CN102164977A - 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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- CN102164977A CN102164977A CN2009801376921A CN200980137692A CN102164977A CN 102164977 A CN102164977 A CN 102164977A CN 2009801376921 A CN2009801376921 A CN 2009801376921A CN 200980137692 A CN200980137692 A CN 200980137692A CN 102164977 A CN102164977 A CN 102164977A
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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
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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
- 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
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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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- 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
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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
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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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
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- Epoxy Resins (AREA)
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 chromium cpd, luminous sensitivity height, photosensitive polymer combination of filming and having good rerum natura, can utilize diluted alkaline to develop that is obtained of not containing ultraviolet exposure.
Background technology
In recent years, the welding resistance printing ink of various printed circuit board (PCB)s is widely used is the liquid photosensitive welding resistance printing ink of diluted alkaline developable.The photoresist of diluted alkaline developable is for example known to have the hydroxyl reaction that makes acid anhydrides and Epocryl and the sour side chain type Epocryl that obtains.In the past, in order to obtain good thermostability and development range of management, used chromium naphthenate in the synthetic catalyst of this sour side chain type Epocryl always.But, to the consciousness raising of environmental problem or the numerous and diverse aspect of liquid waste disposal after the development, preferably do not use the chromium cpd of chromium naphthenate and so on as synthetic catalyst from now.Therefore, for example in patent documentation 1, proposed the use organo phosphorous compounds, under prescribed condition, made the reaction of polyfunctional epoxy resin and unsaturated monoprotic acid as synthetic catalyst, and then the photoresist that is obtained with anhydride reaction.
The prior art document
Patent documentation 1: the Japanese Patent spy opens the 2005-41958 communique
Summary of the invention
But the photoresist of record can't be taken into account performances such as the desired luminous sensitivity of nearest welding resistance printing ink, thermostability, development range of management, thermotolerance, solvent resistance with high level in the patent documentation 1, also has the leeway of improvement.
Therefore, the object of the present invention is to provide a kind of photosensitive polymer combination, it does not contain chromium cpd, can ultraviolet exposure and utilize dilute alkaline aqueous solution to develop, be suitable as the luminous sensitivity height, and thermostability and development range of management are good, the welding resistance printing ink of filming and demonstrating excellent properties.
The inventor etc. carry out active research in order to solve described problem, found that, cooperated the photosensitive polymer combination of following photoresist to meet described purpose, described photoresist obtains by following manner: in the presence of at least a in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate, make the reaction of multi-functional epoxy compound and unsaturated monoprotic acid, and then with multi-anhydride reaction and generate carboxyl, make mono-epoxy compounds and water-soluble mono epoxy compounds and described carboxyl reaction then with unsaturated double-bond; Thereby finish the present invention.
Promptly, the present invention is a kind of photosensitive polymer combination, it is characterized in that containing: (A) photoresist, this photoresist obtains by following manner: in the presence of at least a in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate, make the reaction of multi-functional epoxy compound and unsaturated monoprotic acid, and then with multi-anhydride reaction and generate carboxyl, make mono-epoxy compounds and water-soluble mono epoxy compounds and described carboxyl reaction then with unsaturated double-bond; (B) Resins, epoxy; (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: in the presence of the first step, at least a in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate, make the reaction of multi-functional epoxy compound and unsaturated monoprotic acid; Second step makes the resultant reaction that obtains in multi-anhydride and the first step; And third step, make the resultant reaction that obtains in mono-epoxy compounds with unsaturated double-bond and the water-soluble mono epoxy compounds and second step.
[invention effect]
According to the present invention, following photosensitive polymer combination can be provided, this photosensitive polymer combination does not contain chromium cpd, can ultraviolet exposure and utilize dilute alkaline aqueous solution to develop, be suitable as the luminous sensitivity height, and thermostability and development range of management are good, the welding resistance printing ink of filming and demonstrating excellent properties.
Embodiment
Below, the present invention is described in detail.
At first, photosensitive polymer combination of the present invention is described.
(A) composition in the photosensitive polymer combination of the present invention is by in the presence of at least a in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate, make the reaction of multi-functional epoxy compound and unsaturated monoprotic acid, and then generate carboxyl thus with multi-anhydride reaction, make mono-epoxy compounds with unsaturated double-bond and water-soluble mono epoxy compounds and described carboxyl reaction then and the photoresist that obtains.
The rerum natura of (A) of the present invention composition, the influence of the catalyzer that uses when synthetic is bigger, exists the development range of management also to be subjected to the tendency of the influence of catalyzer.In addition, under the situation that the catalyzer that will have different qualities uses together, occur the tendency of various shortcomings, but discoveries such as the inventor, under situation with at least a use of trivalent organophosphorus compounds in zirconium naphthenate and zirconium caprylate, opposite with anticipation can obtain and use the equal rerum natura of situation of chromium-based catalysts.
The usage quantity of catalyzer is preferably with respect to polyfunctional epoxy resin and unsaturated monacid total amount 100 mass parts, and at least a total amount in trivalent organophosphorus compounds and zirconium naphthenate and the zirconium caprylate becomes the amount of 1.2 mass parts～6.0 mass parts.At this moment, in quality criteria, at least 4 times of at least a preferred use trivalent organophosphorus compounds in zirconium naphthenate and the zirconium caprylate more preferably use 4 times～6 times.If at least a total amount in trivalent organophosphorus compounds and zirconium naphthenate and the zirconium caprylate is very few, perhaps at least a usage quantity in zirconium naphthenate and the zirconium caprylate is less than 4 times of trivalent organophosphorus compounds, then has the situation that can't bring into play function as catalysts fully.On the other hand, if trivalent organophosphorus compounds is too much, the tendency that then exists the thermostability of the photoresist obtained to descend, in addition, even in zirconium naphthenate and the zirconium caprylate at least a too much, the also effect that does not match with usage quantity, and uneconomical.
The multi-functional epoxy compound who uses among the present invention is not particularly limited, and for example can enumerate: Resins, epoxy 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 halogen atoms such as bromine atoms or chlorine atom etc. in these Resins, epoxy.Preferred especially cresols phenolic resin varnish type epoxy resin in these compounds.
The unsaturated monoprotic acid that uses among the present invention for example can be enumerated: vinylformic acid, methacrylic acid, butenoic acid, styracin, sorb saccharic acid (sorbitan acid), acrylic acid dimer etc. so long as contain the monoprotic acid of 1 carboxyl and 1 above polymerizability unsaturated group and get final product.In these unsaturated monoprotic acid, especially, preferably use vinylformic acid from obtaining the aspect of higher active energy ray light solidified.These unsaturated monoprotic acid both can be used alone, and also can be used in combination two or more.
These unsaturated monoprotic acid preferably make 0.8 equivalent～1.1 equivalent reactions with respect to multi-functional epoxy compound's epoxy group(ing) 1.0 equivalents.If unsaturated monacid ratio is lower than 0.8 equivalent, then there is the storage stability variation, produce the situation of problems such as gelation when perhaps synthesizing, on the other hand,, then exist to produce foul smell, perhaps the tendency of thermotolerance decline if surpass 1.1 equivalents.
The multi-anhydride that uses among the present invention, can enumerate: dibasic acid anhydrides such as maleic anhydride, succinyl oxide, itaconic anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, interior methylene radical Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, chlorendic anhydride, multi-anhydrides such as trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid anhydrides.In these multi-anhydrides, especially, preferably use Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride from the aspect of galvanic corrosion excellence.
It is 0.4 mole～0.9 mole ratio that the usage quantity of these multi-anhydrides is preferably with respect to 1.0 moles of the hydroxyls of the resultant that makes multi-functional epoxy compound and unsaturated monoprotic acid reaction gained, more preferably reacts with 0.6 mole～0.9 mole ratio.If the usage quantity of multi-anhydride is less than 0.4 mole, the situation that can't obtain sufficient alkali-developable is then arranged, on the other hand,, then there is the tendency of the declines such as electrical specification of cured coating film if surpass 0.9 mole.
The mono-epoxy compounds with unsaturated double-bond that uses among the present invention for example can be enumerated: (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 make and so on.
The water-soluble mono epoxy compounds can be enumerated: following formula (I)
[changing 1]
(in the formula, R
1The expression alkyl or aryl, R
2The expression repeating unit is polyethylene oxide or a poly(propylene oxide) 3 or more) shown in compound (for example, growing Denacol (registered trademark) EX-145, the EX-171 etc. of the manufacturing of rapids changing into (Nagase ChemteX) limited-liability company), following formula (II)
[changing 2]
Shown compound (for example, the SY-GTA80 of this pharmaceutical industries of slope limited-liability company manufacturing) etc.Because have the most external that is incorporated into resin with the mono-epoxy compounds that derives from the carboxyl bonded unsaturated double-bond of multi-anhydride,, uviolizing had higher light sensitivity so the reactivity during uviolizing is higher comprehensively.In addition, the 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 when preserving.
If consider luminous sensitivity, development and the electrical specification etc. of the photoresist that is obtained, the mono-epoxy compounds with unsaturated double-bond that reacts with the carboxyl that reaction generated by multi-anhydride and the amount of water-soluble mono epoxy compounds are that 0.15 mole～0.25 mole ratio is reacted with total amount with respect to 1 mole of the carboxyl that is generated preferably.Wherein, the amount of water-soluble mono epoxy compounds is for 1 mole to be lower than 0.03 mole ratio, more preferably 0.01 mole～0.025 mole ratio with respect to the carboxyl that is generated preferably at this moment.Be less than 0.15 mole if having the mono-epoxy compounds of unsaturated double-bond and the total amount of water-soluble mono epoxy compounds, then there is effect as the high luminous sensitivityization of one of the object of the invention inadequate tendency that becomes, on the other hand, if surpass 0.25 mole, the tendency that then exists alkali-developable to descend.In addition, be that the effect that is increased is also lower more than 0.03 mole even if make the amount of water-soluble mono epoxy compounds, also unrealistic from previously described alkali-developable aspect.
As the Resins, epoxy of (B) composition in the 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, the cresols phenolic resin varnish type epoxy resin, Dicyclopentadiene (DCPD)-phenol novolak type epoxy resin, phenol-cresols phenolic varnish cocondensation mould assembly Resins, epoxy, bisphenol-A phenolic varnish type Resins, epoxy, the halogenation epoxy compounds of bisphenol F phenolic varnish type Resins, epoxy or these Resins, epoxy, triphenol methylmethane type Resins, epoxy, triphenol methylmethane type Resins, epoxy through the alkyl replacement, the Resins, epoxy that four phenolic group ethane type Resins, epoxy etc. are obtained Epicholorohydrin and the reaction of multifunctional phenol, the Resins, epoxy that the reaction of Epicholorohydrin and multifunctional hydroxyl naphthalene class is obtained, modifying epoxy resin by organosilicon, the 6-caprolactone modified epoxy, by the glycidyl amine type epoxy resin that Epicholorohydrin and uncle or secondary amine reaction are obtained, hetero ring type Resins, epoxy such as isocyanic acid three-glycidyl ester etc.These Resins, epoxy both can be used alone, and also can be used in combination two or more.
The use level of these Resins, epoxy is preferably 3 mass parts～100 mass parts with respect to photoresist 100 mass parts, more preferably 6 mass parts～75 mass parts.If the use level of Resins, epoxy is less than 3 mass parts, then the carboxyl in the photoresist is less than the amount of reaction in fact, so tendency that exists water tolerance, alkali resistance, electrical specification to descend, on the other hand, if surpass 100 mass parts, then can generate linear polymer, so there is thermotolerance, the solvent resistance inadequate situation that becomes with unreacted epoxy groups.
In addition, for the connecting airtight property that further improves Resins, epoxy, chemical-resistant, thermotolerance etc., preferably use 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 be used alone, and 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 Resins, epoxy, and the active hydrogen amount of solidifying agent is 0.5 mole～1.2 moles a ratio.
Photoepolymerizationinitiater initiater as (C) composition in the photosensitive polymer combination of the present invention, can enumerate: st-yrax, benzoin methyl ether, benzoin isopropyl ether, st-yrax and derivatives thereof such as benzoin isobutyl ether, benzil, benzil dimethyl ketal benzil and derivatives thereof such as (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), (2-methyl-1-(4-methylthio phenyl)-2-morpholinopropan-1-one) waits methyl phenyl ketone and derivative thereof to 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone, 2-methylanthraquinone (2-methyl anthraquinone), 2-chloroanthraquinone, 2-ethyl-anthraquinone, anthraquinone and derivatives thereof such as 2-tertiary butyl anthraquinone, thioxanthone (thioxanthone) (thioxanthone), 2,4-dimethyl thia anthrone, thioxanthone and derivatives thereof such as 2-chlorothiaxanthenone, benzophenone, N, benzophenone and derivatives thereof such as N-dimethylamino benzophenone.These Photoepolymerizationinitiater initiaters both can be used alone, and also can be used in combination two or more.Well-known is by further as required various amine compound being used with these Photoepolymerizationinitiater initiaters, promote photopolymerization to cause effect, also can being used in combination in the present invention.
The use level of these Photoepolymerizationinitiater initiaters is preferably 0.1 mass parts～20 mass parts with respect to photoresist 100 mass parts, more preferably 1 mass parts～10 mass parts.If the use level of Photoepolymerizationinitiater initiater is less than 0.1 mass parts, then can't obtain fully effect sometimes as Photoepolymerizationinitiater initiater, on the other hand, and even surpass 20 mass parts, the also effect that does not match with use level, and uneconomical.
Use in order to improve as the reactive diluent of (D) composition in the photosensitive polymer combination of the present invention to the solidified nature of active-energy light and/or when the coating of usability photosensitive resin composition during as etching resisting ink.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, the N-pyrrolidone, the N-acryloyl morpholine, N, the N-DMAA, N, N-diethyl acrylamide, vinylformic acid N, the N-dimethylamino ethyl ester, vinylformic acid N, N-dimethylamino propyl ester, the methoxy poly (ethylene glycol) acrylate, the oxyethyl group polyethylene glycol acrylate, the trimeric cyanamide acrylate, the 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, the 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 be used alone, and also can be used in combination two or more.
The use level of reactive diluent is preferably 5 mass parts～200 mass parts with respect to photoresist 100 mass parts, more preferably 10 mass parts～100 mass parts.If the use level of reactive diluent is less than 5 mass parts, then can't obtain sufficient light sensitivity sometimes, on the other hand, if surpass 200 mass parts, then exist when the excess stickiness decline during of usability photosensitive resin composition, as the patience of the cured coating film inadequate situation that becomes as etching resisting ink.
In addition, in order to adjust coating, solvent and reactive diluent can be used together.This solvent can be enumerated: ketones such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, aromatic hydrocarbons such as toluene, dimethylbenzene, 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 be used alone, and also can be used in combination two or more.
Using under the situation of photosensitive polymer combination of the present invention as liquid etching resisting ink, except described (A)～(D) composition, also can further add inorganic fillers such as silicon-dioxide, lime carbonate, barium sulfate, clay, talcum as required, painted pigment such as phthalocyanine green, phthalocyanine blue, titanium oxide, carbon black, various additives such as defoamer, flow agent, stoppers such as Resorcinol, Resorcinol, pyrocatechol, pyrogallol, hydroquinone monomethyl ether, tert-butyl catechol, thiodiphenylamine.
Secondly, the manufacture method to photoresist of the present invention describes.
In first step, in the presence of at least a in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate, utilize well-known method to make multi-functional epoxy compound and the reaction of unsaturated monoprotic acid.In addition, the aspect of the thermopolymerization when preventing to react, this reaction is preferably added well-known polymerization retarders such as Resorcinol, methyl hydroquinone to and is carried out in the system, carries out on one side perhaps be blown into air on one side in system.
Temperature of reaction in the first step is preferably 60 ℃～150 ℃, and the reaction times is preferably 5 hours～and 20 hours.Under the multi-functional epoxy compound is liquid situation, can under solvent-free condition, reacts, but under the multi-functional epoxy compound is solid-state situation, preferably in solvent, react.Here employed solvent for example can be enumerated: ketones such as methyl ethyl ketone, pimelinketone, toluene, dimethylbenzene etc. are aromatic hydrocarbon based, glycol ethers such as dipropylene glycol dme, 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, oil series solvents such as sherwood oil, petroleum naphtha, solvent naphtha.
In second step, the resultant reaction that utilizes well-known method to make to obtain in multi-anhydride and the 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, the resultant reaction that obtains in the mono-epoxy compounds that utilizes well-known method to make to have unsaturated double-bond and the water-soluble mono epoxy compounds and second step.Temperature of reaction in the 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 〉
The ethyl carbitol acetic ester that in flask, adds 192 mass parts with 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 makes, 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 Resorcinol of 0.23 mass parts, the triphenylphosphine of 0.4 mass parts and the zirconium naphthenate (metal content is 6 quality %) of 2 mass parts, gas introduction tube from the liquid level bottom is blown into air on one side, continue to carry out reaction in 10 hours at 130 ℃ on one side, obtaining acid number is the reactant (epoxy acrylate) of 0.5mgKOH/g.Then to the Tetra Hydro Phthalic Anhydride that wherein adds 111.03 mass parts (0.73 mole), it was further reacted 2 hours at 120 ℃, obtaining the solids component acid number is the reactant of 105.3mgKOH/g.(the long rapids limited-liability company that changes into makes to Denacol (registered trademark) EX-145 of glycidyl methacrylate of wherein adding 22.72 mass parts (0.16 mole) and 9 mass parts (0.02 mole) then, epoxy equivalent (weight) is 450), it was further reacted 3 hours at 120 ℃, and then reach 60% mode with nonvolatile component and append the ethyl carbitol acetic ester, obtaining the solids component acid number is the photoresist A of 73.4mgKOH/g.
＜synthesis example 2 〉
Except the zirconium caprylate (metal content is 12 quality %) that uses 2 mass parts replaces the zirconium naphthenate (metal content 6 quality %) of 2 mass parts, carry out and synthesis example 1 identical operations, obtain photoresist B.
＜comparison synthesis example 1 (embodiment 1 that is equivalent to patent documentation 1) 〉
The ethyl carbitol acetic ester that in the flask that possesses stirrer, gas introduction tube and return line, adds 192 mass parts, the cresols phenolic resin varnish type epoxy resin (Dongdu changes into Epotohto (registered trademark) YDCN704 that limited-liability company makes, 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-two-tertiary butyl-4-methoxyphenol, 0.415 mass parts, gas introduction tube from the liquid level bottom is blown into air on one side, continue to carry out to react in 10 hours in 130 ℃ on one side, obtaining acid number is the reactant (epoxy acrylate) of 1.0mgKOH/g.Follow naphthenic acid lithium (metal content is 3%) to Tetra Hydro Phthalic Anhydride that wherein adds 111.03 mass parts (0.73 mole) and 0.707 mass parts, it was further reacted 2 hours at 120 ℃, and obtaining the solids component acid number is the reactant of 105.3mgKOH/g.(the long rapids limited-liability company that changes into makes to Denacol (registered trademark) EX-145 of glycidyl methacrylate of wherein adding 22.72 mass parts (0.16 mole) and 9 mass parts (0.02 mole) then, epoxy equivalent (weight) is 450), it was further reacted 3 hours at 120 ℃, and then reach 60% mode with nonvolatile component and append the ethyl carbitol acetic ester, obtaining the solids component acid number is the photoresist C of 73.4mgKOH/g.
Cooperate each composition according to the cooperation ratio shown in the table 1, utilize three-roll grinder to mix fully, the preparation photosensitive polymer combination.Moreover the quality of the photoresist in the table 1 is to represent with the value of resin solid composition.
Then, on the tellite of handling through face in advance,, utilize silk screen print method to be coated with described photosensitive polymer combination,, be cooled to room temperature, obtain dry coating at 80 ℃ after predrying 20 minutes to reach the mode of 30 μ m～40 μ m.Then use jade-like stone difficult to understand to make the extra-high-pressure mercury vapour lamp exposure apparatus that institute (ORC Manufacturing) makes, with 250mJ/cm
2This is filmed expose, use hot-air drier then, obtain cured coating film 150 ℃ of heating 30 minutes.According to evaluation test method shown below, gained filmed carry out various evaluation of physical property.These be the results are shown in table 2.
＜luminous sensitivity 〉
Luminous sensitivity is set on the dry coating after predrying measures with stage phototimer (Kodak (Kodak) 21 lattice), the extra-high-pressure mercury vapour lamp exposure apparatus that uses jade-like stone making manufacturing difficult to understand is with 250mJ/cm
2Expose, utilize 1% aqueous sodium carbonate then, press 2.0kgf/mm to spray
2Carry out developing in 60 seconds, measure the lattice number that does not have the part of removal in the development post-exposure part.Do not have the lattice number of the part removed big more, luminous sensitivity is high more.
＜development range of management 〉
Use is changed into the dry coating of 20 minutes, 40 minutes, 60 minutes or 80 minutes with the predrying time, utilizes 1% aqueous sodium carbonate, presses 2.0kgf/mm to spray
2Develop, have or not after observation is developed and film, estimate according to following standard.Even time of drying, the long development range of management of filming that also can develop was good.
Zero: development time is after 60 seconds, do not have with visual observation and films.
△: development time is after 120 seconds, do not have with visual observation and films.
*: development time had residual film with visual observation after 120 seconds.
＜scolding tin thermotolerance 〉
According to JIS C6481, the mode that is impregnated in the scolding tin with whole face floats in the scolding tin cured coating film, makes its in 260 ℃ solder bath floating 3 times, and each 10 seconds, after the taking-up, observe and expand or the state of filming such as peel off, estimate according to following standard.
Zero: the outward appearance no change.
*: outward appearance changes.
＜solvent resistance 〉
To being flooded, cured coating film is coated with membrane stage evaluation after 30 minutes in methylene dichloride.
Zero: the outward appearance no change
△: outward appearance changes slightly
*: 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, will estimate as gelation time up to the time till 120 ℃ of mobile disappearances.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 (5)
1. photosensitive polymer combination, it is characterized in that containing: (A) photoresist, this photoresist is to obtain by following manner: in the presence of at least a in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate, make the reaction of multi-functional epoxy compound and unsaturated monoprotic acid, and then with multi-anhydride reaction and generate carboxyl, make mono-epoxy compounds and water-soluble mono epoxy compounds and described carboxyl reaction then with unsaturated double-bond; (B) Resins, epoxy; (C) Photoepolymerizationinitiater initiater; And (D) reactive diluent.
2. photosensitive polymer combination according to claim 1, it is characterized in that: described photoresist is the described carboxyl with respect to 1 mole, making total amount is that mono-epoxy compounds and the reaction of described water-soluble mono epoxy compounds that 0.15 mole～0.25 mole described has a unsaturated double-bond obtains, and wherein the water-soluble mono epoxy compounds is less than 0.03 mole.
3. photosensitive polymer combination according to claim 1 and 2 is characterized in that: using in quality criteria is at least a in 4 times described zirconium naphthenate of trivalent organophosphorus compounds and the zirconium caprylate at least.
4. the manufacture method of a photoresist is characterized in that comprising:
In the presence of the first step, at least a in trivalent organophosphorus compounds and zirconium naphthenate and zirconium caprylate, make the reaction of multi-functional epoxy compound and unsaturated monoprotic acid;
Second step makes the resultant reaction that obtains in multi-anhydride and the first step; And
Third step makes the resultant reaction that obtains in mono-epoxy compounds with unsaturated double-bond and the water-soluble mono epoxy compounds and second step.
5. the manufacture method of photoresist according to claim 4 is characterized in that: carry out reaction in the described first step while be blown into air.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| 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 |
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| CN102164977A true CN102164977A (en) | 2011-08-24 |
| CN102164977B CN102164977B (en) | 2014-01-29 |
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| Country | Link |
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| JP (1) | JP5161032B2 (en) |
| KR (1) | KR101267111B1 (en) |
| CN (1) | CN102164977B (en) |
| WO (1) | WO2010050272A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103890659A (en) * | 2011-08-26 | 2014-06-25 | 罗门哈斯电子材料韩国有限公司 | Photopolymerizable unsaturated resin, photosensitive resin composition comprising the same, and light shielding spacer and liquid crystal display device formed therefrom |
| CN105086602A (en) * | 2015-07-02 | 2015-11-25 | 深圳市容大感光科技股份有限公司 | Photocuring-thermocuring resin composition ink, application and circuit board using photocuring-thermocuring resin composition ink |
| CN105086605A (en) * | 2015-07-13 | 2015-11-25 | 深圳市容大感光科技股份有限公司 | Photocuring-thermocuring composite ink, application and circuit board containing photocuring-thermocuring composite ink |
| 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 |
| WO2019148538A1 (en) * | 2018-02-01 | 2019-08-08 | 江南大学 | Modified epoxy acrylate and solder mask comprising same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP2017088538A (en) * | 2015-11-10 | 2017-05-25 | 日本メナード化粧品株式会社 | Filaggrin production promoter |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001026624A (en) * | 1999-07-15 | 2001-01-30 | Tamura Kaken Co Ltd | Photosensitive resin, photosensitive resin composition and printed-wiring board |
| JP2001247649A (en) * | 1999-12-28 | 2001-09-11 | Dainippon Ink & Chem Inc | Photosensitive resin, process for preparation thereof, and solder-resist ink composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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- 2008-10-27 JP JP2008276084A patent/JP5161032B2/en active Active
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2009
- 2009-07-08 KR KR1020117006587A patent/KR101267111B1/en not_active IP Right Cessation
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001026624A (en) * | 1999-07-15 | 2001-01-30 | Tamura Kaken Co Ltd | Photosensitive resin, photosensitive resin composition and printed-wiring board |
| JP2001247649A (en) * | 1999-12-28 | 2001-09-11 | Dainippon Ink & Chem Inc | Photosensitive resin, process for preparation thereof, and solder-resist ink composition |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103890659A (en) * | 2011-08-26 | 2014-06-25 | 罗门哈斯电子材料韩国有限公司 | Photopolymerizable unsaturated resin, photosensitive resin composition comprising the same, and light shielding spacer and liquid crystal display device formed therefrom |
| CN110007562A (en) * | 2011-08-26 | 2019-07-12 | 罗门哈斯电子材料韩国有限公司 | Photopolymerizable unsaturated-resin and photosensitive resin composition containing the photopolymerizable unsaturated-resin |
| CN105086602A (en) * | 2015-07-02 | 2015-11-25 | 深圳市容大感光科技股份有限公司 | Photocuring-thermocuring resin composition ink, application and circuit board using photocuring-thermocuring resin composition ink |
| CN105086605A (en) * | 2015-07-13 | 2015-11-25 | 深圳市容大感光科技股份有限公司 | Photocuring-thermocuring composite ink, application and circuit board containing photocuring-thermocuring composite ink |
| 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 |
| 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 |
| WO2019148538A1 (en) * | 2018-02-01 | 2019-08-08 | 江南大学 | Modified epoxy acrylate and solder mask comprising same |
| US10907009B1 (en) | 2018-02-01 | 2021-02-02 | Jiangnan University | Preparation of modified epoxy acrylates and solder resist containing modified epoxy acrylates |
Also Published As
| Publication number | Publication date |
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| JP2010102270A (en) | 2010-05-06 |
| CN102164977B (en) | 2014-01-29 |
| KR101267111B1 (en) | 2013-05-24 |
| JP5161032B2 (en) | 2013-03-13 |
| KR20110044326A (en) | 2011-04-28 |
| WO2010050272A1 (en) | 2010-05-06 |
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