CN107663262A - Resin, hardening resin composition and cured film - Google Patents

Abstract

The present invention relates to resin, hardening resin composition and cured film.A kind of resin, it has：With α, the construction unit (Aa) of β unsaturated carbonyls, the construction unit (Ab) of active methylene or active methylene and the construction unit (Ac) with acidic group.

Description

Resin, hardening resin composition and cured film

Technical field

The present invention relates to resin, the hardening resin composition of the resin is used and has made the hardening resin composition The cured film being solidified to form.

Background technology

As display device, it is known to liquid crystal display, plasma scope, class paper display (Paper-like Display), touch panel etc..Wherein, for liquid crystal display, touch panel etc., existed using photosensitive polymer combination The colour filter (color filter) for forming display device sets sept to keep the interval of two substrates between array base palte It is known.

A kind of photosensitive polymer combination has been recorded in the embodiment of the flat 3-172301 publications of Japanese Patent Application Laid-Open, It, which is included, makes methyl methacrylate, EMA and methacrylic polymeric, it is contracted with methacrylic acid afterwards Reaction product is as resin component obtained from the reaction of water glyceride.

The content of the invention

The present invention includes following proposal.

(1) resin, it has：Construction unit (Aa), active methylene or activity with alpha, beta-unsaturated carbonyl The construction unit (Ab) of methine and the construction unit (Ac) with acidic group.

(2) hardening resin composition, it includes resin, polymerizable compound and the polymerization initiator described in (1).

(3) cured film, it is to be solidified to form the hardening resin composition described in (2).

(4) manufacture method of cured film, it includes following processes：Hardening resin composition described in (2) is coated on Process on substrate, by the way that hardening resin composition drying is formed into the process of cured resin composition layer, it will solidify Property resin composition layer exposure process, the process heated to exposed cured resin composition layer.

(5) manufacture method of the cured film as described in (4), wherein, in less than more than 150 DEG C 200 DEG C of temperature to through exposing The cured resin composition layer of light is heated.

Embodiment

＜ resins ＞

The resin (below, is referred to as " resin (A) " by the resin of the present invention.) mainly as the viscous of hardening resin composition Agent resin (binder resin) is tied to use.Resin (A) is the resin for having following construction units：With alpha, beta-unsaturated carbonyl Construction unit (Aa), active methylene or active methylene construction unit (Ab) and with acidic group construction unit (Ac)。

It is as described below on resin (A), more detailed content.

Resin (A) includes：With α, the construction unit (below, is referred to as " structure list by the construction unit of beta-unsaturated carbonyl First (Aa) ".), the construction unit (Ab) of active methylene or active methylene (it is following, the construction unit is referred to as " structure Unit (Ab) ".) and there is the construction unit (Ac) of acidic group (below, by the construction unit referred to as " construction unit (Ac) ".).

The resin can also include other repeat units (Ad).In addition, in the resin, construction unit (Aa), construction unit (Ab) and construction unit (Ac) can be included two or more respectively.

From the viewpoint of can resin (A) be used as the resin glue of hardening resin composition, resin (A) is excellent Elect alkali soluble resins as.So-called alkali solubility, refer to the property dissolved in the developer solution as the aqueous solution of alkali compounds.

Resin (A) easily assigns alkali solubility due to comprising the polymer containing construction unit (Ac).

" (methyl) acrylic acid series structure list will be also known as " from (methyl) acrylic acid and/or the construction unit of its ester " Member ".It should be noted that " (methyl) acrylic acid " refers to " methacrylic acid and/or acrylic acid ".Hereinafter, to each construction unit It is described in detail.

, typically, can be by making the construction unit with carboxyl of copolymer (below, for construction unit (Aa) The construction unit is referred to as " construction unit (Aa ') ".) with having α, the compound of beta-unsaturated carbonyl carries out addition and obtained, Or can be by making the construction unit with epoxy radicals of copolymer be reacted with (methyl) acrylic acid to obtain.Need Bright, construction unit (Aa ') is a kind in construction unit described later (Ac).

With α, if the compound of beta-unsaturated carbonyl can with carboxylic acid reaction possessed by construction unit (Aa '), It is not particularly limited.As with α, the compound of beta-unsaturated carbonyl, (methyl) acrylate with epoxy radicals can be enumerated (Aa”)。

(methyl) acrylate (Aa ") with epoxy radicals is with selected from by ester ring type epoxy radicals and aliphatic epoxy base group Into group at least one kind of group.So-called ester ring type epoxy radicals, refer to ester ring type unsaturated hydrocarbons be at least partially epoxidized obtained from base Group；So-called aliphatic epoxy base, refer to the unsaturated aliphatic hydrocarbon of straight-chain or branched be at least partially epoxidized obtained from group.

As the concrete example of (methyl) acrylate with ester ring type epoxy radicals, can enumerate：

(methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates,

Ring [the 5.2.1.0 of (methyl) acrylic acid 5,6- epoxies-three^2,6] decane -8- base esters,

Ring [the 5.2.1.0 of (methyl) acrylic acid 5,6- epoxies-three^2,6] decane -8- base epoxides methyl esters,

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

(methyl) acrylic acid 2- hydroxyls -3- (2,3- epoxycyclopentyls epoxide) cyclopenta methyl esters,

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

Ring [the 5.2.1.0 of (methyl) acrylic acid 5,6- epoxies-three^2,6] decane -8- base esters,

Ring [the 5.2.1.0 of (methyl) acrylic acid 5,6- epoxies-three^2,6] decane -8- base epoxides methyl esters,

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

(methyl) acrylic acid 2- hydroxyls -3- (2,3- epoxycyclopentyls epoxide) cyclopenta methyl esters,

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

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

(methyl) acrylic acid 3- (3,4- epoxycyclohexyls) -9- hydroxyl -1,5- dioxo spiros [5,5] hendecane -8- base esters,

(methyl) acrylic acid 3- (3,4- epoxycyclohexyls) -9- hydroxyl -2,4- dioxo spiros [5,5] hendecane -8- base esters Deng.

They can be used alone, and also and can use two or more in addition.In these, (methyl) acrylic acid 3,4- is preferably used Epoxycyclohexanecarboxylate.

By making (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates and (methyl) acrylic acid series structure list with carboxyl Elementary reaction and in the case of obtaining construction unit (Aa), obtained construction unit (Aa) is represented by formula (Aa-1).

[in formula, R¹And R^xHydrogen atom or methyl are represented independently of each other.]

As the concrete example of (methyl) acrylate with aliphatic epoxy base, it is sweet that the shrink of (methyl) acrylic acid can be enumerated Grease etc. (methyl) acrylic acid epoxy ylmethyl ester (epoxy methyl (meth) acrylate), glycidyl itoconate Deng.In these, (methyl) acrylic acid epoxy ylmethyl ester is preferably used.

By making GMA and (methyl) the acrylic acid series construction unit with carboxyl react to obtain In the case of construction unit (Aa), obtained construction unit (Aa) is represented by formula (Aa-2).

[in formula, R⁵And R^yHydrogen atom or methyl are represented independently of each other.]

As the copolymer for including construction unit (Aa '), for example, can enumerate：Using unsaturated carboxylic acid being total to as construction unit Polymers；Make the copolymer for having imported carboxyl with alcohol, amine reaction using unsaturated acid anhydride as the anhydride group of the copolymer of construction unit； Make the copolymer for having imported carboxyl with anhydride reaction using unsaturated hydroxy compounds as the hydroxyl of the copolymer of construction unit.

In the case that construction unit (Ac) described later has carboxyl, can using construction unit (Ac) as construction unit (Aa '), It is set to be reacted with (methyl) acrylate (Aa ") with epoxy radicals and obtain construction unit (Aa).

Construction unit (Ab) is the structure list as derived from the unsaturated compound of active methylene or active methylene Member.

The construction unit can be by using the unsaturated compound of active methylene or active methylene as monomer And copolymer is obtained so as to obtain.Or also can be by making other structures unit (Ab ') and active methylene or activity time The compound (Ab ") of methyl is reacted and obtained.

As the unsaturated compound of active methylene, the compound that formula (I) represents can be enumerated.As active The unsaturated compound of methine, the compound of formula (II) expression can be enumerated.

[in formula (I) and formula (II), R¹¹It is 1 to represent hydrogen atom independently of each other or can contain heteroatomic carbon number ~24 alkyl.

R¹²Expression singly-bound or the bivalent hydrocarbon radical that carbon number is 1~20.

R¹³Divalent group shown in any one of expression (1-1)~formula (1-3).

R¹⁴Group shown in any one of expression (1-4)~formula (1-7).

(R¹⁵For the alkyl that heteroatomic carbon number is 1~24 can be contained.)

Divalent group shown in any one in X expressions (1-8)~formula (1-10).]

R¹¹Preferably hydrogen atom, methyl, ethyl, propyl group, butyl, hexyl, cyclohexyl, methoxyl group, ethyoxyl, propoxyl group, The group that hexyloxy, cyclohexyloxy or formula (1-11)~formula (1-13) represent, more preferably hydrogen atom or methyl.

R¹⁵Preferably methyl, ethyl, propyl group, butyl, hexyl, cyclohexyl, methoxyl group, ethyoxyl, propoxyl group, hexyloxy, The group that cyclohexyloxy or formula (1-11)~formula (1-13) represent, more preferably methyl.

R¹²Preferably singly-bound, methylene, ethylidene, propylidene, butylidene, propylidene, hexylidene, cyclohexylidene, Ya Xin Base, decylene, sub- dodecyl, more preferably singly-bound, methylene, ethylidene.

The compound represented as formula (I), specifically, can enumerate following compound etc..

The compound represented as formula (II), specifically, can enumerate following compound etc..

Formula (I-1)~(I-7), (I-16), (II-1), (II-2) and (II-5) are with CH₃-CH₂=CH- compound, The CH in these chemical formulas can also be enumerated₃-CH₂=CH- is replaced by H-CH₂=CH- compound.

Construction unit (Ab) is preferably the construction unit that formula (Ab-1) represents.

[in formula (Ab-1), R³Represent hydrogen atom or methyl, R⁴Expression hydrogen atom or the alkyl that carbon number is 1~6.]

The compound of the construction unit represented as derivative formula (Ab-1), for example, acetoacetate 2- (metering systems can be enumerated Acyloxy) ethyl ester (compound that formula (I-1) represents).

Construction unit (Ac) is from construction unit derived from the unsaturated compound with acidic group.

As acidic group, carboxyl, phenolic hydroxyl, sulfonic group etc. can be enumerated.The carboxyl can also carry out acid anhydrides.

The construction unit can obtain copolymer so as to obtain by using the unsaturated compound with acidic group as monomer Arrive.In addition, also can be by making other structures unit (Ac ') be reacted with the compound (Ac ") with acidic group to obtain.

Unsaturated compound with acidic group is preferably unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides.As unsaturated carboxylic acid or The concrete example of unsaturated carboxylic acid anhydrides, it can enumerate：

The unsaturated monocarboxylics such as (methyl) acrylic acid, butenoic acid；

The unsaturated dicarboxylics such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid；

The acid anhydride of foregoing unsaturated dicarboxylic；

Mono succinate (2- (methyl) acryloyl-oxyethyl) ester, phthalic acid list (2- (methyl) acryloxy second Base) more than the binary such as ester polybasic carboxylic acid single ((methyl) acryloxyalkyl) ester of unsaturation；

The such unsaturation third containing hydroxyl and carboxyl in same molecule of (methyl) acrylic acid α-(hydroxymethyl) ester Olefin(e) acid ester etc..

In these, the dissolubility from copolyreaction and in alkaline aqueous solution considers, preferably uses (methyl) propylene Acid and maleic anhydride etc..They may be used alone or in combination use.

Resin (A) can have the structure list in addition to construction unit (Aa), construction unit (Ab) and construction unit (Ac) Member (it is following, the construction unit is referred to as " construction unit (Ad) ".).

Construction unit (Ad) is the structure lists different from construction unit (Aa), construction unit (Ab) and construction unit (Ac) Member.Construction unit (Ad) can derive self energy with it is derivative be other structures unit (for example, construction unit (Aa), construction unit (Ab) And construction unit (Ac)) monomer polymerization monomer.

As the concrete example of such monomer, can enumerate：

(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid Zhong Ding (methyl) alkyl acrylates such as ester, (methyl) tert-butyl acrylate；

The alkyl acrylates such as methyl acrylate, isopropyl acrylate；

(methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- methyl cyclohexyls, the ring [5.2.1.0 of (methyl) acrylic acid three^{2 ,6}] decane -8- base esters (in the art, as trivial name, are referred to as (methyl) acrylic acid Bicvclopentyl ester (dicyclopentanyl(meth)acrylate).), (methyl) acrylic acid Bicvclopentyl epoxide ethyl ester (methyl) acrylic acid such as (dicyclopentanyl oxyethyl (meth) acrylate), (methyl) isobornyl acrylate Cyclic alkyl ester；

(methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- methyl cyclohexyls, the ring [5.2.1.0 of (methyl) acrylic acid three^{2 ,6}] decane -8- base esters (in the art, as trivial name, are referred to as (methyl) acrylic acid Bicvclopentyl ester.), (methyl) third (methyl) acrylic acid cyclic alkyl ester such as olefin(e) acid Bicvclopentyl epoxide ethyl ester, (methyl) isobornyl acrylate；

(methyl) benzyl acrylates such as (methyl) phenyl acrylate, (methyl) benzyl acrylate；

The benzyl acrylates such as phenyl acrylate, benzyl acrylate；Diethyl maleate, diethyl fumarate, itaconic acid The dicarboxylic diesters such as diethylester；

The hydroxyalkyl acrylates such as (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters；

Bicyclic [2.2.1] hept-2-ene", 5- methyl bicycles [2.2.1] hept-2-ene", bicyclic [2.2.1] hept-2-ene" of 5- ethyls, Bicyclic [2.2.1] hept-2-ene" of 5- hydroxyls, bicyclic [2.2.1] hept-2-ene" of 5- carboxyls, bicyclic [2.2.1] the hept- 2- of 5- hydroxymethyls Bicyclic [2.2.1] hept-2-ene" of alkene, 5- (2 '-hydroxyethyl), bicyclic [2.2.1] hept-2-ene" of 5- methoxyl groups, 5- ethyoxyls are bicyclic Bicyclic [2.2.1] hept-2-ene" of [2.2.1] hept-2-ene", 5,6- dihydroxy, bicyclic [2.2.1] hept-2-ene" of 5,6- dicarboxyls, 5,6- Bicyclic [2.2.1] hept-2-ene" of two (hydroxymethyls), bicyclic [2.2.1] hept-2-ene"s of 5,6- bis- (2 '-hydroxyethyl), 5,6- diformazans Bicyclic [2.2.1] hept-2-ene" of epoxide, bicyclic [2.2.1] hept-2-ene" of 5,6- diethoxies, 5- hydroxy-5-methyl bases are bicyclic Bicyclic [2.2.1] hept-2-ene" of [2.2.1] hept-2-ene", 5- hydroxyl -5- ethyls, 5- carboxyl -5- methyl bicycle [2.2.1] hept- 2- Bicyclic [2.2.1] hept-2-ene" of alkene, 5- carboxyl -5- ethyls, 5- hydroxymethyl -5- methyl bicycles [2.2.1] hept-2-ene", 5- carboxylics Bicyclic [2.2.1] hept-2-ene" of base -6- methyl bicycles [2.2.1] hept-2-ene", 5- carboxyl -6- ethyls, 5,6- dicarboxyls are bicyclic [2.2.1] hept-2-ene" acid anhydride (carbic anhydride (himic anhydride)), bicyclic [2.2.1] the hept- 2- of 5- tert-butoxycarbonyls Bicyclic [2.2.1] hept-2-ene" of alkene, 5- cyclohexyl Epoxide carbonyls, bicyclic [2.2.1] hept-2-ene" of 5- phenyloxycarbonyls, 5,6- bis- (tert-butoxycarbonyl) bicyclic [2.2.1] hept-2-ene", bicyclic [2.2.1] hept-2-ene"s of 5,6- bis- (cyclohexyl Epoxide carbonyl) etc. are double Ring unsaturated compound；

N-phenylmaleimide, N- N-cyclohexylmaleimides, N- benzyl maleimides, 3- dimaleoyl imino benzene Formic acid N- succinimide esters, 4- maleimidobutyric acid N- succinimide esters, 6- maleimidocaproic acid N- ambers The dicarbapentaborane acyls such as imide ester, 3- maleimidoproprionic acid N- succinimide esters, N- (9- acridinyls) maleimide are sub- Amine derivative；

Styrene, α-methylstyrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxybenzene second Alkene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3- Butadiene, isoprene, 2,3- dimethyl -1,3- butadiene；Etc..

In these, from the aspect of the reactivity in copolymerization and the dissolubility in alkaline aqueous solution, optimization styrene, N- Phenyl maleimide, N- N-cyclohexylmaleimides, N- benzyl maleimides, bicyclic [2.2.1] hept-2-ene" etc..

Resin (A) can have construction unit of more than two kinds (Ad).

Resin (A) includes containing construction unit (Aa), construction unit (Ab), construction unit (Ac) and then can also contain knot The copolymer of structure unit (Ad), with the molar fraction for the total mole number of construction unit of the copolymer is formed, The ratio of each construction unit is preferably in following scope.

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

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

Construction unit (Ac)：5~50 moles of %,

Construction unit (Ad)：0~70 mole of %.

In addition, when the ratio of construction unit is following scope, the tendency that solvent resistance further becomes good be present, because And more preferably.

Construction unit (Aa)：10~40 moles of %,

Construction unit (Ab)：10~40 moles of %,

Construction unit (Ac)：10~40 moles of %,

Construction unit (Ad)：0~60 mole of %.

Copolymer comprising each construction unit for example can according to document " experimental method of Polymer Synthesizing " (the grand row in big Tianjin writes, The same people of issuer's (strain) chemistry, the 1st edition the 1st printing, distribution on March 1st, 1972) described in method and the document in remember The citation of load is manufactured.

Resin (A) can for example pass through two stage process and manufacture.Specifically, by the derived structure unit of ormal weight (Ab) and each compound of construction unit (Ac) and the compound of derived structure unit (Aa '), polymerization initiator and solvent fill Enter into reaction vessel, oxygen is replaced with nitrogen, thus, be stirred, heat under conditions of in the absence of oxygen (such as 50~140 DEG C), insulation (such as 1~10 hour), so as to obtain with construction unit (Aa '), construction unit (Ab) and construction unit (Ac) Copolymer.Then, the nitrogen in reaction vessel is replaced as oxygen, by (methyl) acrylate (Aa ") with epoxy radicals, reaction Catalyst and polymerization inhibitor etc. are encased in reaction vessel, be stirred, heat (such as 60~130 DEG C), being incubated (such as 1~10 Hour), thus, (methyl) acrylate (Aa ") for making to have epoxy radicals is with construction unit (Aa ') reaction so as to which derivative is structure Unit (Aa), the copolymer with construction unit (Aa), construction unit (Ab) and construction unit (Ac) is obtained.

For obtained copolymer, reacted solution can be used directly, it is possible to use it is concentrated or dilution and The material obtained in solid form using the methods of reprecipitation, can be also dissolved in solvent and used by the solution obtained again.

When manufacture also has resin (A) of construction unit (Ad), in above-mentioned operation, by construction unit (Ad) with deriving The mixed charging of compound one of each compound and derived structure unit (Aa ') of construction unit (Ab) and construction unit (Ac) is Can.

Above, can be by (methyl) acrylate (Aa ") for making there is epoxy radicals when construction unit (Ac) has carboxyl Reacted with the construction unit (Ac) and obtain construction unit (Aa).

The weight average molecular weight according to polystyrene conversion of resin (A) is preferably 3,000~100,000, more preferably 5, 000~50,000, more preferably 10,000~50,000.

For the hardening resin composition of the resin (A) comprising weight average molecular weight in aforementioned range, there is progress Coating during coating becomes good tendency, in addition, have development when be not susceptible to film detraction and also development when it is uncured The good tendency of partial removal.

The decentralization [weight average molecular weight (Mw)/number-average molecular weight (Mn)] of resin (A) is preferably 1.1~6.0, more preferably 1.2~4.0.When decentralization is in foregoing scope, for being combined comprising curable resin of the resin (A) as resin glue For thing, the excellent tendency of developability be present, thus preferably.

The acid number of resin (A) is preferably 70~150mg-KOH/g, more preferably 75~135mg-KOH/g.

In this specification, acid number is the value measured according to JIS K 2501-2003.

＜ hardening resin compositions ＞

The hardening resin composition of the present invention includes resin (A), polymerizable compound and polymerization initiator.The present invention's Hardening resin composition can also include solvent.Hereinafter, by the polymerism chemical combination in the hardening resin composition of the present invention Thing, polymerization initiator and solvent are referred to as polymerizable compound (B), polymerization initiator (C) and solvent (D).

(1) resin (A)

The hardening resin composition of the present invention can form the solidification of excellent solvent resistance due to comprising resin (A) Film.

For the cured film formed by the hardening resin composition comprising resin (A), even in making cured film When, the temperature of the heating process (so-called post-bake process) after exposure is less than 200 DEG C, for example, more than 150 DEG C 200 DEG C with Under, it can also show excellent solvent resistance.

In the hardening resin composition of the present invention, with for the solid state component in hardening resin composition Mass fraction meter, the content of resin (A) is preferably 5~90 mass %, more preferably 10~70 mass %.

When the content of resin (A) is in foregoing scope, following tendency be present：Dissolubility in developer solution is abundant, no Be also easy to produce development residue, moreover, the part that is exposed and solidify is not susceptible to film and detracted in development, be not exposed and The removal of uncured part is good, is preferable.

Herein, solid state component refers to amount obtained from the content of solvent is removed from the total amount of hardening resin composition. The total amount of solid state component and each composition can be utilized known to liquid chromatography or gas chromatography etc. relative to the content of the total amount Analysis means determine.

In addition, also can and with the resin glue for the acrylic acid series that can generally use in the art, as long as not damaging In the range of the effect of the present invention.

(2) polymerizable compound (B)

Polymerizable compound (B) as long as using by light irradiation etc. and from caused by polymerization initiator (D) activity from The compound being polymerize by base etc., is not particularly limited.As polymerizable compound (B), for example, can enumerate has The compound of ethylenic unsaturated bond, the monofunctional monomer with 1 functional group with ethylenic unsaturated bond, tool can be enumerated There are 2 functional monomers of 2 functional groups and the polyfunctional monomer with the functional group of more than 3.

As the concrete example of above-mentioned monofunctional monomer, nonyl phenyl carbitol (methyl) acrylate, (methyl) can be enumerated Acrylic acid 2- hydroxyl -3- phenoxy-propyls, 2- ethylhexyls carbitol (methyl) acrylate, (methyl) acrylic acid 2- hydroxyl second Ester, NVP etc..

As the concrete example of above-mentioned 2 functional monomer, 1,6- hexylene glycols two (methyl) acrylate, ethylene glycol two can be enumerated (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, double (the third of bisphenol-A Alkene trimethylammonium) ether, 3- methyl pentanediols two (methyl) acrylate etc..

As the concrete example of above-mentioned polyfunctional monomer, trimethylolpropane tris (methyl) acrylate, Ji Wusi can be enumerated Alcohol three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two seasons penta Tetrol six (methyl) acrylate, the reactant of (methyl) acrylate of pentaerythrite three and the acid anhydrides, (first of dipentaerythritol five Base) acrylate and acid anhydrides reactant etc..

Wherein, preferably using 2 functional monomers, polyfunctional monomer.

These polymerizable compounds (B) can be used alone, also can and with two or more.

Based on mass fraction for relative to the total amount of resin (A) and polymerizable compound (B), polymerizable compound (B) content is preferably 1~70 mass %, more preferably 5~60 mass %.The content of polymerizable compound (B) is foregoing In the range of when, solidification film strength, flatness and the solvent resistance for being solidified to form hardening resin composition be present becomes Good tendency, it is preferable.

(3) polymerization initiator (C)

Polymerization initiator (C) as long as living radical, acid etc., poly- so as to trigger can be produced by the effect of light, heat The compound of conjunction, is not particularly limited, and known polymerization initiator can be used.

As polymerization initiator (C), preferably acetophenone system, bisglyoxaline (biimidazole) system, oxime system, triazine system, acyl Polymerization initiator, the polymerization initiator as organic boron salt of base phosphine oxide system.

By triggering auxiliary agent to be used in combination with polymerizeing these polymerization initiators (C), the hardening resin composition obtained from More high sensitive will be turned into, therefore, when forming pattern using it, the productivity ratio of pattern improves, thus preferably.

As foregoing acetophenone based compound, diethoxy acetophenone, 2- hydroxy-2-methyl -1- phenyl third can be enumerated Alkane -1- ketone, benzil dimethyl ketal, 2- hydroxyls -1- (4- (2- hydroxyl-oxethyls) phenyl) -2- methylpropane -1- ketone, 1- hydroxyls Butylcyclohexyl phenyl ketone, 2- methyl isophthalic acids-(4- methylsulfanylphenyls) -2- morpholinoes (morpholino) propane -1- ketone, 2- benzyls Base -2- dimethylaminos -1- (4- morphlinophenyls) butane -1- ketone, 2- (2- methyl-benzyls) -2- dimethylamino -1- (4- Quinoline is for phenyl)-butanone, 2- (3- methyl-benzyls) -2- dimethylaminos -1- (4- morphlinophenyls)-butanone, 2- (4- methyl benzyls Base) -2- dimethylaminos -1- (4- morphlinophenyls)-butanone, 2- (2- Ethylbenzyls) -2- dimethylaminos -1- (4- morpholines For phenyl)-butanone, 2- (2- benzyls) -2- dimethylaminos -1- (4- morphlinophenyls)-butanone, 2- (2- butyl benzyls Base) -2- dimethylaminos -1- (4- morphlinophenyls)-butanone, 2- (2,3- dimethyl benzyls) -2- dimethylamino -1- (4- Morphlinophenyl)-butanone, 2- (2,4- dimethyl benzyls) -2- dimethylaminos -1- (4- morphlinophenyls)-butanone, 2- (2- Chlorobenzyl) -2- dimethylaminos -1- (4- morphlinophenyls)-butanone, 2- (2- bromobenzyls) -2- dimethylamino -1- (4- Quinoline is for phenyl)-butanone, 2- (3- chlorobenzyls) -2- dimethylaminos -1- (4- morphlinophenyls)-butanone, 2- (4- chlorobenzyls) - 2- dimethylaminos -1- (4- morphlinophenyls)-butanone, 2- (3- bromobenzyls) -2- dimethylaminos -1- (4- morpholino benzene Base)-butanone, 2- (4- bromobenzyls) -2- dimethylaminos -1- (4- morphlinophenyls)-butanone, 2- (2- methoxy-benzyls) -2- Dimethylamino -1- (4- morphlinophenyls)-butanone, 2- (3- methoxy-benzyls) -2- dimethylaminos -1- (4- morpholino benzene Base)-butanone, 2- (4- methoxy-benzyls) -2- dimethylaminos -1- (4- morphlinophenyls)-butanone, 2- (2- methyl -4- methoxies Base benzyl) -2- dimethylaminos -1- (4- morphlinophenyls)-butanone, 2- (2- methyl -4- bromobenzyls) -2- dimethylaminos - 1- (4- morphlinophenyls)-butanone, 2- (the bromo- 4- methoxy-benzyls of 2-) -2- dimethylaminos -1- (4- morphlinophenyls)-fourth Ketone, 2- hydroxy-2-methyls -1- (oligomer of 4- (1- methyl ethylenes) phenyl propane -1- ketone etc..

As foregoing united imidazole, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl connection miaow can be enumerated Azoles, 2,2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline (referring to Japanese Unexamined Patent Publication 6-75372 publications, Japanese Unexamined Patent Publication 6-75373 publications etc..), 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (dioxanes Phenyl) bisglyoxaline, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxalines are (referring to Japanese special Public clear 48-38403 publications, Japanese Unexamined Patent Application 62-174204 publications etc..), the phenyl of 4,4 ' 5,5 '-position is by alkoxy carbonyl The imidazolium compounds of base (carboalkoxy) substitution is (referring to Japanese Unexamined Patent Publication 7-10913 publications etc..) etc., preferably enumerate 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-four benzene Base bisglyoxaline.

As foregoing oxime compound, O- ethoxy carbonyls-α-epoxide imino group -1- phenyl-propane -1- ketone, formula can be enumerated (P3) compound that compound, the formula (P4) represented represents etc..

As foregoing triazine based compound, double (the trichloromethyl) -6- (4- methoxyphenyls) -1,3,5- of 2,4- can be enumerated Double (trichloromethyl) -6- (4- methoxyl groups the naphthyl) -1,3,5- triazines of triazine, 2,4-, double (the trichloromethyl) -6- piperonyls of 2,4- - Double (trichloromethyl) -6- (4- the methoxyl-styrenes) -1,3,5- triazines of 1,3,5- triazines, 2,4-, 2,4- double (trichloromethyls) - Double (trichloromethyl) -6- (2- (furans -2- bases) second of 6- (2- (5- methylfuran -2- bases) vinyl) -1,3,5- triazines, 2,4- Alkenyl) -1,3,5- triazines, double (the trichloromethyl) -6- (2- (4- diethylamino -2- aminomethyl phenyls) vinyl) -1,3 of 2,4-, Double (trichloromethyl) -6- (2- (3,4- Dimethoxyphenyls) vinyl) -1,3,5- triazines of 5- triazines, 2,4- etc..

As foregoing acylphosphine oxide series initiators, TMDPO can be enumerated Deng.

As foregoing organic boron salt initiators, normal-butyl triphenyl boric acid tetramethyl-ammonium, isobutyl group triphenyl can be enumerated Tetraethylammonium borate, (4- tert-butyl-phenyls) the boric acid tetra-n-butyl of normal-butyl three ammonium, the naphthalenylboronic acid tetra-n-butyl ammonium of normal-butyl three, Methyl three (4- methyl naphthyl) boric acid tetra-n-butyl ammonium, triphenylsulfonium normal-butyl triph-enylborate, the positive fourth of triphenyl oxygen sulfonium Base triph-enylborate, triphenyl oxygen normal-butyl triph-enylborate, N- picoline normal-butyls triph-enylborate, four Ben Ji Phosphonium normal-butyls triph-enylborate, diphenyl iodine normal-butyl triph-enylborate etc..

, as the polymerization initiator, benzene can be enumerated further and with polymerization initiator usually used in this field etc. Acyloin based compound, benzophenone based compound, thioxanthones based compound, anthracene based compound etc..More specifically, can enumerate with Under compound, they can individually be used, or can be combined two or more and be used.

As foregoing benzoin based compound, it is even that benzoin, benzoin methyl ether, benzoin ethyl ether, benzene can be enumerated Relation by marriage isopropyl ether, benzoin isobutyl ether etc..

As foregoing benzophenone based compound, benzophenone, o-benzoyl yl benzoic acid methyl esters, 4- phenyl can be enumerated Benzophenone, 4- benzoyls -4 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2, 4,6- tri-methyl benzophenones etc..

As foregoing thioxanthones based compound, ITX, ITX, 2,4- diethyls can be enumerated Base thioxanthones, the clopenthixal ketones of 2,4- bis-, the chloro- 4- propoxythioxanthones of 1- etc..

As foregoing anthracene based compound, 9,10- dimethoxys anthracene, EDMO, 9 can be enumerated, 10- diethoxies anthracene, 2- ethyl -9,10- diethoxy anthracenes etc..

In addition, it can also enumerate 10- butyl -2- chloro-acridines ketone, 2- EAQs, benzil, 9,10- phenanthrenequione, camphorquinone, benzene Yl glyoxylic methyl ester, titanocenes (Titanocene) compound etc. are used as polymerization initiator.

As the polymerization initiator with the group that can cause chain tra nsfer, Japanese Unexamined Patent Application Publication 2002-544205 public affairs can be used Polymerization initiator described in report.As the foregoing polymerization initiator with the group that can cause chain tra nsfer, for example, can enumerate The polymerization initiator that formula (P5)~(P10) is represented.

The foregoing polymerization initiator with the group that can cause chain tra nsfer also as foregoing resin (A) composition into (Ad) is divided to use.Moreover, obtained resin (A) can be used as to the resin glue of the hardening resin composition of the present invention.

Also polymerization initiator can be used with polymerizeing initiation auxiliary combination.Trigger auxiliary agent, preferably amine compounds as polymerization Thing and following carboxylic acid compounds, amines are more preferably aromatic amines compound.

Trigger the concrete example of auxiliary agent as polymerization, the fat such as triethanolamine, methyl diethanolamine, triisopropanolamine can be enumerated Race's amines, 4- dimethylaminobenzoic acids methyl esters, EDMAB, 4- dimethylaminobenzoic acids are different Pentyl ester, 4- dimethylaminobenzoic acid 2- ethylhexyls, benzoic acid 2- dimethylamino ethyl esters, N, N- dimethyl-p-toluidines, The aromatic amines compounds such as 4,4 '-bis- (dimethylamino) benzophenone, 4,4 '-bis- (diethylamino) benzophenone.

As foregoing carboxylic acid compound, phenylsulfartyl acetic acid, aminomethyl phenyl ethyl thioglycollic acid, ethylphenyl sulfenyl can be enumerated Acetic acid, Methylethyl phenyl ethyl thioglycollic acid, 3,5-dimethylphenyl ethyl thioglycollic acid, methoxyphenyl ethyl thioglycollic acid, Dimethoxyphenyl Ethyl thioglycollic acid, chlorophenyl sulfanyl acetic acid, dichlorophenyl ethyl thioglycollic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio second The miscellaneous acetic acid of aromatic series such as acid, N- naphthyls glycine, naphthoxy acetic acid.

Based on mass fraction for relative to the total amount of resin (A) and polymerizable compound (B), polymerization initiator (C) Content be preferably 0.1~40 mass %, more preferably 1~30 mass %.

Based on mass fraction for relative to the total amount of resin (A) and polymerizable compound (B), polymerization triggers auxiliary agent Content is preferably 0.01~50 mass %, more preferably 0.1~40 mass %.

When the total amount of polymerization initiator (C) is in foregoing scope, exist hardening resin composition as high sensitive, The solidification film strength and the flatness on the surface of said curing film formed using foregoing hardening resin composition becomes good Good tendency, is preferable.In addition to that mentioned above, when polymerization triggers the amount of auxiliary agent in foregoing scope, exist to obtain consolidates The life for the pattern substrate that the susceptibility of the property changed resin combination further improves, is formed using foregoing hardening resin composition The tendency that yield improves, is preferable.

(4) solvent (D)

The hardening resin composition of the present invention preferably comprises solvent (D).Foregoing solvent (D) can be in curability tree The various organic solvents used in oil/fat composition field.As its concrete example, can enumerate：

Ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether and second as ethylene glycol monobutyl ether Glycol monoalkyl ether；

Diethylene glycol monomethyl ether, TC, diethylene glycol list propyl ether and diethylene glycol monobutyl ether Such diethylene glycol monoalky lether；

Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether And diethylene glycol dialkyl ether as diethylene glycol dibutyl ether；

Second as methylcellosolve acetate (methyl cellosolve acetate) and ethyl cellosolve acetate Glycol alkyl ether acetic acid esters；

Propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, propylene glycol monopropyl ether acetic acid esters, acetic acid first Aklylene glycol alkylether acetates as epoxide butyl ester and acetic acid methoxyl group pentyl ester；

DPGME, dihydroxypropane single-ethyl ether and DPG list alkane as DPG list propyl ether Base ether；

DPGME acetic acid esters, dihydroxypropane single-ethyl ether acetic acid esters and DPG list propyl ether acetic acid esters Such dipropylene glycol monoalkylether acetic acid esters；

Aromatic hydrocarbon as benzene,toluene,xylene and mesitylene；

Methyl ethyl ketone, acetone, methyl amyl ketone, methyl iso-butyl ketone (MIBK) and ketone as cyclohexanone；

Ethanol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol and alcohol as glycerine；

Ester as 3- ethoxyl ethyl propionates and 3- methoxy methyl propionates；

Cyclic ester as gamma-butyrolacton；Etc..

In above-mentioned solvent, from the aspect of coating, drying property, preferably enumerate aforementioned solvents mid-boiling point for 100~ 200 DEG C of organic solvent, it may be more preferable to enumerate aklylene glycol alkylether acetates, ketone, 3- ethoxyl ethyl propionates and 3- first The esters such as epoxide methyl propionate, it can further preferably enumerate propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, ring Hexanone, 3- ethoxyl ethyl propionates and 3- methoxy methyl propionates.

Solvent (D) can be used alone or mix two or more and use.With the matter for hardening resin composition Fraction meter is measured, the containing ratio of solvent (D) is preferably 60~90 mass %, more preferably 70~85 mass %.Solvent if (D's) contains Amount is then utilizing spin coater, slit spin coater, slit coater (also sometimes referred to as die coating machine, curtain stream in foregoing scope Formula coating machine.), the apparatus for coating such as ink-jet application machine is when being coated, coating may be caused to become good, be preferable.

(5) additive (F)

In the hardening resin composition of the present invention, as needed, also can and with colouring agent, filler, other macromolecules Compound, pigment dispersing agent, closely sealed accelerator, antioxidant, ultra-violet absorber, chain-transferring agent, acid agent, generated base alkaline agent etc. add Add agent (F).The hardening resin composition of colour filter can for example be formed by adding colouring agent.

As colouring agent, dyestuff and/or pigment etc. can be enumerated.They can be used alone, or also can will be of more than two kinds Toner is applied in combination, in this case, can be the only combination containing dyestuff, only in the combination of the combination containing pigment, dyestuff and pigment It is any.Particularly preferably include dyestuff.

As dyestuff, can enumerate acid dyes, basic-dyeable fibre, direct dyes, sulfur dye, reducing dye, naphthol dye, Reactive dye, disperse dyes etc., it can be selected from the past as colour filter purposes in known dyestuff etc..For example, it can enumerate day This JP 64-90403 publications, Japanese Unexamined Patent Application 64-91102 publications, Japanese Unexamined Patent Publication 1-94301 publications, Japan Unexamined Patent 6-11614 publications, Japanese spy step on No. 2592207, U.S. Patent No. No. 4,808,501 specifications, U.S. Patent No. No. 5,667,920 specifications, No. 5,059,500 specifications of U.S. Patent No., Japanese Unexamined Patent Publication 5-333207 publications, Japan are special Open described in flat 6-35183 publications, Japanese Unexamined Patent Publication 6-51115 publications, Japanese Unexamined Patent Publication 6-194828 publications etc. Pigment.

Specifically, pyrazoles azo, aniline azo, arylazo class, Pyrazolotriazole can be enumerated (pyrazolotriazole) azo, pyridone azo, triphenylmethane, Anthraquinones, anthrapyridones, benzal (benzylidene) class, oxonols (oxonol) class, cyanine class, polymethine (polymethine) class, phenothiazines, pyrrolo- Pyrazoles azomethine class, xanthene class, phthalocyanines, quinophthalone class, benzo pyran, indigo (indigo) class, dioxazines, cumarin Class, square hydrochlorate (squarylium) class, preferably enumerate pyrazoles azo, aniline azo, Pyrazolotriazole azo, pyrrole Pyridine ketone azo, Anthraquinones, anthrapyridones, phthalocyanines, dioxazines, quinophthalone class, xanthene class, it may be more preferable to enumerate pyrazoles Azo, pyridone azo, phthalocyanines, quinophthalone class, xanthene class etc..

As foregoing pigment, organic pigment and inorganic pigment can be enumerated, Colour Index (The Society of can be enumerated Dyers and Colourists are published) in be classified as pigment (Pigment) compound.

For example, it can enumerate：C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94, 109th, the yellow face such as 110,117,125,128,137,138,139,147,148,150,153,154,166,173,194,214 Material；

C.I. the orange pigment 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, 216th, the red pigment such as 224,242,254,255,264,265；

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

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

C.I. the viridine green such as pigment Green 7,36；

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

C.I. the black pigment such as pigment black 1,7.

Wherein, preferably comprise selected from C.I. pigment yellow 13s 8,139,150, C.I. paratoneres 177,209,254, C.I. pigment Purple 23, C.I. pigment blue 15s：At least one of 6 and C.I. pigment green 36s pigment.For these pigment, they can be independent Use, or combine two or more and use.

For the organic pigment in aforesaid pigments, following processing can be implemented as needed：Rosin processing；Use The surface treatment for being imported with pigment derivative, pigment dispersing agent of acidic-group or basic group etc. and carrying out；Utilize macromolecule The grafting processing that compound etc. is carried out to surface of pigments；Handled using the micronized of the progress such as sulfuric acid particles method；Or for except The carrying out washing treatment using the progress such as organic solvent, water of decontamination；The place for being removed ionic impurity using ion-exchange etc. Reason etc..

As foregoing pigment dispersing agent, commercially available surfactant can be used.As such surfactant, can lift Go out surfactant of polysiloxane series, fluorine system, ester system, cation system, anion system, nonionic system, both sexes etc. etc..They can It is used alone, or combines two or more and use.Specifically, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl can be enumerated Ether, polyethylene glycol di, sorbitan fatty acid ester, fatty acid modified polyester, tertiary-amine modified polyurethane, polyethyleneimine Deng.In addition, as the surfactant, the product of following trade names can be enumerated：KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), POLYFLOW (common prosperity chemistry (strain) system), F-Top (TOHKEM PRODUCTS company systems), MEGAFAC (DIC (strain) systems), Fluorad (Sumitomo 3M company systems), AsahiGuard, Surflon (being made above for Asahi Glass (strain)), Solsperse (Zeneca Company system), EFKA (EFKA CHEMICALS company systems), PB821 (aginomoto (strain) system), (BYK Chemie are public by Disperbyk Department's system) etc..

In order to adjust solidification film strength, be coloured, filler can be added.As foregoing filler, specifically, Glass, silica, aluminum oxide, pigment etc. can be enumerated.

In order to adjust solidification film strength, other high-molecular compounds can be added.As other high-molecular compounds, specifically For, curable resin, polyvinyl alcohol, polyacrylic acid, the alkoxy polyalkylene glycol monos such as epoxy resin, maleimide resin can be used Thermoplastic resins such as base ether, poly- fluoroalkyl, polyester, polyurethane etc..

In order to improve the adaptation with substrate, base material, closely sealed accelerator can be added.As foregoing closely sealed accelerator, tool For body, vinyltrimethoxy silane, VTES, vinyl three (2- methoxy ethoxies) silicon can be enumerated Alkane, N- (2- amino-ethyls) -3- amino propyl methyls dimethoxysilane, N- (2- amino-ethyls) -3- aminopropyl trimethoxies Base silane, APTES, 3- glycidoxypropyltrime,hoxysilanes, 3- glycidoxypropyl group first Base dimethoxysilane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- chloropropylmethyldimethoxysilanes, 3- R-chloropropyl trimethoxyl silane, 3- methacryloxypropyl trimethoxy silanes, 3-mercaptopropyi trimethoxy silane etc..

In order to prevent being deteriorated caused by oxidation for cured film, antioxidant can be added.As foregoing antioxidant, Specifically, 2 can be enumerated, 2 '-thiobis (4- methyl-6-tert-butylphenols), 2,6- di-tert-butyl-4-methy phenols etc..

In order to prevent being deteriorated caused by ultraviolet for cured film, ultra-violet absorber can be added.As foregoing purple Ultraviolet absorbers, specifically, 2- (the 3- tert-butyl group -2- hydroxy-5-methyl bases phenyl) -5- chlorobenzotriazoles, alkoxy can be enumerated Benzophenone etc..

In order to control the molecular weight in curing reaction, chain-transferring agent can be added.As foregoing chain-transferring agent, ten can be enumerated Dialkyl group mercaptan, 2,4- diphenyl -4-methyl-1-pentene etc..

As curing reaction catalyst, acid agent can be added.As foregoing acid agent, can enumerate aryl diazonium salts, Diaryl group iodized salt, triarylsulfonium salt, triaryl oxidation sulfonium salt, pyridiniujm, quinolinium, isoquinolin salt, sulphonic acid ester, iron Arene Complex etc..

As curing reaction catalyst, generated base alkaline agent can be added.As foregoing generated base alkaline agent, carbamic acid 1- first can be enumerated Carbamate derivatives, urea, the N such as base -1- (4- xenyls) ethyl ester, carbamic acid 1,1- dimethyl -2- cyanaoethyl methacrylates, N- bis- The dihydrogen pyridine derivatives such as the urea derivatives such as methyl-N '-MU, 1,4- dihydro-nicotinamides, organosilan, the season of organo-borane Carbamic acid benzoylcyclohexan ester, triphenylcarbinol described in ammonium salt, dicyandiamide etc., Japanese Unexamined Patent Publication 4-162040 etc. Compound described in compound, Japanese Unexamined Patent Publication 5-158242 etc..

(6) cured film

The cured film for being solidified to form the hardening resin composition of the present invention is also one of present invention.

The cured film of the present invention can be obtained by following manufacture methods, and the manufacture method includes following processes：This is consolidated The property changed resin combination is coated on the process on substrate；By the way that hardening resin composition drying is formed into curable resin group The process of compound layer；The process that cured resin composition layer is exposed；Exposed cured resin composition layer is carried out The process toasted afterwards.

As the method for the cured film for making the present invention, for example, following methods can be enumerated：Hardening resin composition is applied Cloth forms cured resin composition layer on substrate, by the hardening resin composition drying of coating, as desired by Cured resin composition layer is exposed via modes such as photomasks, and the method developed；By using ink-jet apparatus The operation such as hardening resin composition is coated, so as to manufacture the figuratum cured film of tool (below, sometimes referred to as " pattern ".) side Method.

Herein, as substrate, transparent glass plate, Silicon Wafer, polycarbonate substrate, polyester substrate, aromatic series can be enumerated Resin substrates such as polyamide substrate, polyamideimide-based plate, polyimide substrate etc..

Black matrix", other cured films or colored pattern, the transparent print for adjusting thickness can be formed on aforesaid base plate Case, TFT etc..In this case the thickness of cured film is not particularly limited, and can suitably be adjusted according to material, the purposes etc. used It is whole, for example, 0.1~30 μm or so, preferably 1~20 μm or so, more preferably 1~6 μm or so can be enumerated.

On the coating method of hardening resin composition, it is recessed that Extrusion Coating method, direct rotogravure application method, inverse formula can be enumerated Version cladding process, CAP cladding processes, die coating method etc..In addition, it is possible to use dip coater, bar coater, spin coater, slit spin coater, slit Coating machine (also sometimes referred to as die coating machine, curtain coater, non-rotating coating machine (spinless coater)), roller coat The coating machines such as machine are coated.Wherein, preferably it is coated using spin coater.

As the method for drying hardening resin composition, natural drying, aeration-drying can be enumerated, be dried under reduced pressure. As specific heating-up temperature, 30~120 DEG C or so be it is suitable, preferably 60~100 DEG C or so.As the heat time, 10 Second~be within 60 minutes or so it is suitable, preferably 30 seconds~30 minutes or so.For being dried under reduced pressure, following sides can be enumerated Formula：Under 50~150Pa or so pressure, carried out within the temperature range of 20~25 DEG C or so.The curable resin of the present invention In the case that composition includes solvent (D), by above-mentioned drying, solvent (D) can be removed.

Via photomask radioactive ray can be irradiated to obtained cured resin composition layer.

As photomask, the mask that light shielding part is formd corresponding to target pattern is used.As radioactive ray, g can be used The light such as line, i lines.For the irradiation of radioactive ray, such as mask registration machine (mask aligner), stepper are preferably used (stepper) device such as.After the irradiation for carrying out radioactive ray, cured resin composition layer is developed.Development, which can be directed to, to expose Cured resin composition layer after light utilizes sheathed immersion development method (puddle method), infusion process, spray-on process or spray Leaching method etc. and carry out.It should be noted that the feelings of radioactive ray are not being irradiated to cured resin composition layer via photomask Under condition, it is not necessary to developed.

As developer solution, alkaline aqueous solution generally can be used.As alkaline aqueous solution, the water-soluble of alkali compounds can be used Liquid, alkali compounds can be inorganic alkaline compound or organic basic compound.Table can be contained in alkaline-based developer Face activating agent.

Alkali compounds can be any in inorganic and organic alkali compounds.Tool as inorganic alkaline compound Style, sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid can be enumerated Potassium dihydrogen, sodium metasilicate, potassium silicate, sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus, Boratex, potassium borate, ammonia etc..

As the concrete example of organic basic compound, TMAH, 2- hydroxyethyl trimethyl hydrogen-oxygens can be enumerated Change ammonium, monomethyl amine, dimethyl amine, Trimethylamine, MEA, diethylamide, triethylamine, single isopropylamine, diisopropyl Base amine, monoethanolamine etc..These inorganic and organic basic compounds can be used alone or combine two or more and use respectively.Alkali The concentration of alkali compounds in property developer solution is preferably 0.01~10 mass %, more preferably 0.03~5 mass %.

Surfactant in alkaline-based developer can be nonionic surfactants, anion system surfactant or It is any in cation system surfactant.As the concrete example of nonionic surfactants, can enumerate polyxyethylated Ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivs, oxygen ethene/oxypropylene block are common Polymers, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, Fatty acid glyceride, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine etc..

As the concrete example of anion system surfactant, it is contour that laruyl alcohol sodium sulfovinate, oleyl sulfate sodium can be enumerated Level alcohol sulfuric ester salt, NaLS, alkyl sulfate, neopelex, 12 as Texapon Special Alkylaryl sulfonates as Negel etc..

As the concrete example of cation system surfactant, stearic amine hydrochloride, lauryl trimethyl chlorination can be enumerated Amine salt as ammonium or quaternary ammonium salt etc..These surfactants can be used alone respectively, or two or more also can be combined and makes With.

The concentration of surfactant in alkaline-based developer is preferably 0.01~10 mass % scope, and more preferably 0.05 ~8 mass %, more preferably 0.1~5 mass %.

In the present invention, temperature during baking is preferably more than 150 DEG C afterwards.

In addition, the glass transition temperature (Tg) of substrate of the temperature preferably than forming cured film during rear baking is low, in addition, In the case of the composition deteriorated when comprising colouring agent etc. in the temperature higher than 200 DEG C, preferably start to deteriorate than the composition Temperature it is low.

Therefore, temperature during rear baking can wrap according in the species of the substrate for forming cured film, hardening resin composition Composition contained etc. and suitably determine, for example, it is preferable to for less than more than 150 DEG C 200 DEG C, more preferably more than 150 DEG C 180 DEG C with Under.Temperature during by being toasted after making is more than 150 DEG C, can obtain the cured film with excellent solvent resistance.In addition, use During resin of the present invention, it can obtain having in the case where not reducing the characteristic of substrate, colouring agent etc. excellent resistance to molten The cured film of agent.

By using the hardening resin composition of the present invention, thus, generally carried out to improve solvent resistance in the past The post-bake process being higher than at a temperature of 200 DEG C become not necessarily, therefore, can obtain having excellent solvent resistance, simultaneously And the cured film that the characteristic of substrate, colouring agent etc. will not decline.

Each operation as described above is passed through by the hardening resin composition of the present invention, cured film can be formed on substrate. The cured film is as adjusting the photoetching type sept (photo spacer) used in liquid crystal display device, layer insulation Film, the coat of thickness etc. of colored pattern are useful.

In the manufacture of above-mentioned cured film, if use is used for when carrying out patterned exposure to cured resin composition layer The photomask in hole is formed, then can obtain having porose interlayer dielectric.

It is to have as the colored pattern in colour filter in the case that the hardening resin composition of the present invention includes colouring agent .

In the manufacture of above-mentioned cured film, when being exposed to cured resin composition layer, it can be covered without using light Exposed in the case of mould by whole face and be heating and curing or only form cured film by being heating and curing, the cured film is as guarantor Sheath (overcoat) is useful.

By assembling the cured film obtained in the manner described above, the display devices such as liquid crystal display device are may make up.It is such The display quality of display device is excellent.

[embodiment]

Hereinafter, the present invention is illustrated by embodiment in further detail, but the present invention is not restricted by the embodiments.Respectively In example, unless otherwise specified, represent content or the % of usage amount and part on the basis of quality.

The ＞ of ＜ embodiments 1

Synthesis includes the resin (A1) of following construction units.

Into the flask with stirring vane, reflux condensing tube, thermometer and dropping funel, load propylene glycol monomethyl ether 70 mass parts, it is heated to 90 DEG C.With dropping funel, start that mixed methyl acrylic acid Bicvclopentyl ester is continuously added dropwise into flask 52.6 mass parts, the mass parts of methacrylic acid 2- (acetoacetoxy groups) ethyl ester 20.7, the mass parts of methacrylic acid 26.7, azo The solution that double (isobutyronitrile) 5 mass parts, the mass parts of propylene glycol monomethyl ether 30 form.By in the flask during dropwise addition mixed solution Temperature remains 90 ± 1 DEG C, completes to be added dropwise with 3 hours.After completion of dropwise addition, pot temperature is set to turn into 90 ± 1 DEG C, holding 6 is small When.After reaction, reaction solution is cooled to less than 40 DEG C, puts into the mass parts of 4- metoxyphenols 0.12, acrylic acid 3,4- epoxide rings The mass parts of hexyl methyl esters 17.6, the mass parts of triphenylphosphine 4.7, the mass parts of propylene glycol monomethyl ether 85, pot temperature is heated up To after 110 DEG C, addition reaction is carried out under conditions of being 110 ± 1 DEG C in pot temperature, thus obtains resin (A1).Obtain The weight average molecular weight (Mw) of resin (A1) is 14,300, and decentralization 2.4, acid number is 103 (mg-KOH/g), and solid state component is 37.9 quality %.

The ＞ of ＜ embodiments 2

Synthesis includes the resin (A2) of following construction units.

Into the flask with stirring vane, reflux condensing tube, thermometer and dropping funel, load propylene glycol monomethyl ether 70 mass parts, it is heated to 90 DEG C.With dropping funel, start that the mass of mixed methyl methyl acrylate 44.6 is continuously added dropwise into flask Part, the double (isobutyls of the mass parts of methacrylic acid 2- (acetoacetoxy groups) ethyl ester 28.6, the mass parts of methacrylic acid 26.8, azo Nitrile) solution that forms of 5 mass parts, the mass parts of propylene glycol monomethyl ether 30.Pot temperature during mixed solution is added dropwise is protected Hold as 90 ± 1 DEG C, completed to be added dropwise with 3 hours.After completion of dropwise addition, pot temperature is turned into 90 ± 1 DEG C, kept for 6 hours.Reaction Afterwards, reaction solution is cooled to less than 40 DEG C, puts into the mass parts of 4- metoxyphenols 0.12, acrylic acid 3,4- epoxycyclohexanecarboxylates 24.4 mass parts, the mass parts of triphenylphosphine 5, the mass parts of propylene glycol monomethyl ether 95, after pot temperature is warming up into 110 DEG C, Addition reaction is carried out under conditions of being 110 ± 1 DEG C in pot temperature, thus obtains resin (A2).Obtained resin (A2) Weight average molecular weight (Mw) is 15,800, and decentralization 2.4, acid number is 80 (mg-KOH/g), and solid state component is 38.5 mass %.

The ＞ of ＜ synthesis examples 1

Synthesis includes the resin (A3) of following construction units.

Take the mass parts of propylene glycol monomethyl ether 100 to have agitating device, dropping funel, condenser, thermometer, In the flask of gas introduction tube, nitrogen displacement is carried out while being stirred, is warming up to 120 DEG C.Then, to including metering system The sour mass parts of methyl esters 43, the mass parts of methacrylic acid 25 monomer mixture in, add relative to the mass parts of monomer mixture 100 For be 1 mass parts t-butyl peroxy -2 ethyl hexanoic acid ester (Perbutyl O；Day oily (strain) system).Through 2 hours by it from drop Liquid funnel is added dropwise in flask, and then in 120 DEG C stir within 2 hours, obtains copolymer.Then, sky will be replaced as in flask Gas, by the mass parts of GMA 10, the mass parts of triphenylphosphine 0.44 and the mass parts of methyl hydroquinone 0.08 Input, in 120 DEG C of sustained responses, terminates into the solution of above-mentioned copolymer when the acid number of solid state component turns into 100KOHmg/g Reaction, the mass parts of propylene glycol monomethyl ether 50 are added, thus, obtain weight average molecular weight (Mw) is for 30000, decentralization 2.5th, the resin (A3) that acid number is 100 (mg-KOH/g), solid state component is 40%.

The assay method ＞ of ＜ molecular weight

Weight average molecular weight (Mw) and number-average molecular weight on foregoing methacrylic acid based copolymer (A1)~(A3) (Mn) measure, using GPC method, carry out under the following conditions.

Device：K2479 ((strain) Shimadzu Seisakusho Ltd. system)

Post：SHIMADZU Shim-pack GPC-80M

Column temperature：40℃

Solvent：THF (tetrahydrofuran)

Flow velocity：1.0mL/min

Detector：RI

The weight average molecular weight (Mw) and number-average molecular weight (Mn) that are converted according to polystyrene that will be obtained through the above way Be used for decentralization (Mw/Mn).

(2) preparation of hardening resin composition

The ＞ of ＜ embodiments 3

By 132 parts of resin solution that the solid state component comprising resin (A1) obtained in embodiment 1 is 37.9% (according to changing Calculate and be calculated as 50 parts for solid state component) and 200 parts of mixing of propylene glycol monomethyl ether (following, be designated as " solvent D1 "), obtain Solid state component is 15% hardening resin composition 1.

The ＞ of ＜ comparative examples 1

Instead of 132 parts of the resin solution comprising resin (A1), it is 40% to have used the solid state component comprising resin (A3) 130 parts of resin solution, in addition, is operated similarly to Example 3, is obtained the curable resin that solid state component is 15% and is combined Thing 2.

(3) formation of cured film

It is utilized respectively spin-coating method and hardening resin composition 1 and hardening resin composition 2 is coated on different 2 inches Glass substrate (the Eagle XG of square；Corning company systems) on so that the thickness after rear baking turns into 1.0 μm, then carries out It is dried in vacuo (reaching pressure 66Pa), in 100 DEG C of prebake conditions 3 minutes, thus, obtains cured resin composition layer.

In an oven, in 150 DEG C, toast after being carried out 30 minutes to obtained cured resin composition layer, thus obtain Cured film.

With film thickness measuring device (DEKTAK3；(strain) ULVAC systems) as a result the thickness of cured film that measure obtains is 1.0 μ m。

(4) evaluate

＜ solvent resistances ＞

In 23 DEG C of temperature, obtained cured film is impregnated in 1-METHYLPYRROLIDONE (following, sometimes referred to simply as NMP) 0.5 hour, for the cured film after dipping, use film thickness measuring device (DEKTAK3；(strain) ULVAC systems) measure thickness, calculate The ratio between with the thickness before dipping.Show the result in table 1.

＜ adaptations ＞

In 23 DEG C of temperature, obtained cured film is impregnated 0.5 hour in NMP, for the cured film after dipping, according to JIS K5400, using cutter, with 1mm interval, by as 10 × 10 it is tessellated in a manner of cut out cut channel, fitting is transparent Adhesive tape (cellophanetape), then tears, and observation is unstripped and keeps being sealed at the number of the state of substrate.Result is shown In table 1.

[table 1]

The ＞ of ＜ embodiments 4

132 parts of the resin solution comprising resin (A1) obtained in embodiment 1 (is calculated as 50 according to solid state component is scaled Part) in mixing pentaerythritol triacrylate (A-TMM-3LM-N, Xin Zhong village chemical industry (strain) system) (it is following, be designated as " polymerizeing Property compound (B1) ") 50 parts, Photoepolymerizationinitiater initiater (IRGACURE (registration mark) OXE01, BASF AG's system) (it is following, be designated as " polymerization initiator (C1) ") 3 parts, 502 parts of propylene glycol monomethyl ether (following, be designated as " solvent D1 "), obtain solid-state into It is divided into 15% hardening resin composition 3.

The ＞ of ＜ embodiments 5

It is molten using the resin that the solid state component comprising resin (A2) is 38.5% instead of including resin (A1) resin solution 130 parts of liquid, 504 parts of solvent D1 are mixed, in addition, are operated similarly to Example 4, obtain the solidification that solid state component is 15% Property resin combination 4.

The ＞ of ＜ comparative examples 2

Instead of including resin (A1) resin solution, the resin solution that the solid state component comprising resin (A3) is 40% is used 125 parts, 509 parts of solvent D1 are mixed, in addition, are operated similarly to Example 4, obtain the curability that solid state component is 15% Resin combination 5.

(5) formation 1 of pattern

It is utilized respectively spin-coating method and 3~hardening resin composition of hardening resin composition 5 is coated on 2 inch squares Glass substrate (Eagle XG；Corning company systems) on so that the thickness after rear baking turns into 1.0 μm, then carries out vacuum and does Dry (reaching pressure 66Pa), 3 minutes prebake conditions are carried out in 100 DEG C, thus, obtain cured resin composition layer., will after cooling The interval for foring the substrate of cured resin composition layer and the photomask of quartz glass is set as 80 μm, uses exposure machine (TME-150RSK；Topcon Corporation systems), under air atmosphere, with 100mJ/cm²Light exposure (with 365nm ripples On the basis of length) carry out light irradiation.It should be noted that as photomask, using formed with 50 μm of line and intermittent pattern The photomask of (line-and-space pattern).In 25 DEG C, by the cured resin composition layer after light irradiation in containing Impregnate 60 seconds and developed in the aqueous solution of 0.12% nonionic surfactants and 0.04% potassium hydroxide, after washing, In an oven, toasted after being carried out 30 minutes in 150 DEG C, thus, obtain the pattern formed by cured film.For obtained pattern, Use film thickness measuring device (DEKTAK3；(strain) ULVAC systems) measure thickness, as a result, it is 1.0 μm to confirm thickness.

(6) evaluate

＜ patterns form (patterning) property ＞

For obtained pattern, scanning electron microscope (S-400 is used；(strain) Hitachi Technologies systems) Observed, evaluated according to following metewands.Show the result in table 2.

Metewand

1：Pattern is formed as wire as mask,

2：Situation in addition to 1 (line pattern destroys, and grades in the absence of spacer portion).

＜ solvent resistances ＞

In 23 DEG C of temperature, obtained pattern is impregnated 0.5 hour in NMP, for the pattern after dipping, uses thickness Determine device (DEKTAK3；(strain) ULVAC systems) the ratio between measure thickness, the thickness (1.0 μm) before calculating and impregnating.Result is shown In table 2.

＜ adaptations ＞

Not via mask, without developing procedure, in addition, operated in the same manner as the formation with above-mentioned pattern, consolidate Change film.In 23 DEG C of temperature, obtained cured film is impregnated 0.5 hour in NMP, for the cured film after dipping, according to JIS K5400, using cutter, with 1mm interval, by as 10 × 10 it is tessellated in a manner of cut out cut channel, be bonded adhesive tape, Then tear, observation is unstripped and keeps being sealed at the number of the state of substrate.Show the result in table 2.

[table 2]

The ＞ of ＜ embodiments 6

The synthesis ＞ for the compound that ＜ formulas (A-IV) represent

20 parts of compound and N- propyl group -2,6- dimethylanilines (and the pure medicine of light for representing formula (1x) under dark conditions Industrial (strain) system) 200 parts of mixing, obtained solution stir within 6 hours in 110 DEG C.Obtained reaction solution is cooled to room Wen Hou, add it in the mixed liquor of 800 parts of water, 50 parts of 35% hydrochloric acid, in room temperature stir within 1 hour, as a result separate out Crystallization.Filtered, obtain the crystallization of precipitation as residue is filtered, be then dried, obtain the change of formula (A-IV) expression Compound.

Using following apparatus, analyzed by LC-MS to enter the identification for the compound that line (A-IV) represents.

LC devices：Agilent company systems LC1200 series

Post：Wakosil-II 3C18HG(Φ3.0mm*150mm(W))

MS devices：Agilent company systems LC/MSD6130

(mass spectrum) ionization mode=ESI+：M/z=[M+H]⁺659.9

Accurate molecular weight (Exact Mass)：658.9

The preparation ＞ of ＜ hardening resin compositions

Following substances are mixed：

C.I. pigment blue 15：6 21.4 parts

7.5 parts of acrylic acid series pigment dispersing agent, and

176 parts of propylene glycol monomethyl ether,

It is using ball mill that pigment is fully dispersed, next,

Following substances are obtained by mixing hardening resin composition 6,

The ＞ of formation 2 of ＜ patterns

Hardening resin composition 6 is coated on to the glass substrate (Eagle 2000 of 5cm square using spin-coating method； Corning company systems) on, then, 3 minutes prebake conditions are carried out in 100 DEG C, obtain cured resin composition layer.Place cooling Afterwards, the interval of the substrate for foring cured resin composition layer and quartz glass photomask is set as 100 μm, uses exposure Ray machine (TME-150RSK；Topcon Corporation systems), under air atmosphere, with 80mJ/cm²Light exposure (with 365nm On the basis of) carry out light irradiation.As photomask, 1 formed with 100 μm is used：The photomask of 1 line and intermittent pattern.In 23 DEG C, By the composition layer after light irradiation in contain 0.12% nonionic surfactants and the water system of 0.04% potassium hydroxide development Impregnate 60 seconds and developed in liquid, after washing, on hot plate, carry out toasting for 5 minutes in 150 DEG C, thus obtain pattern.Figure The thickness of case is 2.1 μm.

Method for the formation 2 using pattern, the pattern made by the hardening resin composition 6 of embodiment 6, are utilized Method similar to the above is evaluated, as a result, patternability 1, solvent resistance 1.0, adaptation 100/100.

It can be seen from result more than, the resin of hardening resin composition of the invention due to including the present invention, thus It can obtain patternability, solvent resistance, the pattern of substrate excellent adhesion.

Claims (5)

1. resin, it has：Construction unit (Aa), active methylene or active methylene with alpha, beta-unsaturated carbonyl Construction unit (Ab) and with acidic group construction unit (Ac).

2. hardening resin composition, it includes resin, polymerizable compound and the polymerization initiator described in claim 1.

3. cured film, it is to be solidified to form the hardening resin composition described in claim 2.

4. the manufacture method of cured film, it includes following processes：

Process hardening resin composition described in claim 2 being coated on substrate,

By the way that hardening resin composition is dried so as to form the process of cured resin composition layer,

The process that cured resin composition layer is exposed, and,

The process heated to exposed cured resin composition layer.

5. the manufacture method of cured film as claimed in claim 4, wherein, in less than more than 150 DEG C 200 DEG C of temperature to through exposing The cured resin composition layer of light is heated.