acid, and the like.

When the photosensitive resin composition of this invention contains a polymerization start adjuvant (C1), the content becomes like this. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total content of resin (A) and a polymeric compound (B), More preferably, it is 0.2-10 mass parts. When the amount of the polymerization initiation assistant (C1) is within the above-described range, there is a tendency to become more sensitive when forming a resin pattern.

<Thiol compound (T)>

Thiol compound (T) is a compound which has a sulfanyl group (-SH) in a molecule | numerator.

Especially, the compound which has two or more sulfanyl groups is preferable, and the compound which has two or more sulfanyl groups couple | bonded with the carbon atom of an aliphatic hydrocarbon structure is more preferable. It is preferable to use a thiol compound (T) with a polymerization initiator (D).

Examples of the thiol compound (T) include hexanedithiol, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediolbis (3-sulfanylpropionate), butanediolbis (3-sulfanyl acetate), and ethylene. Glycolbis (3-Sulfanyl Acetate), Trimethylol Propane Tris (3-Sulfanyl Acetate), Butanediol Bis (3-Sulfanyl Propionate), Trimethylol Propane Tris (3-Sulfanyl Propionate), Trimethylol Propane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyltris (3-sulfanylpropionate) And pentaerythritol tetrakis (3-sulfanylbutylate), 1,4-bis (3-sulfanylbutyloxy) butane and the like.

When the photosensitive resin composition of this invention contains a thiol compound (T), the content becomes like this. Preferably it is 10-90 mass parts with respect to 100 mass parts of content of a polymerization initiator (C), More preferably, it is 15-70 mass It is wealth. When content of a thiol compound (T) exists in the said range, there exists a tendency for a sensitivity to become high and developability becomes favorable.

Antioxidant (F)

Examples of the antioxidant (F) include phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants and amine antioxidants. Especially, since a coloring of a cured film is few, a phenolic antioxidant is preferable.

As the phenolic antioxidant, for example, 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-pentylphenylacrylate, 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-methyl Phenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2,2'- Thiobis (6-tert-butyl-4-methylphenol), 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, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine and the like.

You may use a commercial item as said phenolic antioxidant. Commercially available phenolic antioxidants include, for example, Sumerizer (registered trademark) BHT, GM, GS, GP (all manufactured by Sumitomo Kagaku Co., Ltd.), Ilganox (registered trademark) 1010, 1076, 1330, 3114 (more than And BASF Co., Ltd.).

Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate and pentaerythritol tetra Kiss (3-lauryl thio propionate) etc. are mentioned. You may use a commercial item as said sulfur type antioxidant. Commercially available sulfur-based antioxidants include, for example, Sumerizer (TM) TPL-R, TP-D (all of which are manufactured by Sumitomo Chemical Co., Ltd.) and the like.

Examples of phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite etc. are mentioned. You may use a commercial item as said phosphorus antioxidant. Commercially available phosphorus antioxidants include, for example, Ilgafos (registered trademark) 168, 12, 38 (all manufactured by BASF Corporation), Adecastab 329K, Adecastab PEP36 (all manufactured by ADEKA), and the like.

As the amine antioxidant, for example, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-di-isopropyl-p-phenylenediamine, N, N'-dicyclohexyl-p- Phenylenediamine, N, N'- diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, etc. are mentioned. You may use a commercial item as said amine antioxidant. Commercially available amine antioxidants include, for example, Sumerizer (registered trademark) BPA, BPA-M1, 4ML (all manufactured by Sumitomo Chemical Co., Ltd.) and the like.

When curable resin composition of this invention contains antioxidant (F), 0.1 mass part or more and 5 mass parts or less of the content are preferable with respect to 100 mass parts of total content of resin (A) and a polymeric compound (B), More preferably, 0.5 mass part or more and 3 mass parts or less are more preferable. When content of antioxidant (F) exists in the said range, there exists a tendency which is excellent in the heat resistance of a resin pattern and a cured film, and pencil hardness.

<Surfactant (H)>

As surfactant (H), silicone type surfactant, a fluorine type surfactant, the silicone type surfactant which has a fluorine atom, etc. are mentioned, for example.

As silicone type surfactant, surfactant etc. which have a siloxane bond are mentioned. Specifically, doyle silicon (brand name) DC3PA, doyle silicon SH7PA, doyle silicon DC11PA, doyle silicon SH21PA, doyle silicon SH28PA, doyle silicon SH29PA, doyle silicon SH30PA, doyle silicon SH8400 [Doray silicon Do84 Corning] Co., Ltd.], KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsukagaku Kogyo Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 ( Momentive Performance Materials Japan Co., Ltd.).

As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned. Specifically, Fluorade (registered trademark) FC430, Fluoride FC431 (manufactured by Sumitomo 3M Co., Ltd.), Mega Pack (registered trademark) F142D, Mega Pack F171, Mega Pack F172, Mega Pack F173, Mega Pack F177, Mega Pack F183 , Megapack F554, Megapack R30, Megapack RS-718-K (manufactured by DIC Corporation), FTop® EF301, Ftop EF303, Ftop EF351, Ftop EF352 [Mitsubishi Material Denshi Kasei Ltd.], Supron (registered trademark) S381, Supron S382, Supron SC101, Supron SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Co., Ltd.) Can be mentioned.

As silicone type surfactant which has the said fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain | strand are mentioned. Specifically, Mega Pack (R) R08, Mega Pack BL20, Mega Pack F475, Mega Pack F477, Mega Pack F443 (manufactured by DIC Corporation), and the like.

When the photosensitive resin composition of this invention contains surfactant (H), the content is 0.001 mass% or more and 0.2 mass% or less with respect to the total amount of the photosensitive resin composition of this invention, Preferably it is 0.002 mass% or more and 0.1 mass% Hereinafter, More preferably, they are 0.01 mass% or more and 0.05 mass% or less. When content of surfactant (H) exists in the said range, since the flatness of a composition layer can be improved, height deviation becomes small in a resin pattern, and flatness tends to become high in a cured film.

<Solvent (E)>

Solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (solvent containing -COO- in a molecule and no -O-), an ether solvent (solvent containing -O- in a molecule and not containing -COO-), an ether ester solvent ( A solvent containing -COO- and -O- in a molecule, a ketone solvent (a solvent containing -CO- in a molecule and no -COO-), an alcoholic solvent (containing OH in a molecule, -O- , -CO- and -COO- free solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like can be used.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl anisole Etc. can be mentioned.

As the ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate and methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2- Methyl methyl propionate, 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate Bit, di, and the like ethylene glycol monobutyl ether acetate.

As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclo Pentanone, cyclohexanone, isophorone, etc. are mentioned.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, and the like.

As an aromatic hydrocarbon solvent, benzene, toluene, xylene, mesitylene, etc. are mentioned.

Examples of the amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and the like.

Among the solvents described above, organic solvents having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm are preferable in view of coatability and dryness. Especially, as said organic solvent, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-methoxy butyl acetate, and 3-methoxy- 1-butanol are preferable. The solvent (E) is preferably a mixed solvent containing these.

Content of a solvent (E) becomes like this. Preferably it is 60-95 mass% with respect to the total amount of the photosensitive resin composition of this invention, More preferably, it is 70-95 mass%. In other words, solid content of the photosensitive resin composition of this invention becomes like this. Preferably it is 5-40 mass%, More preferably, it is 5-30 mass%. When content of a solvent (E) exists in the said range, since the flatness of the composition layer formed from the photosensitive resin composition of this invention tends to be high, height deviation becomes small in a resin pattern, and flatness tends to become high in a cured film. have.

<Other ingredients>

The photosensitive resin composition of this invention may contain additives known in the said technical field, such as a filler, another high molecular compound, a thermal radical generating agent, a ultraviolet absorber, a chain transfer agent, and an adhesion promoter, as needed.

Glass, silica, alumina, etc. are mentioned as a filler.

As another high molecular compound, thermosetting resins, such as maleimide resin, thermoplastic resins, such as polyvinyl alcohol, polyacrylic acid, polyethyleneglycol monoalkyl ether, polyfluoroalkylacrylate, polyester, and polyurethane, etc. are mentioned.

Specific examples of the thermal radical generator include 2,2'-azobis (2-methylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and the like.

Specific examples of the ultraviolet absorbent include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.

Examples of the chain transfer agent include dodecanethiol, 2,4-diphenyl-4-methyl-1-pentene, and the like.

Examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. , 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3 -Chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltri Methoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxy Column, and 3-amino propyl triethoxysilane, N- phenyl-3-aminopropyltrimethoxysilane, N- phenyl-3-amino propyl silane in the tree.

The photosensitive resin composition of this invention does not contain coloring agents, such as a pigment and dye, substantially. That is, in the photosensitive resin composition of this invention, the content of the coloring agent with respect to the whole composition is for example less than 1 mass%, Preferably it is less than 0.5 mass%.

Moreover, when the photosensitive resin composition of this invention is filled into the quartz cell whose optical path length is 1 cm, and the transmittance | permeability was measured on the conditions of 400-700 nm of measurement wavelengths using the spectrophotometer, average transmittance becomes like this. It is% or more, More preferably, it is 80% or more.

When the photosensitive resin composition of this invention is used as a cured film, the average transmittance of a cured film becomes like this. Preferably it is 90% or more, More preferably, it is 95% or more. This average transmittance | permeability is measured on the cured film whose thickness after heat-hardening (for example, 100 degreeC-250 degreeC, 5 minutes-3 hours) is 2 micrometers using the spectrophotometer on the conditions of the measurement wavelength 400-700 nm. Average value. Thereby, the resin pattern and cured film excellent in transparency in visible region can be provided.

<The manufacturing method of the photosensitive resin composition>

The photosensitive resin composition of this invention mixes resin, a polymeric compound (B), and a polymerization initiator (C) with the solvent (E), surfactant (H), and other components which are used as needed by a well-known method. It can manufacture. After mixing, it is preferable to filter with a filter having a pore diameter of about 0.05 to 1.0 m.

<Method for producing resin pattern>

The resin pattern formed by the photosensitive resin composition of this invention can be manufactured by performing the following process (1)-(4), for example. It is preferable to perform process (5) further after process (4).

Process (1) Process of apply | coating the photosensitive resin composition of this invention to a board | substrate

Process (2) The process of drying the photosensitive resin composition after application | coating and forming a composition layer

Process (3) Process of exposing composition layer through photomask

Process (4) The process of developing the composition layer after exposure

Process (5) Process of heating composition layer after image development

Step (1) is a step of applying the photosensitive resin composition of the present invention to a substrate.

Examples of the substrate include glass, metal, plastic, and the like, and a color filter, an insulating film, a conductive film and / or a driving circuit may be formed on the substrate.

Application | coating on a board | substrate is performed using coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.

Step (2) is a step of drying the photosensitive resin composition after application to form a composition layer. By performing this process, volatile components, such as a solvent in the photosensitive resin composition, can be removed. As a method of drying, heat drying (prebaking) and reduced pressure drying are mentioned.

When carrying out heat drying, the drying temperature is preferably in the range of 30 ° C to 120 ° C, more preferably 50 ° C to 110 ° C, and the drying time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. Heat drying is normally performed using heating apparatuses, such as an oven and a hotplate.

When drying under reduced pressure, it is preferable to carry out in the temperature range of 20 degreeC-25 degreeC under the pressure of 50-150 Pa.

Step (3) is a step of exposing the composition layer formed by step (2) through a photomask. This photomask uses the thing in which the light shielding part was formed corresponding to the part to remove of a composition layer. The shape of the light shielding portion is not particularly limited and can be selected according to the intended use. You may use a halftone mask or a gray scale mask.

As a light source used for exposure, the light source which produces the light of 250-450 nm wavelength is preferable. For example, light below 350 nm can be selectively blocked using a filter that blocks this wavelength range, or selectively selected around 436 nm, 408 nm or 365 nm, using a bandpass filter that picks out these wavelength ranges. You may pay. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

It is preferable to use exposure apparatuses, such as a mask aligner and a stepper, since it can irradiate a parallel light beam uniformly to the whole exposure surface, or can perform exact alignment of a photomask and a composition layer.

Process (4) is a process of developing the composition layer after exposure. By developing the composition layer after exposure in contact with the developer, the unexposed part of the composition layer is dissolved in the developer and removed, thereby forming a resin pattern on the substrate.

As a developing solution, aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide, is preferable, for example. The concentration in the aqueous solution of these alkaline compounds is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. In addition, the developing solution may contain surfactant.

The developing method may be any of a puddle method, a dipping method and a spray method. In addition, you may tilt the board | substrate at arbitrary angles at the time of image development.

It is preferable to wash with water after image development.

Process (5) is a process of heating (post-baking) the composition layer after image development. By heating, the durability of the resin pattern, for example, heat resistance, chemical resistance, mechanical properties, and the like are improved. Heating is usually performed using heating apparatuses, such as an oven and a hotplate. 120 to 250 degreeC is preferable and 150 to 235 degreeC of heating temperature is more preferable. 1 to 180 minutes are preferable and, as for a heat time, 10 to 60 minutes are more preferable.

From the photosensitive resin composition of this invention, the cured film which is not patterned can also be manufactured by the following process. Preferable conditions of each process are the same as the manufacturing method of a resin pattern.

Process (1) Process of apply | coating the photosensitive resin composition of this invention to a board | substrate

Process (2) The process of drying the photosensitive resin composition after application | coating and forming a composition layer

Process (5) Process of heating composition layer after image development

Behind the process (2), as required

Process (3 ') You may perform the process of exposing a composition layer without passing through a photomask. In addition, when performing a process (3 '),

Process (4) You may perform the process of developing the composition layer after exposure.

Thus, since the resin pattern obtained from the photosensitive resin composition of this invention is especially excellent in mechanical characteristics, the photospacer which comprises a part of a color filter board | substrate and / or an array board | substrate, a patternable overcoat, an interlayer insulation film, and a liquid crystal orientation control, for example It is useful as an overcoat which comprises a part of a touch panel member, a color filter substrate, and / or an array substrate, such as a projection, a micro lens, and a coating layer for adjusting film thickness. Moreover, since the resin pattern obtained from the photosensitive resin composition of this invention is excellent in liquid repellency, the partition used in order to manufacture a color filter, the ITO electrode of a liquid crystal display element, an organic electroluminescence display element, a circuit wiring board, etc. by the inkjet method. It is also useful as. The color filter substrate and the array substrate described above are suitably used for liquid crystal display devices, organic EL display devices, electronic papers, and the like.

Example

Hereinafter, an Example demonstrates this invention in more detail. In the examples, "%" and "parts" are% by mass and parts by mass unless otherwise specified.

Synthesis Example 1

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 140 parts by mass of 3-methoxybutyl acetate was added and heated to 70 ° C while stirring.

Subsequently, 40 mass parts of methacrylic acid and the monomer represented by general formula (x3-2-1) [made by Shin-Etsu Chemical Co., Ltd. make, brand names X-22-174DX, Mw; 4600] 4: 50 (molar ratio of 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate [compound represented by formula (I-1) and compound represented by formula (II-1)] ) Mixture] 356 parts by mass was dissolved in 190 parts by mass of 3-methoxybutyl acetate to prepare a solution. This solution was added dropwise into a flask kept at 70 ° C. over 4 hours using a dropping pump.

On the other hand, the flask which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 240 mass parts of 3-methoxybutyl acetate, the flask over 5 hours using the other dropping pump. It was dripped inside. After the dropping of the solution of the polymerization initiator was completed, the solution was maintained at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a copolymer (resin Aa) solution having a solid content of 42.5% by mass. The weight average molecular weight (Mw) of obtained resin Aa was 8000, the molecular weight distribution was 1.95, and the acid value of conversion of solid content was 60 mg-KOH / g. Resin Aa has the following structural units.

Synthesis Example 2

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 140 parts by mass of 3-methoxybutyl acetate was added and heated to 70 ° C while stirring.

Subsequently, 40 mass parts of methacrylic acid, 4 mass parts of monomers [Shin-Etsu Chemical Co., Ltd. make, brand name X-22-2475, average molecular weight 420] represented by general formula (x3-1-1), 3,4 356 parts by mass of epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate [a mixture of 50:50 in molar ratio of the compound represented by the formula (I-1) and the compound represented by the formula (II-1)]. It dissolved in 190 parts by mass of oxybutyl acetate to prepare a solution. This solution was added dropwise into a flask kept at 70 ° C. over 4 hours using a dropping pump.

On the other hand, the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 240 mass parts of 3-methoxybutyl acetates was put into the flask over 5 hours using the separate dropping pump. It dripped. After the dropping of the solution of the polymerization initiator was completed, the solution was maintained at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a copolymer (resin Ab) solution having a solid content of 42.3% by mass. The weight average molecular weight (Mw) of obtained resin Ab was 9300, the molecular weight distribution was 2.11, and the acid value of conversion of solid content was 60 mg-KOH / g. Resin Ab has the following structural unit.

Synthesis Example 3

In a flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed 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 were added thereto while stirring. Heated to 70 ° C. Subsequently, the molar ratio of 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate [compound represented by formula (I-1) and compound represented by formula (II-1) Mixture at 50:50] 240 parts by mass was dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was added dropwise into a flask kept at 70 ° C. over 4 hours using a dropping funnel.

On the other hand, the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of 3-methoxybutyl acetates in the flask over 4 hours using the separate dropping funnel. It dripped. After the dropwise addition of the solution of the polymerization initiator was completed, the solution was maintained at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin Ac) having a solid content of 32.6% by mass. The weight average molecular weight (Mw) of obtained resin Ac was 13,400, the molecular weight distribution was 2.50, and the acid value of conversion of solid content was 110 mg-KOH / g. Resin Ac has the following structural unit.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of obtained resin was performed on condition of the following using GPC method.

Apparatus: K2479 [manufactured by Shimadzu Seisakusho Corporation]

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ℃

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 ml / min

Detector: RI

Calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight of polystyrene conversion obtained above was made into molecular weight distribution.

Examples 1-5 and Comparative Example 1

<Preparation of the photosensitive resin composition>

Each component shown in Table 1 was mixed in the ratio shown in Table 1, and the photosensitive resin composition was obtained.

TABLE 1

In addition, in Table 1, content of resin (A) shows the mass part of solid content conversion.

Resin (A); Aa; Resin Aa

Resin (A); Ab; Resin Ab

Resin (A); Ac; Resin Ac

Polymerizable compound (B); Dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.]

Polymerization initiator (C); 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole [B-CIM; Hodogaya Kagaku Co., Ltd.]

Polymerization initiation aid (C1); 9,10-dibutoxy anthracene [anthracure® UVS-1331; Kawasaki Kasei Co., Ltd. manufacture]

Thiol compound (T); Pentaerythritol tetrakis (3-sulfanylpropionate) [PEMP; SC Yukikagaku Co., Ltd. product]

Surfactant (H); Polyether modified silicone oils [doresilicone SH8400; Toore Dow Corning Co., Ltd.]

Antioxidant (F); 1,3,5-tris (4-hydroxy-3,5-di-tert-butylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione [ IRGANOX® 3114; BASF Corporation]

Solvent (E); Ea; Propylene Glycol Monomethyl Ether Acetate

Solvent (E); Eb; Ethyl 3-ethoxypropionate

Solvent (E); Ec; 3-methoxy-1-butanol

Solvent (E); Ed; 3-methoxybutyl acetate

The solvent (E) was mixed so that solid content of the photosensitive resin composition might be "solid content (%)" of Table 1. The value of each component Ea-Ed in a solvent (E) shows the mass ratio (%) in a solvent (E).

<Measurement of transmittance of the composition>

An ultraviolet-visible near-infrared spectrophotometer [V-650; respectively about the obtained photosensitive resin composition]; The average transmittance (%) in 400-700 nm was measured using Nippon Bunco Co., Ltd. product (quartz cell, optical path length; 1 cm). The results are shown in Table 2.

<Formation of Curing Film>

A square glass substrate (# 1737; manufactured by Corning) with one side of 2 inches was washed sequentially with a neutral detergent, water, and isopropanol, and dried. After spin-coating the photosensitive resin composition on this glass substrate so that the film thickness after post-baking may be set to 3.0 micrometers, it is made to dry by depressurizing and drying until a pressure reduction degree becomes 66 kPa in a pressure reduction dryer (manufactured by Microtec Co., Ltd.) Prebaked at 80 ° C. for 2 minutes and dried to form a composition layer. After cooling, the composition layer was exposed to an exposure machine [TME-150 RSK; Topcon Co., Ltd. light source; Ultra-high pressure mercury lamp] was used for exposure at an exposure dose of 100 mJ / cm 2 (405 nm standard) under an atmospheric atmosphere. In addition, the exposure to the composition layer at this time is performed by the optical filter [LU0400; Asahi Bunko Co., Ltd.] was passed through. After exposure, the aqueous layer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide was immersed and developed while shaking the composition layer after exposure for 100 seconds at 25 ° C, and further washed with water. Then, post-baking was performed at 235 degreeC for 15 minutes in oven, and the cured film was obtained.

<Measurement of transmittance of the cured film>

The average transmittance | permeability (%) in 400-700 nm was measured for the obtained cured film using the microscopic spectrophotometer (OSP-SP200; OLYMPUS company make). The results are shown in Table 2.

<Formation of Resin Pattern>

Except having used the photomask at the time of exposure, operation similar to preparation of a cured film was performed and the resin pattern was obtained. As a photomask, a pattern (one side having a square light transmitting portion having a thickness of 20 μm and having a square interval of 100 μm) (that is, a light transmitting portion) formed on the same plane was used.

Evaluation; Measuring Width and Height of Resin Patterns>

The width and height of the obtained resin pattern were measured using a three-dimensional non-contact surface shape measurement system [Micromap MM527N-PS-M100; Manufactured by Ryoka Systems Co., Ltd.]. The width of the resin pattern was measured at a height position of 5% of the resin pattern height from the substrate surface.

The larger the width of the resin pattern, the higher the sensitivity. The results are shown in Table 2.

Mechanical Characteristics (Total Displacement and Recovery Rate)

Dynamic ultra-fine hardness tester [DUH-W201; The total recovery amount (micrometer) and the elastic displacement amount (micrometer) were measured using the Shimadzu Corporation make, and the recovery rate (%) was computed. The higher the recovery rate of the pattern, the higher the flexibility, which can be said to be useful as a photospacer. When such a resin pattern is used as a photo spacer, it is possible to manufacture the liquid crystal panel excellent in intensity. The results are shown in Table 2. The resin pattern and cured film formed from the same photosensitive resin composition exhibit the same mechanical properties.

-Measuring conditions-

Test mode; Load-Unload Test

Test force; 50 mN

Load speed; 4.41 mN / sec

Retention time; 5 sec

Indenter; Conical indenter (diameter 50 μm)

Recovery rate (%); (Elastic displacement amount (micrometer) / total displacement amount (micrometer)) * 100

<Contact angle>

About the obtained cured film, the contact angle of ion-exchange water and toluene was measured using the contact angle meter (DGD Fast / 60; GBX Corporation make). Higher contact angle means higher liquid repellency. When the contact angle in a cured film is high, the contact angle is also high also in the resin pattern formed using the same photosensitive resin composition. It is preferable to use a resin pattern having a high contact angle as an ink jet partition because the partition does not seep ink, so that there is a tendency to suppress the color mixture of the ink between adjacent pixel regions. The results are shown in Table 2.

TABLE 2

From the result of Table 2, according to the photosensitive resin composition of this invention, it turns out that a recovery rate is high. From this, it was confirmed that the resin pattern formed from the photosensitive resin composition of this invention is excellent in a mechanical characteristic.

According to the photosensitive resin composition of this invention, the pattern excellent in a mechanical characteristic can be obtained.

Claims (7)

The photosensitive resin composition containing following (A), (B) and (C):
(A) a structural unit derived from at least one member selected from the group consisting of (a) unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and (b) a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond A copolymer consisting of only a structural unit derived from a monomer and a structural unit derived from a monomer having a (x) siloxane structure and an ethylenically unsaturated bond, or
It is derived from the structural unit derived from 1 or more types chosen from the group which consists of (a) unsaturated carboxylic acid and unsaturated carboxylic anhydride, and (b) the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond. A structural unit derived from a monomer having a (x) siloxane structure and an ethylenically unsaturated bond, (c) a (meth) acrylic acid ester, a hydroxy group-containing (meth) acrylic acid ester, a dicarboxylic acid diester, and a bicyclo Unsaturated compounds, dicarbonylimide derivatives, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, Structure derived from at least one member selected from the group consisting of vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene A copolymer consisting of Wiman,
Content of the structural unit derived from the monomer which has a siloxane structure and an ethylenically unsaturated bond is 0.01 mass% or more and 5 mass% or less with respect to the total structural units of the said copolymer,
(b) a copolymer wherein the monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond is a monomer having a structure in which the alicyclic unsaturated hydrocarbon is epoxidized (b1-2);
(B) a polymerizable compound having no silicon atom
(C) polymerization initiator. The photosensitive resin composition of Claim 1 whose weight average molecular weights of the monomer which has a siloxane structure and ethylenically unsaturated bond are 300-50000. The photosensitive resin composition of Claim 1 whose (C) polymerization initiator is a polymerization initiator containing a biimidazole compound. delete The resin pattern formed from the photosensitive resin composition of any one of Claims 1-3. The display apparatus containing the resin pattern of Claim 5. It is derived from the structural unit derived from 1 or more types chosen from the group which consists of (a) unsaturated carboxylic acid and unsaturated carboxylic anhydride, and (b) the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond. A copolymer consisting of only a structural unit derived from a monomer having a structural unit and (x) a polysiloxane structure and an ethylenically unsaturated bond, or
It is derived from the structural unit derived from 1 or more types chosen from the group which consists of (a) unsaturated carboxylic acid and unsaturated carboxylic anhydride, and (b) the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond. A structural unit derived from a monomer having a (x) polysiloxane structure and a monomer having an ethylenically unsaturated bond, (c) a (meth) acrylic acid ester, a hydroxy group-containing (meth) acrylic acid ester, a dicarboxylic acid diester and a bicyclo Unsaturated compounds, dicarbonylimide derivatives, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, Derived from one or more selected from the group consisting of vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene A copolymer consisting of only tank unit,
Content of the structural unit derived from the monomer which has a polysiloxane structure and an ethylenically unsaturated bond is 0.01 mass% or more and 5 mass% or less with respect to the total structural units of the said copolymer,
(b) The copolymer whose monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond is a monomer in which the (b1-2) alicyclic unsaturated hydrocarbon has a epoxidized structure.