CN1885162B - Alkali developing photosensitive resin composition - Google Patents
Alkali developing photosensitive resin composition Download PDFInfo
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- CN1885162B CN1885162B CN2006100938192A CN200610093819A CN1885162B CN 1885162 B CN1885162 B CN 1885162B CN 2006100938192 A CN2006100938192 A CN 2006100938192A CN 200610093819 A CN200610093819 A CN 200610093819A CN 1885162 B CN1885162 B CN 1885162B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
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Abstract
An alkali and negative resin combination, which contains the outcome from making oxygen-linked addition compound many entity anhydrides (C) the multi-functional oxygen-linked compound esterified. The oxygen-linked addition compound, possessing a oxygen-linked radical owned by oxygen-linked resin (A), has the structure shaped by combining oxygen-linked resin expressing with unsaturated unified acid (B) whose structure is shaped by combining at the rate on carboxyl group of 0.1-1.0 and the formula (I) in which the definition of each parameter is seen in the introduction. The esterification is carrying out at the rate of one hydroxyl group in the oxygen -linked addition compound, 0.1-1.0 anhydride structure in the many entity anhydrides (C) and 0.1-1.0 oxygen-linked radical in the multi-functional oxygen-linked compound (D).
Description
Technical field
The present invention relates to contain the alkali development resin composition of specific compound, in this alkali development resin composition, contain Photoepolymerizationinitiater initiater and the alkali developing photosensitive resin composition that forms and the manufacture method of this alkali development resin composition with ethylenic unsaturated bond.
Background technology
Alkali developing photosensitive resin composition comprises and contains alkali development resin composition and the Photoepolymerizationinitiater initiater with ethylenic unsaturated bond compound.By to this alkali developing photosensitive resin composition irradiation ultraviolet radiation or electron ray, can make its polymerizing curable, therefore be used to photo-curable printing ink, photosensitive printing version, printed circuit distributing board, various photoresists etc.Recently, be accompanied by compactization of electronic device and the development of high performance, the alkali developing photosensitive resin composition that can precision forms trickle figure well enjoys expectation.
About alkali development resin composition and alkali developing photosensitive resin composition, the photosensitive polymer combination of the prepolymer with ethylenic unsaturated bond has been proposed to contain in the following patent documentation 1.In addition, proposed to comprise the photosensitive polymer combination of the polycarboxylic acid resin that contains unsaturated group in the following patent documentation 2.But the sensitivity of these known alkali developing photosensitive resin compositions is insufficient, is difficult to obtain suitable graphics shape and trickle figure.Therefore, the transparency, cohesive and alkali resistance is good and the alkali developing photosensitive resin composition that can precision forms trickle figure well enjoys expectation.
Patent documentation 1: the spy opens communique 2000-No. 235261
Patent documentation 2: the spy opens flat 2000-No. 355621 communiques
Summary of the invention
As mentioned above, problem to be solved by this invention be also do not have at present a kind of sensitivity fully, can obtain the suitable graphics shape and the alkali development resin composition of trickle figure.
Therefore, the object of the present invention is to provide a kind of sensitivity, exploring degree, the transparency, cohesive and alkali resistance etc. good and can precision form the alkali development resin composition and the alkali developing photosensitive resin composition of trickle figure well.
The present invention is by providing a kind of alkali development resin composition, realized above-mentioned purpose, described alkali development resin composition contains makes epoxy adduct and multi-anhydride (C), the reaction product of carrying out esterification with multi-functional epoxy compound (D) then and obtaining, above-mentioned epoxy adduct has the structure that makes unsaturated monoacid (B) and the epoxy resin of representing with following general formula (I) (A) carry out addition and form, above-mentioned epoxy adduct has with 1 epoxy radicals with respect to above-mentioned epoxy resin (A), the carboxyl of above-mentioned unsaturated monoacid (B) is that 0.1～1.0 ratio carries out the structure that addition forms, and above-mentioned esterification is with 1 hydroxyl with respect to above-mentioned epoxy adduct, the acid anhydride structure of above-mentioned multi-anhydride (C) is 0.1～1.0, above-mentioned multi-functional epoxy compound's (D) epoxy radicals is that 0.1～1.0 ratio carries out.
(in the formula, Cy represents that carbon number is 3～10 naphthenic base, X represents hydrogen atom or can is that the phenyl that replaces of 1～10 alkyl or alkoxy or carbon number are 3～10 naphthenic base by carbon number, Y and Z represent that independently of one another carbon number is that 1～10 alkyl, carbon number are that 1～10 alkoxy, carbon number are 2～10 alkenyl or halogen atom, alkyl, alkoxy and alkenyl can be replaced by halogen atom, n represents 0～10 number, and p represents 0～4 number, and r represents 0～4 number.)
In addition, the present invention contains the alkali developing photosensitive resin composition that Photoepolymerizationinitiater initiater (F) forms by being provided in the above-mentioned alkali development resin composition, realized above-mentioned purpose.
In addition, the invention provides the manufacture method of above-mentioned alkali development resin composition, it is to make unsaturated monoacid (B) and the epoxy resin of representing with above-mentioned general formula (I) (A) carry out addition and obtain epoxy adduct, then with this epoxy adduct with multi-anhydride (C), use multi-functional epoxy compound (D) to carry out esterification then, thereby obtain the manufacture method of the alkali development resin composition of above-mentioned alkali development resin composition.
Embodiment
Below, for alkali development resin composition of the present invention and alkali developing photosensitive resin composition, preferred embodiment be described in detail with regard to it.
Alkali development resin composition of the present invention contains makes epoxy adduct and multi-anhydride (C), carry out esterification with above-mentioned multi-functional epoxy compound (D) and the reaction product that obtains then, above-mentioned epoxy adduct has the structure that makes unsaturated monoacid (B) and the epoxy resin of representing with above-mentioned general formula (I) (A) carry out addition and form, wherein with respect to 1 epoxy radicals of above-mentioned epoxy resin (A), the ratio of the carboxyl of above-mentioned unsaturated monoacid (B) is 0.1～1.0; With respect to 1 hydroxyl of above-mentioned epoxy adduct, the ratio of acid anhydride structure is 0.1～1.0; With respect to 1 hydroxyl of above-mentioned epoxy adduct, the ratio of epoxy radicals is 0.1～1.0.
With respect to 1 epoxy radicals of above-mentioned epoxy resin (A), the ratio of the carboxyl of above-mentioned unsaturated monoacid (B) is preferably 0.4～1.0.In addition, with respect to 1 hydroxyl of above-mentioned epoxy compound, the ratio of the acid anhydride structure of multi-anhydride (C) is preferably 0.4～1.0, and the ratio of above-mentioned multi-functional epoxy compound's (D) epoxy radicals is preferably 0.4～1.0.
As the naphthenic base that in the above-mentioned general formula (I) is 3～10, can list cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl etc. with the carbon number shown in the Cy.
As the carbon number of representing with X is 3～10 naphthenic base, can list for example as the illustrated group of naphthenic base that with the carbon number shown in the Cy is 3～10.The carbon number that as the replaced phenyl of representing with X or carbon number is 3～10 naphthenic base is that 1～10 alkyl, carbon number are 1～10 alkoxy and halogen atom, can list respectively as the material that is exemplified in the back with the group shown in Y and the Z.
Alkyl as with the carbon number shown in Y and the Z being 1～10 can list 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.As the alkoxy that with the carbon number shown in Y and the Z is 1～10, can list methoxyl, ethoxy, propoxyl group, butoxy, sec-butoxy, tert-butoxy, amoxy, own oxygen base, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy etc.Alkenyl as with the carbon number shown in Y and the Z being 2～10 can list vinyl, allyl, butenyl group, propenyl etc., as with the halogen atom shown in Y and the Z, can list fluorine, chlorine, bromine, iodine.
In addition, replaced phenyl of representing with X or carbon number are the abovementioned alkyl of 3～10 naphthenic base and alkoxy and also can be replaced by halogen atom with above-mentioned alkyl, alkoxy and the alkenyl shown in Y and the Z, as this halogen atom, can list fluorine, chlorine, bromine, iodine.For example, be 1～10 alkyl as the carbon number that is replaced by fluorine atom, can list a methyl fluoride, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl etc.
Be used to prepare the epoxy resin (A) of alkali development resin composition of the present invention, because by having the skeleton of triaryl one naphthenic base methane, solidfied material is good to the cohesive of base material, alkali resistance, processability, intensity etc., therefore when non-solidified portion is removed in development, even fine figure also can precision form distinct image well.As epoxy resin (A), preferably in above-mentioned general formula (I), Cy is the compound of cyclohexyl, and X is the compound of phenyl, and p and r are 0 compound, and n is 0～5, particularly 0～1 compound.
As object lesson with the epoxy resin (A) shown in the above-mentioned general formula (I), can list following compound N o.1～compound of No.9.But the present invention is not subjected to any restriction of following compound.
Compound N o.1
Compound N o.2
Compound N o.3
Compound N o.4
Compound N o.5
Compound N o.8
What contained in alkali development resin composition of the present invention makes (B) composition and (A) composition carry out addition and the epoxy adduct of the structure that forms to having, with (C) composition, (D) composition esterification and the reaction product that obtains can be by for example making with the method shown in the reaction equation of following [Chemical formula 1 1] then.
At first, make as unsaturated monoacid (2) of (B) composition and the epoxy resin (1) of conduct (A) composition and carry out addition, obtain containing the resin combination of compound (3) as epoxy adduct.(B) composition can carry out according to conventional method with (A) addition reaction of composition, but the carboxyl that preferably use to satisfy 1 epoxy radicals with respect to (A) composition, (B) composition is (A) composition and (B) composition of amount of 0.1～1.0 ratio, and 90～150 ℃ of reactions 5～30 hours down.
Then, make as epoxy adduct compound (3) with as the reaction of the multi-anhydride (4) of (C) composition, carry out esterification, thereby obtain containing the resin combination of compound (5) as ester compounds.Epoxy adduct and (C) esterification of composition can carry out according to conventional method, but the acid anhydride structure that preferably use to satisfy 1 hydroxyl with respect to above-mentioned epoxy adduct, (C) composition is the epoxy adduct and (C) composition of amount of 0.1～1.0 ratio, and 50～150 ℃ of reactions 5～10 hours down.
Then, make compound (5) further carry out esterification, can obtain to contain resin combination as the compound (7) of goal response product with di-epoxy compounds (6) as the multi-functional epoxy compound of (D) composition as ester compounds.Above-mentioned ester compounds and (D) esterification of composition can carry out according to conventional method, but preferably above-mentioned ester compounds and (D) consumption of composition be the amount of 0.1～1.0 ratio for satisfying with respect to 1 hydroxyl of the epoxy adduct that formerly uses, the epoxy radicals of (D) composition, and under 30～150 ℃, carry out reaction in 2～30 hours.
[Chemical formula 1 1]
By the structure of the compound (7) in [Chemical formula 1 1] as can be known, make (C) composition and above-mentioned epoxy adduct esterification and the above-mentioned ester compounds that obtains and (D) carry out between the carboxyl of esterification (C) composition in coming from above-mentioned ester compounds of composition and the epoxy radicals as the multi-functional epoxy compound of (D) composition.In order to ensure between carboxyl that comes from (C) composition and epoxy radicals, reacting as the multi-functional epoxy compound of (D) composition, (C) composition and (D) consumption of the composition acid anhydride structure that is preferably multi-anhydride be selected from greater than 1.0 amount, particularly 1.1～2.0 amount with respect to the quantity of 1 carboxyl of above-mentioned epoxy adduct and multi-functional epoxy compound's (D) epoxy radicals quantity sum with respect to 1 carboxyl of above-mentioned epoxy adduct.
In addition, acquisition has makes (A) composition and (B) composition carry out addition and the method for the compound (3) of the epoxy adduct of the structure that forms is not limited to the said method shown in above-mentioned [Chemical formula 1 1], for example, when the n in the compound (3) is 0, as shown in the reaction equation of following [Chemical formula 1 2], also can obtain compound (3) with the method that makes bis-phenol (8) and contain the mono-epoxy compounds reaction of glycidyl methacrylate (9).
[Chemical formula 1 2]
The unsaturated monoacid (B) that is used to obtain alkali development resin composition of the present invention uses for the sensitivity that improves this alkali development resin composition, can list for example acrylic acid; methacrylic acid; crotonic acid; cinnamic acid; sorbic acid; the hydroxyethyl meth acrylate malate; the hydroxy ethyl methacrylate malate; hydroxypropyl methyl acrylate malate; the hydroxypropyl acrylate malate; dicyclopentadiene malate or have a carboxyl and multifunctional (methyl) acrylate of two or more (methyl) acryloyl groups etc.Wherein, be preferably acrylic acid, methacrylic acid and have a carboxyl and multifunctional (methyl) acrylate of two or more (methyl) acryloyl groups.
Above-mentioned multifunctional (methyl) acrylate with a carboxyl and two or more (methyl) acryloyl groups can be by for example making multifunctional (methyl) acrylate and dibasic acid anhydride or the carboxylic acid reaction acquisition that has a hydroxyl and two or more (methyl) acryloyl groups in a part.
As above-mentioned multifunctional (methyl) acrylate with a carboxyl and two or more (methyl) acryloyl groups, can enumerate following compound N o.10～No.14.
Compound N o.10
Compound N o.11
Compound N o.12
Compound N o.13
Compound N o.14
Be used to obtain the multi-anhydride (C) of alkali development resin composition of the present invention thus be to improve trickle figure for the acid number that increases this alkali development resin composition, development and developing powder use, can list for example succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic dianhydride, 2,2 '-3,3 '-benzophenone tetracarboxylic anhydride, 3,3 '-4,4 '-benzophenone tetracarboxylic anhydride, two trimellitic anhydride second diester, three trimellitic anhydride glyceride, phthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, tetrabydrophthalic anhydride, Na Dike (Nadic) acid anhydrides, the methyl carbic anhydride, the trialkyl tetrabydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxy tetrahydrofuran base)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyl tetrabydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methyl-3,6-endo-methylene group-1,2,3,6-tetrabydrophthalic anhydride (Methyl Himic Anhydride) etc.Wherein preferred succinic anhydride, trimellitic anhydride, hexahydrophthalic anhydride.
Thereby the molecular weight that is used to obtain the multi-functional epoxy compound (D) of alkali development resin composition of the present invention can be used for increasing above-mentioned optical polymerism unsaturated compound is adjusted developing powder, for example can use the poly glycidyl ester of the polyglycidyl ether of polyvalent alcohol or its alkylene oxide addition product, polyprotonic acid, compound by containing cyclohexene ring or cyclopentene ring are carried out compound that contains cyclohexene oxide or cyclopentene oxide that epoxidation obtains etc. with oxygenant, can list following compound particularly.
That is alkylidene bisphenols polyglycidyl ether type epoxy resin such as bisphenol A type epoxy resin, bisphenol b type epoxy resin, bisphenol-c type epoxy resin, bisphenol E-type epoxy resin, bisphenol f type epoxy resin, bis-phenol M type epoxy resin, bis-phenol P type epoxy resin, bisphenol-s epoxy resin, bisphenol Z type epoxy resin; The A Hydrogenated Bisphenol A type diglycidyl ether that the epoxy resin hydrogenation of above-mentioned alkylidene bisphenols polyglycidyl ether type is obtained; Ethylene glycol diglycidylether, 1,3-propylene glycol diglycidylether, 1,2-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-1,3-propylene glycol diglycidylether, the diethylene glycol diglycidyl ether, the triethylene glycol diglycidyl ether, the TEG diglycidyl ether, six ethylene glycol diglycidylethers, 1,4-cyclohexanedimethanodiglycidyl diglycidyl ether, 1,1,1-three (glycidoxy methyl) propane, 1,1,1-three (glycidoxy methyl) ethane, 1,1,1-three (glycidoxy methyl) methane, 1,1,1,1-four (glycidoxy methyl) methane, T 55, trihydroxymethylpropanyltri diglycidyl ether, D-sorbite four glycidol ethers, the glycidol ether of aliphatic polyols such as dipentaerythritol six glycidol ethers; By two kinds of polyvalent alcohol additions such as propylene glycol, trimethylolpropane, glycerine or more kinds of alkylene oxides and the polyglycidyl ether of the polyether glycol that obtains; Phenolic varnish type epoxy compounds such as phenol phenolic varnish type epoxy compound, biphenyl phenolic varnish type epoxy compound, cresols phenolic varnish type epoxy compound, bisphenol-A phenolic varnish type epoxy compound, bicyclopentadiene phenolic varnish type epoxy compound; 3,4-epoxy-3-methyl cyclohexane ylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylic acid ester, 3,4-epoxy-5-methyl cyclohexane ylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylic acid ester, 3,4-epoxy-6-methyl cyclohexane ylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylic acid ester, 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexane carboxylate, 1-epoxy ethyl-3,4-7-oxa-bicyclo[4.1.0, two (3,4-epoxycyclohexyl methyl) adipate, di-2-ethylhexylphosphine oxide (3,4-7-oxa-bicyclo[4.1.0), isopropylidene two (3,4-7-oxa-bicyclo[4.1.0), the bicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexane carboxylate), 1,2-epoxy-alicyclic epoxy compounds such as 2-epoxy ethyl cyclohexane; The ethylene oxidic ester of dibasic acid such as o-phthalic acid diglycidyl ester, tetrahydrophthalic acid 2-glycidyl ester, dipolymer acid glycidyl ester; Four glycidyl group diaminodiphenyl-methane, triglycidyl group para-aminophenol, N, glycidyl amines such as N-diglycidylaniline; Hetero ring type epoxy compounds such as 1,3-diglycidyl-5,5-dimethyl hydantoin, triglycidyl group isocyanuric acid ester; Dioxide such as bicyclopentadiene dioxide; Naphthalene type epoxy compound, triphenyl methane type epoxy compound, dicyclopentadiene-type epoxy compound etc.
As above-mentioned multi-functional epoxy compound, can use commercially available material, can list for example BREN-S, EPPN-201, EPPN-501N, EOCN-1020, GAN, GOT (Japanese chemical drug company produce), ADEKA RESINS EP-4000, ADEKA RESINS EP-4003S, ADEKA RESINS EP-4080, ADEKA RESINS EP-4085, ADEKA RESINSEP-4088, ADEKA RESINS EP-4100, ADEKA RESINS EP-4900, ADEKARESINS ED-505, ADEKA RESINS ED-506, ADEKA RESINS KRM-2110, ADEKA RESINSKRM-2199, ADEKA RESINS KRM-2720 (Asahi Denka Co., Ltd.'s production), R-508, R-531, R-710 (production of Mitsui Chemicals company), Epikote190P, Epikote191P, Epikote604, Epikote801, Epikote828, Epikote871, Epikote872, Epikote1031, Epikote RXE15, Epikote YX-4000, Epikote YDE-205, Epikote YDE-305 (production of Japan Epoxy Resins company), Sumiepoxy ELM-120, Sumiepoxy ELM-434 (sumitomo chemical company production), Denacol EM-150, DenacolEX-201, Denacol EX-211, Denacol EX-212, Denacol EX-313, DenacolEX-314, Denacol EX-322, Denacol EX-411, Denacol EX-421, DenacolEX-512, Denacol EX-521, Denacol EX-614, Denacol EX-711, DenacolEX-721, Denacol EX-731, Denacol EX-811, Denacol EX-821, DenacolEX-850, Denacol EX-851, Denacol EX-911, (production of Nagase chemtex company), EpoLight70P, EpoLight200P, EpoLight400P, EpoLight40E, EpoLight100E, EpoLight200E, EpoLight400E, EpoLight80MF, EpoLight100MF, EpoLight 1500NP, EpoLight 1600, EpoLight 3002, EpoLight 4000, EpoLight FR-1500, EpoLight M-1230, EpoLight EHDG-L (production of chemical company of common prosperity society), SB-20 (Gang Cun system oil company produces), Epiclon720 (big Japanese ink chemical company produces), UVR-6100, UVR-6105, UVR-6110, UVR-6200, UVR-6228 (production of Union Carbide company), CELLOXIDE2000, CELLOXIDE2021, CELLOXIDE2021P, CELLOXIDE2081, CELLOXIDE2083, CELLOXIDE2085, CELLOXIDE3000, CYCLMERA200, CYCLMERM100, CYCLMER M101, EPOLEAD GT-301, EPOLEAD GT-302, EPOLEAD401, EPOLEAD403, EPOLEAD HD300, EHPE-3150, ETHB, EPOFRIEND (production of Daicel chemical company), PY-306,0163, DY-022 (production of CibaSpecialty Chemicals company), Suntohto ST0000, Epotohto YD-011, Epotohto YD-115, Epotohto YD-127, Epotohto YD-134, Epotohto YD-172, Epotohto YD-6020, Epotohto YD-716, Epotohto YD-7011R, EpotohtoYD-901, Epotohto YDPN-638, Epotohto YH-300, Neotohto PG-202, Neotohto PG-207 (Dongdu changes into company and produces), BLEMMER G (Nof Corp.'s production) etc.
Among the present invention, can also make epoxy compound (E) and above-mentioned reaction again.This epoxy compound (E) thus be in order to adjust that acid number further improves the development of alkali development resin composition of the present invention and the material that uses.As this epoxy compound (E), can list glycidyl methacrylate, methyl glycidyl ether, ethyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, the isobutyl glycidol ether, tert-butyl group glycidol ether, the amyl group glycidol ether, hexyl glycidyl ether, the heptyl glycidol ether, octyl glycidyl ether, the nonyl glycidol ether, decyl glycidyl ether, the undecyl glycidol ether, lauryl diglycidyl ether, the tridecyl glycidol ether, the myristyl glycidol ether, the pentadecyl glycidol ether, cetyl glycidyl ether, 2-ethylhexyl glycidol ether, allyl glycidyl ether, the propargyl glycidol ether, to the methoxy ethyl glycidol ether, phenyl glycidyl ether, to the methoxyl glycidol ether, the p-butylphenol glycidol ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonyl phenyl glycidyl ether, benzyl glycidyl ether, to the cumyl phenyl glycidyl ether, the trityl glycidol ether, methacrylic acid-2,3-epoxy propyl ester, epoxidised soybean oil, epoxidised linseed oil, Glycidyl butyrate, the vinyl cyclohexane monoxide, 1,2-epoxy-4-vinyl cyclohexane, styrene oxide, the oxidation firpene, oxidation methyl styrene, cyclohexene oxide, propylene oxide, following compound N o.15, No.16 etc.
The acid number of the solid state component of alkali development resin composition of the present invention is preferably the scope of 20～120mgKOH/g, and the consumption of epoxy compound (E) is preferably selected according to the mode that satisfies above-mentioned acid number.
Compound N o.15
Compound N o.16
Alkali development resin composition of the present invention can further add Photoepolymerizationinitiater initiater (F) and make alkali developing photosensitive resin composition.
Above-mentioned alkali development resin composition as having added the solution shape composition that the solvent that can make above-mentioned each composition dissolving or disperse forms, is used for alkali developing photosensitive resin composition of the present invention usually.
As above-mentioned solvent, usually so long as the solvent that can dissolve or disperse above-mentioned each composition just, have no particular limits, can list for example ketones such as MEK, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl Ketone, methyl isobutyl ketone, cyclohexanone; Ether solvents such as ether, diox, tetrahydrofuran, 1,2-dimethoxy-ethane, 1,2-diethoxyethane, dipropylene glycol 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; Alcohols solvents such as methyl alcohol, ethanol, isopropyl alcohol or n-propanol, isobutyl alcohol or 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 turpentine, Swasolve#310 (Cosmo Guia Hill oil (strain)), Solvesso#100 paraffinic solvents such as (Exxon chemistry (strains)); Halogenation aliphatic hydrocarbon kind solvents such as phenixin, chloroform, triclene, methylene chloride; Halogenated aromatic varsols such as chlorobenzene; Carbitol kind solvent, aniline, triethylamine, pyridine, acetate, acetonitrile, carbon disulphide, tetrahydrofuran, N, N-dimethyl formamide, N-methyl pyrrolidone etc., preferred especially ketone or cellosolve kind solvent.These solvents can use a kind of, perhaps as two kinds or more kinds of mixed solvent uses.
In the alkali developing photosensitive resin composition of the present invention, the content of above-mentioned solvent is that 5～40 quality %, the particularly mode of 15～30 quality % are adjusted according to total solid constituent concentration shared in the alkali developing photosensitive resin composition preferably.
The epoxy adduct of the structure that makes (B) composition and (A) composition carry out addition to having and form, with (C) composition, use (D) composition to carry out esterification then, the content of the reaction product that (E) composition is reacted and obtain, in above-mentioned solution shape composition, be preferably 1～70 weight %, be preferably 3～30 weight % especially.
As the above-mentioned Photoepolymerizationinitiater initiater (F) that is used for alkali developing photosensitive resin composition of the present invention; can use compound known in the past; can list for example benzophenone; phenyl biphenyl ketone; 1-hydroxyl-1-benzoyl group cyclohexane; benzil; benzyl dimethyl ketal; 1-benzyl-1-dimethylamino-1-(4 '-morpholino benzoyl group) propane; 2-morpholinyl-2-(4 '-methyl mercapto) benzoyl group propane; thioxanthones; 1-chlorine-4-propoxyl group thioxanthones; isopropyl thioxanthone; diethyl thioxanthone; EAQ; 4-benzoyl group-4 '-methyldiphenyl base sulfide; the benzoin butyl ether; 2-hydroxyl-2-benzoyl group propane; 2-hydroxyl-2-(4 '-isopropyl) benzoyl group propane; 4-butyl benzene acyl group methenyl choloride; 4-phenoxy group benzoyl group methylene chloride; the benzoyl group methyl formate; 1; 7-two (9 '-acridinyl) heptane; 9-normal-butyl-3; 6-two (2 '-morpholino isobutyryl) carbazoles; 2-methyl-1-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone; 2-methyl-4; 6-two (trichloromethyl)-s-triazine; 2-phenyl-4; 6-two (trichloromethyl)-s-triazine; 2-naphthyl-4,6-two (trichloromethyl)-s-triazine; following compound N o.17; No.18 etc.Preferred especially benzophenone, 2-methyl-1-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone.
Compound N o.17
(in the formula, X
1Expression halogen atom or alkyl, R
1Expression R, OR, COR, SR, CONRR ' or CN, R
2Expression R, OR, COR, SR or NRR ', R
3Expression R, OR, COR, SR or NRR ', R and R ' expression alkyl, aryl, aralkyl or heterocyclic radical, they can be replaced by halogen atom and/or heterocyclic radical, wherein the alkylene moiety of alkyl and aralkyl also can be inserted unsaturated link, ehter bond, thioether bond or ester bond, R and R ' also can form ring together in addition, and n is 0～5.)
Compound N o.18
(in the formula, X
1, R
1, R
2, R
3, R and R ' definition identical with above-claimed cpd No.17, X
1' expression halogen atom or alkyl, Z represents oxygen atom or sulphur atom, m and n represent 1～4 number, R respectively
1' expression R, OR, COR, SR, CONRR ' or CN, R
2' expression R, OR, COR, SR or NRR ', R
3' represent R, OR, COR, SR or NRR ', R respectively
4Expression diol residue or two mercaptan residues.)
In the alkali developing photosensitive resin composition of the present invention, the above-mentioned solution shape composition that the content of above-mentioned Photoepolymerizationinitiater initiater (F) forms with respect to add solvent in alkali development resin composition of the present invention, be preferably 0.1～30 weight %, be preferably 0.5～5 weight % especially.
Can further be used in combination in alkali development resin composition of the present invention and the alkali developing photosensitive resin composition with the monomer with unsaturated link, chain-transferring agent, surfactant etc.
As above-mentioned monomer with unsaturated link, can list acrylic acid-2-hydroxy methacrylate, acrylic acid-2-hydroxy propyl ester, isobutyl acrylate, the acrylic acid n-octyl, Isooctyl acrylate monomer, acrylic acid ester in the different ninth of the ten Heavenly Stems, octadecyl acrylate, acrylic acid methoxyl ethyl ester, acrylic acid dimethylamino ethyl ester, zinc acrylate resin, 1,6-hexanediyl ester, trimethylolpropane triacrylate, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxy propyl ester, butyl methacrylate, the metering system tert-butyl acrylate, cyclohexyl methacrylate, trimethylol-propane trimethacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, tristane dihydroxymethyl diacrylate etc.
As above-mentioned chain-transferring agent; can list mercaptoacetic acid; thiomalic acid; o-mercaptobenzoic 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; 2-sulfydryl ethyl sulfonic acid; 3-sulfydryl propane sulfonic acid; 4-sulfydryl fourth sulfonic acid; dodecyl (4-methyl mercapto) phenyl ether; 2-mercaptoethanol; 3-sulfydryl-1,2-propylene glycol; 1-sulfydryl-2-propyl alcohol; 3-sulfydryl-2-butanols; mercapto-phenol; 2-mercaptoethylmaine; 2-mercaptoimidazole; 2-sulfydryl-3-pyridol; 2-mercaptobenzothiazoler; mercaptoacetic acid; 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; 2-iodohydrin; 2-iodine ethyl sulfonic acid; iodate alkylates such as 3-iodine propane sulfonic acid etc.
As above-mentioned surfactant, can use fluorine surfactants such as perfluoralkyl phosphate, perfluoroalkyl carboxylate, negative ion such as higher fatty acid alkali salt, alkyl sulfonate, alkyl sulfate are surfactant, kations such as higher amines halo hydrochlorate, quaternary ammonium salt are surfactant, non-ionic surfactants such as polyethylene glycol alkyl ether, cithrol, sorbitan fatty acid ester, glycerine monofatty ester, amphoteric surfactant, surfactants such as silicone-based surfactant, their uses that also can combine.
In alkali development resin composition of the present invention and alkali developing photosensitive resin composition,, can also improve the characteristic of solidfied material by further use thermoplastic organic polymer.As this thermoplastic organic polymer, can list for example polystyrene, polymethylmethacrylate, methyl methacrylate-ethyl acrylate copolymer, poly-(methyl) acrylic acid, styrene-(methyl) acrylic copolymer, (methyl) acrylic acid-methylmethacrylate copolymer, polyvinylbutyral, cellulose esters, polyacrylamide, saturated polyester etc.
In addition, in alkali development resin composition of the present invention and alkali developing photosensitive resin composition, as required, can add thermal polymerization inhibitors such as methyl phenyl ethers anisole, quinhydrones, catechol, tert-butyl catechol, phenothiazine; Plastifier; Adhesion promotor; Filling agent; Defoamer; The additive that levelling agent etc. are habitual.
Alkali developing photosensitive resin composition of the present invention can pass through roller coat device, curtain formula spreader, various printing, impregnating known method, is applied on the support bases such as metal, paper, plastics.In addition, can also temporarily be implemented on the support bases such as film after, copy to again on other support base, its application process without limits.
Alkali developing photosensitive resin composition of the present invention mainly mixes with above-mentioned solvent and above-mentioned Photoepolymerizationinitiater initiater, as alkali developing photosensitive resin composition, so this alkali developing photosensitive resin composition can be used for photo-curable coating, Photocurable adhesive agent, galley, printed circuit distributing board and have no particular limits with various uses such as photoresist, its purposes.
In addition, the light source of employed active light when alkali developing photosensitive resin composition of the present invention is solidified, can use and produce wavelength is the light source of the light of 300～450nm, for example can use ultra high pressure mercury, mercuryvapour arc, carbon arc, xenon arc etc.
Embodiment
Below, the present invention will be described in more detail by enumerating embodiment etc., but the present invention is not subjected to the restriction of these embodiment.
The manufacturing of [embodiment 1] alkali development resin composition No.1
＜step 1〉manufacturing of 1,1-two (4 '-hydroxy phenyl)-1-(1 "-xenyl)-1-cyclohexyl-methane
Add 70.5g xenyl cyclohexyl ketone, 200.7g phenol and 10.15g thioacetic acid, following at 18 ℃ with 20 minutes dropping 40.0g trifluoromethanesulfonic acid.Reaction is after 18 hours down at 17～19 ℃, and adding 500g water stops reaction, adds 500g toluene, and the organic layer washing is reached 3～4 until its pH, separates organic layer.Heat up in a steamer toluene, water and excessive phenol.In residue, add toluene, filter the solid of being separated out, disperse to clean, obtain 59.2g light yellow crystal (yield is 51%) with toluene.The fusing point of this light yellow crystal is 239.5 ℃, confirms that this light yellow crystal is a target compound.
＜step 2〉manufacturing of 1,1-two (4 '-glycidoxy phenyl)-1-(1 "-xenyl)-1-cyclohexyl-methane
Resulting 1,1-two (4 '-hydroxy phenyl)-1 in the adding 57.5g step 1-(1 "-xenyl)-1-cyclohexyl-methane and 195.8g epichlorokydrin, add the 0.602g benzyltriethylammonium chloride, stirred 18 hours down at 64 ℃.Then be cooled to 54 ℃, drip 43.0g24 weight % sodium hydrate aqueous solution, stirred 30 minutes.Heat up in a steamer decyclization oxygen chloropropane and water, after the washing of adding 216g methylisobutylketone, drip 2.2g24 weight % NaOH.After 2 hours, be cooled to room temperature 80 ℃ of stirrings, with the neutralization of 3 weight % biphosphate sodium water solutions, washing.Heat up in a steamer and desolvate, (fusing point is 64.2 ℃, and epoxide equivalent is 282, n=0.04) to obtain 57g (yield is 79%) yellow solid.Confirm that this yellow crystals is a target compound.
＜step 3〉manufacturing of alkali development resin composition No.1
Add in the 1695g step 2 resulting 1,1-two (4 '-glycidoxy phenyl)-1-(1 "-xenyl)-1-cyclohexyl-methane (below be also referred to as compound a), 443g acrylic acid (below be also referred to as compound b-1), 6g2; 6-BHT, 11g TBuA acetic acid esters and 1425g propylene glycol-1-monomethyl ether-2-acetic acid esters stirred 16 hours down at 120 ℃.Be cooled to room temperature, add 718g propylene glycol-1-monomethyl ether-2-acetic acid esters and 482g succinic anhydride (below be also referred to as compound c-1) and 25g TBuA acetic acid esters, 100 ℃ of stirrings 5 hours down.Add in the 508g step 2 resulting 1 again, 1-two (4 '-glycidoxy phenyl)-1-(1 "-xenyl)-1-cyclohexyl-methane (below be also referred to as compound d-1) and 218g propylene glycol-1-monomethyl ether-2-acetic acid esters; stirred 12 hours down at 120 ℃; 80 ℃ were stirred 2 hours down; 40 ℃ are stirred after 2 hours down; add 1463g propylene glycol-1-monomethyl ether-2-acetic acid esters; thus target product alkali development resin composition No.1 (Mw=4200 obtained as propylene glycol-1-monomethyl ether-2-acetate solution form, Mn=2100, acid number (solid state component) is 55mgKOH/g).
In addition, the reaction product that alkali development resin composition No.1 contained is to carry out addition and 1 hydroxyl of the epoxy adduct of the structure that forms, be 0.8 ratio, be that 0.3 ratio makes epoxy adduct, compound c-1 and compound d-1 carry out esterification to obtain as the epoxy radicals of the compound d of (D) composition as the acid anhydride structure of the compound c-1 of (C) composition with respect to having to make as the compound b-1 of (B) composition and compound a as (A) composition.In addition, to have with the carboxyl with respect to 1 epoxy radicals of compound a, compound b be that 1.0 ratio carries out the structure that addition forms to above-mentioned epoxy adduct.
The manufacturing of [embodiment 2] alkali development resin composition No.2
Add 43g1,1-two (4 '-glycidoxy phenyl)-1-(1 "-xenyl)-1-cyclohexyl-methane (compound a), 33.6g acrylic acid (compound b-1), 0.04g2; 6-BHT, 0.21g TBuA acetic acid esters and 18g propylene glycol-1-monomethyl ether-2-acetic acid esters stirred 13 hours down at 120 ℃.Be cooled to room temperature, add 24g propylene glycol-1-monomethyl ether-2-acetic acid esters and 10g succinic anhydride (compound c-1), stirred 3 hours down at 100 ℃.Add 8g bisphenol Z glycidol ether (compound d-2) again, stirred 4 hours down at 120 ℃, 90 ℃ were stirred 3 hours down, 60 ℃ were stirred 2 hours down, 40 ℃ were stirred down after 5 hours, added 29g propylene glycol-1-monomethyl ether-2-acetic acid esters, obtained the target product alkali development resin composition No.2 (Mw=4600 as propylene glycol-1-monomethyl ether-2-acetate solution form, Mn=2100, acid number (solid state component) is 54mgKOH/g).
In addition, the reaction product that alkali development resin composition No.2 contained is to carry out addition and 1 hydroxyl of the epoxy adduct of the structure that forms, be 0.8 ratio, be that 0.3 ratio makes epoxy adduct, compound c-1 and compound d-2 carry out esterification to obtain as the epoxy radicals of the compound d-2 of (D) composition as the acid anhydride structure of the compound c-1 of (C) composition with respect to having to make as the compound b-1 of (B) composition and compound a as (A) composition.In addition, to have with the carboxyl with respect to 1 epoxy radicals of compound a, compound b be that 1.0 ratio carries out the structure that addition forms to above-mentioned epoxy adduct.
The manufacturing of [embodiment 3] alkali development resin composition No.3
Add 1695g1,1-two (4 '-glycidoxy phenyl)-1-(1 "-xenyl)-1-cyclohexyl-methane (compound a), 443g acrylic acid (compound b-1), 6g2; 6-BHT, 11g TBuA acetic acid esters and 1425g propylene glycol-1-monomethyl ether-2-acetic acid esters stirred 16 hours down at 120 ℃.Be cooled to room temperature, add 931g propylene glycol-1-monomethyl ether-2-acetic acid esters and 741g hexahydrophthalic anhydride (below be also referred to as compound c-2) and 25g tetra-n-butyl ammonium acetic acid esters, 70 ℃ of stirrings 4 hours down.Add 313g ethylene glycol diglycidylether (below be also referred to as compound d-3) and 1463g propylene glycol-1-monomethyl ether-2-acetic acid esters again, thereby obtain target product alkali development resin composition No.3 (Mw=3000 as propylene glycol-1-monomethyl ether-2-acetate solution form, Mn=1700, acid number (solid state component) is 43mgKOH/g).
In addition, the reaction product that alkali development resin composition No.3 contained is to carry out addition and 1 hydroxyl of the epoxy adduct of the structure that forms, be 0.8 ratio, be that 0.4 ratio makes epoxy adduct, compound c-2 and compound d-3 carry out esterification to obtain as the epoxy radicals of the compound d-3 of (D) composition as the acid anhydride structure of the compound c-2 of (C) composition with respect to having to make as the compound b-1 of (B) composition and compound a as (A) composition.In addition, to have with the carboxyl with respect to 1 epoxy radicals of compound a, compound b be that 1.0 ratio carries out the structure that addition forms to above-mentioned epoxy adduct.
The manufacturing of [embodiment 4] alkali development resin composition No.4
Add 37.3g light acrylate PE-3A (acrylic acid derivative; common prosperity society chemical production), 12.5g succinic anhydride, 0.087g triphenylphosphine and 0.050g2; 6-BHT; stirred 3 hours down at 100 ℃, obtain to have the unsaturated monoacid (below be also referred to as compound b-2) of multifunctional acryloyl group.Be cooled to room temperature, add 138g1,1-two (4 '-glycidoxy phenyl)-1-(1 "-xenyl)-1-cyclohexyl-methane (compound a), 27.7g acrylic acid (compound b-1), 0.51g2; 6-BHT, 0.90g TBuA acetic acid esters and 144g propylene glycol-1-monomethyl ether-2-acetic acid esters stirred 12 hours down at 120 ℃.Be cooled to room temperature, add 65.4g propylene glycol-1-monomethyl ether-2-acetic acid esters and 40.0g succinic anhydride (compound c-1) and 2.1g TBuA acetic acid esters, stirred 5 hours down at 100 ℃.Add 41.4gl again, 1-two (4 '-glycidoxy phenyl)-1-(1 "-xenyl)-1-cyclohexyl-methane (compound d-1) and 0.56g2; 6-BHT and 18.0g propylene glycol-1-monomethyl ether-2-acetic acid esters; stirred 1 hour down at 90 ℃, 120 ℃ were stirred 8 hours down.Be cooled to room temperature, add 136g propylene glycol-1-monomethyl ether-2-acetic acid esters, obtain target product alkali development resin composition No.4 (acid number (solid state component) is 51mgKOH/g for Mw=6700, Mn=2700) as propylene glycol-1-monomethyl ether-2-acetate solution form.
In addition, the reaction product that alkali development resin composition No.4 contained is to carry out addition as the compound b-1 of (B) composition and b-2 and as the compound a of (A) composition and 1 hydroxyl of the epoxy adduct of the structure that forms, be 0.8 ratio, be that 0.3 ratio makes epoxy adduct, compound c-1 and compound d-1 carry out esterification to obtain as the epoxy radicals of the compound d-1 of (D) composition as the acid anhydride structure of the compound c-1 of (C) composition with respect to having to make.In addition, to have with the carboxyl with respect to 1 epoxy radicals of compound a, compound b-1 be that 0.75, the carboxyl of compound b-2 are that 0.25 ratio carries out the structure that addition forms to above-mentioned epoxy adduct.
The manufacturing of [embodiment 5] alkali development resin composition No.5
Add 26.8g lightweight ester G201P (methacrylic acid derivative; common prosperity society chemical production), 12.5g succinic anhydride, 0.087g triphenylphosphine and 0.039g2; 6-BHT; stirred 3 hours down at 100 ℃, obtain to have the unsaturated monoacid (below be also referred to as compound b-3) of multifunctional (methyl) acryloyl group.Be cooled to room temperature, add 138g1,1-two (4 '-glycidoxy phenyl)-1-(1 "-xenyl)-1-cyclohexyl-methane (compound a), 27.7g acrylic acid (compound b-1), 0.50g2; 6-BHT, 0.90g TBuA acetic acid esters and 137g propylene glycol-1-monomethyl ether-2-acetic acid esters stirred 12 hours down at 120 ℃.Be cooled to room temperature, add 63.8g propylene glycol-1-monomethyl ether-2-acetic acid esters and 40.0g succinic anhydride (compound c-1) and 2.1g TBuA acetic acid esters, stirred 5 hours down at 100 ℃.Add 41.4gl again, 1-two (4 '-glycidoxy phenyl)-1-(1 "-xenyl)-1-cyclohexyl-methane (compound d-1) and 0.56g2; 6-BHT and 18.0g propylene glycol-1-monomethyl ether-2-acetic acid esters; stirred 1 hour down at 90 ℃, 120 ℃ were stirred 8 hours down.Be cooled to room temperature, add 132g propylene glycol-1-monomethyl ether-2-acetic acid esters, obtain target product alkali development resin composition No.5 (acid number (solid state component) is 54mgKOH/g for Mw=4800, Mn=2400) as propylene glycol-1-monomethyl ether-2-acetate solution form.
In addition, the reaction product that alkali development resin composition No.5 contained is to carry out addition as the compound b-1 of (B) composition and b-3 and as the compound a of (A) composition and 1 hydroxyl of the epoxy adduct of the structure that forms, be 0.8 ratio, be that 0.3 ratio makes epoxy adduct, compound c-1 and compound d-1 carry out esterification to obtain as the epoxy radicals of the compound d-1 of (D) composition as the acid anhydride structure of the compound c-1 of (C) composition with respect to having to make.In addition, to have with the carboxyl with respect to 1 epoxy radicals of compound a, compound b-1 be that 0.75, the carboxyl of compound b-3 are that 0.25 ratio carries out the structure that addition forms to above-mentioned epoxy adduct.
The manufacturing of [embodiment 6] alkali developing photosensitive resin composition No.1
In 14g embodiment 1, among the resulting alkali development resin composition No.1, add 5.9g trimethylolpropane triacrylate, 2.1g benzophenone and 78g ethyl cellosolve, fully stir, obtain alkali developing photosensitive resin composition No.1.
The manufacturing of [embodiment 7] alkali developing photosensitive resin composition No.2
In 14g embodiment 2, among the resulting alkali development resin composition No.2, add 5.9g trimethylolpropane triacrylate, 2.1g benzophenone and 78g ethyl cellosolve, fully stir, obtain alkali developing photosensitive resin composition No.2.
The manufacturing of [embodiment 8] alkali developing photosensitive resin composition No.3
In 14g embodiment 3, among the resulting alkali development resin composition No.3, add 5.9g trimethylolpropane triacrylate, 2.1g benzophenone and 78g ethyl cellosolve, fully stir, obtain alkali developing photosensitive resin composition No.3.
The manufacturing of [embodiment 9] alkali developing photosensitive resin composition No.4
In 12g embodiment 1 among the resulting alkali development resin composition No.1, add 8.1g dipentaerythritol acrylate, 1.9g benzophenone, 47g ethyl cellosolve and 31g cyclohexanone, fully stir, obtain alkali developing photosensitive resin composition No.4.
The manufacturing of [embodiment 10] alkali developing photosensitive resin composition No.5
In 7.2g embodiment 1 among the resulting alkali development resin composition No.1, add 4.3g trimethylolpropane triacrylate, 1.5g2-methyl-1-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone and 87g ethyl cellosolve, fully stir, obtain alkali developing photosensitive resin composition No.5.
The manufacturing of [embodiment 11] alkali developing photosensitive resin composition No.6
In 20g embodiment 1 among the resulting alkali development resin composition No.1, add 8.7g trimethylolpropane triacrylate, 4.6g acrylic acid series copolymer, 1.7g2-methyl-1-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone and 65g ethyl cellosolve, fully stir, obtain alkali developing photosensitive resin composition No.6.
In addition, aforesaid propylene acid based copolymer obtains by following method: the methacrylic acid of 20 weight portions, the methacrylic acid hydroxyl ethyl ester of 15 weight portions, the methyl methacrylate of 10 weight portions and the butyl methacrylate of 55 weight portions are dissolved in the ethyl cellosolve of 300 weight portions, the azoisobutyronitrile that adds 0.75 weight portion under the nitrogen atmosphere was 70 ℃ of reactions 5 hours.
The manufacturing of [embodiment 12] alkali developing photosensitive resin composition No.7
In 14g embodiment 4, among the resulting alkali development resin composition No.4, add 5.9g trimethylolpropane triacrylate, 2.1g benzophenone and 78g ethyl cellosolve, fully stir, obtain alkali developing photosensitive resin composition No.7.
The manufacturing of [embodiment 13] alkali developing photosensitive resin composition No.8
In 14g embodiment 5, among the resulting alkali development resin composition No.5, add 5.9g trimethylolpropane triacrylate, 2.1g benzophenone and 78g ethyl cellosolve, fully stir, obtain alkali developing photosensitive resin composition No.8.
The manufacturing of [comparative example 1] alkali development resin composition No.6
Add 184g bisphenol fluorene type epoxy resin (epoxide equivalent is 231), 58g acrylic acid, 0.26g2,6-BHT, 0.11g TBuA acetic acid esters and 23g propylene glycol-1-monomethyl ether-2-acetic acid esters stirred 16 hours at 120 ℃.Be cooled to room temperature, add 35g propylene glycol-1-monomethyl ether-2-acetic acid esters and 41g tetrabydrophthalic anhydride, stirred 3 hours down at 100 ℃.Add the 6.5g ethylene glycol diglycidylether again, stirred 4 hours down at 120 ℃, 90 ℃ were stirred 3 hours down, 60 ℃ were stirred 2 hours down, 40 ℃ were stirred down after 5 hours, added 90g propylene glycol-1-monomethyl ether-2-acetic acid esters, obtained the target product alkali development resin composition No.6 (Mw=5000 as propylene glycol-1-monomethyl ether-2-acetate solution form, Mn=2100, acid number (solid state component) is 92.7mgKOH/g).
The manufacturing of [comparative example 2] alkali development resin composition No.7
Add 154g bisphenol A type epoxy resin (epoxide equivalent is 190), 59g acrylic acid, 0.26g2,6-BHT, 0.11g TBuA acetic acid esters and 23g propylene glycol-1-monomethyl ether-2-acetic acid esters stirred 13 hours at 120 ℃.Be cooled to room temperature, add 365g propylene glycol-1-monomethyl ether-2-acetic acid esters and 45g phthalic anhydride, stirred 3 hours down at 100 ℃.Add 7.0g bisphenol A type epoxy resin (epoxide equivalent is 190) again, stirred 4 hours down at 120 ℃, 90 ℃ were stirred 3 hours down, 60 ℃ were stirred 2 hours down, 40 ℃ were stirred down after 5 hours, added 90g propylene glycol-1-monomethyl ether-2-acetic acid esters, obtained the target product alkali development resin composition No.7 (Mw=7500 as propylene glycol-1-monomethyl ether-2-acetate solution form, Mn=2100, acid number (solid state component) is 91mgKOH/g).
The manufacturing of [comparative example 3] alkali development resin composition No.8
＜step 1〉manufacturing of 1,1-two (4 '-hydroxy phenyl)-1-(1 "-xenyl) ethane
75g phenol and 50g4-acetyl biphenyl at 60 ℃ of following heating and meltings, are added 5g3-mercaptopropionic acid, be blown into hydrogen chloride gas in 24 hours, reacted then 72 hours while stir.After 70 ℃ hot water cleaning, under reduced pressure be heated to 180 ℃, heat up in a steamer the devaporation material.In residue, add the dimethylbenzene cooling, filter the crystal of being separated out, obtain 65g light yellow crystal (yield is 68%) behind the drying under reduced pressure.The fusing point of this light yellow crystal is 184 ℃, confirms that this light yellow crystal is a target compound.
＜step 2〉manufacturing of 1,1-two (4 '-glycidoxy phenyl)-1-(1 "-xenyl) ethane
Resulting 1,1-two (4 '-hydroxy phenyl)-1 in the adding 37g step 1-(1 "-xenyl) ethane and 149.5g epichlorokydrin, add the 0.45g benzyltriethylammonium chloride, stirred 18 hours down at 64 ℃.Then cool to 54 ℃, drip 32.6g24 weight % sodium hydrate aqueous solution, stirred 30 minutes.Heat up in a steamer decyclization oxygen chloropropane and water, after the washing of adding 140g methylisobutylketone, drip 1.7g24 weight % NaOH.After 2 hours, be cooled to room temperature 80 ℃ of stirrings, with the neutralization of 3 weight % biphosphate sodium water solutions, washing.Heat up in a steamer and desolvate, (epoxide equivalent is 248, n=0.04) to obtain 38.7g (yield is 80%) yellow viscous liquid.Confirm that this yellow viscous liquid is a target compound.
＜step 3〉manufacturing of alkali development resin composition No.8
Add 49.6g1,1-two (4 '-glycidoxy phenyl)-1-(1 "-xenyl) ethane, 14.4g acrylic acid, 0.05g2; 6-BHT, 0.14g TBuA acetic acid esters and 27.4g propylene glycol-1-monomethyl ether-2-acetic acid esters stirred 13 hours down at 120 ℃.Be cooled to room temperature, add 41.5g propylene glycol-1-monomethyl ether-2-acetic acid esters and 4.3g succinic anhydride, stirred 3 hours down at 100 ℃.Add the 0.34g ethylene glycol diglycidylether again, stirred 4 hours down at 120 ℃, 90 ℃ were stirred 3 hours down, 60 ℃ were stirred 2 hours down, 40 ℃ were stirred down after 5 hours, added 34g propylene glycol-1-monomethyl ether-2-acetic acid esters, obtained the target product alkali development resin composition No.8 (Mw=3700 as propylene glycol-1-monomethyl ether-2-acetate solution form, Mn=1900, acid number (solid state component) is 93mgKOH/g).
The manufacturing of [comparative example 4] alkali developing photosensitive resin composition No.9
In 14g comparative example 1, among the resulting alkali development resin composition No.6, add 5.9g trimethylolpropane triacrylate, 2.1g benzophenone and 78g ethyl cellosolve, fully stir, obtain alkali developing photosensitive resin composition No.9.
The manufacturing of [comparative example 5] alkali developing photosensitive resin composition No.10
In 14g comparative example 2, among the resulting alkali development resin composition No.7, add 5.9g trimethylolpropane triacrylate, 2.1g benzophenone and 78g ethyl cellosolve, fully stir, obtain alkali developing photosensitive resin composition No.10.
The manufacturing of [comparative example 6] alkali developing photosensitive resin composition No.11
In 14g comparative example 3, among the resulting alkali development resin composition No.8, add 5.9g trimethylolpropane triacrylate, 2.1g benzophenone and 78g ethyl cellosolve, fully stir, obtain alkali developing photosensitive resin composition No.11.
The evaluation of resulting alkali developing photosensitive resin composition No.1～11 is following to be carried out.
That is, spin coating γ on substrate-glycidoxy propyl group methyl ethoxy silane, and behind the abundant Rotary drying, it is dry that spin coating (1300r.p.m, 50 seconds) above-mentioned alkali developing photosensitive resin composition also makes it.After carrying out 20 minutes prebake under 70 ℃, be coated with the poly-vinyl alcohol solution of 5 weight %, form the oxygen barrier film.After under 70 ℃ dry 20 minutes, use the mask of regulation, after exposing as light source with ultrahigh pressure mercury lamp, in dipping development in 30 seconds in 2.5 weight % sodium carbonate liquors under 25 ℃, fully washing.Behind the washing and drying, made the figure photographic fixing in 1 hour 230 ℃ of following roastings.Carry out following evaluation for resulting figure.It the results are shown in the table 1.
＜sensitivity 〉
During exposure, exposure is 100mJ/cm
2Promptly fully the note of exposure is a, at 100mJ/cm
2Down insufficient and at 200mJ/cm
2The note of following exposure is b.
＜exploring degree 〉
During exposure imaging, live width also can form the A that is evaluated as of figure well smaller or equal to 10 μ m, can form the B that is evaluated as of figure when live width is 10～30 μ m well, and live width must could form the C that is evaluated as of good figure more than or equal to 30 μ m.
＜cohesive 〉
According to the test method of JIS D0202, on filming, insert cross pattern and become the chessboard trellis, carry out disbonded test with the viscose paper band then, peel off state evaluation by visualization is tessellated.The note of not peeling off fully does zero, and the note that occurs peeling off does *.
＜alkali resistance 〉
Filming after the heat treated a) flooded 24 hours, b in the 5 weight %NaOH aqueous solution respectively) in 4 weight %KOH aqueous solution, flood 10 minutes, c down in 50 ℃) in 1 weight %NaOH aqueous solution, flood under each condition of 5 minutes of dipping down in 80 ℃, the outward appearance after flooding by visualization is estimated.Will be under any one condition outward appearance all less than changing and also not having the note of peeling off of resist to do zero fully, will under any one condition, find the resist projection, the note that resist peels off occurs and do *.
[table 1]
| Alkali developing photosensitive resin composition | Sensitivity | The exploring degree | Cohesive | Alkali resistance |
| No.1 (embodiment 6) | a | A | ○ | ○ |
| No.2 (embodiment 7) | a | A | ○ | ○ |
| No.3 (embodiment 8) | a | A | ○ | ○ |
| No.4 (embodiment 9) | a | A | ○ | ○ |
| No.5 (embodiment 10) | a | A | ○ | ○ |
| No.6 (embodiment 11) | a | A | ○ | ○ |
| No.7 (embodiment 12) | a | A | ○ | ○ |
| No.8 (embodiment 13) | a | A | ○ | ○ |
| No.9 (comparative example 4) | b | C | × | × |
| No.10 (comparative example 5) | b | C | × | × |
| No.11 (comparative example 6) | b | C | × | × |
The alkali developing photosensitive resin composition of embodiment 6～13 is high sensitivity and the good composition of exploring degree.In addition, resulting film also good with the cohesive and the alkali resistance of substrate.
Relative with it, the alkali developing photosensitive resin composition of comparative example 4～6 has to increase exposure owing to sensitivity is low, the exploring degree is low, and live width must could form figure more than or equal to 30 μ m, and resulting film also undesirable with the cohesive and the alkali resistance of substrate.
In sum, the sensitivity of alkali developing photosensitive resin composition of the present invention, exploring degree, the transparency, cohesive, alkali resistance are good, can precision form trickle figure well.
Claims (4)
1. alkali development resin composition, it contains makes epoxy adduct and multi-anhydride (C), the reaction product of carrying out esterification with multi-functional epoxy compound (D) then and obtaining, described epoxy adduct has the structure that makes unsaturated monoacid (B) and the epoxy resin of representing with following general formula (I) (A) carry out addition and form, described epoxy adduct has with 1 epoxy radicals with respect to described epoxy resin (A), the carboxyl of described unsaturated monoacid (B) is that 0.1～1.0 ratio carries out the structure that addition forms, described esterification is with 1 hydroxyl with respect to described epoxy adduct, the acid anhydride structure of described multi-anhydride (C) is 0.1～1.0, described multi-functional epoxy compound's (D) epoxy radicals is that 0.1～1.0 ratio carries out
In the formula, Cy represents that carbon number is 3～10 naphthenic base; X represents hydrogen atom or can is that 1～10 alkyl, carbon number are that the phenyl that replaces of 1～10 alkoxy or halogen atom or carbon number are 3～10 naphthenic base by carbon number; Y and Z represent that independently of one another carbon number is that 1～10 alkyl, carbon number are that 1～10 alkoxy, carbon number are 2～10 alkenyl or halogen atom; Described alkyl, described alkoxy and described alkenyl can be replaced by halogen atom; N represents 0～10 number; P represents 0～4 number; R represents 0～4 number,
Described multi-functional epoxy compound (D) is selected from alkylidene bisphenols polyglycidyl ether type epoxy resin, A Hydrogenated Bisphenol A type diglycidyl ether, the glycidol ether of aliphatic polyol, the polyglycidyl ether of polyether glycol, the phenolic varnish type epoxy compound, the alicyclic epoxy compound, the ethylene oxidic ester of dibasic acid, the glycidyl amine, the hetero ring type epoxy compound, dioxide, naphthalene type epoxy compound, triphenyl methane type epoxy compound, the dicyclopentadiene-type epoxy compound.
2. alkali development resin composition as claimed in claim 1, wherein, in the described general formula (I), Cy is a cyclohexyl, X is a phenyl, and p and r are 0.
3. alkali developing photosensitive resin composition, it is to contain Photoepolymerizationinitiater initiater (F) to form in the alkali development resin composition described in claim 1 or 2.
4. the manufacture method of the described alkali development resin composition of claim 1, it is to make unsaturated monoacid (B) and epoxy resin (A) with described general formula (I) expression carry out addition and after obtaining epoxy adduct, make this epoxy adduct and multi-anhydride (C), carry out esterification with multi-functional epoxy compound (D) then, thereby obtain the manufacture method of the alkali development resin composition of the described alkali development resin composition of claim 1
Described multi-functional epoxy compound (D) is selected from alkylidene bisphenols polyglycidyl ether type epoxy resin, A Hydrogenated Bisphenol A type diglycidyl ether, the glycidol ether of aliphatic polyol, the polyglycidyl ether of polyether glycol, the phenolic varnish type epoxy compound, the alicyclic epoxy compound, the ethylene oxidic ester of dibasic acid, the glycidyl amine, the hetero ring type epoxy compound, dioxide, naphthalene type epoxy compound, triphenyl methane type epoxy compound, the dicyclopentadiene-type epoxy compound.
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| JP178857/2005 | 2005-06-20 | ||
| JP2006155876A JP4916224B2 (en) | 2005-06-20 | 2006-06-05 | Alkali-developable photosensitive resin composition |
| JP155876/2006 | 2006-06-05 |
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| JP4738190B2 (en) * | 2006-02-01 | 2011-08-03 | 株式会社Ａｄｅｋａ | Epoxy resin, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
| JP4667261B2 (en) * | 2006-02-01 | 2011-04-06 | 株式会社Ａｄｅｋａ | Alkali-developable photosensitive resin composition |
| JP4878876B2 (en) * | 2006-03-15 | 2012-02-15 | 株式会社Ａｄｅｋａ | Epoxy resin, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
| JP5311750B2 (en) * | 2007-02-28 | 2013-10-09 | 株式会社Ａｄｅｋａ | Phenol resin, epoxy resin, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
| JP2009275148A (en) * | 2008-05-15 | 2009-11-26 | Adeka Corp | New compound, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
| JP5844267B2 (en) * | 2010-09-22 | 2016-01-13 | 株式会社Adeka | Dye and colored photosensitive composition |
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| CN1433532A (en) * | 2000-01-17 | 2003-07-30 | 昭和高分子株式会社 | Photosensitive resin composition |
| CN1459049A (en) * | 2000-09-16 | 2003-11-26 | 互応化学工业株式会社 | Ultraviolet-curable resin composition and photosolder resist ink contaning the composition |
| CN1860415A (en) * | 2004-09-17 | 2006-11-08 | 旭电化工业株式会社 | Alkaline developable resin composition |
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| JP3148429B2 (en) * | 1992-02-04 | 2001-03-19 | 新日本製鐵株式会社 | Photopolymerizable unsaturated compound and alkali-developable photosensitive resin composition |
| JP2000053746A (en) * | 1998-08-06 | 2000-02-22 | Nippon Shokubai Co Ltd | Production of photosensitive resin and photosensitive resin composition containing resin produced by the method |
| JP3593066B2 (en) * | 2001-06-28 | 2004-11-24 | 株式会社日本触媒 | Photosensitive resin for liquid crystal spacer and photosensitive resin composition |
| JP2003177528A (en) * | 2001-09-21 | 2003-06-27 | Tamura Kaken Co Ltd | Photosensitive resin composition and printed wiring board |
| JP4554170B2 (en) * | 2003-06-03 | 2010-09-29 | 株式会社タムラ製作所 | UV curable alkali-soluble resin, UV curable resin for solder resist film and printed wiring board |
| JP4698586B2 (en) * | 2004-03-25 | 2011-06-08 | 株式会社Ａｄｅｋａ | Novel phenolic compound and novel epoxy resin derivable from the phenolic compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1433532A (en) * | 2000-01-17 | 2003-07-30 | 昭和高分子株式会社 | Photosensitive resin composition |
| CN1459049A (en) * | 2000-09-16 | 2003-11-26 | 互応化学工业株式会社 | Ultraviolet-curable resin composition and photosolder resist ink contaning the composition |
| CN1860415A (en) * | 2004-09-17 | 2006-11-08 | 旭电化工业株式会社 | Alkaline developable resin composition |
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| TWI372943B (en) | 2012-09-21 |
| KR101308954B1 (en) | 2013-09-24 |
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