CN1860415A - Alkaline developable resin composition - Google Patents
Alkaline developable resin composition Download PDFInfo
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- CN1860415A CN1860415A CNA200580000757XA CN200580000757A CN1860415A CN 1860415 A CN1860415 A CN 1860415A CN A200580000757X A CNA200580000757X A CN A200580000757XA CN 200580000757 A CN200580000757 A CN 200580000757A CN 1860415 A CN1860415 A CN 1860415A
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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
- C08F290/02—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 end groups
- C08F290/06—Polymers provided for in subclass C08G
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
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Abstract
An alkaline developing resin composition comprising a reaction product obtained by esterifying an epoxy adduct having a structure formed by adding an unsaturated monobasic acid and a compound (C) selected from the group consisting of phenol compounds, alcohol compounds, amine compounds and carboxylic acids to an epoxy resin (A) represented by the following general formula (I), and a polybasic acid anhydride (D). Wherein Cy represents a cycloalkyl group having 3 to 5 carbon atoms, X represents H, an alkyl group having 1 to 10 carbon atoms, or the like, Y and Z represent an alkyl group having 1 to 10 carbon atoms, or the like, n represents a number of 0 to 10, p represents a number of 0 to 5, and r represents a number of 0 to 4.
Description
Technical field
The present invention relates to contain the alkali development resin composition of specific compound and in this alkali development resin composition, contain Photoepolymerizationinitiater initiater and the alkali developing photosensitive resin composition that forms 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, its polymerizing curable be can make, photo-curable printing ink, photosensitive printing version, printed circuit distributing board, various photoresists etc. therefore are used to.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.
As this alkali development resin composition and alkali developing photosensitive resin composition, in following patent documentation 1, optical polymerism unsaturated compound and the alkali development-type photosensitive resin composition that contains this compound have been proposed.In addition, in following patent documentation 2, the photosensitive polymer combination that has proposed to contain the resin combination of polycarboxylic acid resin and contained this resin combination.In addition, in following patent documentation 3, alkali-soluble unsaturated polyester and the radiation-sensitive resin composition that contains this resin have been proposed.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 are good, and the alkali developing photosensitive resin composition that can precision forms trickle figure well enjoys expectation.
Patent documentation 1: specially permit communique No. 3148429
Patent documentation 2: the spy opens the 2003-107702 communique
Patent documentation 3: the spy opens the 2003-89716 communique
Summary of the invention
As mentioned above, problem to be solved by this invention is also not have alkali development resin composition and the alkali developing photosensitive resin composition that a kind of sensitivity is abundant, can obtain suitable graphics shape and trickle figure at present.
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 contains the alkali development resin composition that makes the reaction product that epoxy adduct and multi-anhydride (D) esterification obtain by providing, thereby has realized above-mentioned purpose.Described epoxy adduct has by with the unsaturated monoacid of epoxy resin (A) addition (B) shown in the following general formula (I) be selected from phenolic compounds, alcoholic compound, compound among amines and the carboxylic acid (C) and the structure that forms, 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 0.1～1.0, the phenol hydroxyl of above-claimed cpd (C), alcohol hydroxyl group, amino or carboxyl are 0～0.9, and above-mentioned unsaturated monoacid (B) and above-claimed cpd (C) sum are that 0.1～1.0 ratio carries out the structure that addition forms, above-mentioned esterification is with 1 hydroxyl with respect to above-mentioned epoxy adduct, and the acid anhydride structure of above-mentioned multi-anhydride (D) 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, 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, abovementioned alkyl, above-mentioned alkoxy and above-mentioned alkenyl can be replaced by halogen atom, n represents 0～10 number, p represents 0～5 number, and r represents 0～4 number.)
In addition, the present invention has realized above-mentioned purpose by the alkali developing photosensitive resin composition that contains above-mentioned alkali development resin composition and Photoepolymerizationinitiater initiater is provided.
Preferred forms
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 the reaction product that makes epoxy adduct and multi-anhydride (D) esterification and obtain.Described epoxy adduct has by with the unsaturated monoacid of epoxy resin (A) addition (B) shown in the above-mentioned general formula (I) be selected from phenolic compounds, alcoholic compound, compound among amines and the carboxylic acid (C) and the structure that forms, 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 0.1～1.0, the phenol hydroxyl of above-claimed cpd (C), alcohol hydroxyl group, amino or carboxyl are 0～0.9, and (B) composition and (C) the composition sum be that 0.1～1.0 ratio carries out the structure that addition forms, above-mentioned esterification is with 1 hydroxyl with respect to above-mentioned epoxy adduct, and the acid anhydride structure of above-mentioned multi-anhydride (D) is that 0.1～1.0 ratio carries out.
1 epoxy radicals with respect to above-mentioned epoxy resin (A), the ratio of the carboxyl of above-mentioned unsaturated monoacid (B) is preferably 0.4～1.0, the ratio of phenol hydroxyl, alcohol hydroxyl group, amino or the carboxyl of above-claimed cpd (C) and is preferably 0～0.6, and (B) composition and (C) the composition sum be preferably 0.4～1.0.In addition, with respect to 1 hydroxyl of above-mentioned epoxy adduct, the ratio of the acid anhydride structure of multi-anhydride (D) is preferably 0.4～1.0.
As the naphthenic base that in the above-mentioned general formula (I) is 3～10 with the carbon number shown in the Cy, can list cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, suberyl, the ring octyl group, the ring nonyl, ring decyl etc., as the alkyl that with the carbon number shown in Y and the Z is 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 one ethylhexyls, nonyl, different nonyl, decyl, isodecyl, one methyl fluoride, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluor ethyl etc., it as carbon number 1～10 alkoxy, can list methoxyl, ethoxy, propoxyl group, butoxy, methoxy ethyl, ethoxyethyl group, the propoxyl group ethyl, methoxyethoxyethyl, the ethoxy ethoxy ethyl, the propoxyl group ethoxyethyl group, methoxy-propyl etc., it as carbon number 2～10 alkenyl, can list vinyl, allyl, butenyl group, propenyl etc., as halogen atom, can list fluorine, chlorine, bromine, iodine.
Be used to prepare the epoxy resin (A) of alkali development resin composition of the present invention, owing to have 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, can list the compound of following No.1～No.9 with the epoxy resin (A) shown in the above-mentioned general formula (I).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.6
Compound N o.7
Compound N o.8
Compound N o.9
In alkali development resin composition of the present invention, contained by behind (A) composition addition (B) composition and (C) composition as required, esterification (D) composition and the reaction product that obtains can be made by for example method shown in the following reaction equation.
At first, by as epoxy resin (1) addition of (A) composition as the unsaturated monoacid (2) of (B) composition and (3) such as phenolic compounds of conduct as required (C) composition, thereby obtain containing the resin combination of compound (4) as epoxy adduct.Then, compound (4) and the multi-anhydride (5) of conduct (D) composition are reacted, carry out esterification, thereby obtain containing resin combination as the compound (6) of goal response product.And then, optionally, compound (6) and the epoxy compound (7) of conduct (E) composition are reacted, thereby can obtain containing the resin combination of compound (8).
The method that obtains the compound as epoxy adduct shown in the above-mentioned reaction equation (4) is not limited to above-mentioned method, for example when the n in the compound (4) is 0, shown in following reaction equation, also can obtain compound (4) by the method that makes bis-phenol (9) and contain the mono-epoxy compounds reaction of glycidyl methacrylate (10).
As the unsaturated monoacid (B) that is used to obtain alkali development resin composition of the present invention, can list for example acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl meth acrylate malate, hydroxy ethyl methacrylate malate, hydroxypropyl methyl acrylate malate, hydroxypropyl acrylate malate, dicyclopentadiene malate etc.
As the phenolic compounds that can be used as the compound (C) that obtains alkali development resin composition of the present invention and use, can list for example phenol, chlorophenol, cresols, ethyl-phenol, propylphenol, cumyl phenol, tert-butyl phenol, tert-amyl phenol, hexylphenol, octyl phenol, isooctyl phenol, tert-octyl phenol, nonyl phenol, dodecyl phenol, octadecyl phenol, 2, the 4-DI-tert-butylphenol compounds, 2, the 5-DI-tert-butylphenol compounds, 3, the 5-DI-tert-butylphenol compounds, 2,4, the 6-tribromphenol, 4-(1,1,3, the 3-tetramethyl butyl) phenol, 2-(3,5-dimethyl heptyl) phenol, 4-(3,5-dimethyl heptyl) phenol, terpene phenol, naphthols etc.
As the alcoholic compound that can be used as the compound (C) that obtains alkali development resin composition of the present invention and use, can list methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, isopropyl alcohol, sec-butyl alcohol, 2-amylalcohol, 3-amylalcohol, 2-hexanol, 3-hexanol, 2-enanthol, 3-enanthol, 4-enanthol, sec-n-octyl alcohol, 3-octanol, 4-octanol, the tert-butyl alcohol, 2-methyl-2-butanols, 2-methyl-2-amylalcohol, 2-methyl-2-hexanol, 2-methyl-2-enanthol etc.
As the amines that can be used as the compound (C) that obtains alkali development resin composition of the present invention and use, can list for example methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, heptyl amice, octylame, dimethylamine, diethylamine, di-n-propylamine, dibutylamine, diamylamine, dihexylamine, two heptyl amices, dioctylamine, morpholine, piperidines etc.
As the carboxylic acid that can be used as the compound (C) that obtains alkali development resin composition of the present invention and use, can list for example acetic acid, propionic acid, 2, aliphatics, aromatic series or alicyclic monocarboxylic acid such as 2-dihydromethyl propionic acid, lactic acid, butyric acid, sad, lauric acid, linoleic acid, ricinoleic acid, benzoic acid, toluic acid, cinnamic acid, phenylacetic acid, cyclohexane carboxylic.
As the multi-anhydride that is used to obtain alkali development resin composition of the present invention (D), can list 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, 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, the 2-dicarboxylic anhydride, trialkyl tetrabydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methyl-3,6-endo-methylene group-1,2,3,6-tetrabydrophthalic anhydride monobasic acid anhydrides such as (Methyl Himic Anhydride), 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-hexichol tetrasulfonic acid dianhydride, 4,4 '-hydroxyl, two O-phthalic acid dianhydrides, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 1,2,3,4-encircles penta tetracarboxylic dianhydride, dianhydrides such as methylhexahydrophthalic anhydride, the combination of wherein preferred dianhydride or dianhydride and monobasic acid anhydrides.
In the present invention, above-mentioned epoxy compound (E) is used to adjust acid number, also can be used to improve the development of alkali development resin composition of the present invention.As epoxy compound, 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 cresylglycidylether, 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.10, No.11 etc.
The acid number of the preferred solid state component of alkali development resin composition of the present invention is the scope of 60～120mgKOH/g, and the consumption of epoxy compound (E) is preferably selected according to the mode that satisfies above-mentioned acid number.
Compound N o.10
Compound N o.11
Alkali development resin composition of the present invention can further add Photoepolymerizationinitiater initiater and make alkali developing photosensitive resin composition.
Alkali development resin composition of the present invention and alkali developing photosensitive resin composition normally use as the solution shape composition that has added the solvent that can dissolve or disperse above-mentioned each composition as required, and described solvent is acetone, MEK, methylisobutylketone, cyclohexanone, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether acetate, chloroform, methylene chloride, hexane, heptane, octane, cyclohexane, benzene,toluene,xylene, methyl alcohol, ethanol, isopropyl alcohol for example.In this solution shape composition, the content of solvent is preferably 30～90 weight %, is preferably 40～70 weight % especially.
By esterification (D) composition behind (A) composition addition (B) composition and (C) composition as required, (E) composition is reacted and the content of the reaction product that obtains, in above-mentioned solution shape composition, be preferably 1～70 weight %, be preferably 3～30 weight % especially.
As the above-mentioned Photoepolymerizationinitiater initiater that is used for alkali developing photosensitive resin composition of the present invention; can use compound known up to now; 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-chloro-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; two (9 '-acridinyl) heptane of 7-; 9-normal-butyl-3; two (the 2 '-morpholino isobutyryl) carbazoles of 6-; 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone; 2-methyl-4; two (the trichloromethyl)-s-triazine of 6-; 2-phenyl-4; two (the trichloromethyl)-s-triazine of 6-; 2-naphthyl-4, two (the trichloromethyl)-s-triazine of 6-; following compound N o.12; No.13 etc.
Compound N o.12
(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 can be inserted and be selected among unsaturated link, ehter bond, thioether bond and the ester bond one or more, R and R ' also can form ring together in addition, and n is 0～5.)
Compound N o.13
(in the formula, X
1, R
1, R
2, R
3, R and R ' definition identical with above-claimed cpd No.12, 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 obtains with respect to add solvent in alkali development resin composition of the present invention, be preferably 0～30 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 2-Hydroxy ethyl acrylate, 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 hexanediol diacrylate, 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 etc.
As above-mentioned chain-transferring agent; can list mercaptoacetic acid; thiomalic acid; o-mercaptobenzoic acid; 2 mercaptopropionic acid; the 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, the 2-propylene glycol; 1-sulfydryl-2-propyl alcohol; 3-sulfydryl-2-butanols; mercapto-phenol; the 2-mercaptoethylmaine; the 2-mercaptoimidazole; 2-sulfydryl-3-pyridol; 2-mercaptobenzothiazole; 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; ethylene 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 development 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 development resin composition of the present invention 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 making alkali developing photosensitive resin composition of the present invention sclerosis, 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, but the present invention is not subjected to any restriction of these embodiment.
The manufacturing of [embodiment 1] alkali development resin composition No.1
＜step 1〉1, the manufacturing of two (4 '-hydroxy phenyl)-1-of 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 that obtains separating out, disperse to clean, obtain the faint yellow crystalline solid of 59.2g (yield is 51%) with toluene.The fusing point of this faint yellow crystalline solid is 239.5 ℃, confirms that this faint yellow crystalline solid is a target compound.
＜step 2〉1, the manufacturing of two (4 '-glycidoxy phenyl)-1-of 1-(1 "-xenyl)-1-cyclohexyl-methane
Add in the 57.5g step 1 resultingly 1, two (4 '-hydroxy phenyl)-1-of 1-(1 "-xenyl)-1-cyclohexyl-methane and 195.8g epichlorokydrin adds the 0.602g benzyltriethylammonium chloride, stirs 18 hours down at 64 ℃.Then be cooled to 54 ℃, drip 43.0g 24 weight % sodium hydrate aqueous solutions, stirred 30 minutes.Heat up in a steamer decyclization oxygen chloropropane and water, after the washing of adding 216g methylisobutylketone, drip 2.2g 24 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 crystal body is a target compound.
＜step 3〉manufacturing of alkali development resin composition No.1
Add in the 43g step 2 resulting 1, two (4 '-glycidoxy phenyl)-1-of 1-(1 "-xenyl)-1-cyclohexyl-methane (below be also referred to as compound a), 11g acrylic acid (below be also referred to as compound b), 0.05g 2; 6-BHT, 0.11g TBuA acetic acid esters and 23g propylene glycol-1-monomethyl ether-2-acetic acid esters stirred 16 hours down at 120 ℃.Be cooled to room temperature, add 35g propylene glycol-1-monomethyl ether-2-acetic acid esters and 9.4g biphenyl tetracarboxylic dianhydride (below be also referred to as compound d-1), stirred 8 hours down at 120 ℃, add 6.0g tetrabydrophthalic anhydride (below be also referred to as compound d-2) again, stirred 4 hours down at 120 ℃, 100 ℃ were stirred 3 hours down, 80 ℃ were stirred 4 hours down, 60 ℃ were stirred 6 hours down, 40 ℃ were stirred down after 11 hours, added 29g propylene glycol-1-monomethyl ether-2-acetic acid esters, obtained the target product alkali development resin composition No.1 (Mw=4000 as propylene glycol-1-monomethyl ether-2-acetate solution form, Mn=2100, acid number (solid state component) is 86mgKOH/g).
In addition, the reaction product that alkali development resin composition No.1 is contained is with 1 hydroxyl with respect to epoxy adduct, it as the acid anhydride structure of the compound d-1 of (D) composition and compound d-2 0.68 ratio, make epoxy adduct, compound d-1 and compound d-2 carry out esterification and obtain, above-mentioned epoxy adduct has the structure that is formed by the compound b of compound a addition conduct (B) composition of conduct (A) composition.In addition, above-mentioned epoxy adduct has with 1 epoxy radicals with respect to compound a, and the carboxyl of compound b is that 1.0 ratio carries out the structure that addition forms.
The manufacturing of [embodiment 2] alkali development resin composition No.2
Add 43g 1, two (4 '-glycidoxy phenyl)-1-of 1-(1 "-xenyl)-1-cyclohexyl-methane (compound a), 11g acrylic acid (compound b), 0.05g 2; 6-BHT, 0.11g TBuA acetic acid esters and 23g propylene glycol-1-monomethyl ether-2-acetic acid esters stirred 16 hours down at 120 ℃.Be cooled to room temperature, add 35g propylene glycol-1-monomethyl ether-2-acetic acid esters and 16g biphenyl tetracarboxylic dianhydride (compound d-1), stirred 8 hours down at 120 ℃.Add 0.7g tetrabydrophthalic anhydride (compound d-2) again, stirred 4 hours down at 120 ℃, 100 ℃ were stirred 3 hours down, 80 ℃ were stirred 4 hours down, and 60 ℃ were stirred 6 hours down, and 40 ℃ are stirred after 11 hours down, add 29g propylene glycol-1-monomethyl ether-2-acetic acid esters, obtain target product alkali development resin composition No.2 (acid number (solid state component) is 89mgKOH/g for Mw=8100, Mn=2900) as propylene glycol-1-monomethyl ether-2-acetate solution form.
In addition, the reaction product that alkali development resin composition No.2 is contained is with 1 hydroxyl with respect to epoxy adduct, it as the acid anhydride structure of the compound d-1 of (D) composition and compound d-2 0.74 ratio, make epoxy adduct, compound d-1 and compound d-2 carry out esterification and obtain, above-mentioned epoxy adduct has the structure that is formed by the compound b of compound a addition conduct (B) composition of conduct (A) composition.In addition, above-mentioned epoxy adduct has with 1 epoxy radicals with respect to compound a, and the carboxyl of compound b is that 1.0 ratio carries out the structure that addition forms.
The manufacturing of [embodiment 3] alkali development resin composition No.3
Add 43g 1, two (4 '-glycidoxy phenyl)-1-of 1-(1 "-xenyl)-1-cyclohexyl-methane (compound a), 11g acrylic acid (compound b), 0.05g 2; 6-BHT, 0.11g TBuA acetic acid esters and 23g propylene glycol-1-monomethyl ether-2-acetic acid esters stirred 16 hours down at 120 ℃.Be cooled to room temperature, add 35g propylene glycol-1-monomethyl ether-2-acetic acid esters, 16g biphenyl tetracarboxylic dianhydride (compound d-1) and 39mg bromination tetra-n-butyl ammonium, stirred 4 hours down at 120 ℃, 100 ℃ were stirred 3 hours down, 80 ℃ were stirred 4 hours down, 60 ℃ were stirred 6 hours down, 40 ℃ are stirred after 11 hours down, add 29g propylene glycol-1-monomethyl ether-2-acetic acid esters, obtain target product alkali development resin composition No.3 (Mw=8600 as propylene glycol-1-monomethyl ether-2-acetate solution form, Mn=3000, acid number (solid state component) is 87mgKOH/g).
In addition, the reaction product that alkali development resin composition No.3 is contained is with 1 hydroxyl with respect to epoxy adduct, it as the acid anhydride structure of the compound d-1 of (D) composition 0.71 ratio, make epoxy adduct and compound d-1 carry out esterification and obtain, above-mentioned epoxy adduct has the structure that is formed by the compound b of compound a addition conduct (B) composition of conduct (A) composition.In addition, above-mentioned epoxy adduct has with 1 epoxy radicals with respect to compound a, and the carboxyl of compound b is that 1.0 ratio carries out the structure that addition forms.
The manufacturing of [embodiment 4] alkali development resin composition No.4
Add 43g 1, two (4 '-glycidoxy phenyl)-1-of 1-(1 "-xenyl)-1-cyclohexyl-methane (compound a), 11g acrylic acid (compound b), 0.05g 2; 6-BHT, 0.11g TBuA acetic acid esters and 23g propylene glycol-1-monomethyl ether-2-acetic acid esters stirred 16 hours down at 120 ℃.Be cooled to room temperature, add 35g propylene glycol-1-monomethyl ether-2-acetic acid esters and 10g biphenyl tetracarboxylic dianhydride (compound d-1), stirred 8 hours down at 120 ℃.Add 6g tetrabydrophthalic anhydride (compound d-2) again, stirred 4 hours down at 120 ℃, 100 ℃ were stirred 3 hours down, 80 ℃ were stirred 4 hours down, 60 ℃ were stirred 6 hours down, 40 ℃ were stirred down after 11 hours, added 6.3g cresyl glycidyl ether (Verbindung), stirred 10 hours down at 120 ℃.Be cooled to 50 ℃, add 29g propylene glycol-1-monomethyl ether-2-acetic acid esters, obtain target product alkali development resin composition No.4 (acid number (solid state component) is 45mgKOH/g for Mw=4700, Mn=2500) as propylene glycol-1-monomethyl ether-2-acetate solution form.
In addition, the reaction product that alkali development resin composition No.4 contained has following structures: with respect to have by as the compound a addition of (A) composition as the compound b of (B) composition and 1 hydroxyl of the epoxy adduct of the structure that forms, it as the acid anhydride structure of the compound d-1 of (D) composition and compound d-2 0.7 ratio, make epoxy adduct, compound d-1 and compound d-2 carried out esterification, and 0.36 carboxyl that the Verbindung that resulting esterification products further is used as (E) composition will come from acid anhydride structure carries out esterification and the structure that forms.In addition, above-mentioned epoxy adduct has with 1 epoxy radicals with respect to compound a, and the carboxyl of compound b is that 1 ratio carries out the structure that addition forms.
The manufacturing of [embodiment 5] alkali development resin composition No.5
Add 43g 1, two (4 '-glycidoxy phenyl)-1-of 1-(1 "-xenyl)-1-cyclohexyl-methane (compound a), 5.7g phenol (below be also referred to as compound c) and 25g propylene glycol-1-monomethyl ether-2-acetic acid esters are heated to 115 ℃.Add the 0.2g triphenyl phasphine, stirred 4 hours down, add 50g propylene glycol-1-monomethyl ether-2-acetic acid esters, be cooled to 50 ℃ at 120 ℃.Add 48mg 2,6 ditertiary butyl p cresol, 0.49g bromination benzyl triethyl ammonium and 6.6g acrylic acid (compound b), stirred 5 hours, be cooled to 50 ℃ at 120 ℃.Add 10.27g biphenyl tetracarboxylic dianhydride (compound d-1), stirred 8 hours down at 120 ℃.Add 6.23g tetrabydrophthalic anhydride (compound d-2) again, stirred 4 hours down at 120 ℃, 100 ℃ were stirred 3 hours down, and 80 ℃ were stirred 4 hours down, and 60 ℃ were stirred 6 hours down, and 40 ℃ were stirred 11 hours down.Be cooled to 50 ℃, add 58.3g propylene glycol-1-monomethyl ether-2-acetic acid esters, obtain target product alkali development resin composition No.5 (acid number (solid state component) is 87mgKOH/g for Mw=4300, Mn=2200) as propylene glycol-1-monomethyl ether-2-acetate solution form.
In addition, the reaction product that alkali development resin composition No.5 is contained is with 1 hydroxyl with respect to epoxy adduct, it as the acid anhydride structure of the compound d-1 of (D) composition and compound d-2 0.73 ratio, make epoxy adduct, compound d-1 and compound d-2 carry out esterification and obtain, above-mentioned epoxy adduct has the structure that is formed by the compound c of the compound b of compound a addition conduct (B) composition of conduct (A) composition and conduct (C) composition.In addition, above-mentioned epoxy adduct has with 1 epoxy radicals with respect to compound a, and the carboxyl of compound b is that 0.6, the phenolic hydroxyl group of compound c are that 0.4 and compound b and compound c sum are that 1.0 ratio carries out the structure that addition forms.
The manufacturing of [embodiment 6] alkali development resin composition No.6
Add 43g 1, two (4 '-glycidoxy phenyl)-1-of 1-(1 "-xenyl)-1-cyclohexyl-methane (compound a), 7.1g phenol (compound c) and 25g propylene glycol-1-monomethyl ether-2-acetic acid esters are heated to 115 ℃.Add the 0.2g triphenyl phasphine, stirred 4 hours down, add 50g propylene glycol-1-monomethyl ether-2-acetic acid esters, be cooled to 50 ℃ at 120 ℃.Add 48mg 2,6 ditertiary butyl p cresol, 0.49g bromination benzyl triethyl ammonium and 5.5g acrylic acid (compound b), stirred 5 hours, be cooled to 50 ℃ at 120 ℃.Add 10.27g biphenyl tetracarboxylic dianhydride (compound d-1), stirred 8 hours down at 120 ℃.Add 6.23g tetrabydrophthalic anhydride (compound d-2) again, stirred 4 hours down at 120 ℃, 100 ℃ were stirred 3 hours down, and 80 ℃ were stirred 4 hours down, and 60 ℃ were stirred 6 hours down, and 40 ℃ were stirred 11 hours down.Be cooled to 50 ℃, add 58.3g propylene glycol-1-monomethyl ether-2-acetic acid esters, obtain target product alkali development resin composition No.6 (acid number (solid state component) is 86mgKOH/g for Mw=4400, Mn=2230) as propylene glycol-1-monomethyl ether-2-acetate solution form.
In addition, the reaction product that alkali development resin composition No.6 is contained is with respect to 1 hydroxyl in the epoxy adduct, it as the acid anhydride structure of the compound d-1 of (D) composition and compound d-2 0.7 ratio, make epoxy adduct, compound d-1 and compound d-2 carry out esterification and obtain, above-mentioned epoxy adduct has the structure that is formed by the compound c of the compound b of compound a addition conduct (B) composition of conduct (A) composition and conduct (C) composition.In addition, above-mentioned epoxy adduct has with 1 epoxy radicals with respect to compound a, and the carboxyl of compound b is that 0.5, the phenolic hydroxyl group of compound c are that 0.5 and compound b and compound c sum are that 1.0 ratio carries out the structure that addition forms.
The manufacturing of [embodiment 7] 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 8] 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 9] alkali developing photosensitive resin composition No.3
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.3.
The manufacturing of [embodiment 10] alkali developing photosensitive resin composition No.4
In 7.2g embodiment 1 among the resulting alkali development resin composition No.1, add 4.3g trimethylolpropane triacrylate, 1.5g 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone and 87g ethyl cellosolve, fully stir, obtain alkali developing photosensitive resin composition No.4.
The manufacturing of [embodiment 11] alkali developing photosensitive resin composition No.5
In 20g embodiment 1 among the resulting alkali development resin composition No.1, add 8.7g trimethylolpropane triacrylate, 4.6g acrylic acid series copolymer, 1.7g 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone and 65g ethyl cellosolve, fully stir, obtain alkali developing photosensitive resin composition No.5.
In addition, aforesaid propylene acid based copolymer is by 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 obtained 70 ℃ of reactions in 5 hours.
The manufacturing of [comparative example 1] alkali development resin composition No.7
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, 59g diphthalic anhydrides and 0.24g bromination tetra-n-butyl ammonium, stirred 4 hours down at 120 ℃.Add the 20g tetrabydrophthalic anhydride again, stirred 4 hours down at 120 ℃, 100 ℃ were stirred 3 hours down, 80 ℃ were stirred 4 hours down, and 60 ℃ were stirred 6 hours down, and 40 ℃ are stirred after 11 hours down, add 90g propylene glycol-1-monomethyl ether-2-acetic acid esters, obtain target product alkali development resin composition No.7 (acid number (solid state component) is 92.7mgKOH/g for Mw=5000, Mn=2100) as propylene glycol-1-monomethyl ether-2-acetate solution form.
The manufacturing of [comparative example 2] alkali development resin composition No.8
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 16 hours at 120 ℃.Be cooled to room temperature, add 365g propylene glycol-1-monomethyl ether-2-acetic acid esters, 67g diphthalic anhydrides and 0.24g bromination tetra-n-butyl ammonium, stirred 4 hours down at 120 ℃, 100 ℃ were stirred 3 hours down, 80 ℃ were stirred 4 hours down, 60 ℃ were stirred 6 hours down, 40 ℃ are stirred after 11 hours down, add 90g propylene glycol-1-monomethyl ether-2-acetic acid esters, obtain target product alkali development resin composition No.8 (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.9
＜step 1〉1, the manufacturing of two (4 '-hydroxy phenyl)-1-of 1-(1 "-xenyl) ethane
75g phenol and 50g 4-acetyl biphenyl 60 ℃ of following heating for dissolving, are added 5g 3-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 crystalline solid that obtains separating out, obtain the faint yellow crystalline solid of 65g (yield is 68%) behind the drying under reduced pressure.The fusing point of this faint yellow crystalline solid is 184 ℃, confirms that this faint yellow crystalline solid is a target compound.
＜step 2〉1, the manufacturing of two (4 '-glycidoxy phenyl)-1-of 1-(1 "-xenyl) ethane
Add in the 37g step 1 resultingly 1, two (4 '-hydroxy phenyl)-1-of 1-(1 "-xenyl) ethane and 149.5g epichlorokydrin add the 0.45g benzyltriethylammonium chloride, stir 18 hours down at 64 ℃.Then cool to 54 ℃, drip 32.6g 24 weight % sodium hydrate aqueous solutions, stirred 30 minutes.Heat up in a steamer decyclization oxygen chloropropane and water, after the washing of adding 140g methylisobutylketone, drip 1.7g 24 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.9
Add 49.6g 1, two (4 '-glycidoxy phenyl)-1-of 1-(1 "-xenyl) ethane, 14.4g acrylic acid, 0.05g 2; 6-BHT, 0.14g TBuA acetic acid esters and 27.4g propylene glycol-1-monomethyl ether-2-acetic acid esters stirred 16 hours down at 120 ℃.Be cooled to room temperature, add 41.5g propylene glycol-1-monomethyl ether-2-acetic acid esters and 12.4g biphenyl tetracarboxylic dianhydride, stirred 8 hours down at 120 ℃.Add the 7.9g tetrabydrophthalic anhydride again, stirred 4 hours down at 120 ℃, 100 ℃ were stirred 3 hours down, 80 ℃ were stirred 4 hours down, and 60 ℃ were stirred 6 hours down, and 40 ℃ are stirred after 11 hours down, add 34g propylene glycol-1-monomethyl ether-2-acetic acid esters, obtain target product alkali development resin composition No.9 (acid number (solid state component) is 93mgKOH/g for Mw=3700, Mn=1900) as propylene glycol-1-monomethyl ether-2-acetate solution form.
The manufacturing of [comparative example 4] alkali developing photosensitive resin composition No.6
In 14g comparative example 1, 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.6.
The manufacturing of [comparative example 5] alkali developing photosensitive resin composition No.7
In 14g comparative example 2, 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.7.
The manufacturing of [comparative example 6] alkali developing photosensitive resin composition No.8
In 14g comparative example 3, among the resulting alkali development resin composition No.9, add 5.9g trimethylolpropane triacrylate, 2.1g benzophenone and 78g ethyl cellosolve, fully stir, obtain alkali developing photosensitive resin composition No.8.
The evaluation of resulting alkali developing photosensitive resin composition No.1～8 is following to be carried out.
That is, spin coating r-glycidoxy propyl group methyl ethoxy silane on substrate, and behind the abundant Rotary drying, it is dry that spin coating (1300r.p.m, 50 seconds) above-mentioned alkali developing photosensitive resin composition No.1～7 also make it.The poly-vinyl alcohol solution of coating 5 weight % forms the oxygen barrier film after carrying out 20 minutes prebake under 70 ℃.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 less than 10 μ m also can form the A that is evaluated as of figure well, can form the B that is evaluated as of figure when live width is 10～30 μ m well, and live width must be at 30 μ m or the above C that is evaluated as that could form good figure.
＜cohesive 〉
According to the test method of JIS D 0202, 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.Outward appearance does not change and does not have the note of peeling off of resist to do zero fully yet, 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 7) | a | A | ○ | ○ |
| No.2 (embodiment 8) | a | A | ○ | ○ |
| No.3 (embodiment 9) | a | A | ○ | ○ |
| No.4 (embodiment 10) | a | A | ○ | ○ |
| No.5 (embodiment 11) | a | A | ○ | ○ |
| No.6 (comparative example 4) | b | C | × | × |
| No.7 (comparative example 5) | b | C | × | × |
| No.8 (comparative example 6) | b | C | × | × |
The alkali developing photosensitive resin composition of embodiment 7～11 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 or abovely could form figure at 30 μ m, and resulting film also undesirable with the cohesive and the alkali resistance of substrate.
In sum, the transparency of alkali developing photosensitive resin composition of the present invention, cohesive and alkali resistance etc. are good, and can precision form trickle figure well.
Claims (4)
1. alkali development resin composition that contains the reaction product that makes epoxy adduct and multi-anhydride (D) esterification and obtain, described epoxy adduct has by with the unsaturated monoacid of epoxy resin (A) addition (B) shown in the following general formula (I) be selected from phenolic compounds, alcoholic compound, compound among amines and the carboxylic acid (C) and the structure that forms, described epoxy adduct has with 1 epoxy radicals with respect to described epoxy resin (A), the carboxyl of described unsaturated monoacid (B) is 0.1～1.0, the phenol hydroxyl of described compound (C), alcohol hydroxyl group, amino or carboxyl are 0～0.9, and described unsaturated monoacid (B) and described compound (C) sum are 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 (D) 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, 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, described alkyl, described alkoxy and described alkenyl can be replaced by halogen atom, n represents 0～10 number, p represents 0～5 number, and r represents 0～4 number.
2. alkali development resin composition as claimed in claim 1 wherein, further reacts described reaction product with epoxy compound (E).
3. alkali development resin composition as claimed in claim 1 or 2, wherein, in the described general formula (I), Cy is a cyclohexyl, X is a phenyl, and p and r are 0.
4. alkali developing photosensitive resin composition, it contains each described alkali development resin composition and Photoepolymerizationinitiater initiater in the claim 1～3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP271688/2004 | 2004-09-17 | ||
| JP2004271688A JP4198101B2 (en) | 2004-09-17 | 2004-09-17 | Alkali developable resin composition |
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| Publication Number | Publication Date |
|---|---|
| CN1860415A true CN1860415A (en) | 2006-11-08 |
| CN100580555C CN100580555C (en) | 2010-01-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200580000757A Expired - Lifetime CN100580555C (en) | 2004-09-17 | 2005-08-30 | Alkaline developable resin composition |
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| Country | Link |
|---|---|
| JP (1) | JP4198101B2 (en) |
| KR (1) | KR101168438B1 (en) |
| CN (1) | CN100580555C (en) |
| TW (1) | TW200625005A (en) |
| WO (1) | WO2006030630A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1885162B (en) * | 2005-06-20 | 2011-06-22 | 株式会社艾迪科 | Alkaline developable photosensitive resin composition |
| CN102736415A (en) * | 2011-03-31 | 2012-10-17 | 太阳油墨制造株式会社 | Phtotocuring thermocuring resin composition, dry film and cured resin thereof, and printed circuit board using the same |
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| KR101317223B1 (en) | 2005-06-20 | 2013-10-15 | 가부시키가이샤 아데카 | Colored alkali-developable photosensitive resin composition and color filters made by using the same |
| JP5546093B2 (en) * | 2006-12-26 | 2014-07-09 | 株式会社Ａｄｅｋａ | Polymerizable compound and polymerizable 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 |
| WO2016129195A1 (en) * | 2015-02-10 | 2016-08-18 | Jsr株式会社 | Photosensitive resin composition and resin composition, patterned resin film and method for manufacturing same, and cell culture device |
| JP7428365B2 (en) * | 2019-10-16 | 2024-02-06 | 互応化学工業株式会社 | Photosensitive composition, transparent cured film, laminate, and method for producing the laminate |
| CN112250836B (en) * | 2020-12-08 | 2021-03-30 | 北京市银帆涂料有限责任公司 | High molecular compound, coating composition containing high molecular compound and preparation method of coating 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 |
| WO2001053890A1 (en) * | 2000-01-17 | 2001-07-26 | Showa Highpolymer Co., Ltd. | Photosensitive resin composition |
| TW521547B (en) * | 2000-09-16 | 2003-02-21 | Goo Chemical Co Ltd | Ultraviolet-curable resin composition and photosolder resist ink containing the composition |
| US6555592B2 (en) * | 2001-02-27 | 2003-04-29 | Advance Materials Corporation | Photothermosetting composition comprising acrylated epoxy resin |
| JP2003107702A (en) | 2001-09-27 | 2003-04-09 | Sumitomo Chem Co Ltd | Resin composition |
| JP4087650B2 (en) * | 2002-07-12 | 2008-05-21 | 太陽インキ製造株式会社 | Photocurable / thermosetting resin composition and cured product thereof |
| JP2004061566A (en) * | 2002-07-25 | 2004-02-26 | Taiyo Ink Mfg Ltd | Photosetting/thermosetting resin composition and printed-wiring board using the same |
| JP2004137328A (en) * | 2002-10-16 | 2004-05-13 | Japan U-Pica Co Ltd | Photocurable compound and photocurable thermosetting resin composition and its cured product |
| CN100386298C (en) * | 2004-03-25 | 2008-05-07 | 株式会社艾迪科 | Novel phenolic compound and novel epoxy resin derivable from the phenolic compound |
-
2004
- 2004-09-17 JP JP2004271688A patent/JP4198101B2/en not_active Expired - Lifetime
-
2005
- 2005-08-30 KR KR1020067000500A patent/KR101168438B1/en not_active Expired - Lifetime
- 2005-08-30 WO PCT/JP2005/015719 patent/WO2006030630A1/en not_active Ceased
- 2005-08-30 CN CN200580000757A patent/CN100580555C/en not_active Expired - Lifetime
- 2005-09-07 TW TW094130706A patent/TW200625005A/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1885162B (en) * | 2005-06-20 | 2011-06-22 | 株式会社艾迪科 | Alkaline developable photosensitive resin composition |
| CN102736415A (en) * | 2011-03-31 | 2012-10-17 | 太阳油墨制造株式会社 | Phtotocuring thermocuring resin composition, dry film and cured resin thereof, and printed circuit board using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006084985A (en) | 2006-03-30 |
| KR20070051762A (en) | 2007-05-18 |
| TW200625005A (en) | 2006-07-16 |
| CN100580555C (en) | 2010-01-13 |
| WO2006030630A1 (en) | 2006-03-23 |
| JP4198101B2 (en) | 2008-12-17 |
| TWI375863B (en) | 2012-11-01 |
| KR101168438B1 (en) | 2012-07-25 |
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