CN108693708A

CN108693708A - Hardening resin composition and cured film

Info

Publication number: CN108693708A
Application number: CN201810312669.2A
Authority: CN
Inventors: 河西裕
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2017-04-12
Filing date: 2018-04-09
Publication date: 2018-10-23
Also published as: KR102601673B1; KR20180115225A; JP7180994B2; TW201900697A; JP2018178110A

Abstract

The present invention relates to hardening resin composition and cured films.Hardening resin composition, it includes:Resin (A), the resin (A) are comprising the copolymer with α, the structural unit (Aa) of beta-unsaturated carbonyl and active methylene or the structural unit (Ab) of active methylene;At least one kind of compound in the group being made of quaternary ammonium salt, quaternary alkylphosphonium salts and tertiary sulfonium salt;And at least one kind of compound in the group being made of epoxide and five-membered ring carbonate ester compound.

Description

Hardening resin composition and cured film

Technical field

The cured film formed the present invention relates to hardening resin composition and by the hardening resin composition.

Background technology

In the embodiment of Japanese Unexamined Patent Publication 3-172301 bulletins, it includes to make methyl methacrylate, methyl to describe Ethyl acrylate and methacrylic polymeric and then reaction product conduct obtained from being reacted with glycidyl methacrylate The composition of resin component;And make cured film obtained from the composition solidification in 230 DEG C.

Invention content

The present invention includes following scheme.

(1) hardening resin composition, it includes:

Resin (A), the resin (A) are comprising with α, the structural unit (Aa) of beta-unsaturated carbonyl and active Asia The copolymer of the structural unit (Ab) of methyl or active methylene;

At least one kind of compound in the group being made of quaternary ammonium salt, quaternary alkylphosphonium salts and tertiary sulfonium salt is (hereinafter, by the compound Referred to as " the 1st additive ".);And

At least one kind of compound in the group being made of epoxide and five-membered ring carbonate ester compound will be (hereinafter, will The compound is known as " the 2nd additive ".).

(2) hardening resin composition as described in (1), it includes quaternary ammonium salts and epoxide.

(3) hardening resin composition as described in (1) or (2), wherein aforementioned epoxy compound is to have in 1 intramolecular There is the epoxide of at least two oxiranyl (oxiranyl group).

(4) cured film is formed by the hardening resin composition described in any one of (1)~(3).

Specific implementation mode

It, unless otherwise specified, can be independent for the compound enumerated as each ingredient in this specification It uses, or combines a variety of and use.

[Gu Huaxingshuzhizuhewu ]

The hardening resin composition of the present invention includes resin (hereinafter referred to as resin (A).), the 1st additive and the 2nd adds Add agent.The hardening resin composition of the present invention also may include solvent (hereinafter referred to as solvent (E).).

Resin (A) is comprising with α, structural unit (the hereinafter referred to as structural unit (Aa) of beta-unsaturated carbonyl.) and tool Structural unit (the hereinafter referred to as structural unit (Ab) of active methylene or active methylene.) copolymer.

1st additive is at least one kind of compound in the group being made of quaternary ammonium salt, quaternary alkylphosphonium salts and tertiary sulfonium salt.

2nd additive is at least one kind ofization in the group being made of epoxide and five-membered ring carbonate ester compound Close object.

By making resin (A) and the 1st additive and the 2nd additive coexist, the cured film to make becomes solvent resistant The excellent film of property.

The hardening resin composition of the present invention may include polymerizable compound (hereinafter referred to as polymerizable compound (C).).Preferably also include polymerization initiator (hereinafter referred to as polymerization initiator (D) when comprising polymerizable compound (C).).

The hardening resin composition of the present invention may include other compositions, for example, polymerization trigger auxiliary agent is (hereinafter referred to as poly- It closes and causes auxiliary agent (H).), levelling agent (leveling agent) (hereinafter referred to as levelling agent (B).), colorant (hereinafter referred to as Colorant (K).).

< resins (A) >

Resin (A) has structural unit (Aa) and structural unit (Ab).Resin (A) also may include other structures unit (with Under, referred to as structural unit (Ac).).

Resin (A) can include respectively structural unit (Aa) of more than two kinds and structural unit (Ab).

Resin (A) is preferably alkali soluble resins.So-called alkali solubility refers to the aqueous solution being dissolved in as alkali compounds Property in developer solution.Resin (A) preferably comprises structural unit (the hereinafter referred to as structural unit (Ac1) with acidic group.) conduct Structural unit (Ac).Resin (A) can also include structural unit (the hereinafter referred to as structural unit other than structural unit (Ac1) (Ac2).) it is used as structural unit (Ac).Hereinafter, each structural unit is described in detail.

It should be noted that in this specification, it is so-called " (methyl) acrylic acid ", it indicates selected from by acrylic acid and metering system At least one kind of compound in the group of acid composition.The records such as " (methyl) acryloyl group " and " (methyl) acrylate " also have same The meaning of sample.

(1) structural unit (Aa)

In this specification, α, beta-unsaturated carbonyl is that (X indicates arbitrary substituent group to-CO-CX=CX- independently of each other.) The structure of expression, preferably-CO-CX=CH-.As X, hydrogen atom, the alkyl of carbon atom number 1~6, carbon atom number 1 can be enumerated ~6 hydroxy alkyl and the carboxyalkyl etc. of carbon atom number 1~6, can preferably enumerate hydrogen atom or methyl.

Structural unit (Aa) for example can be by making with α, compound (the hereinafter referred to as carboxylic acid reaction of beta-unsaturated carbonyl Property compound.) addition is in structural unit (the hereinafter referred to as structural unit (Aa ') with carboxyl.) and obtain.It is anti-as carboxylic acid Answering property compound can be enumerated with oxiranyl and α, compound (the hereinafter referred to as monomer (Aa ") of beta-unsaturated carbonyl.). As structural unit (Aa '), the structural unit with carboxyl in aftermentioned structural unit (Ac1) can be enumerated.

Structural unit (Aa) for example also can be by making to have the structural unit of oxiranyl to be reacted with (methyl) acrylic acid And it obtains.

As monomer (Aa "), can enumerate:Unsaturated fatty hydrocarbons with straight-chain or branched is through made of epoxidation Structure and α, compound (the hereinafter referred to as monomer (Aa " -1) of beta-unsaturated carbonyl.) and have unsaturated ester ring type hydrocarbon through ring Structure and α made of oxidation, compound (the hereinafter referred to as monomer (Aa " -2) of beta-unsaturated carbonyl.).

As aforementioned monomer (Aa " -1), (methyl) glycidyl acrylate, the contracting of (methyl) acrylic acid Beta-methyl can be enumerated Water glyceride, (methyl) propenoic acid beta-ethyl glycidyl ester, glycidyl itoconate etc..

As the concrete example of aforementioned monomer (Aa " -2), can enumerate:

(methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates,

(methyl) acrylic acid 5,6- epoxy San Huans [5.2.1.0^2,6]Decane -8- base esters,

(methyl) acrylic acid 5,6- epoxy San Huans [5.2.1.0^2,6]Decane -8- base oxygroup methyl esters,

(methyl) acrylic acid 2,3- epoxycyclopentyl methyl esters,

(methyl) acrylic acid 2- hydroxyls -3- (2,3- epoxycyclopentyl oxygroup) cyclopenta methyl esters,

(methyl) acrylic acid 3- (3,4- epoxycyclohexyl-methyl Epoxide carbonyl) -6- hydroxy-cyclohexyl methyl esters,

(methyl) acrylic acid 5,6- epoxy San Huans [5.2.1.0^2,6]Decane -8- base esters,

(methyl) acrylic acid 2,3- epoxycyclopentyl methyl esters,

(methyl) acrylic acid 2- hydroxyls -5- (3,4- epoxycyclohexyl carbonyloxymethyl) cyclohexylmethyl,

(methyl) acrylic acid 3- (3,4- epoxycyclohexyls) -9- hydroxyl -1,5- Er Yangzaluos [5,5]Hendecane -8- base esters,

(methyl) acrylic acid 3- (3,4- epoxycyclohexyls) -9- hydroxyl -2,4- Er Yangzaluos [5,5]Hendecane -8- base esters, Etc..

They can be used alone, and in addition can also be used in combination of two or more.In these, preferably (methyl) acrylic acid is used to contract Water glyceride or (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates.

For example, making (methyl) acrylic acid 3, the addition of 4- epoxycyclohexanecarboxylates is obtained in (methyl) acrylic acid structure unit Structural unit (Aa) by formula (Aa-1) indicate.

(Aa-1)

[In formula (Aa-1), R1 and R^xHydrogen atom or methyl are indicated independently of each other.]

For example, making (methyl) glycidyl acrylate addition structure list obtained from (methyl) acrylic acid structure unit Member is indicated by formula (Aa-2).

(Aa-2)

[In formula (Aa-2), R⁵And R^yHydrogen atom or methyl are indicated independently of each other.]

The structural unit indicated as structural unit (Aa), preferred formula (Aa-1) structural unit indicated or formula (Aa-2).

(2) structural unit (Ab)

As structural unit (Ab), the unsaturated compound for example by active methylene or active methylene can be enumerated Derivative structural unit.The so-called structural unit derived from the unsaturated compound of active methylene or active methylene, It refer to the structural unit from the unsaturated compound as obtained from making the unsaturated polymerizable compound.

The unsaturated compound of active methylene as derivative structure unit (Ab) can enumerate formula (I) expression Compound can enumerate the compound of formula (II) expression as the unsaturated compound of active methine.

R¹¹-R¹²-R¹³-CH₂-R¹⁴ (I)

[In formula (I) and formula (II),

R¹¹The group that any formula in expression (1-1)~formula (1-4) indicates.

R¹²Indicate that (* is indicated and R by singly-bound ,-X- or-X-O-*¹³Connecting key.).

R¹³Expression-CO- or-SO₂-。

R¹⁴Expression-CO-R¹⁵,-SO₂-R¹⁵, cyano or nitro.

X indicates the divalent alkyl of carbon atom number 1~20.

R¹⁵Indicate the alkyl of carbon atom number 1~24 or the alkoxy of carbon atom number 1~12.]

[In formula (1-1)~formula (1-4), R¹⁶And R¹⁸Hydrogen atom or the alkyl of carbon atom number 1~24 are indicated independently of each other.

R¹⁷Indicate that the alkyl of carbon atom number 1~24, the methylene for including in the alkyl can be replaced by-CO- or-O-.]

As R¹⁵~R¹⁸In carbon atom number 1~24 alkyl, the alkane such as methyl, ethyl, propyl, butyl, hexyl can be enumerated Base;Naphthenic base such as cyclohexyl etc..

R¹⁷In aforementioned alkyl in include methylene be replaced by-O- or-CO- in the case of, the carbon atom of the alkyl Number is 2~24.The methylene for including in alkyl as carbon atom number 2~24 is replaced by group obtained from-O- or-CO-, The alkoxies such as methoxyl group, ethyoxyl, propoxyl group, hexyl oxygroup can be enumerated;The cycloalkyloxies such as cyclohexyl oxygroup;2,4- dioxos penta Base, 3,5- dioxos hexyl, 1,3- dioxobutyl oxygroup ethyls etc. contain the alkyl etc. of oxo (oxo) base.

As the divalent alkyl of the carbon atom number 1~20 in X, methylene, ethylidene, propane diyl, butane two can be enumerated The divalent chain type aliphatic alkyl of the carbon atom numbers 1~20 such as base, hexane diyl, octane diyl, decane diyl, dodecane diyl;Ring The divalent ring type aliphatic alkyl of the carbon atom numbers 3~20 such as the group that hexane diyl, tristane diyl, following formula indicate;Sub- benzene Divalent aromatic hydrocarbyl of the carbon atom numbers such as base 6~20 etc. can preferably enumerate methylene or ethylidene.

R¹¹The group that the group that preferably formula (1-1) or formula (1-4) indicate, more preferably formula (1-1) indicate.

R¹²Indicate that (* is indicated and R by singly-bound ,-X- or-X-O-*¹³Connecting key.), preferably X is the divalent of carbon atom number 1~12 Saturated hydrocarbyl.

R¹³Preferably-CO-.

R¹⁴Preferably-CO-R¹⁵。

R¹⁵The preferably alkyl of carbon atom number 1~6 or the alkoxy of carbon atom number 1~6, more preferably carbon atom number 1~6 Alkyl.

R¹⁶Preferably hydrogen atom or the alkyl of carbon atom number 1~6, more preferably hydrogen atom or methyl.

R¹⁷The preferably naphthenic base of the alkyl of carbon atom number 1~12 or carbon atom number 3~12.

R¹⁸Preferably hydrogen atom or the alkyl of carbon atom number 1~6, more preferably hydrogen atom.

As the compound that formula (I) indicates, specifically, compound below etc. can be enumerated.

As the compound that formula (II) indicates, specifically, compound below etc. can be enumerated.

The compound that any formula in formula (I-1)~formula (I-7), formula (I-16), formula (II-1) and formula (II-2) indicates is R¹¹The group and R indicated for formula (1-1)¹⁶For the compound of methyl, R can be also enumerated¹⁶Methyl be replaced by hydrogen atom and Compound of the obtained compound as derivative structure unit (Ab).

Structural unit (Ab) is preferably the structural unit that formula (Ab-1) indicates.

(Ab-1)

[In formula (Ab-1), R³Indicate hydrogen atom or methyl, R⁴Indicate hydrogen atom or the alkyl of carbon atom number 1~6.]

As R⁴In carbon atom number 1~6 alkyl, methyl, ethyl, n-propyl, isopropyl, normal-butyl, secondary can be enumerated Butyl, tertiary butyl, n-pentyl and n-hexyl etc..

As R⁴, can preferably enumerate hydrogen atom and methyl.

As the compound for the structural unit that derivative formula (Ab-1) indicates, such as (methyl) acrylic acid 2- (1,3- can be enumerated Dioxobutyl oxygroup) ethyl ester (compound that formula (I-1) indicates).

(3) structural unit (Ac1)

Structural unit (Ac1) is the structural unit derived from the unsaturated compound with acidic group.As acidic group, can enumerate Carboxyl, phenolic hydroxyl, sulfo group etc..Unsaturated compound with 2 or more carboxyls can be acid anhydrides.It is so-called by with acidic group Structural unit derived from unsaturated compound refers to:It polymerize the unsaturated compound as monomer obtained from altogether The structural unit from the unsaturated compound in polymers.Copolymer with the structural unit can be by that will have acidic group Unsaturated compound is polymerize to obtain as monomer.In addition, also can be by making acid anhydrides addition in containing hydroxyl The copolymer of structural unit is to obtain.

Resin (A) preferably has structural unit (Ac1).

As the unsaturated compound with acidic group, preferably unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides.As unsaturated carboxylic The concrete example of acid and unsaturated carboxylic acid anhydrides, can enumerate:

(methyl) acrylic acid, crotonic acid, vinyl benzoic acid, 5- norbornene -2,3- dicarboxylic acid methylesters, 5- carboxyls are bicyclic [2.2.1]Hept-2-ene", 5- carboxyl -5- Jia Jishuanhuans [2.2.1]Hept-2-ene", 5- carboxyl -5- ethyl Shuan Huans [2.2.1]Hept- 2- Alkene, 5- carboxyl -6- Jia Jishuanhuans [2.2.1]Hept-2-ene", 5- carboxyl -6- ethyl Shuan Huans [2.2.1]Hept-2-ene", α-(hydroxyl first Base) unsaturated monocarboxylics such as (methyl) acrylic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3- vinylphthalic acids, 4- vinyl neighbours benzene two Formic acid, 3,4,5,6- tetrahydrophthalic acids, 1,2,3,6- tetrahydrophthalic acids, dimethyl tetrahydro phthalic acid, hexamethylene Alkene -1,4- dioctyl phthalate, 5,6- dicarboxyl Shuan Huans [2.2.1]The unsaturated dicarboxylics such as hept-2-ene";

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acids acid anhydride, 4- vinylphthalic acids acid anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, 1,2,3,6- tetrabydrophthalic anhydrides, dimethyl tetrahydro phthalic anhydride, 5,6- Dicarboxyl Shuan Huan [2.2.1]The unsaturated dicarboxylics acid anhydrides such as hept-2-ene" acid anhydride (carbic anhydride (himic anhydride));

Mono succinate (2- (methyl) acryloyl group oxygroup ethyl) ester, phthalic acid list (2- (methyl) acryloyl group oxygen Base ethyl) more than the divalents such as ester unsaturated single ((methyl) acryloyl group oxygroup alkyl) ester of polybasic carboxylic acid;Etc..

In these, (methyl) acrylic acid and maleic anhydride are excellent and excellent due to the alkali solubility of copolyreaction and copolymer Choosing.They may be used alone or in combination use.

(4) structural unit (Ac2)

Structural unit (Ac2) is the structural unit different from structural unit (Aa), (Ab) and (Ac1).Structural unit (Ac2) By can be with the monomer derived of the monomer polymerization of derivative other structures unit (for example, structural unit (Aa), (Ab) or (Ac1)).Make For the concrete example of such monomer, can enumerate:

(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) isopropyl acrylate, the positive fourth of (methyl) acrylic acid Ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- first Base cyclohexyl, (methyl) acrylic acid tricyclic;5.2.1.0^2,6]Decane -8- base esters (in the technical field, as trivial name, are claimed For (methyl) acrylic acid Bicvclopentyl ester (dicyclopentanyl (meth) acrylate).), (methyl) acrylic acid tricyclic [5.2.1.0^2,6]Decene -8- base esters (in the technical field, as trivial name, are referred to as " (methyl) acrylic acid double cyclopentenyl Ester (dicyclopentenyl (meth) acrylate) ".), (methyl) acrylic acid Bicvclopentyl oxygroup ethyl ester (dicyclopentanyl oxyethyl (meth) acrylate), (methyl) isobornyl acrylate,

(methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters etc. (methyl) acrylate;

The dicarboxylic diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;

Shuan Huan [2.2.1]Hept-2-ene", 5- Jia Jishuanhuans [2.2.1]Hept-2-ene", 5- ethyl Shuan Huans [2.2.1]Hept-2-ene", 5- hydroxyl Shuan Huans [2.2.1]Hept-2-ene", 5- hydroxymethyl Shuan Huans [2.2.1]Hept-2-ene", 5- (2 '-hydroxyethyl) are bicyclic [2.2.1]Hept-2-ene", 5- methoxyl group Shuan Huans [2.2.1]Hept-2-ene", 5- ethyoxyl Shuan Huans [2.2.1]Hept-2-ene", 5,6- dihydroxies Base Shuan Huan [2.2.1]The bicyclic unsaturated compound such as hept-2-ene";

N-phenylmaleimide, N- N-cyclohexylmaleimides, N- benzyl maleimides, 3- dimaleoyl imino benzene The dicarbonyl imides compounds such as formic acid N- succinimide esters, 4- maleimidobutyric acid N- succinimide esters;

Styrene, α-methylstyrene, m-methyl styrene, p-methylstyrene, vinyltoluene, to methoxybenzene second The distyryl compounds such as alkene;

(methyl) acrylonitrile, vinyl chloride, vinylidene chloride, (methyl) acrylamide, vinyl acetate, 1,3- butadiene, Isoprene, 2,3- dimethyl -1,3- butadiene etc..

In these, from the aspect of the heat resistance of reactivity, copolymer in copolymerization, preferably (methyl) acrylate, benzene Vinyl compound and dicarbonyl imides compound, more preferable (methyl) methyl acrylate, (methyl) n-butyl acrylate, (first Base) acrylic acid San Huan [5.2.1.0^2,6]Decane -8- base esters, styrene, vinyltoluene, N-phenylmaleimide, N- hexamethylenes Base maleimide and N- benzyl maleimides.They may be used alone or in combination use.

(5) resin (A)

Resin (A) is Shu Zhi &#91 below;K1]Huo [K2].

Shu Zhi [K1]:The copolymer being made of structural unit (Aa) and structural unit (Ab);

Shu Zhi [K2]:The copolymer being made of structural unit (Aa), structural unit (Ab) and structural unit (Ac).

Resin (A) is preferably Shu Zhi [K2].In addition, Shu Zhi [K2]In, as structural unit (Ac), preferably comprise structure list First (Ac1) and structural unit (Ac2).

When resin (A) includes structural unit (Ac1), about its ratio, relative to the entire infrastructure unit for constituting resin (A) For, preferably 1~50 mole of %, more preferably 5~40 moles of %.

When resin (A) includes structural unit (Ac2), about its ratio, relative to the entire infrastructure unit for constituting resin (A) For, preferably 1~70 mole of %, more preferably 5~60 moles of %.

About Shu Zhi [K1]In each structural unit ratio, relative to constitute Shu Zhi [K1]Entire infrastructure unit and Speech,

Preferably,

Structural unit (Aa):5~95 moles of %,

Structural unit (Ab):5~95 moles of %;

It is further preferred that

Structural unit (Aa):30~70 moles of %,

Structural unit (Ab):30~70 moles of %.

Constitute Shu Zhi [K1]Structural unit ratio in above-mentioned range when, from the preservation of hardening resin composition It stability, the heat resistance of obtained film and mechanical strength and examines in terms of the cured film of excellent solvent resistance can be formed Consider, is preferred.

About Shu Zhi [K2]In each structural unit ratio, constitute Shu Zhi [K2]Entire infrastructure unit in,

Preferably,

Structural unit (Aa):5~80 moles of %,

Structural unit (Ab):5~80 moles of %,

Structural unit (Ac):1~70 mole of %;

It is further preferred that

Structural unit (Aa):5~60 moles of %,

Structural unit (Ab):5~60 moles of %,

Structural unit (Ac):3~60 moles of %.

Shu Zhi [K2]In only include structural unit (Ac1) be used as structural unit (Ac) when,

Preferably,

Structural unit (Aa):5~80 moles of %,

Structural unit (Ab):5~80 moles of %,

Structural unit (Ac1):5~40 moles of %;

It is further preferred that

Structural unit (Aa):5~50 moles of %,

Structural unit (Ab):5~50 moles of %,

Structural unit (Ac1):10~40 moles of %.

Shu Zhi [K2]In only include structural unit (Ac2) be used as structural unit (Ac) when,

Preferably,

Structural unit (Aa):5~80 moles of %,

Structural unit (Ab):5~80 moles of %,

Structural unit (Ac2):1~70 mole of %;

It is further preferred that

Structural unit (Aa):5~50 moles of %,

Structural unit (Ab):5~50 moles of %,

Structural unit (Ac2):3~60 moles of %.

Shu Zhi [K2]In comprising both structural unit (Ac1) and structural unit (Ac2) as structural unit (Ac) when,

Preferably,

Structural unit (Aa):5~50 moles of %,

Structural unit (Ab):5~50 moles of %,

Structural unit (Ac1):1~50 mole of %,

Structural unit (Ac2):1~60 mole of %;

It is further preferred that

Structural unit (Aa):5~30 moles of %,

Structural unit (Ab):5~30 moles of %,

Structural unit (Ac1):10~40 moles of %,

Structural unit (Ac2):3~55 moles of %.

Shu Zhi [K2]Structural unit ratio in above-mentioned range when, from the preservation of hardening resin composition stablize Property, the heat resistance of obtained film and mechanical strength and from the aspect of the cured film of excellent solvent resistance can be obtained are Preferably.

The weight average molecular weight (Mw) according to polystyrene conversion of resin (A) is preferably 3,000~100,000, more preferably It is 5,000~50,000, further preferably 5,000~30,000, particularly preferably 5,000~20,000.The weight of resin (A) When average molecular weight (Mw) is in aforementioned range, the coating that there is the hardening resin composition of the present invention becomes good and inclines To being preferred.

The Fen Sandu &#91 of resin (A);Weight average molecular weight (Mw)/number-average molecular weight (Mn)s ]Preferably 1.1~6.0, more preferably 1.2~4.0.When dispersion degree is in aforementioned range, the solvent resistance the more favorable the tendency is of the cured film existed.

When resin (A) includes structural unit (Ac1), acid value (converting by solid state component) is preferably 30mg-KOH/g or more 180mg-KOH/g hereinafter, more preferably 40mg-KOH/g or more 150mg-KOH/g hereinafter, further preferably 50mg-KOH/g The above 135mg-KOH/g or less.Herein, acid value refers to being measured as the amount (mg) for neutralizing the required potassium hydroxide of 1g resins Value, can be titrated and be found out by using potassium hydroxide aqueous solution.When the acid value of resin (A) is in aforementioned range, deposit In the tendency of the excellent adhesion of obtained cured film and substrate.

Resin (A) can be by making the monomer of derivative structure unit (Aa), the monomer of derivative structure unit (Ab) and according to need The monomer of derivative structure unit (Ac) wanted and used carries out polymerisation to obtain.

As above-mentioned polymerization, can enumerating document " experimental method of Polymer Synthesizing ", (the big grand row in Tianjin writes, sale room: The same people of (strain) chemistry, the 1st edition the 1st printing, distribution on March 1st, 1972) described in method etc..

Specifically, following methods can be enumerated:By monomer, the derivative structure unit of the derivative structure unit (Aa) of specified amount (Ab) monomer and as needed and the loadings such as monomer, polymerization initiator and solvent of derivative structure unit (Ac) for using extremely In reaction vessel, stirs on one side to form deoxidizing atmosphere by replacing oxygen with such as nitrogen, heated and protected on one side Temperature.

In addition, can also enumerate following methods:The monomer of derivative monomer (Aa ') is carried out using above-mentioned polymerization and is derived The monomer of structural unit (Ab), with the polymerisation of the monomer of derivative structure unit (Ac) that uses as needed, Jin Ertong Cross reacting and forming structural unit (Aa) for structural unit (Aa ') and compound (Aa ").

It should be noted that the polymerization initiator and solvent etc. in the manufacture of resin (A) are not particularly limited, it may be used at Usually used polymerization initiator and solvent etc. in the field.As polymerization initiator, can enumerate for example azo-compound (2, 2 '-azobis isobutyronitriles, 2,2 '-azos bis- (2,4- methyl pentane nitriles) etc.), organic peroxide (benzoyl peroxide etc.), As solvent, as long as the solvent that can dissolve each monomer, can enumerate after being used in hardening resin composition The solvent etc. stated.

It should be noted that for obtained resin, the solution after reaction can be used directly, it is possible to use concentrated Or diluted solution, the substance obtained in the form of solid (powder) using the methods of reprecipitation also can be used.Especially, pass through Solvent is as polymer solvent used in hardening resin composition using the present invention, so as to directly by the solution after reaction For the manufacture of hardening resin composition, therefore, the manufacturing process of hardening resin composition can be simplified.

The containing ratio of the resin (A) of hardening resin composition about the present invention, relative to hardening resin composition In solid state component for, in terms of mass fraction, preferably 5~95 mass %, more preferably 10~95 mass %.

When the containing ratio of resin (A) is in aforementioned range, the solvent resistance of the cured film existed is superior to incline To.Herein, the solid state component in hardening resin composition refers to remaining after removing solvent in hardening resin composition Ingredient.The total amount of solid state component and the content of each ingredient for the total amount of solid state component are for example using liquid chromatogram Analysis means known to method or gas chromatography etc. measure.

The 1st additive > of <

(1) quaternary ammonium salt

As quaternary ammonium salt, the compound that for example formula (IV) indicates can be enumerated.

[In formula (IV), R⁴¹~R⁴⁴Indicating independently of each other can be with the alkyl of the carbon atom number 1~24 of substituent group.

Y^z-Indicate the anion of z valences.

Z indicates 1~3 integer.]

As R⁴¹~R⁴⁴In carbon atom number 1~24 alkyl, alkyl, the carbon atom number of carbon atom number 1~24 can be enumerated 3~24 naphthenic base, the aryl of the alkenyl of carbon atom number 2~24, the cycloalkenyl group of carbon atom number 3~24, carbon atom number 6~24 And the aralkyl etc. of carbon atom number 7~24, it can preferably enumerate the alkyl of carbon atom number 1~24 and the aryl of carbon atom number 6~24.

As R⁴¹~R⁴⁴Carbon atom number, in terms of the total carbon atom number of the compound indicated by every 1 molecule formula (IV), preferably It is 4~100.

As the substituent group that aforementioned alkyl can have, can enumerate halogen atom, cyano, acyl group, acyloxy, carboxyl and Alkoxy etc..

As the cation for the compound that formula (IV) indicates, tetramethyl ammonium, tetraethyl ammonium ion, four positive third can be enumerated Base ammonium ion, tetra-n-butyl ammonium ion, three n-octyl ammonium ions, cetyltrimethylammonium ion, benzyltrimethylammon.um Ion, benzyl triethyl ammonium ammonium ion, cetyl benzyl dimethyl ammonium ion, phenyl trimethicone ammonium ion and phenyl triethylammonium ammonium Ion etc. can preferably enumerate tetramethyl ammonium, tetraethyl ammonium ion, tetra-n-propylammonium ion, tetra-n-butyl ammonium ion and three N-octyl ammonium ion.

As the Y in formula (IV)^z-, the halide ion such as chlorion, fluorine ion, bromide ion and iodide ion can be enumerated; Sulfate ion, nitrate ion, phosphate anion, perchlorate, hydrogen sulfate ion and hydroxide ion;Acetic acid The carboxylic acid ions such as radical ion, benzoate anion ion and Salicylate ion;Benzenesulfonate ion, p-methyl benzenesulfonic acid radical ion and The sulfonate ions such as trifluoromethanesulfonic acid radical ion;The phenol such as phenolate ions (phenoxide ion) and p-nitrophenol salt ion Salt ion;Tetrafluoroborate ion, hexafluorophosphoricacid acid ions and tetraphenylboronic acid radical ion etc., can preferably enumerate halide from Son, carboxylic acid ion, sulfonate ion and phenolate ions.

As formula (IV) indicate compound, can by selected from any one of above-mentioned cation with selected from Y^z-In any Kind is formed.

Quaternary ammonium ion other than the compound indicated as formula (IV), can enumerate such as cetyl pyridinium ion, N- Dococylpyridinium ion, N- benzyl -2- picolines ion, N, N, N, N ', N ', N '-vegolysen, 5- pentane diammoniums Ion (pentanediaminium ion) and N, N, N, N ', N ', N '-vegolysen, two ammonium ion of 5- hexanes (hexanediaminium ion) etc..

Quaternary ammonium salt can be the molecule inner salt containing carboxylic acid ion or sulfonate ion in the molecule.

As quaternary ammonium salt, the compound that preferably formula (IV) indicates, more preferably R⁴¹~R⁴⁴Independently of one another carbon atom The compound that the formula (IV) of the alkyl of number 1~24 indicates, further preferably R⁴¹~R⁴⁴Independently of one another carbon atom number 1~6 Alkyl formula (IV) indicate compound.As quaternary ammonium salt, more preferable tetrabutylammonium chloride, tetrabutylammonium bromide, the tetrabutyl Ammonium salicylate, tetrabutyl ammonium nitrate, 4-butyl ammonium hydrogen sulfate, tetrabutyl trifluoromethanesulfacid acid ammonium, p-nitrophenol tetrabutylammonium and 3-[Dimethyl (myristyl) An Ji ]Propane -1- sulfonate (3-[dimethyl(tetradecyl)ammonio]propane- 1-sulfonate)。

(2 〕 quaternary alkylphosphonium salts

As quaternary alkylphosphonium salt, the compound of formula (V) expression can be enumerated.

[In formula (V), R⁵¹~R⁵⁴The alkyl of carbon atom number 1~24 is indicated independently of each other.

Y^y-Indicate the anion of y valences.

Y indicates 1~3 integer.]

As R⁵¹~R⁵⁴In carbon atom number 1~24 alkyl, alkyl, the carbon atom number of carbon atom number 1~24 can be enumerated 3~24 naphthenic base, the aryl of the alkenyl of carbon atom number 2~24, the cycloalkenyl group of carbon atom number 3~24, carbon atom number 6~24 And the aralkyl etc. of carbon atom number 7~24, it can preferably enumerate the alkyl of carbon atom number 1~24 and the aryl of carbon atom number 6~24.

As quaternary phosphine ions in formula (V), tetraethylphosphonium ion, Si Zheng Ding Ji phosphonium ions, three n-octyl ethyls can be enumerated Phosphonium ion, hexadecane base San Yi Ji phosphonium ions, cetyl San Zheng Ding Ji phosphonium ions, normal-butyl triphenyl phosphonium ion, n-pentyl Triphenyl phosphonium ion, Jia base triphenyl phosphoniums ion, Bian base triphenyl phosphonium ions and tetraphenylphosphoniphenolate ion etc..

As the Y in formula (V)^y-, can enumerate and the Y in formula (IV)^z-Same anion, preferably halide ion.

As quaternary alkylphosphonium salt, preferably four ethyl phosphonium bromide Phosphonium, four normal-butyl phosphonium chlorides and tetra-n-butyl second acid Phosphonium.

(3) tertiary sulfonium salt

As tertiary sulfonium salt, the compound of formula (VI) expression can be enumerated.

[In formula (VI), R⁶¹~R⁶³The alkyl of carbon atom number 1~24 is indicated independently of each other.

Y^x-Indicate the anion of x valences.

X indicates 1~3 integer.]

As R⁶¹~R⁶³In alkyl, can enumerate the alkyl of carbon atom number 1~24, the naphthenic base of carbon atom number 3~24, The alkenyl of carbon atom number 2~24, the cycloalkenyl group of carbon atom number 3~24, the aryl of carbon atom number 6~24 and carbon atom number 7~ 24 aralkyl etc. can preferably enumerate the alkyl of carbon atom number 1~24 and the aryl of carbon atom number 6~24.

As the tertiary sulfonium cation in formula (VI), such as di-n-butyl methyl sulfonium cation, three normal-butyl sulfonium cations, two can be enumerated Hexyl methyl sulfonium cation, dicyclohexylmethyl sulfonium cation and dodecyl methyl ethyl sulfonium cation etc..

As the Y in formula (VI)^x-, can enumerate and the Y in formula (IV)^z-Same anion, preferably halide ion.

As tertiary sulfonium salt, preferably di-n-butyl methylpyridinium iodide sulfonium, three normal-butyl tetrafluoro boric acid sulfoniums and dodecyl methyl second Base chlorination sulfonium.

1st additive is preferably quaternary ammonium salt.

About the content of the 1st additive, for 100 mass parts of resin (A), preferably 0.1~15 mass parts, more Preferably 0.5~10 mass parts, further preferably 1~7 mass parts.When the content of 1st additive is in aforementioned range, deposit It is preferred in the tendency that the solvent resistance by the cured film formed comprising its hardening resin composition further increases.

The 2nd additive > of <

(1) epoxide

Epoxide is the compound with 1 or more, preferably 2 or more oxiranyls in 1 intramolecular.

The weight average molecular weight of epoxide in the present invention is preferably shorter than 1000.The epoxide is that have preferably 10 The compound of a following, more preferable 6 oxiranyls below.

In the hardening resin composition of the present invention, as the 2nd additive, epoxy compound as follows is preferably used Object.

(2) five-membered ring carbonate ester compound

Five-membered ring carbonate ester compound be in the molecule have at least one five-membered ring carbonate ester structure, preferably 2 or more five The compound of membered ring carbonate structure.

As five-membered ring carbonate ester compound, 1,3- dioxolane -2- ketone, 4- butyl -1,3- dioxas can be enumerated Pentamethylene -2- ketone, 4,5- dimethyl -1,3- dioxolane -2- ketone, allyl succinic anhydride, 4- (methyl) acryloyl group Oxygroup methyl-1,3-dioxy heterocyclic pentane -2- ketone, 4- allyloxymethyl -1,3- dioxolane -2- ketone and 4- ethylene Base oxygroup methyl-1,3-dioxy heterocyclic pentane -2- ketone etc..

2nd additive is preferably epoxide.

About the content of the 2nd additive, for 100 mass parts of resin (A), preferably 0.1~100 mass parts, More preferably 1~50 mass parts.When the content of 2nd additive is in aforementioned range, there is the curable resin by including it The tendency that the solvent resistance for the cured film that composition is formed further increases, is preferred.

For the weight ratio of the 1st additive and the 2nd additive, the 1st additive:2nd additive is preferably 1:1~1: 20, more preferably 1:1~1:10, further preferably 1:1~1:5.

< polymerizable compounds (C) >

Polymerizable compound (C) is not particularly limited, as long as using by light irradiate etc. bys by polymerization initiator (D) The compound that the living radical etc. of generation is polymerize can enumerate the compound for example with ethylenic bond unsaturated bond, It is preferred that (methyl) acrylic compounds can be enumerated.

As the compound with 1 ethylenic bond unsaturated bond, can enumerate and the derivative each structural unit for constituting resin (A) The same compound of monomer etc..

As the compound with 2 ethylenic bond unsaturated bonds, 1,3-BDO two (methyl) acrylate, 1 can be enumerated, 3- butanediols (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethyl Glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, tetrem two Alcohol two (methyl) acrylate, polyethyleneglycol diacrylate, bisphenol-A bis- (acryloyl-oxyethyl) ethers, ethylene oxide change Property bisphenol-A two (methyl) acrylate, epoxy pronane modification neopentyl glycol two (methyl) acrylate, ethylene-oxide-modified new penta (methyl) acrylate of glycol two and 3- methyl pentanediols two (methyl) acrylate etc..

As the compound with 3 or more ethylenic bond unsaturated bonds, trimethylolpropane tris (methyl) propylene can be enumerated Acid esters, pentaerythrite three (methyl) acrylate, three (2- hydroxyethyls) (methyl) acrylate of isocyanuric acid ester three (tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate), ethylene-oxide-modified trimethylolpropane tris (first Base) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylic acid Ester, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol four (methyl) third Olefin(e) acid ester, tripentaerythritol five (methyl) acrylate, tripentaerythritol six (methyl) acrylate, seven (first of tripentaerythritol Base) acrylate, tripentaerythritol eight (methyl) acrylate, pentaerythrite three (methyl) acrylate react with acid anhydrides Object, the reactant of dipentaerythritol five (methyl) acrylate and acid anhydrides, (methyl) acrylate of tripentaerythritol seven and acid anhydrides Reactant, caprolactone modification trimethylolpropane tris (methyl) acrylate, caprolactone modification pentaerythrite three (methyl) third Olefin(e) acid ester, caprolactone modification three (2- hydroxyethyls) isocyanuric acid ester three (methyl) acrylate, caprolactone modification pentaerythrite Four (methyl) acrylate, caprolactone modification dipentaerythritol five (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate, caprolactone modification tripentaerythritol four (methyl) acrylate, five (first of caprolactone modification tripentaerythritol Base) acrylate, caprolactone modification tripentaerythritol six (methyl) acrylate, caprolactone modification tripentaerythritol seven (methyl) Acrylate, caprolactone modification tripentaerythritol eight (methyl) acrylate, caprolactone modification pentaerythrite three (methyl) propylene The reactant and caprolactone of the reactant of acid esters and acid anhydrides, caprolactone modification dipentaerythritol five (methyl) acrylate and acid anhydrides The reactant etc. of modified tripentaerythritol seven (methyl) acrylate and acid anhydrides.

As the compound with ethylenic bond unsaturated bond, preferably there is the compound of 3 or more ethylenic bond unsaturated bonds, More preferable dipentaerythritol six (methyl) acrylate.These compounds can be used alone, also can and with two or more.

When the hardening resin composition of the present invention includes polymerizable compound (C), about its content, relative to resin (A) for 100 mass parts, preferably 20~200 mass parts, more preferably 30~150 mass parts.Polymerizable compound (C) When content is in aforementioned range, exist the solidification film strength for making to be solidified to form comprising its hardening resin composition, Flatness and reliability become good tendency, are preferred.

< polymerization initiators (D) >

Polymerization initiator (D) is not particularly limited, as long as living radical, acid can be generated by the effect of light or heat Deng the compound of the polymerization to cause polymerizable compound (C), known polymerization initiator can be used.

As polymerization initiator (D), can preferably enumerate comprising selected from by O- acyl groups oxime compound, alkyl phenones (alkylphenone) compound, triaizine compounds, acylphosphine oxide compound and bisglyoxaline (biimidazole) compound group At group at least one kind of polymerization initiator, can more preferably enumerate the polymerization initiator for including O- acyl group oxime compounds.

When polymerization initiator (D) is these polymerization initiators, including the susceptibility of their hardening resin composition is high, And incline in the presence of what transmitance of the cured film by being formed comprising its hardening resin composition in visible light region improved To.

O- acyl group oxime compounds are the compound of the structure indicated with formula (D1).

Hereinafter, * indicates connecting key.

As O- acyl group oxime compounds, N- benzoyls Oxy-1-(4- phenylsulfartyls (sulfanyl) phenyl) can be enumerated Butane-1- ketone-2- imines, N- benzoyls Oxy-1-(4- phenylsulfartyls phenyl) octane-1- ketone-2- imines, N- benzoyls Oxy-1-(4- phenylsulfartyls phenyl)-3- cyclopenta propane-1- ketone-2- imines, N- acetoxyl groups-1-[9- ethyls -6- (2- first Base benzoyl) -9H- carbazole -3- Jis ]Ethane -1- imines, N- acetoxyl groups -1-[9- ethyls -6- { 2- methyl -4- (3,3- bis- Methyl -2,4- dioxolyl methyl oxygroup) benzoyl } -9H- carbazole -3- Jis ]Ethane -1- imines, N- acetoxyl groups - 1-[9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- Jis ]- 3- cyclopenta propane -1- imines and N- benzoyl oxygen Base -1-[9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- Jis ]- 3- cyclopenta propane -1- ketone -2- imines.It can be used IRGACURE (registered trademark) OXE01, OXE02 (being made above for BASF (strain)), N-1919, NCI-831 and NCI-930 ((strain) ADEKA systems) etc. commercially available products.

Alkyl phenones compound is the compound of the structure of the structure or formula (D2-2) expression that are indicated with formula (D2-1).This In a little structures, phenyl ring can have substituent group.

As the compound of the structure indicated with formula (D2-1), 2- methyl -2- morpholinoes (morpholino)-can be enumerated 1- (4- methylsulfanylphenyls) propane -1- ketone, 2- dimethylaminos -1- (4- morphlinophenyls) -2- benzyls butane -1- ketone and 2- (dimethylamino) -2-[(4- aminomethyl phenyls) Jia Ji ]-1-[4- (4- morpholinyls (morpholinyl)) Ben Ji ]Butane -1- ketone. The commercially available products such as IRGACURE (registered trademark) 369,907 and 379 (being made above for BASF (strain)) can be used.Japanese spy can also be used The polymerization initiator with the group that chain tra nsfer can occur described in table 2002-544205 bulletins.As with formula (D2- 2) compound of the structure indicated, can enumerate such as 2- hydroxy-2-methyls -1- phenyl-propane -1- ketone, 2- hydroxy-2-methyls -1- (4- (2- hydroxyl-oxethyls) phenyl propane -1- ketone, 1- hydroxycyclohexylphenylketones, 2- hydroxy-2-methyls -1- (4- isopropyl alkene Base phenyl) propane -1- ketone oligomer, α, α-diethoxy acetophenone and benzil dimethyl ketal.It is examined in terms of susceptibility Consider, as alkyl phenones compound, the compound of the structure preferably indicated with formula (D2-1).

As triaizine compounds, bis- (the trichloromethyl) -6- (4- methoxyphenyls) of such as 2,4- -1,3,5- tri- can be enumerated Piperazine, 2,4- bis- (trichloromethyl) -6- (4- methoxyl groups naphthalene) -1,3,5- triazines, bis- piperonyl -1 (trichloromethyl) -6- 2,4-, Bis- (trichloromethyl) -6- (4- the methoxyl-styrenes) -1,3,5- triazines of 3,5- triazines, 2,4-, bis- (the trichloromethyl) -6- of 2,4- (2- (5- methylfuran -2- bases) vinyl) -1,3,5- triazines, bis- (the trichloromethyl) -6- of 2,4- (2- (furans -2- bases) ethylene Base) -1,3,5- triazines, bis- (the trichloromethyl) -6- of 2,4- (2- (4- diethylamino -2- aminomethyl phenyls) vinyl) -1,3,5- Triazine and bis- (the trichloromethyl) -6- of 2,4- (2- (3,4- Dimethoxyphenyls) vinyl) -1,3,5- triazines.

As acylphosphine oxide compound, 2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. can be enumerated.It can be used The commercially available products such as IRGACURE819 (BASFJapan (strain) systems).

As united imidazole, can enumerate such as 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (for example, with reference to Japanese Unexamined Patent Publication 6-75372 public affairs Report, Japanese Unexamined Patent Publication 6-75373 bulletins etc..), 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (alkoxyl phenyls) join miaow Azoles, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxalines, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxalines are (for example, with reference to Japanese Patent Publication 48-38403 bulletins, Japanese Unexamined Patent Application 62- No. 174204 bulletins etc..) and 4,4 ', the phenyl of 5,5 '-positions joins miaow obtained from alkoxy carbonyl (carboalkoxy) substitution Azole compounds (for example, with reference to Japanese Unexamined Patent Publication 7-10913 bulletins etc.).

In addition, as polymerization initiator (D), benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin can be enumerated The benzoins compound such as isopropyl ether, benzoin isobutyl ether;Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4- phenyl two Benzophenone, 4- benzoyls -4 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4, The benzophenone cpds such as 6- tri-methyl benzophenones;The naphtoquinone compounds such as 9,10- phenanthrenequione, 2- ethyl hydrazine, camphorquinone;10- fourths Base -2- chloro-acridines ketone, benzil, methyl benzoylformate, titanocenes compound etc..They can be with aftermentioned polymerization trigger auxiliary agent (H) (especially amine) is applied in combination.

When the hardening resin composition of the present invention includes polymerization initiator (D), about its content, relative to resin (A) For 100 mass parts of total content of polymerizable compound (C), preferably 0.1~30 mass parts, more preferably 0.5~20 matter Measure part, further preferably 5~20 mass parts.When the content of polymerization initiator (D) is in aforementioned range, exist to have a down dip To:The solvent resistance of cured film by being formed comprising its hardening resin composition is better, also, visible light transmittance It is high.

< polymerization trigger auxiliary agents (H) >

Polymerization trigger auxiliary agent (H) is to promote to have been caused by polymerization initiator (D) polymerizable compound (C) of polymerization The compound or sensitizer for polymerizeing and being used together with polymerization initiator (D).

As polymerization trigger auxiliary agent (H), thiazolinium compounds, amine compounds, alkoxy anthracene compound, thioxanthones can be enumerated Compound, carboxylic acid compound etc..

As thiazolinium compounds, compound, the Japanese Unexamined Patent Publication 2008- that formula (H1-1)~formula (H1-3) indicates can be enumerated The compound etc. that No. 65319 bulletins are recorded.

As amine compounds, triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylamino benzene first can be enumerated Sour methyl esters, ethyl 4-dimethylaminobenzoate, 4- dimethylaminobenzoic acids isopentyl ester, benzoic acid 2- dimethylaminoethyls Ester, 4- dimethylaminobenzoic acid 2- ethylhexyls, N, N- dimethyl-p-toluidines, 4,4 '-bis- (dimethylamino) hexichol first Ketone (common name Michler's keton (Michler ' s ketone)), 4,4 '-bis- (diethylamino) benzophenone, 4,4 '-bis- (ethyl-methyls Amino) benzophenone etc., wherein it is preferred that 4,4 '-bis- (diethylamino) benzophenone.EAB-F (hodogaya chemical works can be used Industry (strain) make) etc. commercially available products.

As alkoxy anthracene compound, 9,10- dimethoxys anthracene, 2-ethyl-9,10-dimethoxypyrene, 9,10- can be enumerated Diethoxy anthracene, 2- ethyl -9,10- diethoxies anthracene, 9,10- dibutoxies anthracene, 2- ethyl -9,10- dibutoxy anthracenes etc..

As thioxanthone compounds, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- diethyl thioxanthenes can be enumerated Ketone, bis- clopenthixal ketones of 2,4-, the chloro- 4- propoxythioxanthones of 1- etc..

As carboxylic acid compound, phenylsulfartyl acetic acid (phenylsulfanyl acetic acid), methylbenzene can be enumerated Base ethyl thioglycollic acid, ethylphenyl ethyl thioglycollic acid, Methylethyl phenyl ethyl thioglycollic acid, 3,5-dimethylphenyl ethyl thioglycollic acid, methoxybenzene Base ethyl thioglycollic acid, Dimethoxyphenyl ethyl thioglycollic acid, chlorophenyl sulfanyl acetic acid, dichlorophenyl ethyl thioglycollic acid, N-phenylglycine, Phenoxyacetic acid, naphthylthio acetic acid, N- naphthalenes glycine, naphthoxy acetic acid etc..

When the hardening resin composition of the present invention includes polymerization trigger auxiliary agent (H), about its content, relative to resin (A) with for 100 mass parts of total content of polymerizable compound (C), preferably 0.1~30 mass parts, more preferably 0.2~10 Mass parts.When the amount of polymerization trigger auxiliary agent (H) is in aforementioned range, there are following tendencies:By including its curable resin When composition forms pattern, susceptibility becomes higher.

< levelling agents (B) >

As levelling agent (B), silicone based surfactants (being wherein free of fluorine atom), fluorine system surfactant can be enumerated (wherein not silicon atoms) and silicone based surfactants etc. with fluorine atom.They can have polymerism base on side chain Group.

As silicone based surfactants (being wherein free of fluorine atom), the table with siloxanes key in the molecule can be enumerated Face activating agent etc..Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray can be enumerated Silicone DC11PA,Toray Silicone SH21PA,Toray Silicone SH28PA,Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name, Dow Corning Toray Co., Ltd. systems), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (Momentive Performance Materials Japan LLC systems) etc..

As fluorine system surfactant above-mentioned (wherein not silicon atoms), the table with fluorocarbon chain in the molecule can be enumerated Face activating agent etc..Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (Sumitomo 3M can be enumerated Ltd. make), MEGAFACE (メガ Off ァッ Network) (registered trademark) F142D, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173,MEGAFACE F177,MEGAFACE F183,MEGAFACE F554,MEGAFACE R30,MEGAFACE RS-718-K (DIC (strain) systems), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd. system), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass (strain) system) and E5844 (Daikin Fine Chemical Kenkyusho, K.K. system) etc..

As the silicone based surfactants above-mentioned with fluorine atom, can enumerate in the molecule have siloxanes key and The surfactant etc. of fluorocarbon chain.Specifically, can enumerate MEGAFACE (registered trademark) R08, MEGAFACE BL20, MEGAFACE F475, MEGAFACE F477 and MEGAFACE F443 (DIC (strain) systems) etc..

As levelling agent (B), preferably fluorine system surfactant (wherein not silicon atoms).

When containing levelling agent (B), about its containing ratio, for the solid state component in hardening resin composition, Preferably 0.001 mass % or more, 0.2 mass % hereinafter, more preferably 0.002 mass % or more, 0.1 mass % hereinafter, into one Step is preferably 0.005 mass % or more, 0.1 mass % or less.

< solvents (E) >

The hardening resin composition of the present invention may include solvent (E).Solvent (E) is not particularly limited, and may be used at this Usually used solvent in field.For example, can enumerate ester solvent (in the molecule include-COO- but not comprising-O- solvent), Ether solvents (including-O- but the solvent not comprising-COO- in the molecule), ether-ether solvent (include-COO-'s and-O- in the molecule Solvent), ketone solvent (including-CO- but the solvent not comprising-COO- in the molecule), alcoholic solvent (include OH but not in the molecule Including the solvent of-O- ,-CO- and-COO-), aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide (DMSO) etc..

As ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2- hydroxy-methyl isobutyl acids, acetic acid second can be enumerated Ester, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, fourth Acid butyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Hexacyclonic Acid Ester and gamma-butyrolacton etc..

As ether solvents, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol can be enumerated Single-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, third Glycol list ethylether, propylene glycol monopropyl ether, glycol monobutyl ether, 3- methoxyl groups-n-butyl alcohol, 3- methoxyl group -3- methyl fourths Alcohol, tetrahydrofuran, oxinane, 1,4- dioxanes, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl phenyl ethers anisole, phenetole and methylanisole etc..

As ether-ether solvent, methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethoxy can be enumerated Acetic acid methyl ester, ethoxy ethyl acetate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxypropanoates, 3- ethoxyl ethyl propionates, 2- methoxy methyl propionates, 2- methoxypropionates, 2- methoxy propyls propyl propionate, 2- ethyoxyls Methyl propionate, 2- ethoxyl ethyl propionates, 2- methoxyl groups -2 Methylpropionic acid methyl esters, 2- ethyoxyls -2 Methylpropionic acid ethyl ester, second Sour 3- methoxybutyls, acetic acid 3- methyl -3- methoxybutyls, propylene glycol monomethyl ether, propylene glycol monoethyl second Acid esters, propylene glycol monopropyl ether acetic acid esters, ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, diethylene glycol Single monoethyl ether acetate and diethylene glycol monobutyl ether acetic acid esters etc..

As ketone solvent, 4- hydroxy-4-methyl-2-pentanones, acetone, 2- butanone, 2-HEPTANONE, 3- heptanone, 4- heptan can be enumerated Ketone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone and isophorone etc..

As alcoholic solvent, methanol, ethyl alcohol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerine can be enumerated Deng.

As aromatic hydrocarbon solvents, benzene,toluene,xylene and mesitylene (mesitylene) etc. can be enumerated.

As amide solvent, n,N-Dimethylformamide, n,N-dimethylacetamide and N-Methyl pyrrolidone can be enumerated Deng.

In above-mentioned solvent, from the aspect of coating, drying property, boiling point under preferably 1atm, which is 100~200 DEG C, to be had Solvent.As solvent, preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, 3- methoxy methyl propionates, 3- second Oxygroup ethyl propionate, ethylene glycol ethyl ethers ylmethyl ether, cyclohexanone, methoxybutanol and methoxy butyl acetate, more preferable propylene glycol Monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol ethyl ethers ylmethyl ether, methoxybutanol and methoxy butyl acetate.

About the containing ratio of the solvent (E) in the hardening resin composition of the present invention, combined relative to curable resin For the total amount of object, preferably 60~95 mass %, more preferably 70~95 mass %.In other words, curability tree of the invention The solid state component of oil/fat composition is preferably 5~40 mass %, more preferably 5~30 mass %.The containing ratio of solvent (E) is aforementioned In the range of when, there are the coatings of hardening resin composition to become good tendency.

< colorants (K) >

The hardening resin composition of the present invention may include colorant (K).As colorant (K), can enumerate dyestuff and/or Pigment etc..They can be used alone or also can only have illicit sexual relations by colorant combination of more than two kinds, in this case It is the combination of material, only any in the combination of the combination of pigment, dyestuff and pigment.

For dyestuff, known dyestuff can be used without particular limitation, can enumerate solvent dye, acid dyes, Direct dyes, mordant dye etc..As dyestuff, can enumerate for example in Colour Index (The Society of Dyers and Colourists is published) in be classified as compound, the Dyeing of the substance with tone other than pigment (Pigment) Known dyestuff described in Note (Se Ran companies).In addition, according to chemical constitution, azo dyes, cyanine dyes, triphen can be enumerated Methylmethane dyestuff, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dyestuff, quinoneimine dye, methine (methine) dyestuff, Azomethine (azomethine) dyestuff, square hydrochlorate (squarylium) dyestuff, acridine dye, styryl dye, tonka-bean Uniformly dyeing material, quinoline dye and nitro dye etc..

Specifically, can enumerate:

C.I. solvent yellow 4 (hereinafter, omitting the record of C.I. solvent yellows, only records number.),14,15,23,24,38,62, 63,68,82,94,98,99,117,162,163,167,189;

C.I. solvent red 45,49,111,125,130,143,145,146,150,151,155,168,169,172,175, 181,207,218,222,227,230,245,247;

C.I. solvent orange 2,7,11,15,26,56,77,86;

C.I. solvent violet 11,13,14,26,31,36,37,38,45,47,48,51,59,60;

C.I. solvent blue 4,5,14,18,35,36,37,45,58,59,59:1,63,67,68,69,70,78,79,83, 90,94,97,98,100,101,102,104,105,111,112,122,128,132,136,139;

C.I. the green C.I. solvent dyes such as 1,3,4,5,7,28,29,32,33,34,35 of solvent,

C.I. Indian yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98, 99,111,112,113,114,116,119,123,128,134,135,138,139,140,144,150,155,157,160, 161,163,168,169,172,177,178,179,184,190,193,196,197,199,202,203,204,205,207, 212,214,220,221,228,230,232,235,238,240,242,243,251;

C.I. azogeramine, 4,8,14,17,18,26,27,29,31,33,34,35,37,40,42,44,50,51,52, 57,66,73,76,80,87,88,91,92,94,95,97,98,103,106,111,114,129,133,134,138,143, 145,150,151,155,158,160,172,176,182,183,195,198,206,211,215,216,217,227,228, 249,252,257,258,260,261,266,268,270,274,277,280,281,289,308,312,315,316,339, 341,345,346,349,382,383,388,394,401,412,417,418,422,426;

C.I. acid orange 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108, 169,173;

C.I. acid violet 6B, 7,9,15,16,17,19,21,23,24,25,30,34,38,49,72,102;

C.I. Blue VRS, 3,5,7,9,11,13,15,17,18,22,23,24,25,26,27,29,34,38,40,41, 42,43,45,48,51,54,59,60,62,70,72,74,75,78,80,82,83,86,87,88,90,90:1,91,92,93, 93:1,96,99,100,102,103,104,108,109,110,112,113,117,119,120,123,126,127,129, 130,131,138,140,142,143,147,150,151,154,158,161,166,167,168,170,171,175,182, 183,184,187,192,199,203,204,205,210,213,229,234,236,242,243,256,259,267,269, 278,280,285,290,296,315,324:1,335,340;

C.I. acid green 1,3,5,6,7,8,9,11,13,14,15,16,22,25,27,28,41,50,50:1,58,63, 65, the C.I. acid dyes such as 80,104,105,106,109,

C.I. directly Huang 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98, 102,108,109,129,136,138,141;

C.I. directly red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177, 179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250;

C.I. direct orange 26,34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107;

C.I. direct purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104;

C.I. directly indigo plant 1,2,3,6,8,15,22,25,28,29,40,41,42,47,52,55,57,71,76,77,78, 80,81,84,85,86,90,93,94,95,97,98,99,100,101,106,107,108,109,113,114,115,117, 119,120,137,149,150,153,155,156,158,159,160,161,162,163,164,165,166,167,168, 170,171,172,173,188,189,190,192,193,194,195,196,198,199,200,201,202,203,207, 209,210,212,213,214,222,225,226,228,229,236,237,238,242,243,244,245,246,247, 248,249,250,251,252,256,257,259,260,268,274,275,293;

C.I. the C.I. such as direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82 directly contaminate Material,

C.I. disperse yellow 51,54,76;

C.I. disperse violet 26,27;

C.I. the C.I. disperse dyes such as disperse blue 1,14,56,60,

C.I. alkali red 1:1,10;

C.I. alkali blue 1,3,5,7,9,19,21,22,24,25,26,28,29,40,41,45,47,54,58,59,60, 64,65,66,67,68,81,83,88,89;

C.I. alkalescence purple 2;

C.I. alkaline red 9;

C.I. Viride Nitens 1;Equal C.I. basic dyes,

C.I. active yellow 2,76,116;

C.I. reactive orange 16;

C.I. active red 36;Equal C.I. reactive dye,

C.I. medium yellow (Mordant Yellow) 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62, 65;

C.I. medium red 1,2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,27,29,30,32,33, 36,37,38,39,41,42,43,45,46,48,52,53,56,62,63,71,74,76,78,85,86,88,90,94,95;

C.I. medium orange 3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47, 48;

C.I. medium purple 1,1:1,2,3,4,5,6,7,8,10,11,14,15,16,17,18,19,21,22,23,24,27, 28,30,31,32,33,36,37,39,40,41,44,45,47,48,49,53,58;

C.I. medium indigo plant 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39, 40,41,43,44,48,49,53,61,74,77,83,84;

C.I. the green C.I. such as 1,3,4,5,10,13,15,19,21,23,26,29,31,33,34,35,41,43,53 of medium Mordant dyes,

C.I. equal C.I. reducing dyes of vat green 1 etc..

In addition, Japanese Unexamined Patent Publication 2010-32999 bulletins, Japanese Patent No. No. 4492760 bulletins, Japanese Unexamined Patent Publications can be enumerated Dyestuff etc. described in 2013-50693 bulletins and Japanese Unexamined Patent Publication 2013-178478 bulletins.

For these dyestuffs, as expected the spectrophotometric spectra of colour filter and suitably select.

As pigment above-mentioned, organic pigment and inorganic pigment can be enumerated, can be enumerated in Colour Index (The Society Of Dyers and Colourists are published) in be classified as the pigment of pigment (Pigment).

As pigment, can enumerate for example C.I. pigment yellows 1,3,12,13,14,15,16,17,20,24,31,53,83,86, 93,94,109,110,117,125,128,129,137,138,139,147,148,150,153,154,166,173,185, 194, the yellow uitramarines such as 214;

C.I. the orange pigments such as pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71,73;

C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,209,215, 216, the red pigments such as 224,242,254,255,264,265;

C.I. pigment blue 15,15:3,15:4,15:6, the blue pigments such as 60;

C.I. the violet pigments such as pigment violet 1,19,23,29,32,36,38;

C.I. the viridine greens such as pigment Green 7,36,58,59;

C.I. the browns such as pigment brown 23,25;

C.I. black pigments such as pigment black 1,7 etc..

Wherein, it preferably comprises selected from C.I. pigment yellow 13s 8,139,150, C.I. paratoneres 177,242,254, C.I. pigment Purple 23, C.I. pigment blue 15s:6 and C.I. pigment Green 7s, 36,58, at least one of 59 pigment.For these pigment, They can be used alone, or two or more is applied in combination.

For pigment, as needed, following processing can be implemented:Rosin processing;Using being imported with acidic-group or alkali The surface treatment of the progress such as the pigment derivative of property group;Using high-molecular compound etc. at the grafting that surface of pigments carries out Reason;It is handled using the micronized of the progress such as sulfuric acid particles method;Or utilize the progress such as organic solvent, water to remove impurity Carrying out washing treatment;The processing etc. for being removed ionic impurity using ion-exchange etc..

As pigment dispersing agent above-mentioned, such as cationic system, anionic system, nonionic system, both sexes, polyester can be enumerated The surfactant etc. of system, polyamine system, acrylic acid series etc..They can be used alone, or two or more is applied in combination.Tool For body, if being indicated with trade name, can enumerate KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), FLOWLEN (common prosperity society chemistry (strain) system), SOLSPERSE (Zeneca (strain) systems), EFKA (CIBA corporations), AJISPER (Ajinomoto Fine-Techno Co., Inc. make), Disperbyk (BYK-Chemie corporations) etc..

When using pigment dispersing agent, about its usage amount, for 100 mass parts of total amount of pigment, preferably 1 matter More than amount part 100 is below mass part, and more than more preferably 5 mass parts 50 is below mass part.

When the usage amount of pigment dispersing agent is in aforementioned range, exists and the uniform dispersible pigment dispersion of dispersity can be obtained Tendency.

When the hardening resin composition of the present invention includes colorant (K), about its containing ratio, relative to solid state component For total amount, preferably 5~70 mass %, more preferably 8~65 mass %, further preferably 10~60 mass %.Coloring When the containing ratio of agent (K) is in aforementioned range, target colorimetric may be adjusted to.

< other compositions >

In the hardening resin composition of the present invention, as needed, filler can be contained, other high-molecular compounds, resisted The known additive in this technical field such as oxidant, ultra-violet absorber, chain-transferring agent, closely sealed accelerating agent.

In the case that the hardening resin composition of the present invention does not include colorant, in the stone of filling to a length of 1cm of light path In English absorption cell (cell), when measuring transmitance under conditions of measuring wavelength and being 400~700nm using spectrophotometer, Mean transmissivity is preferably 70% or more, and more preferably 80% or more.

In the case that the hardening resin composition of the present invention does not include colorant, the cured film that is formed by the composition Mean transmissivity is preferably 90% or more, and more preferably 95% or more.The mean transmissivity is for being heating and curing (100~250 DEG C, 5 minutes~3 hours) after thickness be 2 μm film, using spectrophotometer measure wavelength be 400~700nm condition Under average value when being measured.Thus, it is possible to provide the transparent excellent cured film in visible light region.

[The Zhi Zaofangfa &#93 of hardening resin composition;

The hardening resin composition of the present invention can be by using known method by resin (A), the 1st additive and the 2nd Additive and as needed and use solvent (E), polymerizable compound (C), polymerization initiator (D), polymerization trigger auxiliary agent (H), levelling agent (B), colorant (K) and other compositions mix to manufacture.It is preferred that it is 0.05~5 μm or so to use aperture upon mixing Filter be filtered.

[The Zhi Zaofangfa &#93 of cured film;

The present invention cured film can by by the present invention hardening resin composition be coated on substrate and be dried, Then it is heated to manufacture.More specifically, the manufacturing method of cured film of the invention includes process below (1)~(3).

Process (1):The process that the hardening resin composition of the present invention is coated on substrate,

Process (2):Hardening resin composition after coating is dried under reduced pressure and/or heat drying, to be formed The process of composition layer,

Process (3):The process that composition layer is heated.

In addition, when the hardening resin composition of the present invention includes polymerizable compound (C) and polymerization initiator (D), it can The figuratum cured film of tool is manufactured by carrying out following processes.

Process (2a):The process for exposing composition layer across photomask,

Process (2b):The process that composition layer after exposure is developed,

Process (3a):The process that composition layer after development is heated.

Process (1) is the process that the hardening resin composition of the present invention is coated on substrate (basal substrate).As base Plate can enumerate glass, metal, plastics etc., and colour filter, insulating film, conductive film and/or driving circuit can be formed on substrate Deng.It is preferable to use spin coater, slit spin coater, slit coater, spray equipment, roll coater, leachings for coating on substrate The apparatus for coating such as painting machine carry out.

Process (2) be the hardening resin composition after coating is dried under reduced pressure and/or heat drying, to be formed The process of composition layer.By carrying out the process, to which the volatile ingredients such as solvent in hardening resin composition be removed.Subtract It press dry and dry is carried out preferably under the pressure of 50~150Pa, within the temperature range of 20~25 DEG C.Can before being dried under reduced pressure or it After be thermally dried (prebake conditions).Heat drying is carried out usually using heating devices such as baking oven, heating plates.The temperature of heat drying Preferably 30~120 DEG C, more preferably 50~110 DEG C of degree.In addition, heating time is preferably 10 seconds~60 minutes, more preferably 30 seconds~30 minutes.

Process (3) is the process (rear baking) heated to composition layer.Heating adds usually using baking oven, heating plate etc. Thermal carries out.Heating temperature is preferably 80~220 DEG C, more preferably 90~200 DEG C, further preferably 90~150 DEG C.Add The hot time is preferably 1~120 minute, more preferably 3~60 minutes.By being heated in such a situa-tion, so as to The cured film for the solvent resistance for having excellent is obtained in the case of the characteristic for not reducing substrate etc..

Process (2a) is the process that will be exposed by the composition layer that process (2) is formed across photomask.It is covered about the light Mould uses the photomask that light shielding part is accordingly formed with the part of composition layer to be removed.The shape of light shielding part is without spy It does not limit, can be selected according to intended applications.As the light source that can be used for exposing, the light of the wavelength of 250~450nm is preferably generated Light source.It is hindered using the optical filter that can stop (cut) wavelength region less than the light of 350nm for example, can be directed to It cuts, alternatively, can be for the light near 436nm, near 408nm, near 365nm and using these wavelength regions can be extracted Bandpass filter (band pass filter) is subject to selective extraction to it.As light source, mercury lamp, light-emitting diodes can be enumerated Pipe, metal halide lamp, halogen lamp etc..

In order to equably irradiate parallel rays to entire plane of exposure or carry out the accurate right of photomask and composition layer Position is, it is preferable to use the exposure devices such as mask aligner, stepper.

Process (2b) is the process of the composition layer development after exposing.By making composition layer and developer solution after exposure It contacts and is developed, is removed to make the unexposed portion of composition layer be dissolved in developer solution, form tool on substrate Figuratum composition layer.As developer solution, the preferably alkalinity such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide The aqueous solution of compound.The concentration of these alkali compounds in aqueous solution is preferably 0.01~10 mass %, more preferably 0.03~5 mass %.In addition, developer solution may include surfactant.Developing method can be sheathed submergence (puddle) method, leaching Any method in stain method and spray-on process etc..In addition, in development, it can be by substrate with arbitrary angle tilt.It is preferred that developing After washed.

Process (3a) is the process heated to the composition layer after development.By in the same manner as foregoing sequence (3) into Row heating forms on substrate to make the figuratum composition layer solidification of tool and has figuratum cured film.

When using hardening resin composition of the invention, even if for example, by 140 DEG C~150 DEG C consolidating in a low temperature of equal Change can also make the cured film with excellent solvent resistance.The cured film is as the photonasty interval used in display device Object (photo spacer), external coating (overcoat), interlayer dielectric are useful.In addition, the curable resin combination of the present invention When object includes colorant, as in the display devices such as liquid crystal display device, organic el device, Electronic Paper and solid photographic device The colour filter used is useful.

Embodiment

Hereinafter, illustrating the present invention in further detail by embodiment.Unless otherwise instructed, " % " and " part " in example is Refer to quality % and mass parts.

(synthesis example 1:The synthesis of copolymer (a1))

It is packed into propylene glycol monomethyl ether into the flask with stirring blade, reflux condensing tube, thermometer and dropping funel 80 parts, it is heated to 90 DEG C.Start operations described below:With dropping funel by 41.3 parts of mixed ethylene base toluene, methacrylic acid 2- (1, 3- dioxobutyls oxygroup) 26.6 parts of ethyl ester, 27.1 parts of methacrylic acid, 5 parts of azo bis- (isobutyronitriles), propylene glycol monomethyl ether Solution is continuously added dropwise in flask made of 30 parts.Pot temperature during mixed solution is added dropwise remains 90 ± 1 DEG C, warp Terminate within 3 hours to be added dropwise.After completion of dropwise addition, it is 90 ± 1 DEG C to make pot temperature, is kept for 6 hours.After reaction, reaction solution is cooled down To 40 DEG C hereinafter, 0.12 part of input 4- metoxyphenols, acrylic acid 3,22.6 parts of 4- epoxycyclohexanecarboxylates, triphenylphosphine 4.7 Part, 90 parts of propylene glycol monomethyl ether, 110 DEG C are warming up to by pot temperature, then, are carried out with 110 ± 1 DEG C of pot temperature Addition reaction obtains copolymer (a1) solution that solid state component is 36.5% as a result,.The weight average molecular weight (Mw) of copolymer (a1) It is 16,500, dispersion degree 2.4, the acid value by solid state component conversion is 92mg-KOH/g.Copolymer (a1) has knot below Structure unit.

(synthesis example 2:The synthesis of copolymer (a2))

It is packed into propylene glycol monomethyl ether into the flask with stirring blade, reflux condensing tube, thermometer and dropping funel 70 parts, it is heated to 90 DEG C.Start operations described below:With dropping funel by 52.6 parts of mixed methyl acrylic acid bicyclopentyl ester, methyl Acrylic acid 2- (1,3- dioxobutyls oxygroup) 20.7 parts of ethyl ester, 26.7 parts of methacrylic acid, 5 parts of azo bis- (isobutyronitriles), third Solution is continuously added dropwise in flask made of 30 parts of glycol monomethyl ether.Pot temperature during mixed solution is added dropwise is kept It is 90 ± 1 DEG C, terminated to be added dropwise through 3 hours.After completion of dropwise addition, it is 90 ± 1 DEG C to make pot temperature, is kept for 6 hours.After reaction, Reaction solution is cooled to 40 DEG C hereinafter, 0.12 part of input 4- metoxyphenols, acrylic acid 3,17.6 parts of 4- epoxycyclohexanecarboxylates, 4.7 parts of triphenylphosphine, 85 parts of propylene glycol monomethyl ether, 110 DEG C are warming up to by pot temperature, then, with 110 ± 1 DEG C of burning Temperature carries out addition reaction in bottle, obtains copolymer (a2) solution that solid state component is 37.9% as a result,.Obtained copolymer (a2) weight average molecular weight (Mw) is 14,300, dispersion degree 2.4, and the acid value by solid state component conversion is 103mg-KOH/g.Altogether Polymers (a2) has structural unit below.

(synthesis example 3:The synthesis of copolymer (a3))

It is packed into propylene glycol monomethyl ether into the flask with stirring blade, reflux condensing tube, thermometer and dropping funel 70 parts, it is heated to 90 DEG C.Start operations described below:With dropping funel by 44.6 parts of mixed methyl methyl acrylate, methacrylic acid 2- (1,3- dioxobutyls oxygroup) 28.6 parts of ethyl ester, 26.8 parts of methacrylic acid, 5 parts of azo bis- (isobutyronitriles), propylene glycol list Solution is continuously added dropwise in flask made of 30 parts of methyl ether.Pot temperature during mixed solution is added dropwise remains 90 ± 1 DEG C, terminated to be added dropwise through 3 hours.After completion of dropwise addition, it is 90 ± 1 DEG C to make pot temperature, is kept for 6 hours.After reaction, it will react Liquid is cooled to 40 DEG C hereinafter, 0.12 part of input 4- metoxyphenols, acrylic acid 3,24.4 parts of 4- epoxycyclohexanecarboxylates, triphenyl 5 parts of phosphine, 95 parts of propylene glycol monomethyl ether, 110 DEG C are warming up to by pot temperature, then, with 110 ± 1 DEG C of pot temperature Addition reaction is carried out, obtains copolymer (a3) solution that solid state component is 38.5% as a result,.The weight of obtained copolymer (a3) is equal Molecular weight (Mw) is 15,800, dispersion degree 2.4, and the acid value by solid state component conversion is 80mg-KOH/g.Copolymer (a3) has There is structural unit below.

(synthesis example 4:The synthesis of resin (a))

To with agitating device, dropping funel, condenser, thermometer, gas introduction tube flask in be packed into propylene glycol list 100 parts of methylether acetate is stirred while carrying out nitrogen displacement and is warming up to 120 DEG C.Next, through 2 hours from 43 parts of mixed methyl methyl acrylate, 25 parts of methacrylic acid and peroxidating -2 ethyl hexanoic acid are added dropwise into flask for dropping funel The tert-butyl ester (Perbutyl O;Day oily (strain) system) liquid made of 0.68 part, and then in 120 DEG C stir within 2 hours, it is total to Polymers.Next, by air is replaced as in flask, glycidyl methacrylate 10 is put into above-mentioned copolymer solution 0.08 part of part, 0.44 part of triphenylphosphine and methyl hydroquinone, in 120 DEG C of sustained responses, solid state component acid value reaches 100mg- When KOH/g, reaction was completed.By adding 50 parts of propylene glycol monomethyl ether thereto, it is to obtain solid state component 40% resin (a) solution.The weight average molecular weight (Mw) of resin (a) is 30,000, and dispersion degree 2.5 converts by solid state component Acid value be 100mg-KOH/g.Resin (a) has structural unit below.

For the obtained weight average molecular weight (Mw) of resin and the measurement of number-average molecular weight (Mn), using GPC method, It is carried out under the conditions of below.

Device:HLC-8120GPC (Tosoh (strain) systems)

Column:TSK-GELG2000HXL

Column temperature:40℃

Solvent:THF (tetrahydrofuran)

Flow velocity:1.0mL/min

The solid component concentration of prepare liquid:0.001~0.01 mass %

Sample size:50μL

Detector:RI

Correction standard substance:TSK STANDARD POLYSTYRENE F-40,F-4,F-288,A-2500,A-500 (Tosoh (strain) systems)

By the weight average molecular weight (Mw) to convert according to polystyrene obtained through the above way and number-average molecular weight (Mn) The ratio between (Mw/Mn) be used as dispersion degree.

(synthesis example 5:The synthesis for the compound that formula (A-IV) indicates)

20 parts of compound for indicating formula (1x) under dark conditions and N- propyl -2,6- dimethylanilines (and the pure medicine of light Industrial (strain) system) 200 parts of mixing, obtained solution stir within 6 hours in 110 DEG C.Obtained reaction solution is cooled to room Temperature is then added in the mixed liquor of 800 parts of water, 50 parts of 35% hydrochloric acid, in room temperature stir within 1 hour, crystalline substance has as a result been precipitated Body.The crystal of precipitation is obtained as the residue of suction filtration, is then dried, and the compound of formula (A-IV) expression is obtained.

The identification for the compound that formula (A-IV) indicates

(mass spectrum) ionization mode=ESI+:M/z=[M+H]⁺659.3

Accurate molecular weight (Exact Mass):658.3

[Embodiment 1~19,21~23, comparative example 1 and 2]

The preparation > of < hardening resin compositions

Following hardening resin compositions are obtained, the hardening resin composition includes table 1 with ratio shown in table 1 Shown in each ingredient, the solvent (E) of each hardening resin composition is propylene glycol monomethyl ether and propylene glycol monomethyl (mixed proportion is 1 by quality ratio to the mixed solvent of ether:1), also, the hardening resin composition is to become 1 institute of table What the mode of the solid component concentration shown was obtained by mixing.

In table 1, the number of each ingredient indicates the mass parts by solid state component conversion.

[Table 1]

Copolymer (a1):The copolymer obtained by synthesis example 1

Copolymer (a2):The copolymer obtained by synthesis example 2

Copolymer (a3):The copolymer obtained by synthesis example 3

Resin (a):The copolymer obtained by synthesis example 4

(x1):Tetrabutylammonium chloride

(x2):P-nitrophenol tetrabutylammonium

(x3):Tetrabutylammonium bromide

(x4):Tetrabutyl ammonium salicylate

(x5):Tetrabutyl ammonium nitrate

(x6):Tetrabutyl trifluoromethanesulfacid acid ammonium

(x7):4-butyl ammonium hydrogen sulfate

(x8):3-[Dimethyl (myristyl) An Ji ]Propane -1- sulfonate (is made for Tokyo chemical conversion industry (strain)) above

(y1):Compound (the ED-529 that following formula indicates;(strain) ADEKA systems)

(y2):Compound (the DA-MGIC that following formula indicates;Four countries' chemical conversion industry (strain) is made)

(y3):Compound (the MA-DGIC that following formula indicates;Four countries' chemical conversion industry (strain) is made)

(y4):Compound (the TEPIC (registered trademark) that following formula indicates;Nissan Chemical Industries (strain) are made)

(y5):Compound (the S-184 that following formula indicates;SYNASIA corporations)

(y6):Compound (the TG-G that following formula indicates;Four countries' chemical conversion industry (strain) is made)

(y7):Compound (the S-500 that following formula indicates;SYNASIA corporations)

(y8):Compound (the S-186 that following formula indicates;SYNASIA corporations)

(y9):Compound (the S-400 that following formula indicates;SYNASIA corporations)

(f1):Fluorine system levelling agent (MEGAFACE (registered trademark) F554;DIC (strain) makes)

1 > of making of < cured films

Glass substrate (the Eagle XG of 2 inch squares are washed with neutral detergent, water and isopropanol successively;Corning is public Department's system), then make it dry.The film thickness after baking becomes 1.5 μm of mode later, and hardening resin composition is spun on this On substrate.Next, using pressure Reduction Dryer (VCD MicroTech Corporation systems), it is in rotation revolution speed 1000rpm, supercharging revolution speed are 700rpm, under conditions of 25 DEG C of room temperature, are dried under reduced pressure, until degree of decompression reaches 66Pa. Then, on hot plate, carry out toasting for 3 minutes in 140 DEG C, obtain cured film as a result,.

< solvent resistances evaluate >

Obtained cured film is impregnated 3 minutes in propylene glycol monomethyl ether in 23 DEG C, then, is fully washed with water It washs.Before dipping and after water washing, film thickness (film thickness before dipping being denoted as t1, the film thickness after water washing is denoted as t2) is measured, Ratio (t2/t1) of the film thickness relative to film thickness before dipping after calculating water washing.It should be noted that when carrying out film thickness measuring, make With film thickness measuring device (DEKTAK XT;Japanese vacuum technique (strain) system)).Show the result in table 1.

[Embodiment 20]

The preparation > of < hardening resin compositions

Following substances are mixed,

C.I. pigment blue 15:6 23.5 parts

8.2 parts of acrylic acid series pigment dispersing agent, and

193 parts of propylene glycol monomethyl ether

Using ball mill, keep pigment fully dispersed, next, following substances are mixed, obtains hardening resin composition.

2 > of making of < cured films

Hardening resin composition is coated on to the glass substrate (Eagle 2000 of 5cm square using spin-coating method; Corning corporations) on, 3 minutes prebake conditions then are carried out in 100 DEG C, obtain composition layer.After placing cooling, make to form 100 μm are divided between the substrate and quartz glass photomask of composition layer, uses exposure machine (TME-150RSK;TOPCON CORPORATION systems), under air atmosphere, with 80mJ/cm²Light exposure (on the basis of 365nm) carry out light irradiation.As Photomask, using be formed with 100 μm 1:The photomask of 1 line and intermittent pattern (line-and-space pattern).In 23 DEG C, the composition layer after light is irradiated is shown in the water system comprising nonionic surfactants 0.12% and potassium hydroxide 0.04% It impregnates 60 seconds, develops in shadow liquid, after washing, on hot plate, carry out toasting for 5 minutes in 150 DEG C, be had as a result, The cured film of pattern.

For cured film made from the method for making 2 using cured film, the hardening resin composition by embodiment 20, Solvent resistance evaluation is carried out using method same as above, as a result, (t2/t1) is 1.

Through the invention, it is possible to provide the hardening resin composition of the cured film of excellent solvent resistance can be formed, the solidification Film is suitable for display device etc..

Claims

1. hardening resin composition, it includes:

Resin (A), the resin (A) are comprising with α, the structural unit (Aa) of beta-unsaturated carbonyl and active methylene Or the copolymer of the structural unit (Ab) of active methylene;

At least one kind of compound in the group being made of quaternary ammonium salt, quaternary alkylphosphonium salts and tertiary sulfonium salt;And

At least one kind of compound in the group being made of epoxide and five-membered ring carbonate ester compound.

2. hardening resin composition as described in claim 1, it includes quaternary ammonium salts and epoxide.

3. hardening resin composition as claimed in claim 1 or 2, wherein the epoxide is to have in 1 intramolecular The epoxide of at least two oxiranyl.

4. cured film is formed by hardening resin composition as claimed in claim 1 or 2.