CN102164977B - Photosensitive resin composition and method for producing photosensitive resin used therein - Google Patents
Photosensitive resin composition and method for producing photosensitive resin used therein Download PDFInfo
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- CN102164977B CN102164977B CN200980137692.1A CN200980137692A CN102164977B CN 102164977 B CN102164977 B CN 102164977B CN 200980137692 A CN200980137692 A CN 200980137692A CN 102164977 B CN102164977 B CN 102164977B
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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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/681—Metal alcoholates, phenolates or carboxylates
- C08G59/685—Carboxylates
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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
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
-
- 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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- 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
- C08F290/064—Polymers containing more than one epoxy group per molecule
-
- 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
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
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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
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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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
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
Abstract
A photosensitive resin composition containing: (A) a photosensitive resin which is obtained by reacting a monoepoxy compound having an unsaturated double bond and a water-soluble monoepoxy compound with a carboxyl group which is produced by reacting a polyfunctional epoxy compound with an unsaturated monobasic acid in the presence of a trivalent organophosphorus compound and at least one of zirconium naphthenate and zirconium octoate and then further reacting the resulting product with a polybasic acid anhydride; (B) an epoxy resin; (C) a photopolymerization initiator; and (D) a reactive diluent. The photosensitive resin composition is suitable as a highly sensitive solder resist ink which contains no chromium compound and can be developed by ultraviolet exposure and a dilute aqueous alkali solution, while having good thermal stability and control width of development. A coating film of the solder resist ink has excellent properties.
Description
Technical field
The present invention relates to a kind of photosensitive polymer combination, more specifically, relate to a kind of containing chromium cpd,, the photosensitive polymer combination of filming thering is good physical property, can utilize diluted alkaline develop that obtain high to the luminous sensitivity of ultraviolet exposure.
Background technology
In recent years, the welding resistance ink of various printed circuit board (PCB)s is widely used is the liquid photosensitive welding resistance ink of diluted alkaline developable.The photoresist of diluted alkaline developable is for example known a sour side chain type Epocryl that makes the hydroxyl reaction of acid anhydrides and Epocryl and obtain.In the past, in order to obtain good thermostability and development range of management, in the synthetic catalyst of this sour side chain type Epocryl, used chromium naphthenate always.But the numerous and diverse aspect of liquid waste disposal from now the consciousness of environmental problem being improved or developing, is not preferably used the chromium cpd of chromium naphthenate and so on as synthetic catalyst.Therefore, for example, in patent documentation 1, proposed use organo phosphorous compounds as synthetic catalyst, under prescribed condition, made polyfunctional epoxy resin react with unsaturated monoprotic acid, and then the photoresist obtaining with anhydride reaction.
Prior art document
Patent documentation 1: Japanese Patent Laid-Open 2005-41958 communique
Summary of the invention
But the photoresist of recording in patent documentation 1 cannot be taken into account with high level the performances such as the desired luminous sensitivity of nearest welding resistance ink, thermostability, development range of management, thermotolerance, solvent resistance, also has the leeway of improvement.
Therefore, the object of the present invention is to provide a kind of photosensitive polymer combination, it is containing chromium cpd, can ultraviolet exposure and utilize dilute alkaline aqueous solution to develop, be suitable as luminous sensitivity high, and thermostability and development range of management are good, filming demonstrates the welding resistance ink of excellent properties.
The inventor etc. carry out active research in order to solve described problem, found that, coordinated the photosensitive polymer combination of following photoresist to meet described object, described photoresist obtains by following manner: under the existence of at least one in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate, multi-functional epoxy compound is reacted with unsaturated monoprotic acid, and then react with multi-anhydride and generate carboxyl, then make to have mono-epoxy compounds and water-soluble mono epoxy compounds and the described carboxyl reaction of unsaturated double-bond; Thereby complete the present invention.
; the present invention is a kind of photosensitive polymer combination; it is characterized in that containing: (A) photoresist; this photoresist obtains by following manner: under the existence of at least one in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate; multi-functional epoxy compound is reacted with unsaturated monoprotic acid; and then react with multi-anhydride and generate carboxyl, then make to have mono-epoxy compounds and water-soluble mono epoxy compounds and the described carboxyl reaction of unsaturated double-bond; (B) epoxy resin; (C) Photoepolymerizationinitiater initiater; And (D) reactive diluent.
In addition, the present invention is a kind of manufacture method of photoresist, it is characterized in that comprising: first step, under the existence of at least one in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate, makes multi-functional epoxy compound react with unsaturated monoprotic acid; Second step, makes multi-anhydride react with the resultant obtaining in first step; And third step, mono-epoxy compounds and the water-soluble mono epoxy compounds with unsaturated double-bond are reacted with the resultant obtaining in second step.
[invention effect]
According to the present invention, following photosensitive polymer combination can be provided, this photosensitive polymer combination is not containing chromium cpd, can ultraviolet exposure and utilize dilute alkaline aqueous solution to develop, be suitable as luminous sensitivity high, and thermostability and development range of management are good, filming demonstrates the welding resistance ink of excellent properties.
Embodiment
Below, the present invention is described in detail.
First, photosensitive polymer combination of the present invention is described.
(A) composition in photosensitive polymer combination of the present invention is by under at least one the existence in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate, multi-functional epoxy compound is reacted with unsaturated monoprotic acid, and then react and generate thus carboxyl with multi-anhydride, then make to have the mono-epoxy compounds of unsaturated double-bond and water-soluble mono epoxy compounds and described carboxyl reaction and the photoresist that obtains.
The physical property of (A) of the present invention composition, the impact of the catalyzer using when synthetic is larger, exists development range of management to be also subject to the tendency of the impact of catalyzer.In addition, in the situation that the catalyzer with different qualities is used together, occur the tendency of various shortcomings, but the discoveries such as the inventor, in the situation that trivalent organophosphorus compounds and zirconium naphthenate are used with together with at least one in zirconium caprylate, contrary with anticipation, can obtain the physical property equal with the situation of using chromium-based catalysts.
The usage quantity of catalyzer, with respect to polyfunctional epoxy resin and unsaturated monacid total amount 100 mass parts, is preferably, and the total amount of at least one in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate becomes the amount of 1.2 mass parts～6.0 mass parts.Now, in quality criteria, at least one in zirconium naphthenate and zirconium caprylate preferably used at least 4 times of trivalent organophosphorus compounds, more preferably uses 4 times～6 times.If the total amount of at least one in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate is very few, or the usage quantity of at least one in zirconium naphthenate and zirconium caprylate is less than 4 times of trivalent organophosphorus compounds, there is the situation that cannot bring into play fully function as catalysts.On the other hand, if trivalent organophosphorus compounds is too much, the tendency that exists the thermostability of the photoresist obtain to decline, in addition, and even if at least one in zirconium naphthenate and zirconium caprylate is too much, the effect also not matching with usage quantity, and uneconomical.
The multi-functional epoxy compound who uses in the present invention is not particularly limited, such as enumerating: epoxy resin such as bisphenol A-type, Bisphenol F type, phenol phenolic varnish type, cresols phenolic varnish type, bisphenol-A phenolic varnish type, cyclic aliphatic epoxy resin, heterocyclic type and imported compound of the halogen atoms such as bromine atoms or chlorine atom etc. in these epoxy resin.Cresols phenolic resin varnish type epoxy resin particularly preferably in these compounds.
The unsaturated monoprotic acid using in the present invention is so long as contain 1 carboxyl and the monoprotic acid of 1 above polymerizability unsaturated group, such as enumerating: vinylformic acid, methacrylic acid, butenoic acid, styracin, sorb saccharic acid (sorbitan acid), acrylic acid dimer etc.In these unsaturated monoprotic acid, especially, from obtaining the aspect of higher active energy ray light solidified, preferably use vinylformic acid.These unsaturated monoprotic acid both can have been used separately a kind of, also can be used in combination two or more.
These unsaturated monoprotic acid, with respect to multi-functional epoxy compound's epoxy group(ing) 1.0 equivalents, preferably make 0.8 equivalent～1.1 equivalent reaction.If unsaturated monacid ratio, lower than 0.8 equivalent, exists storage stability variation, or produce the situation of the problems such as gelation when synthetic, on the other hand, if surpass 1.1 equivalents, exist and produce foul smell, or the tendency that declines of thermotolerance.
The multi-anhydride using in the present invention, can enumerate: the dibasic acid anhydrides such as maleic anhydride, succinyl oxide, itaconic anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, Nadic anhydride, methyl tetrahydrophthalic anhydride, chlorendic anhydride, the multi-anhydrides such as trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid anhydrides.In these multi-anhydrides, especially, from the aspect of galvanic corrosion excellence, preferably use Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride.
The usage quantity of these multi-anhydrides be preferably with respect to make multi-functional epoxy compound react with unsaturated monoprotic acid gained resultant 1.0 moles of hydroxyls and be the ratio of 0.4 mole～0.9 mole, more preferably with the ratio of 0.6 mole～0.9 mole, react.If the usage quantity of multi-anhydride is less than 0.4 mole, there is the situation that cannot obtain sufficient alkali-developable, on the other hand, if surpass 0.9 mole, there is the tendency of the declines such as electrical specification of cured coating film.
The mono-epoxy compounds with unsaturated double-bond using in the present invention, for example, can enumerate: (methyl) acrylate with ester ring type epoxy group(ing) of Cyclomer A200, M100 that glycidyl methacrylate, glycidyl acrylate, Daicel (Daicel) chemical industry limited-liability company manufacture and so on.
Water-soluble mono epoxy compounds can be enumerated: following formula (I)
[changing 1]
(in formula, R
1represent alkyl or aryl, R
2represent that repeating unit is more than 3 polyethylene oxide or poly(propylene oxide)) shown in compound (for example, grow Denacol (registered trademark) EX-145, the EX-171 etc. of the manufacture of rapids changing into (Nagase ChemteX) limited-liability company), following formula (II)
[changing 2]
Shown compound (SY-GTA80 manufacturing such as ，Ban Ben pharmaceutical industries limited-liability company) etc.Because the mono-epoxy compounds with the unsaturated double-bond of being combined with the carboxyl that derives from multi-anhydride is incorporated into the most external of resin, so reactivity during uviolizing is comprehensively higher, uviolizing is had to higher light sensitivity.In addition, water-soluble mono epoxy compounds can improve the affinity of resin to alkali, and then moderately suppresses to have the mobility of unsaturated double-bond of the mono-epoxy compounds of unsaturated double-bond, the stability of giving the resin while preserving.
If consider luminous sensitivity, developability and the electrical specification etc. of obtained photoresist, with the amount of the mono-epoxy compounds with unsaturated double-bond reacting by the generated carboxyl of reacting of multi-anhydride and water-soluble mono epoxy compounds, preferably take total amount and react with respect to the ratio of 1 mole as 0.15 mole～0.25 mole of the carboxyl being generated.Wherein, now the amount of water-soluble mono epoxy compounds is preferably the ratio lower than 0.03 mole with respect to 1 mole of generated carboxyl, the ratio of more preferably 0.01 mole～0.025 mole.If there is the mono-epoxy compounds of unsaturated double-bond and the total amount of water-soluble mono epoxy compounds is less than 0.15 mole, there is effect as the high luminous sensitivity of one of the object of the invention inadequate tendency that becomes, on the other hand, if surpass 0.25 mole, the tendency that exists alkali-developable to decline.In addition, even if make the amount of water-soluble mono epoxy compounds, be more than 0.03 mole, the effect increasing is also lower, also unrealistic from previously described alkali-developable aspect.
As the epoxy resin of (B) composition in photosensitive polymer combination of the present invention, can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, Dicyclopentadiene (DCPD)-phenol novolak type epoxy resin, phenol-cresols phenolic varnish cocondensation mould assembly epoxy resin, bisphenol-A phenolic varnish type epoxy resin, the halogenation epoxy compounds of bisphenol F phenolic varnish type epoxy resin or these epoxy resin, triphenol methylmethane type epoxy resin, the triphenol methylmethane type epoxy resin replacing through alkyl, four phenolic group ethane type epoxy resin etc. make Epicholorohydrin react obtained epoxy resin with multifunctional phenol, make Epicholorohydrin react obtained epoxy resin with multifunctional hydroxyl naphthalene class, modifying epoxy resin by organosilicon, 6-caprolactone modified epoxy, by making Epicholorohydrin react obtained glycidyl amine type epoxy resin with uncle or secondary amine, the hetero ring type epoxy resin such as isocyanic acid three-glycidyl ester etc.These epoxy resin both can have been used separately a kind of, also can be used in combination two or more.
The use level of these epoxy resin, with respect to photoresist 100 mass parts, is preferably 3 mass parts～100 mass parts, more preferably 6 mass parts～75 mass parts.If the use level of epoxy resin is less than 3 mass parts, the carboxyl in photoresist is less than the amount of reaction in fact, so tendency that the water tolerance of existence, alkali resistance, electrical specification decline, on the other hand, if surpass 100 mass parts, can generate the linear polymer with unreacted epoxy group(ing), so there is thermotolerance, the solvent resistance inadequate situation that becomes.
In addition, in order further to improve the adhesion, chemical-resistant, thermotolerance etc. of epoxy resin, preferably use together with epoxy hardener.This epoxy hardener can be enumerated: imdazole derivatives, phenol derivatives, Dyhard RU 100, cyanoguanidine derivative, trimeric cyanamide, melamine resin, hydrazide derivatives, amine, acid anhydrides etc.These epoxy hardeners both can have been used separately a kind of, also can be used in combination two or more.The use level of epoxy hardener is preferably with respect to 1 mole of the epoxy group(ing) of epoxy resin, and the active hydrogen amount of solidifying agent is the ratio of 0.5 mole～1.2 moles.
As the Photoepolymerizationinitiater initiater of (C) composition in photosensitive polymer combination of the present invention, can enumerate: st-yrax, benzoin methyl ether, benzoin isopropyl ether, the benzoin and its derivatives such as benzoin isobutyl ether, benzil, benzil and the derivatives thereof such as benzil dimethyl ketal (benzil dimethyl ketal), methyl phenyl ketone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone (2,2-dimethoxy-2-phenyl acetophenone), 2,2-diethoxy-2-phenyl methyl phenyl ketone (2,2-diethoxy-2-phenyl acetophenone), 1,1-dichloroacetophenone (1,1-dichloroacetophenone), 1-hydroxycyclohexylphenylketone (1-hydroxy cyclohexyl phenyl ketone), methyl phenyl ketone and the derivatives thereof such as 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone (2-methyl-1-(4-methylthio phenyl)-2-morpholinopropan-1-one), 2-methylanthraquinone (2-methyl anthraquinone), 2-chloroanthraquinone, 2-ethyl-anthraquinone, anthraquinone and the derivatives thereof such as 2-tertiary butyl anthraquinone, thioxanthone (thioxanthone) is (thioxanthone), 2,4-dimethyl thia anthrone, thioxanthone and the derivatives thereof such as 2-chlorothiaxanthenone, benzophenone, N, benzophenone and the derivatives thereof such as N-dimethylamino benzophenone.These Photoepolymerizationinitiater initiaters both can have been used separately a kind of, also can be used in combination two or more.Well-known is by further as required various amine compound being used together with these Photoepolymerizationinitiater initiaters, promotes photopolymerization to cause effect, also can be used in combination in the present invention.
The use level of these Photoepolymerizationinitiater initiaters, with respect to photoresist 100 mass parts, is preferably 0.1 mass parts～20 mass parts, more preferably 1 mass parts～10 mass parts.If the use level of Photoepolymerizationinitiater initiater is less than 0.1 mass parts, sometimes cannot obtain fully the effect as Photoepolymerizationinitiater initiater, on the other hand, and even if surpass 20 mass parts, the effect also not matching with use level, and uneconomical.
As the reactive diluent of (D) composition in photosensitive polymer combination of the present invention, in order to improve to the solidified nature of active-energy light and/or when the coating of use sense photosensitive resin composition during as etching resisting ink, use.Reactive diluent preferably has the monomer class of active-energy light solidified nature, can enumerate: vinylformic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate, N-pyrrolidone, N-acryloyl morpholine, N, N-DMAA, N, N-diethyl acrylamide, vinylformic acid N, N-dimethylamino ethyl ester, vinylformic acid N, N-dimethylamino propyl ester, methoxy polyethylene glycol acrylate, oxyethyl group polyethylene glycol acrylate, trimeric cyanamide acrylate, vinylformic acid phenoxy ethyl, vinylformic acid phenoxy group propyl ester, glycol diacrylate, propylene glycol diacrylate, poly-propylene glycol diacrylate, Viscoat 295, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, glycerine diacrylate, isobornyl acrylate, vinylformic acid two cyclopentenes oxygen base ethyl esters and the various methacrylic esters corresponding with these monomers.These reactive diluents both can have been used separately a kind of, also can be used in combination two or more.
The use level of reactive diluent, with respect to photoresist 100 mass parts, is preferably 5 mass parts～200 mass parts, more preferably 10 mass parts～100 mass parts.If the use level of reactive diluent is less than 5 mass parts, sometimes cannot obtain sufficient light sensitivity, on the other hand, if surpass 200 mass parts, exist when the excess stickiness decline during as etching resisting ink of use sense photosensitive resin composition, as the patience of the cured coating film inadequate situation that becomes.
In addition, in order to adjust coating, solvent can be used together with reactive diluent.This solvent can be enumerated: the ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, the aromatic hydrocarbons such as toluene, dimethylbenzene, the Trivalin SF classes such as ethyl cellosolve, ethylene glycol butyl ether, Trivalin SF, diethylene glycol monobutyl ether, ethyl acetate, butylacetate, cellosolve acetic ester, butyl cellosolve acetate, ethyl carbitol acetic ester etc.These solvents both can have been used separately a kind of, also can be used in combination two or more.
In the situation that using photosensitive polymer combination of the present invention as liquid etching resisting ink, except described (A)～(D) composition, also can further add as required the inorganic fillers such as silicon-dioxide, calcium carbonate, barium sulfate, clay, talcum, the tinting pigments such as phthalocyanine green, phthalocyanine blue, titanium oxide, carbon black, the various additives such as defoamer, flow agent, the stoppers such as Resorcinol, Resorcinol, pyrocatechol, pyrogallol, hydroquinone monomethyl ether, tert-butyl catechol, thiodiphenylamine.
Secondly, the manufacture method of photoresist of the present invention is described.
In first step, under the existence of at least one in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate, utilize well-known method that multi-functional epoxy compound is reacted with unsaturated monoprotic acid.In addition, the aspect of the thermopolymerization when preventing from reacting, this reaction is preferably added the well-known polymerization retarders such as Resorcinol, methyl hydroquinone in system to and is carried out, on one side or carry out to being blown into air in system on one side.
Temperature of reaction in first step is preferably 60 ℃～150 ℃, and the reaction times is preferably 5 hours～and 20 hours.Multi-functional epoxy compound, be liquid in the situation that, can under solvent-free condition, react, but, preferably in solvent, react be solid-state in the situation that multi-functional epoxy compound.Here the solvent that used is such as enumerating: the ketones such as methyl ethyl ketone, pimelinketone, toluene, dimethylbenzene etc. are aromatic hydrocarbon based, the glycol ethers such as dipropylene glycol dme, the ester classes such as ethyl acetate, butyl cellosolve acetate, Trivalin SF acetic ester, ethyl carbitol acetic ester, acetate of butyl carbitol, dipropylene glycol monomethyl ether acetic ester, the petroleum solvents such as sherwood oil, petroleum naphtha, solvent naphtha.
In second step, utilize well-known method that multi-anhydride is reacted with the resultant obtaining in first step.Temperature of reaction in second step is preferably 80 ℃～120 ℃, and the reaction times is preferably 1 hour～and 6 hours.
In third step, utilize well-known method that mono-epoxy compounds and the water-soluble mono epoxy compounds with unsaturated double-bond are reacted with the resultant obtaining in second step.Temperature of reaction in third step is preferably 60 ℃～150 ℃, and the reaction times is preferably 0.5 hour～and 20 hours.
Embodiment
Below, utilize embodiment that the present invention is described in further detail, but the present invention is not limited to these embodiment.
< synthesis example 1>
To thering is the ethyl carbitol acetic ester that adds 192 mass parts in the flask of stirrer, gas introduction tube and return line, the cresols phenolic resin varnish type epoxy resin (Dongdu changes into Epotohto (registered trademark) YDCN704 that limited-liability company manufactures, and epoxy equivalent (weight) is 206) of 206 mass parts (1 equivalent) is dissolved in wherein.And then add the vinylformic acid of 72 mass parts (1.0 moles), the triphenylphosphine of the Resorcinol of 0.23 mass parts, 0.4 mass parts and the zirconium naphthenate of 2 mass parts (metal content is 6 quality %), from the basifacial gas introduction tube of liquid, be blown into air on one side, at 130 ℃, continue to carry out reaction in 10 hours on one side, the reactant (epoxy acrylate) that acquisition acid number is 0.5mgKOH/g.Then add wherein the Tetra Hydro Phthalic Anhydride of 111.03 mass parts (0.73 mole), it is further reacted 2 hours at 120 ℃, obtain the reactant that solids component acid number is 105.3mgKOH/g.Then add wherein Denacol (registered trademark) EX-145 (the long rapids limited-liability company's manufacture that changes into of glycidyl methacrylate and 9 mass parts (0.02 mole) of 22.72 mass parts (0.16 mole), epoxy equivalent (weight) is 450), it is further reacted 3 hours at 120 ℃, and then with nonvolatile component, reach 60% mode and append ethyl carbitol acetic ester, obtain the photoresist A that solids component acid number is 73.4mgKOH/g.
< synthesis example 2>
Except using the zirconium caprylate (metal content is 12 quality %) of 2 mass parts to replace the zirconium naphthenate (metal content 6 quality %) of 2 mass parts, carrying out the operation identical with synthesis example 1, obtain photoresist B.
< is synthesis example 1 (embodiment 1 that is equivalent to patent documentation 1) > relatively
To possessing the ethyl carbitol acetic ester that adds 192 mass parts in the flask of stirrer, gas introduction tube and return line, the cresols phenolic resin varnish type epoxy resin (Dongdu changes into Epotohto (registered trademark) YDCN704 that limited-liability company manufactures, and epoxy equivalent (weight) is 206) of 206 mass parts (1 equivalent) is dissolved in wherein.And then add 72 mass parts (1.0 moles) vinylformic acid, 2.17 mass parts 2, the triphenylphosphine of 6-bis--tertiary butyl-4-methoxyphenol, 0.415 mass parts, from the basifacial gas introduction tube of liquid, be blown into air on one side, in 130 ℃, continue to carry out reaction in 10 hours, the reactant (epoxy acrylate) that acquisition acid number is 1.0mgKOH/g on one side.Then add wherein the Tetra Hydro Phthalic Anhydride of 111.03 mass parts (0.73 mole) and the naphthenic acid lithium of 0.707 mass parts (metal content is 3%), it is further reacted 2 hours at 120 ℃, obtain the reactant that solids component acid number is 105.3mgKOH/g.Then add wherein Denacol (registered trademark) EX-145 (the long rapids limited-liability company's manufacture that changes into of glycidyl methacrylate and 9 mass parts (0.02 mole) of 22.72 mass parts (0.16 mole), epoxy equivalent (weight) is 450), it is further reacted 3 hours at 120 ℃, and then with nonvolatile component, reach 60% mode and append ethyl carbitol acetic ester, obtain the photoresist C that solids component acid number is 73.4mgKOH/g.
According to the cooperation ratio shown in table 1, coordinate each composition, utilize three-roll grinder to mix fully, prepare photosensitive polymer combination.Moreover the quality of the photoresist in table 1 is that the value with resin solid composition represents.
Then, on the tellite of processing through face in advance, to reach the mode of 30 μ m～40 μ m, utilize silk screen print method to be coated with described photosensitive polymer combination, at 80 ℃, after predrying 20 minutes, be cooled to room temperature, obtain dry coating.Then use jade-like stone difficult to understand to make the extra-high-pressure mercury vapour lamp exposure apparatus that institute (ORC Manufacturing) manufactures, with 250mJ/cm
2this is filmed and is exposed, then use hot-air drier 150 ℃ of heating 30 minutes, obtain cured coating film.According to evaluation test method shown below, gained is filmed and carried out various evaluation of physical property.These be the results are shown in to table 2.
< luminous sensitivity >
Luminous sensitivity is set on the dry coating after predrying and measures with stage phototimer (Kodak (Kodak) 21 lattice), use the extra-high-pressure mercury vapour lamp exposure apparatus of jade-like stone making manufacturing difficult to understand with 250mJ/cm
2expose, then utilize 1% aqueous sodium carbonate, to spray, press 2.0kgf/mm
2carry out developing for 60 seconds, measure the lattice number that there is no the part of removal in development post-exposure part.Do not have the lattice number of the part removed larger, luminous sensitivity is higher.
< development range of management >
The dry coating of 20 minutes, 40 minutes, 60 minutes or 80 minutes is changed into the predrying time in use, utilizes 1% aqueous sodium carbonate, to spray, presses 2.0kgf/mm
2develop, observation has or not and films after developing, and according to following standard, evaluates.Even if time of drying, the long development range of management of filming that also can develop was good.
Zero: development time is after 60 seconds, with visual observation without filming.
△: development time is after 120 seconds, with visual observation without filming.
*: development time, after 120 seconds, has residual film with visual observation.
< scolding tin thermotolerance >
According to JIS C6481, the mode being impregnated in scolding tin with whole face floats in scolding tin cured coating film, makes its in the solder bath of 260 ℃ floating 3 times, and each 10 seconds, after taking-up, observe and expand or the state of filming such as peel off, according to following standard, evaluate.
Zero: outward appearance is unchanged.
*: outward appearance changes.
< solvent resistance >
Painting membrane stage cured coating film being flooded in methylene dichloride after 30 minutes is evaluated.
Zero: outward appearance is unchanged
△: outward appearance slightly changes
*: film and peel off
< thermostability >
With respect to each resin solid composition 100 mass parts of photoresist A～C, add 10 mass parts Viscoat 295s, mix fully, put into developmental tube, using until the time disappearing 120 ℃ of mobility as gelation time, evaluate.Show the result in table 3.
[table 1]
| Embodiment 1 | Embodiment 2 | Comparative example 1 | |
| Photoresist A | 100 | - | - |
| Photoresist B | - | 100 | - |
| Photoresist C | - | - | 100 |
| Ethylene glycol butyl ether | 20 | 20 | 20 |
| Viscoat 295 | 10 | 10 | 10 |
| 2,2-dimethoxy-2-phenyl-acetone | 3 | 3 | 3 |
| Barium sulfate | 20 | 20 | 20 |
| Fine particle silica | 3 | 3 | 3 |
| Phthalocyanine green | 1 | 1 | 1 |
| Isocyanuric acid three-glycidyl ester | 10 | 10 | 10 |
| Dyhard RU 100 | 3 | 3 | 3 |
[table 2]
[table 3]
| Photoresist A | Photoresist B | Photoresist C | |
| Gelation time | 440 | 430 | 370 |
Claims (4)
1. a photosensitive polymer combination, is characterized in that,
Described composition contains: (A) photoresist, described photoresist is to obtain by following manner: under the existence of at least one in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate, multi-functional epoxy compound is reacted with unsaturated monoprotic acid, and then react with multi-anhydride and generate carboxyl, then make described carboxyl react with mono-epoxy compounds, described mono-epoxy compounds is mono-epoxy compounds and the water-soluble mono epoxy compounds with unsaturated double-bond; (B) epoxy resin; (C) Photoepolymerizationinitiater initiater; And (D) reactive diluent, described reactive diluent is the monomer with active-energy light solidified nature,
Described photoresist is the described carboxyl with respect to 1 mole, make total amount be 0.15 mole～0.25 mole described in there is the mono-epoxy compounds of unsaturated double-bond and the reaction of described water-soluble mono epoxy compounds obtains, wherein water-soluble mono epoxy compounds is less than 0.03 mole.
2. photosensitive polymer combination according to claim 1, is characterized in that: using is at least the described zirconium naphthenate of 4 times of trivalent organophosphorus compounds and at least one in zirconium caprylate in quality criteria.
3. a manufacture method for the photoresist in photosensitive polymer combination claimed in claim 1, is characterized in that, comprising:
First step, under the existence of at least one in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate, makes multi-functional epoxy compound react with unsaturated monoprotic acid;
Second step, makes multi-anhydride react with the resultant obtaining in first step; And
Third step, makes mono-epoxy compounds and the water-soluble mono epoxy compounds with unsaturated double-bond react with the resultant obtaining in second step.
4. the manufacture method of photoresist according to claim 3, is characterized in that: while be blown into air, carry out the reaction in described first step.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008276084A JP5161032B2 (en) | 2008-10-27 | 2008-10-27 | Photosensitive resin composition, method for producing photosensitive resin used therefor, and method for producing cured coating film |
| JP2008-276084 | 2008-10-27 | ||
| PCT/JP2009/062446 WO2010050272A1 (en) | 2008-10-27 | 2009-07-08 | Photosensitive resin composition and method for producing photosensitive resin used therein |
Publications (2)
| Publication Number | Publication Date |
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| CN102164977A CN102164977A (en) | 2011-08-24 |
| CN102164977B true CN102164977B (en) | 2014-01-29 |
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| Application Number | Title | Priority Date | Filing Date |
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Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5161032B2 (en) |
| KR (1) | KR101267111B1 (en) |
| CN (1) | CN102164977B (en) |
| WO (1) | WO2010050272A1 (en) |
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| JP4723658B2 (en) * | 2009-02-16 | 2011-07-13 | 昭和電工株式会社 | Photosensitive resin composition and method for producing photosensitive resin used therefor |
| KR101349622B1 (en) * | 2011-08-26 | 2014-01-10 | 롬엔드하스전자재료코리아유한회사 | Photopolymerizable unsaturated resin, photosensitive resin composition comprising the same, and light shielding spacer and liquid crystal display device formed therefrom |
| CN105086602B (en) * | 2015-07-02 | 2017-06-16 | 深圳市容大感光科技股份有限公司 | Photocuring thermally curable resin composition ink, purposes and use its wiring board |
| CN105086605B (en) * | 2015-07-13 | 2018-07-27 | 深圳市容大感光科技股份有限公司 | A kind of photocuring heat-curing composition ink, purposes and the wiring board containing it |
| CN105086604A (en) * | 2015-07-13 | 2015-11-25 | 深圳市容大感光科技股份有限公司 | Printing ink composition, application thereof and printed circuit board |
| JP2017088538A (en) * | 2015-11-10 | 2017-05-25 | 日本メナード化粧品株式会社 | Filaggrin production promoter |
| CN108164686B (en) * | 2018-02-01 | 2020-01-21 | 江南大学 | Modified epoxy acrylate and solder resist containing same |
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| JP2001026624A (en) * | 1999-07-15 | 2001-01-30 | Tamura Kaken Co Ltd | Photosensitive resin, photosensitive resin composition and printed-wiring board |
| JP4655362B2 (en) * | 1999-12-28 | 2011-03-23 | Ｄｉｃ株式会社 | Method for producing photosensitive resin |
| JP2002308957A (en) * | 2001-04-17 | 2002-10-23 | Showa Highpolymer Co Ltd | Modified novolak resin and photosensitive resin composition |
| JP2003057821A (en) * | 2001-08-13 | 2003-02-28 | Showa Highpolymer Co Ltd | Photosensitive resin and photosensitive resin composition |
| JP2004131526A (en) * | 2002-10-08 | 2004-04-30 | Great Eastern Resins Industrial Co Ltd | Photosensitive thermosetting resin and method for producing the same and solder-resistant ink composition comprising the resin |
| JP4682340B2 (en) | 2003-07-25 | 2011-05-11 | 昭和電工株式会社 | Method for producing photosensitive resin |
| JP4655928B2 (en) * | 2005-06-30 | 2011-03-23 | Ｄｉｃ株式会社 | Photosensitive resin composition |
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| JP特开2001-026624A 2001.01.30 |
| JP特开2001-247649A 2001.09.11 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101267111B1 (en) | 2013-05-24 |
| WO2010050272A1 (en) | 2010-05-06 |
| JP5161032B2 (en) | 2013-03-13 |
| JP2010102270A (en) | 2010-05-06 |
| CN102164977A (en) | 2011-08-24 |
| KR20110044326A (en) | 2011-04-28 |
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