CN101657759B - Alkali-developable photosensitive resin composition and beta-diketone - Google Patents

Abstract

Disclosed is an alkali-developable photosensitive resin composition containing (J) a photopolymerizable unsaturated compound having a structure which is obtained by an esterification reaction between (C) a polybasic acid anhydride and a hydroxy group of a reaction product that is obtained by adding (B) a compound having a ss-diketone moiety or a compound having a ss-ketoester group to a (meth)acryloyl group of (A) a compound having two or more (meth)acryloyl groups and a hydroxy group. As the compound having a ss-diketone moiety, a novel compound that is a ss-diketone compound represented by the general formula (I) below is preferably used. (In the formula (I), R1 represents an alkyl group having 1-20 carbon atoms; R2 represents R11, OR11, COR11, SR11, CONR12R13 or CN; R11, R12 and R13 independently represent a hydrogen atom, an alkyl group having 1-20 carbon atoms or the like; a represents an integer of 0-3; and b represents an integer of 0-4).

Description

Alkali-developable photosensitive resin combination and beta-diketone compound

Technical field

The present invention relates to contain the alkali-developable photosensitive resin combination of the specific compound of having given the ethylenic unsaturated link and in this alkali-developable photosensitive resin combination, further contain Photoepolymerizationinitiater initiater and when the alkali-developable photosensitive resin combination that obtains and manufacturing in said composition useful as intermediates have the novel beta-diketone compound of carbazyl.

Background technology

Usually the alkali-developable photosensitive resin combination contains alkali-developable photosensitive resin combination and the Photoepolymerizationinitiater initiater that comprises the compound with ethylenic unsaturated link.This alkali-developable photosensitive resin combination be owing to can make its polymerizing curable through irradiation ultraviolet radiation or electron ray, therefore can be applied in the various photoresists such as photo-curable printing ink, photosensitive printing version, printed wiring board, color filter for liquid crystal display etc.Recently, be accompanied by compactization of electronic equipment and the development of high performance, hope to have the alkali-developable photosensitive resin combination that can form fine pattern with good accuracy.

In addition; The Photoepolymerizationinitiater initiater that uses in the alkali-developable photosensitive resin combination is because cost is high; And the unreacted component of Photoepolymerizationinitiater initiater and analyte can remain in to film and go up and pollute, and therefore hope to have and do not use Photoepolymerizationinitiater initiater or reduce consumption but sensitivity and adhesiveness are excellent and can form the alkali-developable photosensitive resin combination of fine pattern with good accuracy.

On the other hand; In following patent documentation 1～4, record: compound and the beta-diketone compound that contains acryloyl group carries out addition and the reaction product that obtains can be used as that not use Photoepolymerizationinitiater initiater be that curable Photocurable composition uses, but do not put down in writing the example that it is used as the alkali-developable photosensitive resin combination.

Beta-diketone compound is used for catalyzer, detector, fluorescent material etc.Known beta-diketone compound can form complex compound with various metals, becomes the important substance in the electronic device field as CVD, MOD material and metal alkoxide photoresist material etc. in recent years.

, for the compound that contains (methyl) acryloyl group, bring into play the function of light trigger through making this compound and beta-diketone compound addition.For example, in following patent documentation 1～3, record: the methylene moiety of beta-diketone compound is the compound of quaternary carbon atom, and it produces free radical and is used in the Photocurable composition under the effect of light.But compound in the past can not obtain enough performances, therefore has to increase light quantity.

Patent documentation 1: No. 3649331, Jap.P.

Patent documentation 2: TOHKEMY 2005-163041 communique

Patent documentation 3: TOHKEMY 2006-241461 communique

Patent documentation 4: No. 5459178, United States Patent (USP)

Summary of the invention

The problem that the present invention will solve is: aforesaidly do not use or use the little light polymerization initiator but also very excellent aspect sensitivity and the adhesiveness and can obtain the alkali-developable photosensitive resin combination of suitable pattern form or fine pattern even do not exist up to now.

Therefore; The object of the present invention is to provide light absorbingly efficiently to have substituent beta-diketone compound, even and provide and do not use or use the little light polymerization initiator but also very excellent and can form the alkali-developable photosensitive resin combination of fine pattern with good precision at aspects such as sensitivity and adhesivenesses.

The present invention provides a kind of alkali-developable photosensitive resin combination; It is characterized in that; It contains following optical polymerism unsaturated compound (J); Said optical polymerism unsaturated compound (J) has the structure that the esterification through the hydroxyl of reactions product and multi-anhydride (C) obtains, and (methyl) acryloyl group of the compound (B) that said reaction product makes the compound with beta-diketon position or has a 'beta '-ketoester base and the compound (A) with (methyl) acryloyl group and hydroxyl more than 2 carries out addition and obtains.

It is the above-mentioned alkali-developable photosensitive resin combination of the beta-diketone compound of formula (I) expression that the present invention also provides above-mentioned compound with beta-diketon position.

(in the formula, R ¹The expression carbon number is 1～20 alkyl, R ²Expression R ¹¹, OR ¹¹, COR ¹¹, SR ¹¹, CONR ¹²R ¹³Or CN, R ¹¹, R ¹²And R ¹³Represent independently that respectively hydrogen atom, carbon number are that 1～20 alkyl, carbon number are that 6～30 aryl, carbon number are that 7～30 aryl alkyl or carbon number are 2～20 heterocyclic radical, the hydrogen atom of this alkyl, aryl, aryl alkyl and heterocyclic radical can be further by OR ²¹, COR ²¹, SR ²¹, NR ²²R ²³, CONR ²²R ²³,-NR ²²-OR ²³,-NCOR ²²-OCOR ²³,-C (=N-OR ²¹)-R ²²,-C (=N-OCOR ²¹)-R ²², CN, halogen atom ,-CR ²¹=CR ²²R ²³,-CO-CR ²¹=CR ²²R ²³, carboxyl or epoxy radicals replace R ²¹, R ²²And R ²³Represent independently that respectively hydrogen atom, carbon number are that 1～20 alkyl, carbon number are that 6～30 aryl, carbon number are that 7～30 aryl alkyl or carbon number are 2～20 heterocyclic radical, above-mentioned R ¹¹, R ¹², R ¹³, R ²¹, R ²²And R ²³The methylene of the substituent alkylene moiety of expression can be interrupted 1～5 time by unsaturated link, ehter bond, thioether bond, ester bond, thioester bond, amido link or amino-formate bond; Above-mentioned substituent moieties can have branched building block; It also can be cyclic alkyl; Above-mentioned substituent alkyl end can be a unsaturated link, and R ¹²With R ¹³And R ²²With R ²³Can distinguish and form ring, R together ²Can form ring with the phenyl ring of adjacency.R ³And R ⁴Represent R respectively independently ¹¹, OR ¹¹, SR ¹¹, COR ¹¹, CONR ¹²R ¹³, NR ¹²COR ¹¹, OCOR ¹¹, COOR ¹¹, SCOR ¹¹, OCSR ¹¹, COSR ¹¹, CSOR ¹¹, CN, halogen atom, nitro or hydroxyl, a representes 0～3 integer, b representes 0～4 integer, a and b are 2 when above, each a plurality of substituting group can be different substituting group, the beta-diketon part can be the arbitrary structure in the ketoenol tautomerization body.)

The present invention also provides above-mentioned compound (A) with (methyl) acryloyl group and hydroxyl more than 2 to have the above-mentioned alkali-developable photosensitive resin combination of the structure of the reaction product that makes unsaturated monoacid (E) and epoxy compound (D) carry out addition and obtain; Particularly this epoxy compound (D) is the above-mentioned alkali-developable photosensitive resin combination of the structure of formula (II) expression.

(in the formula; Cy representes that carbon number is 3～10 naphthenic base; X representes that hydrogen atom, phenyl or carbon number are 3～10 naphthenic base; This phenyl or naphthenic base can be that 1～10 alkyl, carbon number are that 1～10 alkoxy or halogen atom replace by carbon number, and Y and Z represent independently that respectively carbon number is that 1～10 alkyl, carbon number are that 1～10 alkoxy, carbon number are 2～10 alkenyl or halogen atom, and this alkyl, alkoxy and alkenyl can be replaced by halogen atom; N representes 0～10 number, and p and r represent 0～4 number respectively independently.)

In addition, the present invention also provides the above-mentioned alkali-developable photosensitive resin combination that further contains Photoepolymerizationinitiater initiater (F) and in above-mentioned alkali-developable photosensitive resin combination, further contains colorant (being also referred to as colorant) painted alkali-developable photosensitive resin combination (G).

In addition, the present invention also provides the beta-diketone compound by above-mentioned general formula (I) expression.

Embodiment

Below, according to preferred embodiment, alkali-developable photosensitive resin combination of the present invention and beta-diketone compound are elaborated.

At first, alkali-developable photosensitive resin combination of the present invention is described.

Alkali-developable photosensitive resin combination of the present invention contains optical polymerism unsaturated compound (J); Said optical polymerism unsaturated compound (J) has the structure that the esterification through the hydroxyl of reactions product and multi-anhydride (C) obtains, and (methyl) acryloyl group of the compound (B) that said reaction product makes the compound with beta-diketon position or has a 'beta '-ketoester base and the compound (A) with (methyl) acryloyl group and hydroxyl more than 2 carries out addition and obtains.

As be used to obtain alkali-developable photosensitive resin combination of the present invention, have the compound at beta-diketon position or have the compound (B) of 'beta '-ketoester base; Can enumerate out 2; 4-pentanedione, 2; 4-acetyl butyryl, 2; 4-heptadione, 1-methoxyl-2; 4-pentanedione, 1-phenyl-1; 3-diacetyl, 1; 3-diphenyl-1; 3-propanedione, methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, butyl-acetoacetate, tert-butyl acetoacetate, acetoacetate-2-methoxyl ethyl ester, acetoacetate-2-Octyl Nitrite, acetoacetate lauryl, acetoacetic acid allyl ester, Propionylacetic acid ethyl ester, propionyl butyl acetate, butyryl methyl acetate, methyl benzoylacetate, ethyl benzoylacetate, benzoyl acetic acid butyl ester, 4; 6-dioxo methyl heptanoate, 5,7-dioxo methyl caprylate, acrylic acid-2-acetoacetyl ethyl ester, methacrylic acid-2-acetoacetyl ethyl ester, benzyl acetoacetate, 1,4-butylene glycol diacetyl acetic ester, 1; 6-hexanediol diacetyl acetic ester, neopentyl glycol diacetyl acetic ester, 2-ethyl-2-butyl-1, ammediol diacetyl acetic ester, cyclohexanedimethanol diacetyl acetic ester, ethoxylation bisphenol-A diacetyl acetic ester, trimethylolpropane tris acetoacetic ester, glycerine triacetyl acetic acid esters, pentaerythrite triacetyl acetic acid esters, pentaerythrite tetrem ethyl sodio acetoacetic ester, two (trimethylolpropane) tetrem ethyl sodio acetoacetic ester, the oligomer that contains acetoacetate groups, ethyl acetoacetate and contain product of transesterification reaction and the oligomer that contains acetoacetate groups or the polymkeric substance that the polymerization through methacrylic acid-2-acetoacetyl ethyl ester obtains of oligomer or the polymkeric substance of hydroxyl.

As above-mentioned compound, can enumerate out the beta-diketone compound with carbazyl of above-mentioned general formula (I) expression with beta-diketon position.If this beta-diketone compound is used as the compound that this has the beta-diketon position, the sensitivity of the alkali-developable photosensitive resin combination that then obtains improves, thereby preferred.

As the R in the above-mentioned general formula (I) ¹, R ¹¹, R ¹², R ¹³, R ²¹, R ²²And R ²³The carbon number of expression is 1～20 alkyl, for example can enumerate out methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, sec-butyl, the tert-butyl group, amyl group, isopentyl, tertiary pentyl, hexyl, heptyl, octyl group, iso-octyl, 2-ethylhexyl, uncle's octyl group, nonyl, different nonyl, decyl, isodecyl, undecyl, dodecyl, myristyl, cetyl, octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexyl methyl, vinyl, allyl, butenyl group, ethinyl, propinyl, methoxy ethyl, ethoxyethyl group, propoxyl group ethyl, amoxy ethyl, octyloxy ethyl, methoxyethoxyethyl, ethoxy ethoxy ethyl, propoxyl group ethoxyethyl group, methoxy-propyl, 2-methoxyl-1-methyl ethoxy etc.As R ¹¹, R ¹², R ¹³, R ²¹, R ²²And R ²³The carbon number of expression is 6～30 aryl, for example can enumerate out phenyl, tolyl, xylyl, ethylphenyl, chlorphenyl, naphthyl, anthryl, phenanthryl, by the substituted phenyl of the abovementioned alkyl more than 1, xenyl, naphthyl, anthryl etc.As R ¹¹, R ¹², R ¹³, R ²¹, R ²²And R ²³The carbon number of expression is 7～30 aryl alkyl, for example can enumerate out benzyl, benzyl chloride base, α-Jia Jibianji, α, α-Er Jiajibianji, phenethyl, phenyl vinyl etc.As R ¹¹, R ¹², R ¹³, R ²¹, R ²²And R ²³The carbon number of expression is 2～20 heterocyclic radical; For example can preferably enumerate out 5～7 yuan of heterocycles such as pyridine radicals, pyrimidine radicals, furyl, thienyl, tetrahydrofuran base, dioxolanyl, dimethyl dioxolanyl, benzoxazole-2-base, THP trtrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, thiazolidinyl, isothiazole alkyl, oxazole alkyl, isoxazole alkyl, piperidyl, piperazinyl, morpholinyl; As carbon number is 3～20 Heterocyclylalkyl, and can enumerating out alkyl such as methyl, ethyl, propyl group, butyl, to be used as above-mentioned carbon number be that 2～20 the illustrative substituting group of heterocyclic radical replaces the group that obtains.As R ¹²With R ¹³The ring that can form together, R ²²With R ²³Ring that can form together and R ²With the ring that the phenyl ring of adjacency can form, for example can enumerate out 5～7 yuan of rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, phenyl ring, piperidine ring, morpholine ring, lactonic ring, lactam nucleus.As replacing R ¹¹, R ¹², R ¹³, R ²¹, R ²²And R ²³Halogen atom and R ³And R ⁴The halogen atom of expression can be enumerated out fluorine, chlorine, bromine, iodine.

In the beta-diketone compound of above-mentioned general formula (I) expression, R ¹For methyl, a are that 0 compound is favourable at manufacture view, thereby preferred, b is that 0 compound or b are 1 and R in addition ⁴For can being that 6～20 acylated compound is excellent aspect the sensitivity by the substituted carbon number of halogen atom; Thereby more preferably; Particularly acyl group is can be all excellent in sensitivity and manufacture view by the compound of methyl or the substituted benzoyl of halogen atom, thereby more preferably.

As the object lesson of the beta-diketone compound with carbazyl of above-mentioned general formula (I) expression, can enumerate out following compound N o.1～No.10, but be not limited to these.

Compound N o.1

Compound N o.2

Compound N o.3

Compound N o.4

Compound N o.5

Compound N o.6

Compound N o.7

Compound N o.8

Compound N o.9

Compound N o.10

The beta-diketone compound of above-mentioned general formula (I) expression does not have particular restriction, for example can suchly shown in following [changing 13] be made through the condensation reaction in the presence of base catalyst by acetyl group carbazole compound and carboxylate.

[changing 13]

As above-mentioned carboxylate, adopt to have corresponding substituting group (=R ¹) ester, its ester moiety does not have particular restriction, preferably uses methyl esters, ethyl ester, propyl ester, butyl ester, isopentyl ester, phenylester etc.

As above-mentioned base catalyst, for example can enumerate out inorganic bases such as NaOH, potassium hydroxide, calcium hydroxide, sodium hydride; Metal alkoxides such as sodium methoxide, caustic alcohol, diisopropyl lithium alkoxide, potassium tert-butoxide; Diethylamine, triethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0]-5-nonene, 1,8-diazabicyclo [5,4,0]-amines such as 7-undecylene; Ammonobase such as Sodamide, lithium diisopropylamine; Ammonium hydroxide salt such as TBAH, benzyltrimethylammonium hydroxide.

As above-mentioned compound with beta-diketon position, when using the beta-diketone compound of above-mentioned general formula (I) expression, as required, can and with the illustrative compound that has the compound at beta-diketon position or have the 'beta '-ketoester base in front.When and with above-mentioned when having the compound at beta-diketon position or having the compound of 'beta '-ketoester base, the total of its consumption is preferably below 1 quality times of consumption of beta-diketone compound of above-mentioned general formula (I) expression.

Among the present invention; The hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of above-claimed cpd (B) is preferably 0.1～1.0 with respect to the ratio of 1 of (methyl) acryloyl group of above-claimed cpd (A); Further be preferably 0.3～1.0; The acid anhydride structure of above-mentioned multi-anhydride (C) is preferably 0.1～1.0 with respect to the ratio of 1 of the hydroxyl of above-mentioned reaction product, further is preferably 0.3～0.9.

Among the present invention; The reaction product that reaction through above-claimed cpd (A) and compound (B) obtains and having in the optical polymerism unsaturated compound (J) of the structure that the esterification of hydroxyl and multi-anhydride (C) through this reaction product obtains; Difference according to the addition type of substituted acryl; Have different isomeride sometimes, even but mixture of isomers also can use, no problem.

As be used to obtain alkali-developable photosensitive resin combination of the present invention, have (methyl) acryloyl group and the compound (A) of hydroxyl more than 2, can enumerate out addition alcohol acid in the polyvalent alcohol of t-1 compound, formula (A-1) expression of the polyol compound of hydroxyl or alkylene oxide with 3～t with the structure of the esterification reaction product of interior hydroxyl and unsaturated monoacid (E) and obtain have 3～t t-1 of hydroxy derivative with the compound of the structure of the esterification reaction product of interior hydroxyl and unsaturated monoacid (E) and make epoxide (D) and the compound of the structure of the reaction product that unsaturated monoacid (E) addition obtains etc.

Z ₁₁(OH) _s(-O-CO-L-OH) _t[-(OL) _w-OH] _u(A-1)

(in the formula, Z ₁₁Expression polyvalent alcohol residue, s, t and u represent to add up to the integer more than 3, and L representes alkane 2 basis such as methylene, ethylidene, propylidene, trimethylene, butylidene, tetramethylene, and w representes 1～15 integer.)

Among the present invention, the carboxyl of above-mentioned unsaturated monoacid (E) is preferably 0.1～1.0 with respect to the ratio of 1 of the epoxy radicals of above-mentioned epoxy compound (D), further is preferably 0.5～1.0.

As the object lesson of above-claimed cpd (A), can enumerate out pentaerythritol triacrylate, dipentaerythritol five acrylic ester, trimethylolethane diacrylate, trimethylolpropane diacrylate, tetra methylol propane triacrylate, 2-hydroxyl-3-acryloxy propyl group acrylic ester and following compound N and o.11 wait.

Compound N o.11

The number of (methyl) acryloyl group in the above-claimed cpd (A) is preferably 2～10, further is preferably 2～6, and the number of hydroxyl is preferably 1～8, further is preferably 1～4.If the number of (methyl) acryloyl group and hydroxyl in these scopes, then can obtain the excellent alkali-developable photosensitive resin combination of development property and adhesiveness.

As above-mentioned epoxy compound (D), for example can enumerate out the compound etc. of the structure of following multi-functional epoxy compound and above-mentioned general formula (A-1) expression.

As above-mentioned multi-functional epoxy compound, for example can enumerate out bisphenol type epoxy compound and diglycidyl ethers etc.As this bisphenol type epoxy compound, for example can enumerate out bisphenol type epoxy compounds such as alkylidene bis-phenol polyglycidyl ether type epoxy resin such as bisphenol type epoxy compound, Bisphenol F type epoxy compound, two (hydroxyphenyl) fluorenes type epoxy compound and A Hydrogenated Bisphenol A type epoxy compound.As above-mentioned diglycidyl ethers, for example can enumerate out ethylene glycol diglycidylether, propylene glycol diglycidylether, 1,4-butanediol diglycidyl ether, 1; 6-hexanediol diglycidyl ether, 1,8-ethohexadiol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2; 2-dimethyl-1, ammediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, TEG diglycidyl ether, six ethylene glycol diglycidylethers, 1,4 cyclohexane dimethanol diglycidyl ether, 1; 1,1-three (glycidyl ether oxygen ylmethyl) propane, 1,1; 1-three (glycidyl ether oxygen ylmethyl) ethane, 1,1,1-three (glycidyl ether oxygen ylmethyl) methane, 1; 1,1,1-four (glycidyl ether oxygen ylmethyl) methane etc.

As above-mentioned multi-functional epoxy compound, can also enumerate out phenol phenolic varnish type epoxy compound, (adjacent-,-, right-) phenylphenol phenolic varnish type epoxy compound, (adjacent-,-, right-) cresols phenolic varnish type epoxy compound, (adjacent-,-, right-) phenolic varnish type epoxy compounds such as halogenation phenol phenolic varnish type epoxy compound, bisphenol-A phenolic varnish type epoxy compound, bisphenol F phenolic varnish type epoxy compound, naphthol novolac varnish type epoxy compound; The phenolic varnish type epoxy compound that the cocondensation through above-mentioned epoxy compound or the polycondensation of above-mentioned epoxy compound and aromatic hydrocarbon form; The addition reaction-type epoxy compound of above-mentioned epoxy compound and dicyclopentadiene; 3,4-epoxy-6-methyl cyclohexane ylmethyl-3 ', 4 '-epoxy-6 '-methylcyclohexanecarboxylic acid ester, 3; 4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, 2,2-two (3; The 4-epoxycyclohexyl) propane, 1-epoxy ethyl-3, alicyclic epoxy compounds such as 4-7-oxa-bicyclo[4.1.0; Ethylene oxidic ester classes such as o-phthalic acid diglycidyl ester, tetrahydrophthalic acid 2-glycidyl ester, dimer acid ethylene oxidic ester; Four glycidyl group diaminodiphenyl-methane, triglycidyl group para-aminophenol, N, glycidyl amines such as N-diglycidylaniline; 1,3-diglycidyl-5, hetero ring type epoxy compounds such as 5-dimethyl hydantoin, three-glycidyl based isocyanate; Dioxide such as dicyclopentadiene dioxide; Naphthalene type epoxy compound, triphenyl methane type epoxy compound, dicyclopentadiene type epoxy compound; Will (adjacent-,-, right-) addition polymer of hydroxy styrenes or (adjacent-,-, right-) hydroxyl of the multipolymer of hydroxy styrenes and ethene and/or propylene carries out glycidyl ether and the epoxy compound that obtains etc.

In these epoxy compounds (D), the compound of the structure of above-mentioned general formula (II) expression is good because of the characteristic as epoxy resin, thereby preferred.

In the above-mentioned general formula (II), the carbon number that Cy representes is 3～10 naphthenic base, for example can enumerate out cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl etc.

In the above-mentioned general formula (II), the carbon number of representing as X is 3～10 naphthenic base, for example can enumerate out the carbon number of representing as Cy and be 3～10 naphthenic base institute illustrative those.Phenyl that X representes or carbon number are that 3～10 naphthenic base can be that 1～10 alkyl, carbon number are that 1～10 alkoxy or halogen atom replace by carbon number; As this substituting group, state after can enumerating out respectively the group institute that representes as Y and Z illustrative those.

The carbon number of representing as Y and Z is 1～10 alkyl, for example can enumerate out methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, sec-butyl, the tert-butyl group, amyl group, isopentyl, tertiary pentyl, hexyl, heptyl, octyl group, iso-octyl, uncle's octyl group, 2-ethylhexyl, nonyl, different nonyl, decyl, isodecyl etc.The carbon number of representing as Y and Z is 1～10 alkoxy, for example can enumerate out methoxyl, ethoxy, propoxyl group, butoxy, methoxy ethyl, ethoxyethyl group, propoxyl group ethyl, methoxyethoxyethyl, ethoxy ethoxy ethyl, propoxyl group ethoxyethyl group, methoxy-propyl etc.The carbon number of representing as Y and Z is 2～10 alkenyl, for example can enumerate out vinyl, allyl, butenyl group, propenyl etc., as the halogen atom that Y and Z represent, can enumerate out fluorine, chlorine, bromine, iodine.

Phenyl that X representes and carbon number be 3～10 naphthenic base can substituted abovementioned alkyl and alkoxy and Y and Z abovementioned alkyl, alkoxy and the alkenyl represented can be replaced by halogen atom; As this halogen atom, can enumerate out fluorine, chlorine, bromine, iodine.For example, as the alkyl that by the substituted carbon number of fluorine atom is 1～10, for example can enumerate out single methyl fluoride, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl etc.

As the epoxy compound (D) of above-mentioned general formula (II) expression among the present invention, for example can enumerate out following compound N o.12～No.20 etc.In the following compound, n representes 0～10 number.

Compound N o.12

Compound N o.13

(among the above-claimed cpd No.13, H ₃C-representes that the position is not specific.)

Compound N o.14

Compound N o.15

In the above-mentioned epoxy compound (D), in the compound of the structure of above-mentioned general formula (II) expression, Cy be cyclohexyl, X be phenyl, p and r be 0 compound because raw material obtains easily and throughput rate is high, thereby preferred.

Among the present invention; Manufacturing approach to the epoxy compound (D) of above-mentioned general formula (II) expression does not have particular restriction; For example can shown in following [changing 24], substituted-phenyl naphthenic one (1) and phenol derivatives be reacted in the presence of acidic catalyst, obtain bisphenol compound (2); Itself and epichlorokydrin are reacted in the presence of alkali, lewis acid or phase transfer catalyst, can easily make.

[changing 24]

Above-mentioned bisphenol compound (2) can utilize present known condition to make, and for example can obtain in 1～40 hour through in the presence of acidic catalyst, under 20～200 ℃ temperature, reacting.

As above-mentioned acidic catalyst, for example can enumerate out sulfonic acid classes such as methane-sulforic acid, benzene sulfonic acid, m-xylene sulfonic acid, p-toluenesulfonic acid, hydroxymethyl sulfonic acid, 2-hydroxyethyl sulfonic acid, hydroxypropyl sulfonic acid, TFMS, sulfosalicylic acid, sulfosalicylic phthalate; Heteropoly acids such as sulfuric acid, anhydrous slufuric acid, oleum, chloro sulfuric acid, fluoro sulfuric acid, hydrochloric acid, hydrogen chloride gas, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid, wolframic acid silicon, wolframic acid phosphorus, highly acid ion exchange resin, atlapulgite, boron trifluoride, anhydrous Aluminum chloride, zinc chloride etc.With respect to above-mentioned substituted-phenyl naphthenic one (1) 100 mass parts, this acidic catalyst preferably uses 0.1～70 mass parts, further preferred 40～80 mass parts of using.

In addition, in order to promote reaction, can also use the mercaptan catalyzer.As this mercaptan catalyzer, for example can enumerate out methyl mercaptan, ethanethio, propyl group mercaptan, butanethiol, octyl mercaptan, lauryl mercaptan, 1, alkyl sulfide alcohols such as 6-ethanthiol; Aromatic mercaptans such as thiophenol, thiocresol class; Sulfydryl organic acids such as TGA (thioglycolic acid), 3-mercaptopropionic acid, sulfydryl undecanoic acid, thiobenzoate; Heterocycle family thio-alcohols such as 2-mercaptobenzothiazole etc.

Above-mentioned reaction can be used present known solvent.As this solvent, for example can enumerate out aromatic hydrocarbon solvents such as toluene, xylene, cumene; Terpenes hydrocarbon ils such as terebinthina, D-citrene, firpene; Mineral spirits, Swazol#310 (Cosmo Guia Hill oil Co., Ltd.), Solvesso#100 paraffinic solvents such as (Exxon Chemical Co., Ltd.); Alcohols solvent such as methyl alcohol, ethanol; Ester solvents such as ethyl acetate; Halogen solvents such as ethylene dichloride, phenixin, chloroform, triclene, methylene chloride, chlorobenzene; Cyclic ether kind solvents such as tetrahydrofuran 、 diox; Ethers, cellosolve kind solvent, ketones solvent, aniline, triethylamine, pyridine 、 diox, acetate, acetonitrile, carbon disulphide etc.

The epoxy compound (D) of above-mentioned general formula (II) expression can be made under present known condition by above-mentioned bisphenol compound (2) and epichlorokydrin.For example, in the presence of alkali, lewis acid or the phase transfer catalyst, 20～100 ℃, particularly react in 30～80 ℃ the scope.When being lower than 20 ℃, react slack-off, need reaction for a long time, when surpassing 100 ℃, subsidiary reaction increases, and is therefore not preferred.

As the alkali that uses in the above-mentioned reaction; For example can enumerate out NaOH, potassium hydroxide, calcium hydroxide etc.; As lewis acid; For example can enumerate out above-mentioned illustrative acidic catalyst, butter of tin, boron trifluoride, titanium tetrachloride, atlapulgite, aluminum chloride, magnesium chloride, potassium permanganate, potassium chromate etc.; As phase transfer catalyst; For example can enumerate out tetramethyl ammonium chloride, TBAB, methyl trioctylphosphine ammonium chloride, methyl three decyl ammonium chlorides, benzyltriethylammoinium chloride, N; N-dimethyl chlorination pyrrolidine, N-ethyl-N-methyl iodate pyrrolidine, N-butyl-N-methyl bromination pyrrolidine, N-benzyl-N-methyl chlorination pyrrolidine, N-ethyl-N-methyl bromination pyrrolidine, N-butyl-N-methyl bromination morpholine, N-butyl-N-methyl iodate morpholine, N-allyl-N-methyl bromination morpholine, N-methyl-N-benzyl piperidinium chloride, N-methyl-N-benzyl bromination piperidines, N, N-dimethyl iodate piperidines, N-methyl-N-ethylpiperidine acetate, N-methyl-N-ethyl iodate piperidines etc.

Consumption for the epichlorokydrin of this reaction does, with respect to 1 of the hydroxyl of bisphenol compound (2), uses more than 1 mole; 2～10 moles scope particularly is for alkali, with respect to 1 of hydroxyl; Use 0.1～2.0 mole, particularly 0.3～1.5 mole, for lewis acid or phase transfer catalyst, with respect to 1 of the hydroxyl of bisphenol compound (2); Use 0.01～10 mole of %, particularly 0.2～5 mole of %.

This reaction can be used illustrative solvent in the manufacturing hurdle of bisphenol compound (2).In addition, also can the epichlorokydrin of surplus be used as solvent.

The unsaturated monoacid (E) that is used to obtain alkali-developable photosensitive resin combination of the present invention uses for the sensitivity that improves this alkali-developable photosensitive resin combination.As so unsaturated monoacid (E), for example can enumerate out acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl meth acrylate-malate, hydroxy ethyl methacrylate-malate, hydroxypropyl methyl acrylic ester-malate, hydroxypropyl acrylate-malate, dicyclopentadiene-malate or have 1 carboxyl and multifunctional (methyl) acrylic ester etc. of (methyl) acryloyl group more than 2.

Have 1 carboxyl and multifunctional (methyl) acrylic ester of (methyl) acryloyl group more than 2 as above-mentioned, for example can through with have 1 hydroxyl in 1 molecule and more than 2 multifunctional (methyl) acrylic ester and dibasic acid anhydride or the carboxylic acid reaction of (methyl) acryloyl group obtain.

Have 1 carboxyl and multifunctional (methyl) acrylic ester of (methyl) acryloyl group more than 2 as above-mentioned, for example can enumerate out following compound N o.21～No.23.

Compound N o.21

Compound N o.22

Compound N o.23

As the multi-anhydride that is used to obtain alkali-developable photosensitive resin combination of the present invention (C), for example can enumerate out methylene THPA monoester anhydrides such as (methyl Himic anhydride) in succinic anhydride, maleic anhydride, trimellitic anhydride, phthalic anhydride, methyl tetrahydrophthalic anhydride, tetrabydrophthalic anhydride, carbic anhydride, methyl carbic anhydride, trialkyl tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, the methyl; 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, pyromellitic acid dianhydride, 3,3 '-4; 4 '-benzophenone tetracarboxylic anhydride, ethylene glycol bis (dehydration trimellitate), 2,2 '-3,3 '-benzophenone tetracarboxylic anhydride, 3,3 ', 4; 4 '-diphenyl tetrasulfonic acid dianhydride, 4,4 '-oxydiphthalic acid dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 5-(2; The 5-dioxotetrahydrofuryl)-and 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3; 4-cyclopentane tetracarboxylic dianhydride, trialkyl tetrabydrophthalic anhydride-maleic anhydride adduct, internal compensation-butane-1,2,3, dianhydrides such as 4-tetracarboxylic anhydride; Glycerine three three acid anhydrides such as (dehydration trimellitates) can be with dianhydride and monoester anhydride combination, wherein preferred especially monoester anhydride.

When the present invention's addition in making through the compound (A) with (methyl) acryloyl group and hydroxyl more than 2 has the compound at beta-diketon position or has the reaction product that the compound (B) of 'beta '-ketoester base obtains; Compound (A) with (methyl) acryloyl group and hydroxyl more than 2 is must composition, and can also in the scope of not damaging effect of the present invention (is below 500 mass parts with respect to compound (A) 100 mass parts), mix this compound (A) (methyl) acryloyl group that has does not in addition have the compound (A ') of hydroxyl to make.Have and make multi-anhydride (C) and the reaction product that so obtains carry out esterification and the content of the optical polymerism unsaturated compound (J) of the structure that obtains does; In alkali-developable photosensitive resin combination of the present invention; Be preferably 1～70 quality %; Further be preferably 20～60 quality %, the acid number of solid constituent is preferably 20～100mgKOH/g, further is preferably the scope of 50～100mgKOH/g.

Have (methyl) acryloyl group and do not have the compound (A ') of hydroxyl as above-mentioned, for example can enumerate out tetramethylol methane tetraacrylate, trimethylolpropane triacrylate, tristane dimethanol diacrylate, dipentaerythritol acrylate, two (trimethylolpropane) tetraacrylate, isocyanuric acid EO modification triacrylate, bisphenol-A EO modification diacrylate, Bisphenol F EO modification diacrylate, tripropylene glycol diacrylate, polypropyleneglycol diacrylate, trimethylolpropane PO modification triacrylate etc.

In the alkali-developable photosensitive resin combination of the present invention; Except that above-mentioned optical polymerism unsaturated compound (J); Can also contain solvent; For example when the content of above-mentioned optical polymerism unsaturated compound (J) was in above-mentioned preferred range, optical polymerism unsaturated compound (J) remainder in addition can use solvent.As the object lesson of this solvent, can enumerate out as after the solvent institute that states illustrative those.In addition, from the synthetic above-mentioned optical polymerism unsaturated compound (J) of (A)～(E) composition the time, the solvent of use can not be removed and former state fixedly is contained in the alkali-developable photosensitive resin combination of the present invention.In addition, (A)～(E) each composition can use a kind, also can mix use more than 2 kinds.

Alkali-developable photosensitive resin combination of the present invention can not add Photoepolymerizationinitiater initiater (F) and use as the alkali-developable photosensitive resin combination; But in order to obtain more highly sensitive resin combination; Can itself and Photoepolymerizationinitiater initiater (F) and solvent be processed the alkali-developable photosensitive resin combination.

The content of the above-mentioned optical polymerism unsaturated compound (J) when having used Photoepolymerizationinitiater initiater (F) in the alkali-developable photosensitive resin combination of the present invention is; Be preferably 30～90 quality % with shared proportional meter in the gross mass of from the alkali-developable photosensitive resin combination, removing the total solid composition after desolvating, further be preferably 40～80 quality %.

As above-mentioned Photoepolymerizationinitiater initiater (F); Can use existing known compound; Can enumerate out for example benzoyl peroxide, 2; 2 '-azoisobutyronitrile, Benzophenone, phenylbiphenylyl ketone, 1-hydroxyl-1-2-benzoyl-cyclohexane, benzil, benzil dimethyl ketal, 1-benzyl-1-dimethylamino-1-(4 '-morpholino benzoyl) propane, 2-morpholinyl-2-(4 '-methyl mercapto) benzoyl propane, thioxanthones, 1-chloro-4-propoxyl group thioxanthones, isopropyl thioxanthone, diethyl thioxanthone, EAQ, 4-benzoyl-4 '-methyldiphenyl base sulfide, styrax butyl ether, 2-hydroxyl-2-benzoyl propane, 2-hydroxyl-2-(4 '-isopropyl) benzoyl propane, 4-butyl benzene formoxyl methenyl choloride, 4-phenoxy group benzoyl methylene chloride, benzoyl methyl formate, 1; 7-two (9 '-acridinyl) heptane, 9-normal-butyl-3; 6-two (2 '-morpholino isobutyryl) carbazole, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino third-1-ketone, p-methoxyphenyl-2; 4-two (three chloro methyl)-s-triazine, 2-methyl-4; 6-two (three chloro methyl)-s-triazine, 2-phenyl-4; 6-two (three chloro methyl)-s-triazine, 2-naphthyl-4; 6-two (three chloro methyl)-s-triazine, 2-(to the butyl phenyl ether vinyl)-s-triazine, 2-(to the butyl phenyl ether vinyl)-5-trichloromethyl-1; 3; 4-oxadiazole, 9-phenylacridine, 9,10-dimethylbiphenyl azophenlyene, benzophenone/michaelis ketone, six aryl bisglyoxaline/mercaptobenzimidazoles, thioxanthones/amines, two (2,4; The 6-trimethylbenzoyl)-phenylphosphine oxide, and the compound of putting down in writing in TOHKEMY 2000-80068 communique, TOHKEMY 2001-233842 communique, TOHKEMY 2005-97141 communique, Japan special table 2006-516246 communique, No. 3860170 communique of Jap.P., No. 3798008 communique of Jap.P., the WO2006/018973 communique etc.Wherein, preferred formula (a) or (c) compound of expression.

(in the above-mentioned formula, R ⁷¹, R ⁷²And R ⁷³Represent R, OR, COR, SR, CONRR ' or CN respectively independently; R and R ' represent alkyl, aryl, aryl alkyl or heterocyclic radical respectively independently; They can be replaced by halogen atom and/or heterocyclic radical, and wherein, the alkylene moiety in alkyl and the aryl alkyl can be interrupted by unsaturated link, ehter bond, thioether bond or ester bond; R and R ' can form ring, R together ⁷⁴Expression halogen atom or alkyl, R ⁷⁵The substituting group of expression hydrogen atom, halogen atom, alkyl or formula (b) expression, g representes 0～4 integer, g is 2 when above, a plurality of R ⁷⁴It can be different groups.)

(in the above-mentioned formula, ring M representes naphthenic ring, aromatic rings or heterocycle, X ⁷³Expression halogen atom or alkyl, Y ⁷¹Expression oxygen atom, sulphur atom or selenium atom, Z ⁷¹The expression carbon number is 1～5 alkylidene, and h representes 0～4 integer, and h is 2 when above, a plurality of X ⁷³It can be different groups.)

(in the above-mentioned formula, R ⁵¹And R ⁵²Represent R respectively independently ⁶¹, OR ⁶¹, COR ⁶¹, SR ⁶¹, CONR ⁶²R ⁶³Or CN, R ⁶¹, R ⁶²And R ⁶³Represent independently that respectively hydrogen atom, carbon number are that 1～20 alkyl, carbon number are that 6～30 aryl, carbon number are that 7～30 aryl alkyl or carbon number are 2～20 heterocyclic radical, the hydrogen atom of this alkyl, aryl, aryl alkyl and heterocyclic radical can be further by OR ⁸¹, COR ⁸¹, SR ⁸¹, NR ⁸²R ⁸³, CONR ⁸²R ⁸³,-NR ⁸²-OR ⁸³,-NCOR ⁸²-OCOR ⁸³,-C (=N-OR ⁸¹)-R ⁸²,-C (=N-OCOR ⁸¹)-R ⁸², CN, halogen atom ,-CR ⁸¹=CR ⁸²R ⁸³,-CO-CR ⁸¹=CR ⁸²R ⁸³, carboxyl, epoxy radicals replace R ⁸¹, R ⁸²And R ⁸³Represent independently that respectively hydrogen atom, carbon number are that 1～20 alkyl, carbon number are that 6～30 aryl, carbon number are that 7～30 aryl alkyl or carbon number are 2～20 heterocyclic radical, above-mentioned R ⁶¹, R ⁶², R ⁶³, R ⁸¹, R ⁸²And R ⁸³The methylene of the substituent alkylene moiety of expression can be interrupted 1～5 time by unsaturated link, ehter bond, thioether bond, ester bond, thioester bond, amido link or amino-formate bond; Above-mentioned substituent moieties can have branched building block; It also can be cyclic alkyl; Above-mentioned substituent alkyl end can be a unsaturated link, and R ⁶²With R ⁶³And R ⁸²With R ⁸³Can distinguish and form ring together.R ⁵³And R ⁵⁴Represent R respectively independently ⁶¹, OR ⁶¹, SR ⁶¹, COR ⁶¹, CONR ⁶²R ⁶³, NR ⁶²COR ⁶¹, OCOR ⁶¹, COOR ⁶¹, SCOR ⁶¹, OCSR ⁶¹, COSR ⁶¹, CSOR ⁶¹, CN, halogen atom or hydroxyl, c and d represent 0～4 respectively independently.X ⁵¹Expression directly combines or CO, X ⁵²Expression oxygen atom, sulphur atom, selenium atom, CR ⁹¹R ⁹², CO, NR ⁹³Or PR ⁹⁴, R ⁹¹, R ⁹², R ⁹³And R ⁹⁴Represent R respectively independently ⁶¹, OR ⁶¹, COR ⁶¹, SR ⁶¹, CONR ⁶²R ⁶³Or CN, R ⁵³Can be situated between by-X ⁵²1 carbon atom of the phenyl ring of-adjacency combines to form ring structure, or R ⁵³And R ⁵⁴Can form ring, R together ⁹¹, R ⁹³And R ⁹⁴Form ring with arbitrary phenyl ring of adjacency independently respectively.)

In the alkali-developable photosensitive resin combination of the present invention; The content of above-mentioned Photoepolymerizationinitiater initiater (F) does; Be preferably 0.01～20 quality % with shared proportional meter in the gross mass of from the alkali-developable photosensitive resin combination, removing the total solid composition after desolvating, further be preferably 0.05～20 quality %.Above-mentioned Photoepolymerizationinitiater initiater (F) can use a kind, also can mix use more than 2 kinds.

As the solvent that contains in the alkali-developable photosensitive resin combination of the present invention; Usually so long as can dissolve or disperse the solvent of above-mentioned each composition to get final product; Do not have particular restriction, for example can enumerate out ketones such as MEK, methyl amyl ketone, metacetone, acetone, methyl isopropyl Ketone, methyl isobutyl ketone, cyclohexanone; Ether 、 diox, tetrahydrofuran, 1,2-dimethoxy-ethane, 1, ether solvents such as 2-diethoxyethane, DPG dimethyl ether; Esters solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate; Cellosolve kind solvents such as glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol methyl ether acetate; Methyl alcohol, ethanol, isopropyl alcohol or n-propanol, isobutyl alcohol or alcohols solvents such as normal butyl alcohol, amylalcohol; BTX kind solvents such as benzene,toluene,xylene; Aliphatic hydrocarbon kind solvents such as hexane, heptane, octane, cyclohexane; Terpenes hydrocarbon ils such as terebinthina, D-citrene, firpene; Mineral spirits, Swazol#310 (Cosmo Guia Hill oil Co., Ltd.), Solvesso#100 paraffinic solvents such as (Exxon Chemical Co., Ltd.); Halogenated aliphatic varsols such as phenixin, chloroform, triclene, methylene chloride; Halogenated aromatic varsols such as chlorobenzene; Carbitol kind solvent, aniline, triethylamine, pyridine, acetate, propionitrile, carbon disulphide, N, dinethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide, water etc.Wherein, preferred ketone or cellosolve kind solvent.These solvents can use a kind, also can mix use more than 2 kinds.

In the alkali-developable photosensitive resin combination of the present invention,, be prepared into total solid constituent concentration shared in the alkali-developable photosensitive resin combination and be preferably 5～40 quality %, further be preferably 10～30 quality % and get final product about the content of above-mentioned solvent.

Painted alkali-developable photosensitive resin combination of the present invention obtains through in above-mentioned alkali-developable photosensitive resin combination, containing colorant (G).As this colorant, can enumerate out pigment, dyestuff, natural colouring matter etc.These colorants can use separately, or mix more than 2 kinds and use.

Pigment as in painted alkali-developable photosensitive resin combination of the present invention, using as colorant (G) can use the known pigment of in the manufacturing of present color filter, using arbitrarily.Object lesson with color index (C.I.) numbering expression organic pigment.In addition, in following complete list, " x " expression be can be from optional integer the C.I. numbering.

Alizarol saphirol:

<C.I>1，1:2，1:x，9:x，15，15:1，15:2，15:3，15:4，15:5，15:6，16，24，24:x，56，60，61，62

Naphthol green:

<C.I>1，1:x，2，2:x，4，7，10，36

Pigment orange:

<C.I>2，5，13，16，17:1，31，34，36，38，43，46，48，49，51，52，59，60，61，62，64

Paratonere:

<C.I>1，2，3，4，5，6，7，9，10，14，17，22，23，31，38，41，48:1，48:2，48:3，48:4，49，49:1，49:2，52:1，52:2，53:1，57:1，60:1，63:1，66，67，81:1，81:3，81:x，83，88，90，112，119，122，123，144，146，149，166，168，169，170，171，172，175，176，177，178，179，184，185，187，188，190，200，202，206，207，208，209，210，216，224，226

Pigment violet:

<C.I>1，1:x，3，3:3，3:x，5:1，19，23，27，32，42

Pigment yellow:

<C.I>1，3，12，13，14，16，17，24，55，60，65，73，74，81，83，93，95，97，98，100，101，104，106，108，109，110，113，114，116，117，119，120，126，127，128，129，138，139，150，151，152，153，154，156，175

As black pigment, can enumerate out carbon black #2400, #2350, #2300, #2200, #1000, #980, #970, #960, #950, #900, #850, MCF88, #650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, #4000, #4010, #55, #52, #50, #47, #45, #44, #40, #33, #32, #30, #20, #10, #5, CF9, #3050, #3150, #3250, #3750, #3950, Dia Black A, Dia Black N220M, Dia Black N234, Dia Black I, Dia Black LI, Dia Black LH, Dia Black N339, Dia Black SH, Dia Black SHA, Dia Black LH, Dia Black H, Dia Black HA, Dia Black SF, Dia Black N550M, Dia Black E, Dia Black G, Dia Black R, Dia Black N760M, the Dia Black LR of Mitsubishi Chemical Ind's system; The carbon black Thermax N990 of Cancarb corporate system, N991, N907, N908, N990, N991, N908; The carbon black ASAHI#80 of AsahiCarbon corporate system, ASAHI#70, ASAHI#70L, ASAHI F-200, ASAHI#66, ASAHI#66U, ASAHI#50, ASAHI#35, ASAHI#15, ASAHIThermal; The carbon black ColorBlackFw200 of Degussa corporate system, ColorBlackFw2, ColorBlackFw2V, ColorBlackFw1, ColorBlackFw18, ColorBlackS170, ColorBlackS160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, SpecialBlack250, SpecialBlack350, PrintexU, PrintexV, Printex140U, Printex140V (being trade name) etc.

As other pigment, can use nitroso compound, nitro compound, azo-compound, diazo-compounds, oxa anthracene compound, quinoline compound, anthraquinone compounds, coumarin compound, phthalocyanine compound, isoindoline ketonic compound, isoindoline compounds, quinoline a word used for translation ketonic compound, two also anthrone compound, purple cyclic ketones (perynone) compound, perylene compound, diketopyrrolopyrroles compound, thioindigo compound, dioxazine compound, triphenyl methane compound, quinophthalone compound, naphthalene tetracarboxylic acid; The metal complex of azo dyes, cyanine dyes; Mordant pigment; Carbon black that obtains with oven process, channel process, pyrolysis method or acetylene black, Ketjen black or carbon black such as dim; Above-mentioned carbon black is carried out that acidity or basic surface are handled and the material that obtains; Graphite, Graphon, activated charcoal, carbon fibre, CNT, screw carbon fibre, Carbon Nanohorn, carbon aerogels, fullerene, nigrosine, pigment black 7, titanium are deceived; Hydrophobic resin; Chrome oxide green; Milori blue; Cobalt green; Cobalt blue; Manganese system; Ferrocyanide; The phosphate ultramarine; General Shandong soil is blue; Ultramarine; Cerulean blue; Viridian; Emerald green; Lead sulfate; Chrome yellow; Zinc yellow; Iron oxide (red iron oxide (III)); Cadmium red; Synthetic iron black; Umber (amber); Iron oxide; Titanium dioxide; Lime carbonate; Magnesium carbonate; Silicon dioxide; Aluminium oxide; The cobalt class; Talcum powder; Chromate; Various metal sulfates; Sulfide; Organic pigment or inorganic pigments such as selenide.These pigment can use separately, or multiple mixing is used.

Dyestuff as above-mentioned colorant (G) use; For example can enumerate out dyestuffs such as azo dyes, anthraquinone dye, indigoid dye, triarylmethane dye, xanthene dye, alizarin dyes, acridine dye, stilbene dye, thiazole dye, naphthol dye, quinoline dye, nitro dye, indamines dyestuff 、 oxazine dye, phthalocyanine dye, cyanine dye etc.; They can use a kind, or mix more than 2 kinds and use.

In the painted alkali-developable photosensitive resin combination of the present invention; The content of above-mentioned colorant (G) does; Be preferably 0.5～70 quality % with shared proportional meter in the gross mass of from painted alkali-developable photosensitive resin combination, removing the total solid composition after desolvating, further be preferably 5～60 quality %.

In alkali-developable photosensitive resin combination of the present invention and the painted alkali-developable photosensitive resin combination, can be further also with the monomer with unsaturated link, chain-transferring agent, surfactant etc.

As above-mentioned monomer with unsaturated link; For example can enumerate out acrylic acid-2-hydroxyl ethyl ester, acrylic acid-2-hydroxypropyl acrylate, isobutyl acrylate, acrylic acid n-octyl, Isooctyl acrylate monomer, acrylic acid ester in the different ninth of the ten Heavenly Stems, acrylic acid stearyl, acrylic acid methoxyl ethyl ester, acrylic acid dimethylamino ethyl ester, zinc acrylate resin, 1,6 hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacry-late, methacrylic acid-2-hydroxypropyl acrylate, butyl methacrylate, metering system tert-butyl acrylate, cyclohexyl methacrylate, trimethylol-propane trimethacrylate, dipentaerythritol five acrylic ester, dipentaerythritol acrylate, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, tristane dihydroxymethyl diacrylate etc.

In (painted) of the present invention alkali-developable photosensitive resin combination; Above-mentioned content with monomer of unsaturated link does; Be preferably 0.01～50 quality % with shared proportional meter in the gross mass of from the alkali-developable photosensitive resin combination, removing the total solid composition after desolvating, further be preferably 10～40 quality %.They can use a kind, also can mix use more than 2 kinds.

As above-mentioned chain-transferring agent; For example can enumerate out TGA, thiomalic acid, thiosalicylic acid, 2 mercaptopropionic acid, 3-mercaptopropionic acid, 3-sulfydryl butyric acid, N-(2-mercapto radical propionyl group) glycocoll, 2-sulfydryl nicotinic acid, 3-[N-(2-mercaptoethyl) carbamyl] propionic acid, 3-[N-(2-mercaptoethyl) amino] propionic acid, N-(3-mercapto radical propionyl group) alanine, mistabrom, 3-sulfydryl propane sulfonic acid, 4-sulfydryl fourth sulfonic acid, dodecyl (4-methyl mercapto) phenyl ether, 2 mercapto ethanol, 3-sulfydryl-1, iodate alkylate such as 2-propylene glycol, 1-sulfydryl-2-propyl alcohol, 3-sulfydryl-2-butanols, mercapto-phenol, 2-mercaptoethyl amine, 2-mercaptoimidazole, 2-sulfydryl-3-pyridol, 2-mercaptobenzothiazole, TGA, trimethylolpropane tris (3-mercaptopropionic acid ester), pentaerythrite four sulfhydryl compounds such as (3-mercaptopropionic acid esters), the disulfide that this sulfhydryl compound oxidation is obtained, iodoacetic acid, iodopropionic acid, ethylene iodohydrin, 2-iodine ethyl sulfonic acid, 3-iodine propane sulfonic acid etc.They can use a kind, or mix more than 2 kinds and use.

As above-mentioned surfactant; For example can use surfactants such as non-ionic surfactants such as cationic surfactant, polyethylene glycol alkyl ether, cithrol, sorbitan fatty acid ester, glycerine monofatty ester, amphoteric surfactant, silicone based surfactant such as anionic surface active agent such as fluorine class surfactant, higher fatty acid alkali salt, alkyl sulfonate, alkyl sulfate, higher amines halate, quaternary ammonium salt such as perfluoralkyl phosphate, perfluoroalkyl carboxylate; They can use a kind, or mix more than 2 kinds and use.

In alkali-developable photosensitive resin combination of the present invention and painted alkali-developable photosensitive resin combination, also can improve the characteristic of solidfied material through further use thermoplastic organic polymer.As this thermoplastic organic polymer, for example can enumerate out polystyrene, polymethylmethacrylate, methyl methacrylate-ethyl acrylate copolymer, gather (methyl) acrylic acid, styrene-(methyl) acrylic copolymer, (methyl) acrylic acid-methylmethacrylate copolymer, polyvinyl butyral, cellulose esters, polyacrylamide, saturated polyester etc.They can use a kind, or mix more than 2 kinds and use.

In alkali-developable photosensitive resin combination of the present invention and painted alkali-developable photosensitive resin combination, can add thermal polymerization inhibitors such as anisole, quinhydrones, pyrocatechol, tert-butyl catechol, phenothiazine as required; Plastifier; Adhesion promotor; Filling agent; Foam-breaking agent; Spreading agent; Levelling agent; Silane coupling agent; The additive that fire retardant etc. are commonly used.They can use to mix more than a kind or 2 kinds and use.

Alkali-developable photosensitive resin combination of the present invention and painted alkali-developable photosensitive resin combination can utilize rotary coating machine, rod to be coated with machine, roll coater, curtain formula coating machine, various serigraphy, ink jet printing, the known means of impregnating and be applied on the support substrate such as metal, paper, plastics, glass.Also can temporarily after implementing on the support substrate such as film, be transferred on other support substrate, to the not restriction of its application process.

(painted) of the present invention alkali-developable photosensitive resin combination main and above-mentioned solvent, above-mentioned Photoepolymerizationinitiater initiater and coloring material for mixing; Processing (painted) alkali-developable photosensitive resin combination uses; Purposes that should (painted) alkali-developable photosensitive resin combination does not have particular restriction, can be used for photo-curable coating, Photocurable adhesive agent, galley, printed wiring board with photoresist, be used for pixel portions or the various uses such as formation of projections for liquid crystal division alignment control of the color filter of plasma scope, el panel, video camera, LCD.

The light source of the active light that uses when alkali-developable photosensitive resin combination of the present invention and painted alkali-developable photosensitive resin combination are solidified; The light source of the light that sends wavelength 300～450nm be can use, ultrahigh pressure mercury lamp, mercury vapor arc, carbon arc, xenon arc etc. for example can be used.

Then, beta-diketone compound of the present invention is described.

Beta-diketone compound of the present invention is the new compound of above-mentioned general formula (I) expression; Its intermedium as the raw material of above-mentioned (painted) alkali-developable photosensitive resin combination is useful, can be used for catalyzer, detector, fluorescent material, oximes initiating agent raw material etc. in addition.In addition, the metal complex that contains beta-diketone compound of the present invention can also be used for the purposes of relative broad ranges such as metal alkoxide photoresist material, MOD material.

With beta-diketone compound of the present invention is that the beta-diketone compound of raw material formula (III) expression of deriving also can be used for the purposes described in the last paragraph.

(in the formula, R ¹, R ², R ³, R ⁴, a, b be identical with implication in the above-mentioned general formula (I), A ¹The substituting group of expression formula (IV) expression, A ²The substituting group of expression hydrogen atom or formula (IV) expression is worked as A ¹And A ²In at least one side when being hydrogen atom, the beta-diketon part can be the arbitrary structure in the ketoenol tautomerization body.)

(in the formula, R ³¹, R ³²And R ³³Represent independently that respectively hydrogen atom, carbon number are that 1～20 alkyl or carbon number are 6～30 aryl, R ³⁴Expression hydrogen atom, hydroxyl, carbon number are that 1～20 alkyl, carbon number are that 6～30 aryl, carbon number are that 7～30 aryl alkyl, carbon number are that 1～20 alkoxy, carbon number are that 6～30 aryloxy group or carbon number are 7～30 alkoxy aryl.)

In the above-mentioned general formula (IV), as R ³¹, R ³², R ³³And R ³⁴The carbon number of expression is that 1～20 alkyl and carbon number are 6～30 aryl and R ³⁴The carbon number of expression is 7～30 aryl alkyl, can enumerate out illustrative substituting group in the above-mentioned general formula (I).As R ³⁴The carbon number of expression is 1～20 alkoxy, for example can enumerate out methoxyl, methoxymethoxy, methoxy ethoxy methoxyl, methylthiomethyl, ethoxy, vinyl oxygen base, propoxyl group, isopropoxy, butoxy, isobutoxy, tert-butoxy, t-butyldimethylsilyl oxygen base, tert-butoxycarbonyl methoxyl, amoxy, isoamoxy, uncle's amoxy, neopentyl oxygen, own oxygen base, cyclohexyloxy, dissident's oxygen base, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy, ninth of the ten Heavenly Stems oxygen base, last of the ten Heavenly stems oxygen base, undecane oxygen base, dodecyloxy, tridecane oxygen base, different tridecane oxygen base, myristyl oxygen base, palmityl oxygen base, stearyl oxygen base etc.As R ³⁴The carbon number of expression is 6～30 aryloxy group, for example can enumerate out phenoxy group, toloxyl, xylyloxy, ethyl phenoxy group, chlorophenoxy, naphthoxy, anthracene oxygen base, luxuriant and rich with fragrance oxygen base, the phenoxy group by after abovementioned alkyl more than 1 and the alkoxy replacement, biphenylyloxy, naphthoxy, anthracene oxygen base etc.As carbon number is 7～30 alkoxy aryl, for example can enumerate out benzyl oxygen base, benzyl chloride base oxygen base, α-Jia Jibianji oxygen base, α, α-Er Jiajibianji oxygen base, phenyl ethoxy, phenyl vinyl oxygen base etc.

A in the compound of above-mentioned general formula (I) expression and the above-mentioned general formula (III) ²A in beta-diketone compound that obtains with the compound addition that contains (methyl) acryloyl group in the position of the methylene of 2 carbonyl clampings of beta-diketon part for the compound of hydrogen atom or the above-mentioned general formula (III) ¹And A ²The substituent beta-diketone compound that is above-mentioned general formula (IV) expression is useful as the Photoepolymerizationinitiater initiater with polymerizable compound of ethylenic unsaturated link, can use as the Photoepolymerizationinitiater initiater that uses in the photosensitive composite.This photosensitive composite contains the above-mentioned Photoepolymerizationinitiater initiater that is made up of beta-diketone compound of the present invention and has the polymerizable compound of ethylenic unsaturated link and the mineral compound that uses as required and/or colorant and solvent etc. composition arbitrarily; When above-mentioned compound with ethylenic unsaturated link is the alkali-developable compound, can be used as the alkali-developable photosensitive resin combination.

Above-mentioned beta-diketone compound with carbazyl is highly sensitive to light, for example, this compound with contain (methyl) even the compound of acryloyl group reaction and the Photoepolymerizationinitiater initiater that obtains also can be brought into play the function of initiating agent under a spot of light.

The beta-diketone compound of above-mentioned general formula (I) expression reacts with the compound that contains (methyl) acryloyl group efficiently, thereby preferred the use.A in the above-mentioned general formula (III) ¹And A ²The substituent beta-diketone compound that is above-mentioned general formula (IV) expression can use as Photoepolymerizationinitiater initiater, R in the particularly above-mentioned general formula (IV) ³¹And R ³²Be hydrogen atom, R ³³Be hydrogen atom or methyl, R ³⁴For carbon number be 1～4 alkoxy compound since raw material obtain easily and also have superiority at manufacture view, thereby preferred.

As the object lesson of the beta-diketone compound with carbazyl of above-mentioned general formula (III) expression, can enumerate out following compound N o.24～No.26.

Compound N o.24

Compound N o.25

Compound N o.26

A in the above-mentioned general formula (III) ¹And A ²The substituent beta-diketone compound 2 that is above-mentioned general formula (IV) expression for example can be such shown in following [changing 36], contains beta-diketone compound (beta-diketone compound 1) that substituted acryl compound and above-mentioned general formula (I) represent and react and make through under base catalyst, making to get.

[changing 36]

In addition, the middle A of the compound of above-mentioned general formula (I) expression or above-mentioned general formula (III) in the beta-diketone compound ²For the compound of hydrogen atom carries out addition in the position of the methylene of 2 carbonyl clampings of beta-diketon part with the compound that contains (methyl) acryloyl group, can obtain beta-diketone compound thus.This addition reaction makes beta-diketone compound and the compound that contains (methyl) acryloyl group react in the presence of base catalyst.

Compound as (methyl) acryloyl group of above-mentioned containing; For example can also enumerate out unsaturated monacid esters such as acrylic ester, methacrylate, butenoate, cinnamate, sorbate; As its ester moiety, for example can enumerate out methyl esters, ethyl ester, propyl ester, butyl ester, isopentyl ester etc.In addition, can also enumerate out the EO modification diacrylate of tetramethylol methane tetraacrylate, trimethylolpropane triacrylate, tristane dimethanol diacrylate, dipentaerythritol acrylate, two (trimethylolpropane) tetraacrylate, isocyanuric acid EO modification triacrylate, bisphenol-A, EO modification diacrylate, tripropylene glycol diacrylate, polypropyleneglycol diacrylate, trimethylolpropane PO modification triacrylate, pentaerythritol triacrylate, dipentaerythritol five acrylic ester, trimethylolethane diacrylate, trimethylolpropane diacrylate, tetra methylol propane triacrylate and the 2-hydroxyl-3-acryloxy propyl group acrylic ester of Bisphenol F etc.

As above-mentioned base catalyst, the illustrative base catalyst of base catalyst that uses in the time of can enumerating out as beta-diketone compound 1 manufacturing.

In the beta-diketone compound that obtains through above-mentioned reaction, there is different isomeride in the difference according to the addition type of substituted acryl, even but mixture of isomers also can use, no problem.

Compound or the middle A of above-mentioned general formula (III) for above-mentioned general formula (I) expression ²For the compound of hydrogen atom is R ¹For methyl, a are 0, R ⁴For can by the substituted carbon number of halogen atom be 6～20 acylated compound and above-mentioned containing (methyl) acryloyl group compound be the beta-diketone compound that the addition of (methyl) acrylic ester obtains; Because the progress of above-mentioned addition reaction is fast; Make easily; And it is at long wavelength side absorption is arranged, have high initiating agent function, thereby preferred especially.

Through containing the Photoepolymerizationinitiater initiater that constitutes by above-mentioned beta-diketone compound and having composition arbitrarily such as the polymerizable compound of ethylenic unsaturated link, the mineral compound that uses as required and/or colorant and solvent etc., can process photosensitive composite.

As above-mentioned polymerizable compound with ethylenic unsaturated link; There is not particular restriction; Can adopt those that in the past in photosensitive composite, used, for example can enumerate out unsaturated fatty hydrocarbons such as ethene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene, tetrafluoroethene; (methyl) acrylic acid, α-Lv Daibingxisuan, itaconic acid, maleic acid, citraconic acid, fumaric acid, Na Dike acid, crotonic acid, iso-crotonic acid, vinyl acetate, allyl acetate, cinnamic acid, sorbic acid, mesaconic acid, trimellitic acid, PMA, 2; 2 '-3; 3 '-benzophenone tetrabasic carboxylic acid, 3; 3 '-4,4 '-benzophenone tetrabasic carboxylic acid, mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester, ω-carboxyl polycaprolactone list (methyl) acrylic ester etc. have list (methyl) acrylic ester, hydroxyethyl (methyl) acrylic ester-malate, hydroxypropyl (methyl) acrylic ester-malate, the bicyclopentadiene-malate of the polymkeric substance of carboxyl and hydroxyl or have 1 carboxyl and the unsaturated polyprotonic acids such as multifunctional (methyl) acrylic ester of (methyl) acryloyl group more than 2 at two ends; (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid-2-hydroxy propyl ester, (methyl) glycidyl acrylate, following compound N o.27～No.30, (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) stearyl acrylate ester, (methyl) lauryl acrylate, (methyl) acrylic acid methoxyl ethyl ester, (methyl) acrylic acid dimethylamino methyl esters, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic-amino propyl ester, (methyl) acrylic acid dimethylamino propyl ester, (methyl) acrylic acid ethoxy ethyl ester, (methyl) acrylic acid gather (ethoxy) ethyl ester, (methyl) acrylic acid butoxy ethoxy ethyl ester, (methyl) EHA, (methyl) acrylic acid phenoxy ethyl, (methyl) acrylic acid tetrahydrofuran ester, (methyl) acrylic acid vinyl esters, (methyl) allyl acrylate, (methyl) benzyl acrylate, ethylene glycol bisthioglycolate (methyl) acrylic ester, diethylene glycol two (methyl) acrylic ester, triethylene glycol two (methyl) acrylic ester, polyglycol two (methyl) acrylic ester, propylene glycol two (methyl) acrylic ester, 1; 4-butylene glycol two (methyl) acrylic ester, 1, the ester of unsaturated monoacid such as 6-hexanediol two (methyl) acrylic ester, trimethylolethane trimethacrylate (methyl) acrylic ester, trimethylolpropane tris (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester, pentaerythrite five (methyl) acrylic ester, pentaerythrite four (methyl) acrylic ester, pentaerythrite three (methyl) acrylic ester, tristane dihydroxymethyl two (methyl) acrylic ester, three [(methyl) acryloyl group ethyl] isocyanuric acid ester, polyester (methyl) acrylate oligomer and polyvalent alcohol or polyhydric phenol; The slaine of unsaturated polyprotonic acids such as (methyl) zinc acrylate resin, (methyl) acrylic acid magnesium; Maleic anhydride, itaconic anhydride, citraconic anhydride, methyl tetrahydrophthalic anhydride, tetrabydrophthalic anhydride, trialkyl tetrabydrophthalic anhydride, 5-(2; The 5-dioxotetrahydrofuryl)-and 3-methyl-3-cyclohexene-1, the acid anhydrides of unsaturated polyprotonic acids such as 2-dicarboxylic anhydride, trialkyl tetrabydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methyl carbic anhydride; The acid amides of unsaturated monoacid such as two (methyl) acrylic amides of (methyl) acrylic amide, di-2-ethylhexylphosphine oxide (methyl) acrylic amide, Diethylenetriamine three (methyl) acrylic amide, xylylene, alpha-chloro acrylic amide, N-2-hydroxyethyl (methyl) acrylic amide and polyamine; Unsaturated aldehydes such as acryl aldehyde; Unsaturated nitriles such as (methyl) vinyl cyanide, α-Lv Daibingxijing, vinylidene dinitrile, allyl cyanide; Unsaturated aromatics such as styrene, 4-methyl styrene, 4-ethyl styrene, 4-methoxy styrene, 4-hydroxy styrenes, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinyl benzoic acid, vinylphenol, vinyl sulfonic acid, 4-vinylbenzenesulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidol ether; Beta-unsaturated ketones such as methyl vinyl ketone; Unsaturated amine compounds such as vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl piperidines; Vinyl alcohol such as allyl alcohol, crotonyl alcohol; Vinyl ether such as vinyl methyl ether, EVE, n-butyl vinyl ether, IVE, allyl glycidyl ether; Unsaturated acid imides such as maleimide, N-phenylmaleimide, N-cyclohexyl maleimide; Indenes classes such as indenes, 1-methyl indenes; Aliphatics conjugated dienes such as 1,3-butadiene, isoprene, chlorbutadiene; Polystyrene, gather (methyl) methyl acrylate, gather (methyl) n-butyl acrylate, have the macromonomer class of list (methyl) acryloyl group at the end of polymer molecular chains such as polysiloxane; The vinyl monomer of vinyl chloride, vinylidene chloride, succinic acid divinyl ester, diallyl phthalate, TAP, cyanacrylate, vinyl thioether, vinyl imidazole, Yi Xi Ji oxazole, VCz, vinyl pyrrolidone, vinylpyridine, hydroxyl and the vinyl urethane compound of polyisocyanate compounds, the vinyl monomer of hydroxyl and the vinyl epoxy compound of polyepoxides.Wherein, For list (methyl) acrylic ester that has the polymkeric substance of carboxyl and hydroxyl at two ends, have the ester of 1 carboxyl and multifunctional (methyl) acrylic ester of (methyl) acryloyl group more than 2, unsaturated monoacid and polyvalent alcohol or polyhydric phenol, the Photoepolymerizationinitiater initiater that constitutes with beta-diketone compound of the present invention is fit to.These polymerizable compounds can use separately or mix use more than 2 kinds, and when mixing use more than 2 kinds, can be in advance with they copolymerization, and process multipolymer and use.

Compound N o.27

Compound N o.28

As above-mentioned polymerizable compound with ethylenic unsaturated link, can also use alkali-developable compound with ethylenic unsaturated link, above-mentioned photosensitive composite is processed the alkali-developable photosensitive resin combination.Have the alkali-developable compound of ethylenic unsaturated link as this, for example can use acrylic ester multipolymer or phenol and/or cresols phenolic resin varnish, have the polyphenylene methane type epoxy resin of multi-functional epoxy base and epoxy compound such as epoxy compound and the unsaturated monoacid of formula (V) expression had an effect after again with the multi-anhydride resulting resin of having an effect.Wherein, epoxy compound such as epoxy compound and the unsaturated monoacid of formula (V) expression are had an effect after again with the multi-anhydride resulting resin of having an effect.In addition, above-mentioned alkali-developable compound with ethylenic unsaturated link preferably contains the unsaturated group of 0.2～1.0 equivalent.

(in the above-mentioned formula, X ¹Represent that direct combination, methylene, carbon number are that 1～4 alkylidene, carbon number are 3～20 ester ring type alkyl, O, S, SO ₂, SS, SO, CO, OCO or formula (VI) or formula (VII) expression substituting group, this alkylidene can be replaced by halogen atom, R ⁴¹, R ⁴², R ⁴³And R ⁴⁴Represent independently that respectively hydrogen atom, carbon number are that 1～5 alkyl, carbon number are that 1～8 alkoxy, carbon number are 2～5 alkenyl or halogen atom, this alkyl, alkoxy and alkenyl can be replaced by halogen atom, and n representes 0～10 integer.)

(in the above-mentioned formula, Z ¹The expression hydrogen atom, can be that 1～10 alkyl or the substituted phenyl of alkoxy or carbon number are 3～10 naphthenic base by carbon number, Y ¹The expression carbon number is that 1～10 alkyl, carbon number are that 1～10 alkoxy, carbon number are 2～10 alkenyl or halogen atom, and this alkyl, alkoxy and alkenyl can be replaced by halogen atom, and d representes 0～5 integer.)

As with the above-mentioned unsaturated monoacid of above-mentioned epoxy compound effect, can enumerate out in above-mentioned unsaturated monoacid (E) the illustrative compound of institute etc.As making the have an effect above-mentioned multi-anhydride of back effect of above-mentioned unsaturated monoacid, can enumerate out in above-mentioned multi-anhydride (C) illustrative compound etc.

The reaction mol ratio of above-mentioned epoxy compound, above-mentioned unsaturated monocarboxylic acid and above-mentioned multi-anhydride preferably is described below.That is: in the epoxy adduct of the structure that has had with respect to 1 addition of epoxy radicals of above-mentioned epoxy compound 0.1～1.0 above-mentioned unsaturated monacid carboxyl and obtained, the acid anhydride structure of preferred above-mentioned multi-anhydride is 0.1～1.0 ratio with respect to 1 of the hydroxyl of this epoxy adduct.The reaction of above-mentioned epoxy compound, above-mentioned unsaturated monocarboxylic acid and above-mentioned multi-anhydride can be carried out according to usual method.

In order to improve the development property of above-mentioned (painted) alkali-developable photosensitive resin combination through the adjusting acid number, can further use simple function or multi-functional epoxy compound with above-mentioned alkali-developable compound with ethylenic unsaturated link.For above-mentioned alkali-developable compound with ethylenic unsaturated link, the acid number of preferred solid constituent is the scope of 5～120mgKOH/g, about simple function or multi-functional epoxy compound's consumption, preferably selects with the mode that satisfies above-mentioned acid number.

As above-mentioned monofunctional epoxy compound; For example can enumerate out GMA, methyl glycidyl ether, ethyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidol ether, tert-butyl group glycidol ether, amyl group glycidol ether, hexyl glycidyl ether, heptyl glycidol ether, octyl glycidyl ether, nonyl glycidol ether, decyl glycidyl ether, undecyl glycidol ether, lauryl diglycidyl ether, tridecyl glycidol ether, myristyl glycidol ether, pentadecyl glycidol ether, cetyl glycidyl ether, 2-ethylhexyl glycidol ether, allyl glycidyl ether, propinyl glycidol ether, to methoxy ethyl glycidol ether, phenyl glycidyl ether, to methoxyl glycidol ether, p-butylphenol glycidol ether, cresylglycidylether, 2-methyl cresylglycidylether, 4-nonyl phenyl glycidyl ether, benzyl glycidyl ether, to cumyl phenyl glycidyl ether, trityl glycidol ether, methacrylic acid 2; 3-epoxy radicals propyl ester, epoxidised soybean oil, epoxidation linseed oil, Glycidyl butyrate, vinyl cyclohexane list oxide, 1,2-epoxy-4-vinyl cyclohexane, styrene oxide, oxidation firpene, oxidation methyl styrene, cyclohexene oxide, propylene oxide, above-claimed cpd No.28, No.29 etc.

As above-mentioned multi-functional epoxy compound; If use be selected from the above-mentioned epoxy compound (D) in illustrative bisphenol type epoxy compound and the diglycidyl ethers more than one; Then can obtain better (painted) alkali-developable photosensitive resin combination of characteristic, thus preferred.As this bisphenol type epoxy compound, also can use the epoxy compound of above-mentioned general formula (V) expression.

In the above-mentioned photosensitive composite; The addition of Photoepolymerizationinitiater initiater does not have particular restriction; Addition as the beta-diketone compound of the present invention of Photoepolymerizationinitiater initiater is that above-mentioned polymerizable compound 100 mass parts with respect to having the ethylenic unsaturated link are preferably 1～70 mass parts; Further be preferably 1～50 mass parts, most preferably be 5～30 mass parts.

When particularly above-mentioned photosensitive composite being processed (painted) alkali-developable photosensitive resin combination; Above-mentioned content with alkali-developable compound of ethylenic unsaturated link does, preferably is 1～20 quality %, preferred especially 3～12 quality % in above-mentioned (painted) alkali-developable photosensitive resin combination.

In the above-mentioned photosensitive composite; As Photoepolymerizationinitiater initiater, except that beta-diketone compound of the present invention, can also and use other Photoepolymerizationinitiater initiater or sensitizer as required; Through also using other Photoepolymerizationinitiater initiaters, also can obtain significant cooperative effect sometimes.As the Photoepolymerizationinitiater initiater that use this moment, can enumerate out in above-mentioned Photoepolymerizationinitiater initiater (F) the illustrative compound of institute etc., these Photoepolymerizationinitiater initiaters can use a kind, or combination use more than 2 kinds.When using these other Photoepolymerizationinitiater initiater, its consumption be preferably beta-diketone compound of the present invention consumption 1 quality doubly below.

In above-mentioned photosensitive composite, can further add solvent.As this solvent; Normally can dissolve or disperse the solvent of above-mentioned each composition (beta-diketone compound and have polymerizable compound of ethylenic unsaturated link etc.) to get final product as required; There is not particular restriction; Can enumerate out the illustrative solvent of solvent that uses as in the above-mentioned alkali-developable photosensitive resin combination, these solvents can use a kind, and the mixed solvent that also can be used as more than 2 kinds uses.Wherein, ketone, cellosolve kind solvent etc., particularly propylene glycol-1-monomethyl ether-2-acetic acid esters, cyclohexanone etc. since in photosensitive composite the compatibility with resist and Photoepolymerizationinitiater initiater good, thereby preferred.

In above-mentioned photosensitive composite, can also contain mineral compound.As this mineral compound, for example can enumerate out metal oxides such as nickel oxide, iron oxide, yttrium oxide, titanium dioxide, zinc paste, magnesium oxide, calcium oxide, kali, silicon dioxide, aluminium oxide; Layered clay mineral, milori blue, lime carbonate, magnesium carbonate, cobalt class, manganese class, glass powder, mica, talcum, porcelain earth, ferrocyanide, various metal sulfate, sulfide, selenide, alumina silicate, calcium silicate, hydrate of aluminium, platinum, gold, silver, ketone etc.; Wherein, preferred titanium dioxide, silicon dioxide, layered clay mineral, silver etc.In the above-mentioned photosensitive composite, the content of mineral compound is that above-mentioned polymerizable compound 100 mass parts with respect to having the ethylenic unsaturated link are preferably 0.1～50 mass parts, more preferably 0.5～20 mass parts.These mineral compounds can use more than a kind or 2 kinds.

These mineral compounds for example can be used as filling agent, antireflection agent, conductive agent, stabilizing agent, fire retardant, physical strength improving agent, special wavelength absorbing agent, anti-printing ink agent etc.

In the above-mentioned photosensitive composite (particularly alkali-developable photosensitive resin combination), can further contain colorant and process coloring photosensitive combination.As this colorant, can enumerate out in the above-mentioned colorant (G) institute illustrative those, these colorants can use separately, also can mix use more than 2 kinds.

In the above-mentioned photosensitive composite, the addition of above-mentioned colorant is that above-mentioned polymerizable compound 100 mass parts with respect to having the ethylenic unsaturated link are preferably 50～350 mass parts, further are preferably 100～250 mass parts.

Through using other organic polymers, can also improve the characteristic of solidfied material with above-mentioned polymerizable compound with ethylenic unsaturated link.As this organic polymer, for example can enumerate out polystyrene, polymethylmethacrylate, methyl methacrylate-ethyl acrylate copolymer, gather (methyl) acrylic acid, styrene-(methyl) acrylic copolymer, (methyl) acrylic acid-methylmethacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl base co-polymer, Corvic, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose esters, polyacrylamide, saturated polyester, phenolic resin, phenoxy resin, polyamide-imide resin, polyamic acid resin, epoxy resin etc.Wherein, preferred polystyrene, (methyl) acrylic acid-methylmethacrylate copolymer, epoxy resin.When using other organic polymers, its consumption is preferably 10～500 mass parts with respect to above-mentioned polymerizable compound 100 mass parts with ethylenic unsaturated link.

In above-mentioned photosensitive composite, as required, can also add thermal polymerization inhibitors such as methyl phenyl ethers anisole, quinhydrones, pyrocatechol, tert-butyl catechol, phenothiazine; Plastifier; Adhesion promoters; Filling agent; Foam-breaking agent; Levelling agent; Surface conditioner; Anti-oxidant; Ultraviolet light absorber; Dispersing aid; Anti-coagulants; Catalyzer; Effect promoter; Sensitizer; Crosslinking chemical; The additive that tackifier etc. are commonly used.

In the above-mentioned photosensitive composite; Consumption for any composition beyond the above-mentioned polymerizable compound with ethylenic unsaturated link and the beta-diketone compound of the present invention (but except that above-mentioned other Photoepolymerizationinitiater initiater, inorganic filler, colorant and solvent); Can come suitably to select according to its application target; Do not have particular restriction, preferably, add up to below 50 mass parts with respect to above-mentioned polymerizable compound 100 mass parts with ethylenic unsaturated link.

Above-mentioned photosensitive composite and above-mentioned alkali-developable photosensitive resin combination are same, can be also with the monomer with unsaturated link, chain-transferring agent, surfactant etc.

The method of application of above-mentioned photosensitive composite on support substrate is identical with the situation of above-mentioned alkali-developable photosensitive resin combination.

The light source of the active light that uses when above-mentioned photosensitive composite is solidified can use illustrative light source in above-mentioned alkali-developable photosensitive resin combination.

Above-mentioned photosensitive composite can be used for photoresist that the color filter of color filter, the ccd image sensor of the liquid crystal display cells that colours such as photo-curable coating or varnish, Photocurable adhesive agent, printed wiring board or colour television set, PC monitor, portable information terminal, digital camera show, electrode material, powdery paints, printing-ink, galley, bonding agent, dental composition, gel coat, electronic engineering that plasma display is used use, platedresist, etching resist, aqueous and desciccator diaphragm the two, the scolding tin resist, be used for making color filter that various demonstration purposes use or the manufacturing process of plasma display, electroluminescence display device and LCD be used to form the resist of structure, the composition that is used for sealing electric or electronic unit, magnetic recording material, milli machine parts, waveguide, optical switch, plating with mask, etching mask, colour test system, glass fiber cable coating, serigraphy with masterplate, be used for through stereolithography make the material of three-dimensional body, decoloring material that holographic recording is used with the image recording material of material, image recording material, fine circuits, decoloring material, the decoloring material that is used for image recording material, use micro-capsule, printed wiring board with photo anti-corrosion agent material, UV and visible laser through image be usefulness photo anti-corrosion agent material, be used to form the various uses such as photo anti-corrosion agent material or diaphragm of dielectric layer of the lamination one by one of tellite, its purposes does not have especially and limits.

Embodiment

Below, enumerate embodiment and comparative example illustrates in greater detail the present invention, but the invention is not restricted to these embodiment etc.In addition, in following embodiment etc., " % " means quality %.

Among following embodiment 1-1～1-3, make beta-diketone compound No.1～No.3 of the present invention, among embodiment 2-1 and the 2-2, make beta-diketone compound No.24 and No.25.Among embodiment 3-1, the 3-2, the photosensitive composite No.1 and the No.2 of above-mentioned beta-diketone compound used in preparation.Among embodiment 4-1～4-21, make the alkali-developable photosensitive resin combination that contains optical polymerism unsaturated compound (J).Among embodiment 5-1～5-21, sneak into monomer and solvent in the alkali-developable photosensitive resin combination of in embodiment 4-1～4-21, making, prepare alkali-developable photosensitive resin combination of the present invention with unsaturated link.Among embodiment 6-1～6-5, sneak into colorant (G), monomer and solvent in the alkali-developable photosensitive resin combination of in embodiment 4-17～4-21, making, prepare painted alkali-developable photosensitive resin combination of the present invention with unsaturated link.Among embodiment 7-1～7-16, sneak into Photoepolymerizationinitiater initiater (F), monomer and solvent in the alkali-developable resin combination of in embodiment 4-1～4-16, making, prepare alkali-developable photosensitive resin combination of the present invention with unsaturated link.Among embodiment 8-1～8-21; Sneak into Photoepolymerizationinitiater initiater (F), colorant (G), monomer and solvent in the alkali-developable photosensitive resin combination of in embodiment 4-1～4-21, making, prepare painted alkali-developable photosensitive resin combination of the present invention with unsaturated link.

[embodiment 1-1] 1-(9-propyl group-9H-carbazole-3-yl) butane-1, the manufacturing of 3-diketone (compound N is o.1)

In the 200mL four-hole boiling flask that has stirring apparatus, nitrogen ingress pipe, backflow cooling tube and thermometer, the 1-that packs into (9-propyl group-9H-carbazole-3-yl) ethyl ketone 25.13g, ethyl acetate 88.11g and potassium tert-butoxide 16.83g were blanket of nitrogen refluxed 5 hours.After being cooled to room temperature, add ion exchange water 50mL and 6N hydrochloric acid 50mL successively, stir, obtain organic phase.To wherein adding ethyl acetate 200mL, until neutrality, dewatered in the upper strata with magnesium sulphate with brine wash.Heat up in a steamer and desolvate, when separating out solid, add ethyl acetate 10mL, reflux, and make its dissolving, add normal hexane and carry out partial crystallization.Behind its suction filtration, drying under reduced pressure obtains yellow crystal 23.15g (yield 79%).The fusing point of this yellow crystal is 97 ℃, through various analyses, identifies that it is the beta-diketone compound No.1 with carbazyl of target substance.

[embodiment 1-2] 1-[9-ethyl-6-(4-fluoro-2-methyl benzoyl)-9H-carbazole-3-yl] butane-1, the manufacturing of 3-diketone (compound N is o.2)

In the 1L four-hole boiling flask that has stirring apparatus, nitrogen ingress pipe, backflow cooling tube and thermometer; Pack into 1-[9-ethyl-6-(4-fluoro-2-methyl benzoyl)-9H-carbazole-3-yl] ethyl ketone 74.69g, ethyl acetate 538.66g and potassium tert-butoxide 67.33g were blanket of nitrogen refluxed 1 hour.After being cooled to room temperature,, wash with ethyl acetate 500mL with the white solid suction filtration of separating out.In the solid that obtains, add 2N hydrochloric acid 500mL and ethyl acetate 1.5L, stirring, with the water washing organic phase until neutrality.With the organic phase separatory, with magnesium sulphate 70g dehydration, heat up in a steamer behind the suction filtration and desolvate, obtain faint yellow solid.It is dissolved among the ethyl acetate 150mL, after the backflow, adds normal hexane 100mL, be cooled to room temperature and carry out partial crystallization.Filtrating is dissolved in ethyl acetate 50mL once more, after the backflow, adds normal hexane 100mL, is cooled to room temperature, once more partial crystallization.After the crystallization that obtains suction filtration together, drying under reduced pressure obtains white crystals 8.52g (yield 21%).The fusing point of this white crystals is 132 ℃, through various analyses, identifies that it is the beta-diketone compound No.2 with carbazyl of target substance.

[embodiment 1-3] 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] butane-1, the manufacturing of 3-diketone (compound N is o.3)

In the 1L four-hole boiling flask that has stirring apparatus, nitrogen ingress pipe, backflow cooling tube and thermometer; Pack into 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl) ethyl ketone 35.54g, ethyl acetate 264.33g and potassium tert-butoxide 33.66g, blanket of nitrogen refluxed 5 hours.After being cooled to room temperature, add ion exchange water 100mL and 6N hydrochloric acid 100mL successively, stir, obtain organic phase.With its with brine wash to neutrality, add normal hexane 150mL, ice-cold, carry out partial crystallization.Behind its suction filtration, drying under reduced pressure obtains faint yellow crystallization 17.29g (yield 43%).The fusing point of this faint yellow crystallization is 148 ℃, through various analyses, identifies that it is the beta-diketone compound No.3 with carbazyl of target substance.

The compound N that the foregoing description 1-1～1-3 obtains o.1～qualification result of No.3 is shown in [table 1] and [table 2].

[table 1]

?	?	IR absorbs (cm -1)
			Embodiment 1-1	Compound N o.1	?3436，2966，2944，2927，2875，1824，1592，1491，1469，1388，?1345，1332，1293，1279，1266，1252，1221，1195，1151，1131，?1080，1062，1021，992，903，876，836，812，789，754，721
Embodiment 1-2	Compound N o.2	?3427，3060，2984，2938，1649，1623，1592，1489，1454，1386，?1352，1312，1299，1253，1236，1194，1158，1129，1099，1054，?1023，971，898，862，825，811，775，731，706，669
			Embodiment 1-3	Compound N o.3	?3451，3080，2968，1656，1625，1590，1486，1449，1390，1349，?1313，1293，1261，1234，1189，1161，1131，1024，965，936，913，?834，774，750，727，633

[table 2]

?	?	1H?NMR(ppm)
			Embodiment 1-1	Compound N is (DMSO-d o.1 6)	(1) 0.88 (t, 3H), 1.81 (tq, 2H), 2.27 (s, 3H), 4.37 (s, 2H), 4.42 (t, 2H); 7.29 (ddd, 1H), 7.51 (ddd, 1H), 7.68 (dd, 1H), 7.72 (dd, 1H), 8.05 (dd, 1H); 8.29 (d, 1H), 8.84 (d, 1H) (2) 0.88 (t, 3H), 1.81 (tq, 2H), 2.20 (s, 3H); 4.42 (t, 2H), 6.70 (s, 1H), 7.29 (ddd, 1H), 7.51 (ddd, 1H), 7.68 (dd; 1H), 7.72 (dd, 1H), 8.08 (dd, 1H), 8.29 (d, 1H), 8.88 (d, 1H) (1) ketone/(2) enol=27/73
Embodiment 1-2	Compound N is (DMSO-d o.2 6)	(1) 1.35 (t, 3H), 2.26 (s, 3H), 2.29 (s, 3H), 4.38 (s, 2H). 4.54 (q, 2H), 7.16 (d, 1H); 7.27 (d, 1H), 7.44 (dd, 1H), 7.80 (d, 1H), 7.81 (s, 1H), 7.88 (d, 1H), 8.10 (d; 1H), 8.69 (d, 1H), 8.97 (s, 1H) (2) 1.35 (t, 3H), 2.19 (s, 3H), 2.29 (s, 3H), 4.54 (q; 2H), 6.74 (s, 1H), 7.18 (d, 1H), 7.27 (d, 1H), 7.44 (dd, 1H), 7.80 (d, 1H); 7.81 (s, 1H), 7.90 (dd, 1H), 8.14 (dd, 1H), 8.68 (d, 1H), 8.97 (s, 1H) (1) ketone/(2) enol=27/73
			Embodiment 1-3	Compound N is (DMSO-d o.3 6)	(1) 1.38 (t, 3H), 2.27 (s, 3H), 4.40 (s, 2H), 4.57 (q, 2H), 7.34-7.43 (m, 3H); 7.51 (ddd, 1H), 7.82 (dd, 1H), 7.83 (dd, 1H), 7.87 (dd, 1H), 8.12 (dd, 1H); 8.74 (d, 1H), 8.97 (d, 1H) (2) 1.38 (t, 3H), 2.21 (s, 3H), 4.57 (q, 2H); 6.78 (s, 1H), 7.34-7.43 (m, 3H), 7.50 (ddd, 1H), 7.82 (dd, 1H), 7.83 (dd; 1H), 7.90 (dd, 1H), 8.17 (dd, 1H), 8.72 (d, 1H), 8.99 (d, 1H) (1) ketone/(2) enol=28/72

The 1-of [embodiment 2-1] methyl acrylate [9-ethyl-6-(4-fluoro-2-methyl benzoyl)-9H-carbazole-3-yl] butane-1, the manufacturing of 3-diketone addition product (compound N is o.24)

In the 100mL four-hole boiling flask that has stirring apparatus, nitrogen/airway, backflow cooling tube and thermometer; 1-[9-ethyl-6-(4-fluoro-2-methyl benzoyl)-9H-carbazole-3-yl]-butane-1 of packing into; 3-diketone (compound N is o.2) 8.31g, methyl acrylate 17.22g and 1,8-diazabicyclo [5,4; 0]-7-undecylene 0.30g, under nitrogen/oxygen atmosphere in 70 ℃ of refluxed 8 hours.After the cooling,, add saturated brine 100mL, ion exchange water 100mL and 1N hydrochloric acid 6mL, stir, obtain organic layer to wherein adding the about 150mL of ethyl acetate.It is washed with water to neutrality, adds toluene 10mL, concentrate and do admittedly.110 ℃ of following vacuum drying, obtain amber glass shape material 9.47g (yield 81%) then.This amber glass shape material is carried out various analyses, identify its be in methyl acrylate 2mol addition 1-[9-ethyl-6-(4-fluoro-2-methyl benzoyl)-9H-carbazole-3-yl] butane-1, the target compound No.24 of 3-diketone 1mol.

[embodiment 2-2] acrylic acid 1-[9-ethyl-6-(4-fluoro-2-methyl benzoyl)-9H-carbazole-3-yl] butane-1, the manufacturing of 3-diketone addition product (compound N is o.25)

In the 300mL round-bottomed flask that has stirring apparatus, Dean-Stark pipe and backflow cooling tube; Pack into 1-[9-ethyl-6-(4-fluoro-2-methyl benzoyl)-9H-carbazole-3-yl]-butane-1 of above-mentioned synthetic methyl acrylate; 3-diketone addition product (compound N o.24) 5.39g, tert-butyl alcohol 50mL and 3N hydrochloric acid 10mL; Under 105 ℃ of bath temperatures, stirred 12 hours.In the reaction, heat up in a steamer methyl alcohol, with appending 3N hydrochloric acid 10mL in 8 hours with Dean-Stark pipe.After the reaction, decompression is heated up in a steamer under 120 ℃ of bath temperatures down and is desolvated and hydrochloric acid, does solid.Use ion exchange water 20mL and acetone 20mL to reflux to it, obtain lower floor.This solution concentration is done admittedly,, obtained pale-yellow galss shape material 4.06g (yield 79%) then 70 ℃ of following vacuum drying.This pale-yellow galss shape material has been carried out various analyses, identify its be in acrylic acid 2mol addition 1-[9-ethyl-6-(4-fluoro-2-methyl benzoyl)-9H-carbazole-3-yl] butane-1, the target compound No.25 of 3-diketone 1mol.

The manufacturing of the benzoyl acetone addition product (comparative compound No.1) of [comparative example 1] methyl acrylate

In the 100mL four-hole boiling flask that has stirring apparatus, nitrogen/airway, backflow cooling tube and thermometer; Benzoyl acetone 4.87g, methyl acrylate 6.89g and 1 pack into; 8-diazabicyclo [5; 4,0]-7-undecylene 0.15g, under nitrogen/oxygen atmosphere in 60 ℃ of refluxed 8 hours.After the cooling,, add saturated brine 100mL, ion exchange water 100mL and 1N hydrochloric acid 2mL, stir, obtain organic layer to wherein adding the about 100mL of ethyl acetate.It is washed with water to neutrality, concentrates and do admittedly.60 ℃ of following vacuum drying, obtain brown liquid 9.55g (yield 95%) then.This brown liquid is carried out various analyses, identifies that it is the isomer mixture that contains comparative compound No.1, this comparative compound No.1 be in methyl acrylate 2mol addition benzoyl acetone 1mol and the compound that obtains.

The compound N that the foregoing description 2-1,2-2 and comparative example 1 obtain o.24, the qualification result of No.25 and comparative compound No.1 is shown in [table 3] and [table 4].

[table 3]

?	?	IR absorbs (cm 1)
			Embodiment 2-1	Compound N o.24	3503，2952，1736，1657，1623，1588，1486，1437，1381，1362， 1338，1308，1254，1235，1200，1174，1156，1128，1097，1022， 964，866，819，771，729，674
Embodiment 2-2	Compound N o, 25	3060，2979，1711，1658，1622，1588，1486，1450，1429，1385， 1362，1339，1309，1255，1235，1180，1156，1128，1097，1023， 964，916，866，819，771，729，669
			Comparative example 1	Comparative compound No.1	3628，3490，3060，2953，2847，2595，2361，1976，1738，1672， 1597，1579，1493，1438，1361，1201，1176，1099，1081，1001， 987，887，853，769，731，702

[table 4]

?	?	1H?NMR(ppm)
			Embodiment 2-1	Compound N is (CDCl o.24 3)	1.52(t，3H)，2.06-2.55(m，8H)，2.15(s，3H)，2.39(s，3H)， 3.64(s，6H)，4.43(q，2H)，7.02(dd，1H)，7.07(dd，1H)，7.41 (d，1H)，7.51(d，1H)，7.51(s，1H)，7.94(dd，1H)，8.06(dd， 1H)，8.53(d，1H)，8.67(d，1H)
Embodiment 2-2	Compound N is (CDCl o.25 3)	1.51(t，3H)，2.06-2.57(m，8H)，2.14(s，3H)，2.39(s，3H)， 4.44(q，2H)，6.99(dd，1H)，7.07(d，1H)，7.40(d，1H)，7.49 (d，1H)，7.49(s，1H)，7.93(dd，1H)，8.07(dd，1H)，8.53(d， 1H)，8.67(d，1H)
			Comparative example 1	Comparative compound No.1 (DMSO-d 6)	1.89-2.30(m，8H)，2.13(s，3H)，3.50(s，6H)，7.47-7.67(m， 5H)

The manufacturing of [making example 1] alkali-developable compound

Pack 1 into; 1-is two, and [4-(2; The 3-glycidoxy) phenyl]-1-(4-xenyl)-1-cyclohexyl-methane 390g, acrylic acid 71.1g, 2,6-di-t-butyl-paracresol 1.34g, tetrabutylammonium chloride 1.75g and PGMAc 108g stirred 1 hour down at 90 ℃; Stirred 1 hour down at 100 ℃, stirred 1 hour down and stirred 17 hours down at 120 ℃ at 110 ℃.Be cooled to room temperature; Add bibenzene tetracarboxylic dianhydride 59.2g, tetrabydrophthalic anhydride 45.2g, tetrabutylammonium chloride 4.08g and propylene glycol-1-monomethyl ether-2-acetic acid esters 137g, stirred 5 hours down, stirred 1 hour down at 90 ℃ at 120 ℃; In stirring 2 hours under 60 ℃ and after stirring 3 hours under 40 ℃; Add PGMAc 203g, obtain the alkali-developable compound (Mw=3700, Mn=2000, acid number (solid constituent) 91mgKOH/g) of target substance with the form of PGMAc solution.

[embodiment 3-1,3-2 and comparative example 2] is as the preparation of photosensitive composite No.1, No.2 and the comparison photosensitive composite No.1 of alkali-developable photosensitive resin combination

Add to make compound N that alkali-developable compound 8.9g, trimethylolpropane triacrylate 4.0g, embodiment 2-1,2-2 and comparative example 1 that example 1 obtains obtain o.24, No.25 and each 1.0g of comparative compound No.1, propylene glycol methyl ether acetate 13.1g and cyclohexanone 10.0g; Fully mix, obtain photosensitive composite No.1, No.2 and comparison photosensitive composite No.1.

[evaluation Example 1-1～1-2 and comparative evaluation example 1]

Photosensitive composite No.1, No.2 and comparison photosensitive composite No.1 are carried out following evaluation.Evaluation result is shown in [table 5].

On glass substrate, the above-mentioned photosensitive composite of rotary coating (700r.p.m, 5 seconds), after air-dry 15 minutes, 90 seconds of prebake conditions on 90 ℃ heating plate.Using mask open is the mask of 30 μ m, presses 50～1000mJ/cm with high-pressure sodium lamp ²6 standard exposures after, under 25 ℃ in 2.5 quality % aqueous sodium carbonates dipping develop fully washing 40 seconds.Behind the washing and drying, toasted 1 hour down, make the pattern photographic fixing, measure the live width of the pattern that obtains at 230 ℃.Its result is shown in [table 5].

[table 5]

Photosensitive composite No.1 and No.2's is highly sensitive, even at 50mJ/cm ²Also can form pattern down, even but compare photosensitive composite No.1 at 1000mJ/cm ²Following exposure can not form pattern, and sensitivity is low.

The manufacturing of [embodiment 4-1] alkali-developable photosensitive resin combination No.1-1

< step>1>manufacturing of two (4-hydroxy phenyl)-4-xenyls (cyclohexyl) methane

The xenyl cyclohexyl ketone of packing into 70.5g, phenol 200.7g and thioacetic acid 10.15g, following at 18 ℃ with 20 minutes dropping TFMS 40.0g., add water 500g and stop reaction after 18 hours in reaction under 17～19 ℃, add toluene 500g, the organic layer washing until pH 3～4, is separated organic layer.Heat up in a steamer toluene, water and superfluous phenol.Add toluene to remainder, the solid of separating out is leached, disperse washing, obtain faint yellow crystallization 59.2g (yield 51%) with toluene.The fusing point of this faint yellow crystallization is 239.5 ℃, confirms that this faint yellow crystallization is a target substance.

< step>2>manufacturing of two [4-(2, the 3-glycidoxy) phenyl]-4-xenyl (cyclohexyl) methane

Two (4-hydroxy phenyl)-4-xenyl (cyclohexyl) methane 57.5g and epichlorokydrin 195.8g that the step 1 of packing into obtains add benzyltriethylammoinium chloride 0.602g, stir 18 hours down at 64 ℃.Be cooled to 54 ℃ then, drip 24 weight % sodium hydrate aqueous solution 43.0g, stirred 30 minutes.Heat up in a steamer decyclization oxygen chloropropane and water, add methyl isobutyl ketone 216g, after the washing, drip 24 weight % NaOH 2.2g.Stirred 2 hours down at 80 ℃, be cooled to room temperature then,, wash with the neutralization of the 3 weight % sodium monophosphate WS.Heat up in a steamer and desolvate, obtain yellow solid 57g (yield 79%).(64.2 ℃ of fusing points, epoxide equivalent 282, n=0.04).Confirm that this yellow crystal is a target substance.

< step>3>manufacturing of alkali-developable photosensitive resin combination No.1-1

Packing into, two [4-(2; The 3-glycidoxy) phenyl]-4-xenyl (cyclohexyl) methane (below be also referred to as compound d-1) 89.9g, acrylic acid (below be also referred to as Verbindung-1) 23.5g, 2; 6-di-t-butyl-paracresol 0.457g, benzyltriethylammoinium chloride 0.534g and propylene glycol-1-monomethyl ether-2-acetic acid esters 75.6g stirred 16 hours down at 120 ℃.Be cooled to room temperature, pack 2 into, 4-pentanedione (below be also referred to as compound b-1) 12.0g and triethylamine 1.0g stirred 17 hours down at 92 ℃.Be cooled to room temperature, add succinic anhydride (below be also referred to as compound c-1) 25.6g, tetra-n-butyl ammonium bromide 1.39g and propylene glycol-1-monomethyl ether-2-acetic acid esters 40.42g, stirred 5 hours down at 100 ℃.Be cooled to room temperature; Add propylene glycol-1-monomethyl ether-2-acetic acid esters 46.7g, obtain the alkali-developable photosensitive resin combination No.1-1 (Mw=4090, Mn=2630, acid number (solid constituent) 102mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

In addition; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-1 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-1 carries out the Michael addition polymerization by the ratio below 0.75; And then with respect to 1 of hydroxyl; By 0.8 ratio addition (C) composition be the acid anhydride structure of compound c-1; Thereby obtain optical polymerism unsaturated compound (J), wherein above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-1 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-2] alkali-developable photosensitive resin combination No.1-2

Pack 9 into; 9-is two, and [4-(2; The 3-glycidoxy) phenyl]-9H-fluorenes (below be also referred to as compound d-2) 23.2g, acrylic acid (Verbindung-1) 7.35g, 2; 6-di-t-butyl-paracresol 0.084g, benzyltriethylammoinium chloride 0.167g and propylene glycol-1-monomethyl ether-2-acetic acid esters 20.4g stirred 16 hours down at 120 ℃.Be cooled to room temperature, add 2,4-pentanedione (compound b-1) 3.75g and triethylamine 0.304g stirred 17 hours down at 92 ℃.Be cooled to room temperature, add propylene glycol-1-monomethyl ether-2-acetic acid esters 7.42g.Add succinic anhydride (compound c-1) 8.01g, tetra-n-butyl ammonium bromide 0.389g and propylene glycol-1-monomethyl ether-2-acetic acid esters 14.3g, stirred 5 hours down at 100 ℃.Be cooled to room temperature; Add propylene glycol-1-monomethyl ether-2-acetic acid esters 17.3g, obtain the alkali-developable photosensitive resin combination No.1-2 (Mw=4020, Mn=2580, acid number (solid constituent) 114mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-2 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-1 carries out the Michael addition polymerization by the ratio below 0.75; And then with respect to 1 of hydroxyl; By 0.8 ratio addition (C) composition be the acid anhydride structure of compound c-1; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein above-mentioned A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-2 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-3] alkali-developable photosensitive resin combination No.1-3

Pack 2 into; 2-is two, and [4-(2; The 3-glycidoxy) phenyl] propane (below be also referred to as compound d-3) 185g, acrylic acid (Verbindung-1) 73.5g, 2; 6-di-t-butyl-paracresol 0.718g, benzyltriethylammoinium chloride 1.67g and propylene glycol-1-monomethyl ether-2-acetic acid esters 174g stirred 16 hours down at 120 ℃.Be cooled to room temperature, it is obtained 139g, add 2,4-pentanedione (compound b-1) 12.0g and triethylamine 0.971g stirred 17 hours down at 92 ℃.Be cooled to room temperature, add succinic anhydride (compound c-1) 16.0g, tetra-n-butyl ammonium bromide 14.4g and propylene glycol-1-monomethyl ether-2-acetic acid esters 83.5g, stirred 5 hours down at 100 ℃.Be cooled to room temperature, obtain the alkali-developable photosensitive resin combination No.1-3 (Mw=3170, Mn=2000, acid number (solid constituent) 88.0mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-3 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-1 carries out the Michael addition polymerization by the ratio below 0.75; And then with respect to 1 of hydroxyl; By 0.5 ratio addition (C) composition be the acid anhydride structure of compound c-1; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein, above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-3 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-4] alkali-developable photosensitive resin combination No.1-4

Packing into, two [4-(2; The 3-glycidoxy) phenyl]-4-xenyl (cyclohexyl) methane (compound d-1) 84.3g, acrylic acid (Verbindung-1) 22.1g, 2; 6-di-t-butyl-paracresol 0.429g, benzyltriethylammoinium chloride 0.501g and propylene glycol-1-monomethyl ether-2-acetic acid esters 70.9g stirred 16 hours down at 120 ℃.Be cooled to room temperature, add ethyl acetoacetate (below be also referred to as compound b-2) 13.0g and triethylamine 0.9g, 92 ℃ of stirrings 8 hours down.Be cooled to room temperature, add succinic anhydride (compound c-1) 15.4g, tetra-n-butyl ammonium bromide 1.39g and propylene glycol-1-monomethyl ether-2-acetic acid esters 99.5g, stirred 5 hours down at 100 ℃.Be cooled to room temperature, obtained the alkali-developable photosensitive resin combination No.1-4 (Mw=4310, Mn=2280, acid number (solid constituent) 68.8mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-4 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the ketone ester clamping in the 'beta '-ketoester base of compound b-2 carries out the Michael addition polymerization by the ratio below 0.67; And then with respect to 1 of hydroxyl; By 0.5 ratio addition (C) composition be the acid anhydride structure of compound c-1; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein, above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-1 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-5] alkali-developable photosensitive resin combination No.1-5

Packing into, two [4-(2; The 3-glycidoxy) phenyl]-4-xenyl (cyclohexyl) methane (compound d-1) 84.3g, acrylic acid (Verbindung-1) 22.1g, 2; 6-di-t-butyl-paracresol 0.429g, benzyltriethylammoinium chloride 0.501g and propylene glycol-1-monomethyl ether-2-acetic acid esters 70.9g stirred 16 hours down at 120 ℃.Be cooled to room temperature, add acetoacetic acid allyl ester (below be also referred to as compound b-3) 14.2g and triethylamine 0.9g, 92 ℃ of stirrings 6 hours down.Be cooled to room temperature, add succinic anhydride (compound c-1) 15.0g, tetra-n-butyl ammonium bromide 1.35g and propylene glycol-1-monomethyl ether-2-acetic acid esters 96.9g, stirred 5 hours down at 100 ℃.Be cooled to room temperature, obtained the alkali-developable photosensitive resin combination No.1-5 (Mw=4870, Mn=2440, acid number (solid constituent) 66.2mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-5 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the ketone ester clamping in the 'beta '-ketoester base of compound b-3 carries out the Michael addition polymerization by the ratio below 0.67; And then with respect to 1 of hydroxyl; By 0.5 ratio addition (C) composition be the acid anhydride structure of compound c-1; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein, above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-1 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-6] alkali-developable photosensitive resin combination No.1-6

Packing into, two [4-(2; The 3-glycidoxy) phenyl]-4-xenyl (cyclohexyl) methane (compound d-1) 89.9g, acrylic acid (Verbindung-1) 23.5g, 2; 6-di-t-butyl-paracresol 0.457g, benzyltriethylammoinium chloride 0.534g and propylene glycol-1-monomethyl ether-2-acetic acid esters 75.6g stirred 16 hours down at 120 ℃.Be cooled to room temperature, add 2,4-pentanedione (compound b-1) 12.0g and triethylamine 0.97g stirred 17 hours down at 92 ℃.Be cooled to room temperature, add propylene glycol-1-monomethyl ether-2-acetic acid esters 42.0g.Add succinic anhydride (compound c-1) 16.0g, stirred 5 hours down at 100 ℃.Be cooled to room temperature; Add propylene glycol-1-monomethyl ether-2-acetic acid esters 55.3g, obtained the alkali-developable photosensitive resin combination No.1-6 (Mw=4210, Mn=2630, acid number (solid constituent) 66.6mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-6 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-1 carries out the Michael addition polymerization by the ratio below 0.75; And then with respect to 1 of hydroxyl; By 0.5 ratio addition (C) composition be the acid anhydride structure of compound c-1; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein, above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-1 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-7] alkali-developable photosensitive resin combination No.1-7

Packing into, two [4-(2; The 3-glycidoxy) phenyl]-4-xenyl (cyclohexyl) methane (compound d-1) 89.9g, acrylic acid (Verbindung-1) 23.5g, 2; 6-di-t-butyl-paracresol 0.457g, benzyltriethylammoinium chloride 0.534g and propylene glycol-1-monomethyl ether-2-acetic acid esters 75.6g stirred 16 hours down at 120 ℃.Be cooled to room temperature, add 2,4-pentanedione (compound b-1) 12.0g and triethylamine 0.97g stirred 17 hours down at 92 ℃.Be cooled to room temperature, add propylene glycol-1-monomethyl ether-2-acetic acid esters 42.0g.Add tetrabydrophthalic anhydride (below be also referred to as compound c-2) 24.3g, stirred 5 hours down at 100 ℃.Be cooled to room temperature; Add propylene glycol-1-monomethyl ether-2-acetic acid esters 68.5g, obtained the alkali-developable photosensitive resin combination No.1-7 (Mw=4080, Mn=2410, acid number (solid constituent) 62.3mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-7 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-1 carries out the Michael addition polymerization by the ratio below 0.75; And then with respect to 1 of hydroxyl; By 0.5 ratio addition (C) composition be the acid anhydride structure of compound c-2; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein, above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-1 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-8] alkali-developable photosensitive resin combination No.1-8

Addition reaction-type epoxy compound (the HP-7200H: big Japanese ink corporate system of phenol and dicyclopentadiene packs into; Below be also referred to as compound d-4) 200g, acrylic acid (Verbindung-1) 53.1g, tetrabutyl ammonium acetate 1.31g, 2; 6-di-t-butyl-paracresol 0.698g and propylene glycol-1-monomethyl ether-2-acetic acid esters 309g stirred 26 hours down at 120 ℃.Be cooled to room temperature, add 2,4-pentanedione (compound b-1) 21.7g, benzyltriethylammoinium chloride 1.01g, 2,6-di-t-butyl-paracresol 0.276g and propylene glycol-1-monomethyl ether-2-acetic acid esters 26.5g stirred 9 hours down at 100 ℃.Be cooled to room temperature, add tetrabydrophthalic anhydride (compound c-2) 15.6g and tetra-n-butyl ammonium bromide 0.206g, stirred 3 hours down at 100 ℃.Be cooled to room temperature; Add propylene glycol-1-monomethyl ether-2-acetic acid esters 4.69g, obtained the alkali-developable photosensitive resin combination No.1-8 (Mw=2850, Mn=1660, acid number (solid constituent) 48.7mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-8 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-1 carries out the Michael addition polymerization by the ratio below 0.6; And then with respect to 1 of hydroxyl; By 0.8 ratio addition (C) composition be the acid anhydride structure of compound c-2; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-1 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-9] alkali-developable photosensitive resin combination No.1-9

Pentaerythritol triacrylate (below be also referred to as compound a-1) 60.0g, 2 packs into; 4-pentanedione (compound b-1) 5.01g, triphenylphosphine 0.323g, 2; 6-di-t-butyl-paracresol 0.0647g and propylene glycol-1-monomethyl ether-2-acetic acid esters 52.9g stirred 9 hours down at 100 ℃.Be cooled to room temperature, add tetrabydrophthalic anhydride (compound c-2) 18.1g and tetra-n-butyl ammonium bromide 0.323g, stirred 3 hours down at 100 ℃.Be cooled to room temperature; Add propylene glycol-1-monomethyl ether-2-acetic acid esters 29.9g, obtained the alkali-developable photosensitive resin combination No.1-9 (Mw=1230, Mn=690, acid number (solid constituent) 85.8mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-9 is contained obtains through reactions: be acrylate-based 1 of compound a-1 with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-1 carries out the Michael addition polymerization by the ratio below 0.15; And then with respect to 1 of hydroxyl, by 0.60 ratio addition (C) composition be the acid anhydride structure of compound c-2.

The manufacturing of [embodiment 4-10] alkali-developable photosensitive resin combination No.1-10

Packing into, two [4-(2; The 3-glycidoxy) phenyl]-4-xenyl (cyclohexyl) methane (compound d-1) 84.3g, acrylic acid (Verbindung-1) 22.1g, 2; 6-di-t-butyl-paracresol 0.429g, benzyltriethylammoinium chloride 0.501g and propylene glycol-1-monomethyl ether-2-acetic acid esters 70.9g stirred 16 hours down at 120 ℃.Be cooled to room temperature, add 1-phenyl-1,3-diacetyl (below be also referred to as compound b-4) 16.2g and triethylamine 0.9g are 100 ℃ of stirrings 20 hours down.After being cooled to room temperature, obtain 97.7g, to wherein adding 1,8-diazabicyclo [5,4,0]-7-undecylene 0.7g and propylene glycol-1-monomethyl ether-2-acetic acid esters 42.36g stirred 17 hours down at 100 ℃, stirred 23 hours down at 120 ℃ then.After being cooled to room temperature, add succinic anhydride (compound c-1) 7.5g, tetra-n-butyl ammonium bromide 0.642g and propylene glycol-1-monomethyl ether-2-acetic acid esters 8.58g, stirred 5 hours down at 100 ℃.Be cooled to room temperature, obtained the alkali-developable photosensitive resin combination No.1-10 (Mw=4560, Mn=2340, acid number 66.4 (solid constituent) mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-10 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-4 carries out the Michael addition polymerization by the ratio below 0.67; And then with respect to 1 of hydroxyl; By 0.5 ratio addition (C) composition be the acid anhydride structure of compound c-1; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-1 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-11] alkali-developable photosensitive resin combination No.1-11

Packing into, two [4-(2; The 3-glycidoxy) phenyl]-4-xenyl (cyclohexyl) methane (compound d-1) 84.3g, acrylic acid (Verbindung-1) 22.1g, 2; 6-di-t-butyl-paracresol 0.429g, benzyltriethylammoinium chloride 0.501g and propylene glycol-1-monomethyl ether-2-acetic acid esters 70.9g stirred 16 hours down at 120 ℃.Be cooled to room temperature, add 1,3-diphenyl-1,3-propanedione (below be also referred to as compound b-5) 16.2g and 1,8-diazabicyclo [5,4,0]-7-undecylene 1.4g stirred 3 hours down at 100 ℃, stirred 34 hours down at 120 ℃ then.After being cooled to room temperature, add succinic anhydride (compound c-1) 15.0g, tetra-n-butyl ammonium bromide 1.35g and propylene glycol-1-monomethyl ether-2-acetic acid esters 48.9g, stirred 5 hours down at 100 ℃.Be cooled to room temperature, obtained the alkali-developable photosensitive resin combination No.1-11 (Mw=3590, Mn=2250, acid number 61.0 (solid constituent) mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-11 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-5 carries out the Michael addition polymerization by the ratio below 0.67; And then with respect to 1 of hydroxyl; By 0.5 ratio addition (C) composition be the acid anhydride structure of compound c-1; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-1 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-12] alkali-developable photosensitive resin combination No.1-12

Pack 3 into; 4-epoxy radicals cyclohexyl methyl-3 '; 4 '-epoxy-cyclohexane carboxylate (Celloxide2021:Daicel chemical company system; Below be also referred to as compound d-5) 160g, acrylic acid (Verbindung-1) 85.3g, triphenylphosphine 1.83g, 2,6-di-t-butyl-paracresol 0.648g and propylene glycol-1-monomethyl ether-2-acetic acid esters 288g stirred 17 hours down at 120 ℃.Be cooled to room temperature, add 2,4-pentanedione (compound b-1) 29.6g, tetra-n-butyl ammonium bromide 1.90g and 2,6-di-t-butyl-paracresol 0.276g stirred 20 hours down at 100 ℃.After being cooled to room temperature, add tetrabydrophthalic anhydride (compound c-2) 151g and tetra-n-butyl ammonium bromide 2.34g, stirred 3 hours down at 100 ℃.Be cooled to room temperature; Add propylene glycol-1-monomethyl ether-2-acetic acid esters 48.3g, obtained the alkali-developable photosensitive resin combination No.1-12 (Mw=1530, Mn=930, acid number (solid constituent) 141mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-12 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-1 carries out the Michael addition polymerization by the ratio below 0.5; And then with respect to 1 of hydroxyl; By 0.8 ratio addition (C) composition be the acid anhydride structure of compound c-2; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-5 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-13] alkali-developable photosensitive resin combination No.1-13

Packing into, two [4-(2; The 3-glycidoxy) phenyl]-4-xenyl (cyclohexyl) methane (compound d-1) 281g, acrylic acid (Verbindung-1) 72.0g, 2; 6-di-t-butyl-paracresol 1.43g, benzyltriethylammoinium chloride 1.67g and propylene glycol-1-monomethyl ether-2-acetic acid esters 235g stirred 16 hours down at 120 ℃.Be cooled to room temperature, add tetramethylol methane tetraacrylate (below be also referred to as compound a '-1) 60.0g, 2,4-pentanedione (compound b-1) 75.0g and triethylamine 3.1g are 92 ℃ of stirrings 17 hours down.After being cooled to room temperature, add succinic anhydride (compound c-1) 70.0g and tetra-n-butyl ammonium bromide 4.35g, stirred 5 hours down at 100 ℃.Be cooled to room temperature; Add propylene glycol-1-monomethyl ether-2-acetic acid esters 443g, obtained the alkali-developable photosensitive resin combination No.1-13 (Mw=3770, Mn=2300, acid number (solid constituent) 73mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-13 is contained obtains through reactions: with respect to (A) composition be epoxy adduct with the potpourri of (A ') composition '-1 that is compound a in contain acrylate-based 1; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-1 carries out the Michael addition polymerization by the ratio below 0.75; And then with respect to 1 of hydroxyl; By 0.7 ratio addition (C) composition be the acid anhydride structure of compound c-1; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-1 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-14] alkali-developable photosensitive resin combination No.1-14

Pack 9 into; 9-is two, and [4-(2; The 3-glycidoxy) phenyl]-9H-fluorenes (compound d-2) 232.0g, acrylic acid (Verbindung-1) 72.0g, 2; 6-di-t-butyl-paracresol 1.43g, benzyltriethylammoinium chloride 1.67g and propylene glycol-1-monomethyl ether-2-acetic acid esters 203.0g stirred 16 hours down at 120 ℃.Be cooled to room temperature, add 2,4-pentanedione (compound b-1) 75.0g, tetramethylol methane tetraacrylate (compound a '-1) 88.0g and triethylamine 3.1g stirred 17 hours down at 92 ℃.Be cooled to room temperature, add succinic anhydride (compound c-1) 70.0g and tetra-n-butyl ammonium bromide 4.35g, stirred 5 hours down at 100 ℃.Be cooled to room temperature; Add propylene glycol-1-monomethyl ether-2-acetic acid esters 415g, obtained the alkali-developable photosensitive resin combination No.1-14 (Mw=3700, Mn=2190, acid number (solid constituent) 79mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-14 is contained obtains through reactions: with respect to (A) composition be epoxy adduct with the potpourri of (A ') composition '-1 that is compound a in contain acrylate-based 1; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-1 carries out the Michael addition polymerization by the ratio below 0.75; And then with respect to 1 of hydroxyl; By 0.8 ratio addition (C) composition be the acid anhydride structure of compound c-1; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-2 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-15] alkali-developable photosensitive resin combination No.1-15

Packing into, two [4-(2; The 3-glycidoxy) phenyl]-4-xenyl (cyclohexyl) methane (compound d-1) 281g, acrylic acid (Verbindung-1) 72.0g, 2; 6-di-t-butyl-paracresol 1.43g, benzyltriethylammoinium chloride 1.67g and propylene glycol-1-monomethyl ether-2-acetic acid esters 235g stirred 16 hours down at 120 ℃.Be cooled to room temperature, add trimethylolpropane triacrylate (below be also referred to as compound a '-2) 74.0g, 2,4-pentanedione (compound b-1) 75.0g and triethylamine 3.1g are 92 ℃ of stirrings 17 hours down.After being cooled to room temperature, add succinic anhydride (compound c-1) 70.0g and tetra-n-butyl ammonium bromide 4.35g, stirred 5 hours down at 100 ℃.Be cooled to room temperature; Add propylene glycol-1-monomethyl ether-2-acetic acid esters 426g, obtained the alkali-developable photosensitive resin combination No.1-15 (Mw=3650, Mn=2220, acid number (solid constituent) 75mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-15 is contained obtains through reactions: with respect to (A) composition be epoxy adduct with the potpourri of (A ') composition '-2 that are compound a in contain acrylate-based 1; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-1 carries out the Michael addition polymerization by the ratio below 0.86; And then with respect to 1 of hydroxyl; By 0.7 ratio addition (C) composition be the acid anhydride structure of compound c-1; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-1 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-16] alkali-developable photosensitive resin combination No.1-16

Packing into, two [4-(2; The 3-glycidoxy) phenyl]-4-xenyl (cyclohexyl) methane (compound d-1) 281g, acrylic acid (Verbindung-1) 72.0g, 2; 6-di-t-butyl-paracresol 1.43g, benzyltriethylammoinium chloride 1.67g and propylene glycol-1-monomethyl ether-2-acetic acid esters 235g stirred 16 hours down at 120 ℃.Be cooled to room temperature, add tristane dimethanol diacrylate (below be also referred to as compound a '-3) 145g, 2,4-pentanedione (compound b-1) 75.0g and triethylamine 3.1g are 92 ℃ of stirrings 18 hours down.Be cooled to room temperature, add succinic anhydride (compound c-1) 70.0g and tetra-n-butyl ammonium bromide 4.35g, stirred 5 hours down at 100 ℃.Be cooled to room temperature; Add propylene glycol-1-monomethyl ether-2-acetic acid esters 512g, obtained the alkali-developable photosensitive resin combination No.1-16 (Mw=3780, Mn=2450, acid number (solid constituent) 73mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-16 is contained obtains through reactions: with respect to (A) composition be epoxy adduct with the potpourri of (A ') composition '-3 that are compound a in contain acrylate-based 1; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-1 carries out the Michael addition polymerization by the ratio below 0.75; And then with respect to 1 of hydroxyl; By 0.7 ratio addition (C) composition be the acid anhydride structure of compound c-1; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-1 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-17] alkali-developable photosensitive resin combination No.1-17

< step>1>manufacturing of epoxy acrylate solution A-BC

Packing into, two [4-(2; The 3-glycidoxy) phenyl]-4-xenyl (cyclohexyl) methane (compound d-1) 842.7g, acrylic acid (Verbindung-1) 220.5g, 2; 6-di-t-butyl-paracresol 4.29g, benzyltriethylammoinium chloride 5.42g and propylene glycol-1-monomethyl ether-2-acetic acid esters 708.8g stirred 14 hours down at 120 ℃.After it is cooled to room temperature, obtain epoxy acrylate solution A-BC.

< step>2>manufacturing of alkali-developable photosensitive resin combination No.1-17

Pack into epoxy acrylate solution A-BC 53.5g, 1-(2-naphthyl) butane-1; 3-diketone (below be also referred to as compound b-6) 6.4g, 1,8-diazabicyclo [5,4; 0]-and 7-undecylene 0.8g and propylene glycol-1-monomethyl ether-2-acetic acid esters 17.9g, stirred 4 hours down at 120 ℃.After it is cooled to room temperature,, stirred 5 hours down at 100 ℃ to wherein adding tetrabydrophthalic anhydride (compound c-2) 6.8g and propylene glycol-1-monomethyl ether-2-acetic acid esters 6.8g.Be cooled to room temperature, obtained the alkali-developable photosensitive resin combination No.1-17 (Mw=5200, Mn=2320, acid number 57.0mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-17 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; The hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-6 carries out the Michael addition polymerization by 0.67 ratio; And then with respect to 1 of hydroxyl; By 0.5 ratio addition (C) composition be the acid anhydride structure of compound c-2; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-1 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-18] alkali-developable photosensitive resin combination No.1-18

Epoxy acrylate solution A-BC 19.00g, 1-[9-ethyl-6-(4-fluoro-2-methyl benzoyl)-9H-carbazole-3-yl]-butane-1 pack into; 3-diketone (below be also referred to as compound b-7) 3.32g, 1; 8-diazabicyclo [5; 4,0]-and 7-undecylene 0.24g and propylene glycol-1-monomethyl ether-2-acetic acid esters 0.64g, stirred 12 hours down at 120 ℃.Add propylene glycol-1-monomethyl ether-2-acetic acid esters 6.73g therein, be cooled to room temperature.After the cooling, add succinic anhydride (below be also referred to as compound c-1) 2.9g and propylene glycol-1-monomethyl ether-2-acetic acid esters 6.9g, 100 ℃ of stirrings 5 hours down.Be cooled to room temperature, obtained the alkali-developable photosensitive resin combination No.1-18 (Mw=4430, Mn=2110, acid number 96.5mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-18 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-7 carries out the Michael addition polymerization by 0.5 ratio; And then with respect to 1 of hydroxyl; By 0.9 ratio addition (C) composition be the acid anhydride structure of compound c-1; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-1 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-19] alkali-developable photosensitive resin combination No.1-19

< step>1>manufacturing of epoxy acrylic resin solution

Pack 2 into; 2-is two, and [4-(2; The 3-glycidoxy) phenyl] propane (below; Be also referred to as compound d-3) 185g, acrylic acid (Verbindung-1) 73.5g, 2,6-di-t-butyl-paracresol 0.7g, benzyltriethylammoinium chloride 1.7g and propylene glycol-1-monomethyl ether-2-acetic acid esters 174.0g stirred 16 hours down at 120 ℃.It is cooled to room temperature, obtains the epoxy acrylic ester solution.

< step>2>manufacturing of alkali-developable photosensitive resin combination No.1-19

The epoxy acrylic ester solution 13.93g that the step 1 of packing into obtains, 1-[9-ethyl-6-(4-fluoro-2-methyl benzoyl)-9H-carbazole-3-yl]-butane-1; 3-diketone (compound b-7) 3.32g, 1; 8-diazabicyclo [5; 4,0]-and 7-undecylene 0.24g and propylene glycol-1-monomethyl ether-2-acetic acid esters 0.64g, stirred 8 hours down at 120 ℃.Add propylene glycol-1-monomethyl ether-2-acetic acid esters 5.73g therein, be cooled to room temperature,, stirred 5 hours down at 100 ℃ to wherein adding succinic anhydride (compound c-1) 2.9g and propylene glycol-1-monomethyl ether-2-acetic acid esters 5.8g.Be cooled to room temperature, obtained the alkali-developable photosensitive resin combination No.1-19 (Mw=4300, Mn=2140, acid number 114.5mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-19 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-7 carries out the Michael addition polymerization by 0.5 ratio; And then with respect to 1 of hydroxyl; By 0.9 ratio addition (C) composition be the acid anhydride structure of compound c-1; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-3 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-20] alkali-developable photosensitive resin combination No.1-20

Epoxy acrylate solution A-BC 53.5g, 1-(9-propyl group-9H-carbazole-3-yl)-butane-1 pack into; 3-diketone (below be also referred to as compound b-8) 8.8g, 1; 8-diazabicyclo [5; 4,0]-and 7-undecylene 0.8g and propylene glycol-1-monomethyl ether-2-acetic acid esters 20.3g, stirred 13 hours down at 120 ℃.It is cooled to room temperature, adds tetrabydrophthalic anhydride (below be also referred to as compound c-2) 6.8g and propylene glycol-1-monomethyl ether-2-acetic acid esters 17.62g, 100 ℃ of stirrings 5 hours down.Be cooled to room temperature, obtained the alkali-developable photosensitive resin combination No.1-20 (Mw=4440, Mn=2290, acid number 55.8mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-20 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-8 carries out the Michael addition polymerization by 0.67 ratio; And then with respect to 1 of hydroxyl; By 0.5 ratio addition (C) composition be the acid anhydride structure of compound c-2; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), wherein above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-1 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

The manufacturing of [embodiment 4-21] alkali-developable photosensitive resin combination No.1-21

Epoxy acrylate solution A-BC 35.6g, 1-[9-ethyl-6-(4-fluoro-2-methyl benzoyl)-9H-carbazole-3-yl]-butane-1 pack into; 3-diketone (compound b-7) 8.31g, 1; 8-diazabicyclo [5; 4,0]-and 7-undecylene 0.5g and propylene glycol-1-monomethyl ether-2-acetic acid esters 16.0g, stirred 10 hours down at 120 ℃.After it is cooled to room temperature,, stirred 5 hours down at 100 ℃ to wherein adding tetrabydrophthalic anhydride (compound c-2) 6.4g, propylene glycol-1-monomethyl ether-2-acetic acid esters 14.5g.Be cooled to room temperature, obtained the alkali-developable photosensitive resin combination No.1-21 (Mw=4810, Mn=2190, acid number 65.9mgKOH/g) of target substance with the form of propylene glycol-1-monomethyl ether-2-acetate solution.

And; The optical polymerism unsaturated compound (J) that alkali-developable photosensitive resin combination No.1-21 is contained obtains through reactions: be acrylate-based 1 of epoxy adduct with respect to (A) composition; (B) composition is that the hydrogen atom of the methylene of the diketone clamping in the beta-diketon position of compound b-7 carries out the Michael addition polymerization by 0.67 ratio; And then with respect to 1 of hydroxyl; By 0.7 ratio addition (C) composition be the acid anhydride structure of compound c-2; Thereby obtain above-mentioned optical polymerism unsaturated compound (J), above-mentioned (A) composition be epoxy adduct have with respect to (D) composition be 1 of the epoxy radicals of compound d-1 by 1.0 ratio addition (E) composition be the carboxyl of Verbindung-1 and the structure that obtains.

[comparative example 3-1] relatively uses the manufacturing of resin combination No.1-1

Pack 9 into; 9-is two, and [4-(2; The 3-glycidoxy) phenyl]-9H-fluorenes (compound d-2) 184g, acrylic acid (Verbindung-1) 58.0g, 2; 6-di-t-butyl-paracresol 0.26g, tetra-n-butyl ammonium bromide 0.11g and propylene glycol-1-monomethyl ether-2-acetic acid esters 23.0g stirred 16 hours down at 120 ℃.Be cooled to room temperature; Add propylene glycol-1-monomethyl ether-2-acetic acid esters 35.0g, bibenzene tetracarboxylic dianhydride 59.0g, tetrabydrophthalic anhydride 20.0g and tetra-n-butyl ammonium bromide 0.24g; Stirred 4 hours down at 120 ℃; Stirred 3 hours down at 100 ℃, stirred 4 hours down, stirred 6 hours down and stirred 11 hours down at 40 ℃ at 60 ℃ at 80 ℃.Be cooled to room temperature; Add propylene glycol-1-monomethyl ether-2-acetic acid esters 90.0g, the propylene glycol-1-monomethyl ether-2-acetate solution that obtains target substance is promptly relatively used resin combination No.1-1 (Mw=5000, Mn=2100, acid number (solid constituent) 93mgKOH/g).

[comparative example 3-2] relatively uses the manufacturing of resin combination No.1-2

Pack 2 into; 2-is two, and [4-(2; The 3-glycidoxy) phenyl] propane (compound d-3) 154g, acrylic acid (Verbindung-1) 59.0g, 2,6-di-t-butyl-paracresol 0.26g, tetra-n-butyl ammonium bromide 0.11g and propylene glycol-1-monomethyl ether-2-acetic acid esters 23.0g stirred 16 hours down at 120 ℃.Be cooled to room temperature; Add propylene glycol-1-monomethyl ether-2-acetic acid esters 36.0g, bibenzene tetracarboxylic dianhydride 67.0g and tetra-n-butyl ammonium bromide 0.24g; Stirred 4 hours down at 120 ℃; Stirred 3 hours down at 100 ℃, stirred 4 hours down, stirred 6 hours down and stirred 11 hours down at 40 ℃ at 60 ℃ at 80 ℃.Be cooled to room temperature; Add propylene glycol-1-monomethyl ether-2-acetic acid esters 90.0g, the propylene glycol-1-monomethyl ether-2-acetate solution that obtains target substance is promptly relatively used resin combination No.1-2 (Mw=7500, Mn=2100, acid number (solid constituent) 91mgKOH/g).

[embodiment 5-1～5-16 and comparative example 4-1 and 4-2] alkali-developable photosensitive resin combination No.2-1～2-16 and the preparation of relatively using resin combination No.2-1 and No.2-2

Among the 14g that relatively uses resin combination No.1-1～1-2 that obtains among the alkali-developable photosensitive resin combination No.1-1～1-16 that in embodiment 4-1～4-16, obtains and comparative example 3-1 and the 3-2; Add as tetramethylol methane tetraacrylate (compound a '-1) 5.0g with as the propylene glycol-1-monomethyl ether-2-acetic acid esters 78g of solvent with monomer of unsaturated link; Fully stir, obtain alkali-developable photosensitive resin combination No.2-1～2-16 of the present invention and relatively use resin combination No.2-1 and No.2-2.

[embodiment 5-17～5-21 and comparative example 4-3] alkali-developable photosensitive resin combination No.2-17～2-21 and the preparation of relatively using resin combination No.2-3

Among the 17g that relatively uses resin combination No.2 that obtains among alkali-developable photosensitive resin combination No.1～No.4 that in embodiment 1-1～1-4, obtains and the comparative example 1-2; Add as trimethylolpropane triacrylate (compound a '-2) 7.0g with as the propylene glycol-1-monomethyl ether-2-acetic acid esters 78g of solvent with monomer of unsaturated link; Fully stir, obtain alkali-developable photosensitive resin combination No.2-17～2-21 and relatively use resin combination No.2-3.

[evaluation Example 2-1～2-21 and comparative evaluation example 2-1 and 2-2]

Carry out alkali-developable photosensitive resin combination No.2-1～No.2-21 for preparing among the foregoing description 5-1～5-21 and the comparative example 4-1～4-3 and the evaluation of relatively using resin combination No.2-1～No.2-3 as follows.

That is, on glass substrate, rotary coating (700r.p.m, 5 seconds) developable photosensitive resin combination, after air-dry 15 minutes, 90 seconds of prebake conditions on 90 ℃ heating plate.Using mask open is the mask of 30 μ m, makes public with high-pressure sodium lamp.Then, in dipping development in 60 seconds in 2.5 quality % sodium carbonate liquors under 25 ℃, fully washing.At this moment, during exposure through at 100mJ/cm ²That following exposure has formed pattern is ◎, at 100mJ/cm ²Down insufficient but at 150mJ/cm ²What following exposure had formed pattern is zero, even at 150mJ/cm ²Do not form down yet pattern for *.The result is shown in [table 6].

[table 6]

?	The alkali-developable photosensitive resin combination	Relatively use resin combination	Pattern forms
				Evaluation Example 2-1	No.2-1	?	○
Evaluation Example 2-2	No.2-2	?	○
				Evaluation Example 2-3	No.2-3	?	○
Evaluation Example 2-4	No.2-4	?	○
				Evaluation Example 2-5	No.2-5	?	○
Evaluation Example 2-6	No.2-6	?	○
				Evaluation Example 2-7	No.2-7	?	○
Evaluation Example 2-8	No.2-8	?	○
				Evaluation Example 2-9	No.2-9	?	○
Evaluation Example 2-10	No.2-10	?	○
				Evaluation Example 2-11	No.2-11	?	○
Evaluation Example 2-12	No.2-12	?	○
				Evaluation Example 2-13	No.2-13	?	○
Evaluation Example 2-14	No.2-14	?	○
				Evaluation Example 2-15	No.2-15	?	○
Evaluation Example 2-16	No.2-16	?	○
				Evaluation Example 2-17	No.2-17	?	○
Evaluation Example 2-18	No.2-18	?	◎
				Evaluation Example 2-19	No.2-19	?	◎
Evaluation Example 2-20	No.2-20	?	◎
				Evaluation Example 2-21	No.2-21	?	◎
Comparative evaluation example 2-1	?	No.2-1	×
				Comparative evaluation example 2-2	?	No.2-2	×
Comparative evaluation example 2-3	?	No.2-3	×

Even the alkali-developable photosensitive resin combination of embodiment 5-1～5-21 also can solidify through exposure under the condition that does not have Photoepolymerizationinitiater initiater (F), through alkali development formation pattern.On the other hand, the alkali-developable photosensitive resin combination of comparative example 4-1～4-3 do not have Photoepolymerizationinitiater initiater (F) even condition under make public and also can not solidify, can't develop through alkali forms pattern.

[embodiment 6-1～6-5 and comparative example 5] painted alkali-developable photosensitive resin combination No.1-1～No.1-5 and the preparation of relatively using resin combination No.1

Among the 70g that relatively uses resin combination No.1-2 that obtains among alkali-developable photosensitive resin combination No.1-17～No.1-21 that in embodiment 4-17～4-21, obtains and the comparative example 3-2; Add as trimethylolpropane triacrylate (compound a '-2) 9.0g, as carbon black (Mitsubishi Chemical Ind's system " the MA100 ") 30g of colorant (G) with as the propylene glycol-1-monomethyl ether-2-acetic acid esters 75g of solvent with monomer of unsaturated link; Fully stir, obtain painted alkali-developable photosensitive resin combination No.1-1～1-5 and relatively use colored resin composition No.1.

[evaluation Example 3-1～3-5 and comparative evaluation example 3]

Carry out in embodiment 6-1～6-5 and the comparative example 5 the painted alkali-developable photosensitive resin combination No.1-1～No.1-5 of preparation as follows and relatively use the evaluation of colored resin composition No.1.

That is, on glass substrate, rotary coating (700r.p.m, 5 seconds) alkali-developable photosensitive resin combination, after air-dry 15 minutes, 90 seconds of prebake conditions on 90 ℃ heating plate.Using mask open is the mask of 30 μ m, with high-pressure sodium lamp with 200mJ/cm ²Exposure.Then, in dipping development in 40 seconds in 2.5 quality % sodium carbonate liquors under 25 ℃, fully washing.At this moment, what formed pattern is zero, do not form pattern for *.The result is shown in [table 7].

[table 7]

?	Painted alkali-developable photosensitive resin combination	Relatively use colored resin composition	Pattern forms
				Evaluation Example 3-1	No.1-1	?	×
Evaluation Example 3-2	No.1-2	?	○
				Evaluation Example 3-3	No.1-3	?	○
Evaluation Example 3-4	No.1-4	?	○
				Evaluation Example 3-5	No.1-5	?	○
Comparative evaluation example 3	?	No.1	×

Even the painted alkali-developable photosensitive resin combination of embodiment 6-2～6-5 also can solidify through exposure under the condition of Photoepolymerizationinitiater initiater not having, developing through alkali forms pattern.On the other hand, even the colored resin composition of embodiment 6-1 and comparative example 5 is not having under the condition of Photoepolymerizationinitiater initiater exposure can not solidify yet, can't develop through alkali forms pattern.

[embodiment 7-1～7-16 and comparative example 6-1 and 6-2] alkali-developable photosensitive resin combination No.3-1～No.3-16 and the preparation of relatively using photosensitive polymer combination No.1-1 and No.1-2

Among alkali-developable photosensitive resin combination No.1-1～1-16 that in embodiment 4-1～4-16 and comparative example 3-1 and 3-2, obtains and the 14g that relatively uses photosensitive polymer combination No.1-1 and No.1-2; Add as have trimethylolpropane triacrylate (compound a '-2) 6.0g of the monomer of unsaturated link, as 2 of Photoepolymerizationinitiater initiater (F); 4; 6-trimethylbenzoyl diphenyl phosphine oxide 3.0g and as the propylene glycol-1-monomethyl ether-2-acetic acid esters 78g of solvent; Fully stir, obtain alkali-developable photosensitive resin combination No.3-1～3-16 of the present invention and relatively use photosensitive polymer combination No.1-1 and No.1-2.

[evaluation Example 4-1～4-16 and comparative evaluation example 4-1 and 4-2]

Carry out alkali-developable photosensitive resin combination No.3-1～3-16 for preparing among the foregoing description 7-1～7-16 and comparative example 6-1 and the 6-2 and the evaluation of relatively using photosensitive polymer combination No.1-1 and No.1-2 as follows.

That is, on substrate, rotary coating γ-glycidyl propyl group methyl ethoxy silane, make its abundant Rotary drying after, the above-mentioned alkali-developable photosensitive resin combination of rotary coating (1300r.p.m., 50 seconds) also makes its drying.Carrying out prebake conditions under 70 ℃ after 20 minutes, pva coating 5 quality % solution are processed the oxygen Obstruct membrane.After 70 ℃, 20 minutes the drying, use the mask of regulation, as light source, in 2.5 quality % sodium carbonate liquors, flooding development in 30 seconds, fully washing under 25 ℃ with ultrahigh pressure mercury lamp.Behind the washing and drying, baking made the pattern photographic fixing in 1 hour under 230 ℃.Pattern to obtaining carries out following evaluation.The result is shown in [table 8].

< sensitivity >

During exposure, exposure is 100mJ/cm ²With regard to enough be a, 100mJ/cm ²Down insufficient but at 150mJ/cm ²Following exposure be b, 150mJ/cm ²Down insufficient but at 200mJ/cm ²Following exposure be c.

< exploring degree >

During exposure imaging, below live width 10 μ m, also can form the A that is of good pattern, in live width 10～30 mu m ranges, can form the B that is of pattern well, be the C that could form good pattern more than the 30 μ m in live width only.

< adhesiveness >

Observe to develop the peeling off of the pattern that obtains, what do not observe that pattern peels off is zero, the part observe peel off for *.

[table 8]

?	The alkali-developable photosensitive resin combination	Relatively use photosensitive polymer combination	Sensitivity	The exploring degree	Adhesiveness
						Evaluation Example 4-1	No.3-1	?	a	A	○
Evaluation Example 4-2	No.3-2	?	a	A	○
						Evaluation Example 4-3	No.3-3	?	a	A	○
Evaluation Example 4-4	No.3-4	?	a	A	○
						Evaluation Example 4-5	No.3-5	?	a	A	○
Evaluation Example 4-6	No.3-6	?	a	A	○
						Evaluation Example 4-7	No.3-7	?	a	A	○
Evaluation Example 4-8	No.3-8	?	a	A	○
						Evaluation Example 4-9	No.3-9	?	a	A	○
Evaluation Example 4-10	No.3-10	?	a	A	○
						Evaluation Example 4-11	No.3-11	?	a	A	○
Evaluation Example 4-12	No.3-12	?	a	A	○
						Evaluation Example 4-13	No.3-13	?	a	A	○
Evaluation Example 4-14	No.3-14	?	a	A	○
						Evaluation Example 4-15	No.3-15	?	a	A	○
Evaluation Example 4-16	No.3-16	?	a	A	○
						Comparative evaluation example 4-1	?	No.1-1	c	B	×
Comparative evaluation example 4-2	?	No.1-2	b	C	×

The alkali-developable photosensitive resin combination of embodiment 7-1～7-16 is a high sensitivity, and the exploring degree is excellent.And also excellent with the adhesiveness of substrate, peeling off of pattern is few.Relative therewith, the alkali-developable photosensitive resin combination of comparative example 6-1 and 6-2 is a muting sensitivity, exploring degree and also low with the adhesiveness of substrate.

[embodiment 8-1～8-16 and comparative example 7-1 and 7-2] painted alkali-developable photosensitive resin combination No.2-1～No.2-16 and the preparation of relatively using colored resin composition No.2-1 and No.2-2

Among alkali-developable photosensitive resin combination No.1-1～1-16 that in embodiment 4-1～4-16 and comparative example 3-1 and 3-2, obtains and the 44g that relatively uses photosensitive polymer combination No.1-1 and No.1-2; Add as tetramethylol methane tetraacrylate (compound a '-1) 10.0g, as 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino propane-1-ketone (Irg907) 5.0g of Photoepolymerizationinitiater initiater (F), as carbon black (Mitsubishi Chemical Ind's system " the MA100 ") 19g of colorant (G) with as the propylene glycol-1-monomethyl ether-2-acetic acid esters 75g of solvent with monomer of unsaturated link; Fully stir, obtain painted alkali-developable photosensitive resin combination No.2-1～2-16 of the present invention and relatively use colored resin composition No.2-1 and No.2-2.

[embodiment 8-17～8-21 and comparative example 7-3] painted alkali-developable photosensitive resin combination No.2-17～No.2-21 and the preparation of relatively using colored resin composition No.2-3

Among the 70g that relatively uses resin combination No.1-2 that obtains among alkali-developable photosensitive resin combination No.1-17～No.1-21 that in embodiment 4-17～4-21, obtains and the comparative example 3-2; Add as trimethylolpropane triacrylate (compound a '-2) 9.0g, as IRGACUREOXE02 (the Ciba Specialty Chemicals Co., Ltd. system) 3g of Photoepolymerizationinitiater initiater (F), as carbon black (Mitsubishi Chemical Ind's system " the MA100 ") 30g of colorant (G) with as the propylene glycol-1-monomethyl ether-2-acetic acid esters 75g of solvent with monomer of unsaturated link; Fully stir, obtain painted alkali-developable photosensitive resin combination No.2-17～No.2-21 and relatively use colored resin composition No.2-3.

[evaluation Example 5-1～5-21 and comparative evaluation example 5-1～5-3]

Carry out alkali-developable photosensitive resin combination No.2-1～No.2-21 for preparing among embodiment 8-1～8-21 and the comparative example 7-1～7-3 and the evaluation of relatively using colored resin composition No.2-1～No.2-3 as follows.

That is, on glass substrate, rotary coating (700r.p.m, 5 seconds) alkali-developable photosensitive resin combination after air-dry 15 minutes, carries out 90 seconds of prebake conditions on 90 ℃ heating plate.Use the mask of regulation, after making public as light source with high-pressure sodium lamp, in dipping development in 40 seconds in 2.5 quality % sodium carbonate liquors under 25 ℃, fully washing.Behind the washing and drying, baking made the pattern photographic fixing in 1 hour under 230 ℃.Pattern to obtaining carries out following evaluation.The result is shown in [table 9].

< sensitivity >

During exposure, exposure is 50mJ/cm ²With regard to enough be a, 50mJ/cm ²Down insufficient but at 70mJ/cm ²Following exposure be b, 70mJ/cm ²Down insufficient but at 100mJ/cm ²Following exposure be c, 100mJ/cm ²Down insufficient but at 150mJ/cm ²Following exposure be d.

< exploring degree >

During exposure imaging, below live width 5 μ m, also can form the A that is of pattern well, when live width 20 μ m, can form the B that is of pattern well, be the C that could form good pattern more than the 30 μ m in live width only.

< adhesiveness >

Observe to develop the peeling off of the pattern that obtains do not observe the A that is that pattern peels off, and the B that is that peels off is observed in the part, and whole observation is C to what peel off.

[table 9]

?	Painted alkali-developable photosensitive resin combination	Relatively use colored resin composition	Sensitivity	The exploring degree	Adhesiveness
						Evaluation Example 5-1	No.2-1	?	b	B	B
Evaluation Example 5-2	No.2-2	?	b	B	B
						Evaluation Example 5-3	No.2-3	?	b	B	B
Evaluation Example 5-4	No.2-4	?	b	B	B
						Evaluation Example 5-5	No.2-5	?	b	B	B
Evaluation Example 5-6	No.2-6	?	b	B	B
						Evaluation Example 5-7	No.2-7	?	b	B	B
Evaluation Example 5-8	No.2-8	?	b	B	B
						Evaluation Example 5-9	No.2-9	?	b	B	B
Evaluation Example 5-10	No.2-10	?	b	B	B
						Evaluation Example 5-11	No.2-11	?	b	B	B
Evaluation Example 5-12	No.2-12	?	b	B	B
						Evaluation Example 5-13	No.2-13	?	b	B	B
Evaluation Example 5-14	No.2-14	?	b	B	B
						Evaluation Example 5-15	No.2-15	?	b	B	B
Evaluation Example 5-16	No.2-16	?	b	B	B
						Evaluation Example 5-17	No.2-17	?	b	B	B
Evaluation Example 5-18	No.2-18	?	a	A	A
						Evaluation Example 5-19	No.2-19	?	a	A	A
Evaluation Example 5-20	No.2-20	?	a	A	A
						Evaluation Example 5-21	No.2-21	?	a	A	A
Comparative evaluation example 5-1	?	No.2-1	d	B	C
						Comparative evaluation example 5-2	?	No.2-2	c	C	C
Comparative evaluation example 5-3	?	No.2-3	d	C	C

The painted alkali-developable photosensitive resin combination of embodiment 8-1～8-21 is a high sensitivity, and the exploring degree is excellent.And also excellent with the adhesiveness of substrate, peeling off of pattern is few.Relative therewith, the colored resin composition that relatively uses of comparative example 7-1～7-3 is muting sensitivity, exploring degree and also low with the adhesiveness of substrate.

Utilizability in the industry

Alkali-developable photosensitive resin groups thing of the present invention can be given enough sensitivity, exploring degree and adhesiveness through not using or use a spot of Photoepolymerizationinitiater initiater.

Claims (6)

1. alkali-developable photosensitive resin combination; It is characterized in that; It contains the optical polymerism unsaturated compound, and said optical polymerism unsaturated compound has the structure that the esterification through the hydroxyl of reactions product and multi-anhydride obtains, and (methyl) acryloyl group of the compound that said reaction product makes the compound with beta-diketon position or has a 'beta '-ketoester base and the compound with (methyl) acryloyl group and hydroxyl more than 2 carries out addition and obtains; Wherein

Said multi-anhydride is a methylene THPA in succinic anhydride, maleic anhydride, trimellitic anhydride, phthalic anhydride, methyl tetrahydrophthalic anhydride, tetrabydrophthalic anhydride, carbic anhydride, methyl carbic anhydride, trialkyl tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride or the methyl

The said compound that has the compound at beta-diketon position or have a 'beta '-ketoester base is 2; 4-pentanedione, 2; 4-acetyl butyryl, 2; 4-heptadione, 1-methoxyl-2; 4-pentanedione, 1-phenyl-1; 3-diacetyl, 1; 3-diphenyl-1; 3-propanedione, methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, butyl-acetoacetate, tert-butyl acetoacetate, acetoacetate-2-methoxyl ethyl ester, acetoacetate-2-Octyl Nitrite, acetoacetate lauryl, acetoacetic acid allyl ester, Propionylacetic acid ethyl ester, propionyl butyl acetate, butyryl methyl acetate, methyl benzoylacetate, ethyl benzoylacetate, benzoyl acetic acid butyl ester, 4; 6-dioxo methyl heptanoate, 5; 7-dioxo methyl caprylate, acrylic acid-2-acetoacetyl ethyl ester, methacrylic acid-2-acetoacetyl ethyl ester, benzyl acetoacetate, 1,4-butylene glycol diacetyl acetic ester, 1,6-hexanediol diacetyl acetic ester, neopentyl glycol diacetyl acetic ester, 2-ethyl-2-butyl-1; Ammediol diacetyl acetic ester, cyclohexanedimethanol diacetyl acetic ester, ethoxylation bisphenol-A diacetyl acetic ester, trimethylolpropane tris acetoacetic ester, glycerine triacetyl acetic acid esters, pentaerythrite triacetyl acetic acid esters, pentaerythrite tetrem ethyl sodio acetoacetic ester, two (trimethylolpropane) tetrem ethyl sodio acetoacetic ester, the oligomer that contains acetoacetate groups, ethyl acetoacetate and contain product of transesterification reaction and the oligomer that contains acetoacetate groups or the polymkeric substance that the polymerization through methacrylic acid-2-acetoacetyl ethyl ester obtains of oligomer or the polymkeric substance of hydroxyl

Said compound with (methyl) acryloyl group and hydroxyl more than 2 be pentaerythritol triacrylate, dipentaerythritol five acrylic ester, trimethylolethane diacrylate, trimethylolpropane diacrylate, tetra methylol propane triacrylate, 2-hydroxyl-3-acryloxy propyl group acrylic ester or following compound N o.11

2. alkali-developable photosensitive resin combination as claimed in claim 1 is characterized in that, said compound with beta-diketon position is the beta-diketone compound of formula (I) expression,

In the formula, R ¹The expression methyl, R ²Expression ethyl or propyl group, R ⁴Expression 4-fluoro-2-methyl benzoyl, a representes 0, b representes 0 or 1.

3. alkali-developable photosensitive resin combination as claimed in claim 1 is characterized in that, said beta-diketone compound is R in the said general formula (I) ¹It for methyl, a 0 compound.

4. alkali-developable photosensitive resin combination as claimed in claim 1 is characterized in that, said beta-diketone compound is R in the said general formula (I) ¹Be methyl, R ⁴For can be that 6～20 acyl group, a are 0 by the substituted carbon number of halogen atom, b is 0 or 1 compound.

5. like each described alkali-developable photosensitive resin combination in the claim 1～4, it is characterized in that it further contains Photoepolymerizationinitiater initiater.

6. a painted alkali-developable photosensitive resin combination is characterized in that, in claim 1～5, further contains colorant in each described alkali-developable photosensitive resin combination.