CN101611068B - Process for producing photosensitive resin, photosensitive resin obtained by the process, and photosensitive resin composition - Google Patents
Process for producing photosensitive resin, photosensitive resin obtained by the process, and photosensitive resin composition Download PDFInfo
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- CN101611068B CN101611068B CN2007800514380A CN200780051438A CN101611068B CN 101611068 B CN101611068 B CN 101611068B CN 2007800514380 A CN2007800514380 A CN 2007800514380A CN 200780051438 A CN200780051438 A CN 200780051438A CN 101611068 B CN101611068 B CN 101611068B
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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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- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
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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
- C08G59/18—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
- C08G59/40—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 curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
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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
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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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
- G03F7/20—Exposure; Apparatus therefor
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
Abstract
A process for producing a photosensitive resin which is capable of exposure to ultraviolet and development with a dilute aqueous alkali solution, has high sensitivity, is satisfactory in thermal stability and development control tolerance, and is suitable for use as a solder resist ink giving a coating film having excellent performances; a photoresist resin obtained by the production process; anda composition containing the photosensitive resin. The process for photosensitive resin production comprises reacting a novolak type polyfunctional epoxy resin with an unsaturated monobasic acid and a saturated monobasic acid having a primary alcoholic hydroxy group in the presence of an organic compound of trivalent phosphorus and a specific metal salt catalyst to obtain a resin (reaction product I), reacting the resin with a polybasic acid anhydride, and reacting the resultant resin (reaction product II) with a compound having a radical-polymerizable unsaturated group and an epoxy group anda water-soluble monoepoxy compound.
Description
Technical field
The photoresist and the photosensitive polymer combination that the present invention relates to the method for manufacture of photoresist, obtain through this method of manufacture.In more detail; Relate to and dissolve in diluted alkaline, highly sensitive and excellent heat stability, the photoresist and the photosensitive polymer combination that use with field of electronic materials such as solder resists at printed wiring board solder resist, high-density multi-layered plate phase insulation film, semiconductor subassembly substrate.
Background technology
In recent years, as the resistance solder paste China ink of various printed wiring boards, consider that from productive aspect the photic resistance solder paste of diluted alkaline developable liquid China ink is widely used.For example, the someone has proposed to contain the resin combination that side chain has phenolic varnish type epoxy (methyl) propenoate of carboxyl, becomes main flow (patent documentation 1) now.
In addition, in recent years, the miniaturized of electronic machine, lightweight, high performance constantly develop.Because semi-conductive high-density is assembled, the miniaturized of semiconductor subassembly, spininessization are by practicability, thereby mass productionization constantly develops in addition.Because these backgrounds, it is fine that the pattern of solder resist also becomes, and for corresponding with these, must carry out highly sensitiveization.In addition, along with semi-conductive plastic package, the electronization development of automobile in recent years, in vehicle-mounted purposes, also use electronic material gradually.In these purposes, requirement can be used under the environment harsher than existing electronic machine, and demanding long-term reliability.But prior art can not fully satisfy these requirements, therefore needs to improve.For example, as one of countermeasure, can enumerate through the resin highly sensitiveization is improved the cross-linking density of cured coating film, thereby improve the method for their safety.
Someone proposed to make resin with free-radical polymerised unsaturated group and carboxyl, with have 1 epoxy group(ing) and more than 1 free-radical polymerised unsaturated group the compound reaction and obtain resin; And the resin that report obtains is highly sensitive (for example, patent documentation 2 and 3).Though but usually such resin has been realized highly sensitive but the thermostability of resin significantly reduces; Therefore not only the storage stability of resin itself is poor, and the stability (so-called drying is controlled latitude) when as resistance solder paste China ink dilute alkaline soln being developed is also poor.At first be coated with when for example on double-sided substrate, printing, be easy to generate solvent seasoning face because the heat the during solvent seasoning of opposing face and the problem that can not develop with diluted alkaline; Proceed to the operation of solvent seasoning and under the situation that develops next week, existing too can not be with the problem of operability differences such as diluted alkaline development at weekend.In addition; If for further highly sensitiveization; Have 1 epoxy group(ing) and the addition of the compound of free-radical polymerised unsaturated group more than 1 and increase, then the result exists because the carboxyl amount in the resin reduces that the acid value of resin descends, to the problem of the solvability variation of diluted alkaline.In the document, be not directed against the record of the problems referred to above.
Someone has proposed through making polyfunctional epoxy resin and unsaturated monacid reactant, generating carboxyl with the multi-anhydride reaction; Make this carboxyl and mono-epoxy compounds with unsaturated double-bond and the reaction of water-soluble mono epoxy compounds; Thereby obtain photoresist; And report this resin highly sensitive and excellent heat stability (patent documentation 4), but require further to improve thermostability.
Patent documentation 1: special fair 1-54390 communique
Patent documentation 2: No. 2900137 communique of Japanese Patent
Patent documentation 3: No. 2963069 communique of Japanese Patent
Patent documentation 4: the spy opens the 2001-264977 communique
Summary of the invention
The purpose of this invention is to provide a kind of can ultraviolet exposure and through dilute alkaline aqueous solution develop, highly sensitive and thermostability and the control latitude of developing are good, be suitable as the method for manufacture of the photoresist of the resistance solder paste China ink that shows excellent properties of filming, and the compsn that the photoresist that obtains through this method of manufacture is provided and contains this photoresist.
The present inventor furthers investigate to the problems referred to above; The result finds; The photoresist that obtains through following method; Be highly sensitive and thermostability and the control latitude excellence of developing, be suitable as the black photoresist of resistance solder paste of filming and showing excellent properties, thereby accomplished the present invention, said method promptly; In the presence of 3 valency organo phosphorous compoundss and specific metal salt catalyst; Make phenolic varnish type polyfunctional epoxy resin and unsaturated monoprotic acid and saturated monoprotic acid reaction obtain resin, and make this resin that obtains and multi-anhydride reaction, further with compound with free-radical polymerised unsaturated group and epoxy group(ing) and the reaction of water-soluble mono epoxy compounds with primary hydroxyl group.
That is, the present invention includes following (1)～(6).
(1) method of manufacture of photoresist (A) is characterized in that, comprises following operation I, operation II, operation III,
Operation I is containing in the presence of following (a) and the mixture (b), makes following (c), (d) and (e) reaction, thereby obtains resin, be the operation of reactant I,
(a) 3 valency organo phosphorous compoundss,
(b) be selected from the catalyst compound more than a kind or 2 kinds of chromium naphthenate, zirconium naphthenate or zirconium caprylate,
(c) phenolic resin varnish type epoxy resin,
(d) unsaturated monoprotic acid,
(e) has the saturated monoprotic acid of primary hydroxyl group;
Operation II makes this reactant I further obtain resin with the reaction of (f) multi-anhydride, be the operation of reactant II;
Operation III further reacts this reactant II with (g) with (h), thereby obtains the operation of photoresist (A),
(g) have the mono-epoxy compounds of free-radical polymerised unsaturated group,
(h) water-soluble mono epoxy compounds.
(2) according to (1) described method of manufacture, it is characterized in that, in said operation I, further contain stopper (i).
(3), it is characterized in that said (a) 3 valency organo phosphorous compoundss are triphenylphosphines, and in said operation I, be blown into air and react according to (1) or (2) described method of manufacture.
(4) method of manufacture of each described photoresist of basis (1)～(3); It is characterized in that; With respect to the said photoresist of 100 mass parts (A); The consumption of said (a) 3 valency organo phosphorous compoundss is 0.03～0.33 mass parts, and the consumption of said (b) catalyst compound is 0.1～1.0 mass parts.
(5) photoresist of making through each described method of manufacture of (1)～(4) (A).
And,
(6) a kind of photosensitive polymer combination is characterized in that, contains (5) described photoresist (A), epoxy resin (B), Photoepolymerizationinitiater initiater (C) and reactive diluent (D).
The photosensitive polymer combination that contains the photoresist that obtains through method of manufacture of the present invention; Can ultraviolet exposure and develop through dilute alkaline aqueous solution; Highly sensitive, and thermostability is excellent with the control latitude of developing, the resistance solder paste China ink that being suitable as films shows excellent properties.
Embodiment
Below, content of the present invention at length is described.
(a) the 3 valency organo phosphorous compoundss that use among the reactant I of the present invention can use known compound.Can enumerate triphenylphosphine, tributylphosphine, triethyl phosphine, three adjacent toluyl phosphines, three toluyl phosphines, the three pairs of toluyl phosphines, three (p-methoxyphenyl) phosphine etc. particularly.Wherein, generally from easy acquisition, economy is good so after state the excellent aspect of so-called touch dry property, triphenylphosphine.These compounds can use a kind separately, also can more than 2 kinds and use.
Use is selected from (b) catalyst compound of chromium naphthenate, sad chromium, zirconium naphthenate or zirconium caprylate, with above-mentioned (a) 3 valency organo phosphorous compoundss and usefulness.
The influence that the rerum natura of general photoresist of the present invention receives the catalyzer that uses when synthesizing is bigger, and so-called dry control latitude also tends to receive catalysts influence.In addition, under the situation of using different catalyst, rerum natura relatively poor among both appears in characteristic easily.
(a) though being clamminess property (the so-called touch dry property) excellence of the dry coating of 3 valency organo phosphorous compoundss after solvent seasoning, thermostability is tended to poor slightly.Part is become inert 5 valency phosphorus compounds by thermooxidizing in reaction.In order to obtain sufficient thermostability, and reduce the consumption of 3 valency organo phosphorous compoundss, reaction proceeded under the situation of abundant thermooxidizing, the result tends to become very long the reaction times, thereby not preferred economically.On the other hand, if use above-mentioned (b) catalyst compound, then can obtain the extraordinary photoresist of thermostability, but so-called touch dry sexual orientation is in relatively poor.Use under the situation of these compounds at resistance solder paste China ink, the pattern film that uses during ultraviolet exposure tends to easy adhesion, and operability easily goes wrong.
Usually; Also using under the situation of catalyzer with different qualities; Tend to demonstrate both shortcomings; But under of the present invention and situation with (a) 3 valency organo phosphorous compoundss and above-mentioned (b) catalyst compound, the result who has obtained following that kind on the contrary with anticipation has promptly obtained superior heat-stability and touch dry property as both advantages.
As long as the consumption of these catalysts can be realized the effect that the application invents, not restriction especially.Preferably with respect to 100 mass parts photoresists, (a) 3 valency organo phosphorous compoundss are 0.03～0.33 mass parts, and (b) catalyst compound is 0.1～1.0 mass parts.If (a) consumption of 3 valency organo phosphorous compoundss (a) is less than 0.03 weight part, the effect of then using as catalysts is low, if surpass 0.33 weight part, then thermostability is tended to reduce.On the other hand, if (b) consumption of catalyst compound is less than 0.1 mass parts, the effect of then using as catalysts is low, even and surpass 1.0 mass parts, can not produce and the consumption corresponding effects yet, uneconomical.
As (c) phenolic resin varnish type epoxy resin that in operation I of the present invention, uses, can enumerate phenol phenolic varnish type, cresols phenolic varnish type, bisphenol-A phenolic varnish type, Dicyclopentadiene (DCPD)-phenol phenolic varnish type, naphthol novolac varnish type, aralkyl modified phenol phenolic varnish type, alkyl-modified phenol phenolic varnish type etc.Wherein, preferably use cresols phenolic resin varnish type epoxy resin and phenol novolak type epoxy resin.(c) phenolic resin varnish type epoxy resin can use more than a kind or 2 kinds and use.As long as the molecular weight of this phenolic resin varnish type epoxy resin can be realized the effect that the application invents, restriction especially is not preferably 800～10000.
As (d) unsaturated monoprotic acid, be monoprotic acid with 1 carboxyl and 1 unsaturated conjugated group of above polymerizability.Specifically can enumerate the succinyl oxide affixture of (methyl) vinylformic acid, Ba Dousuan, styracin, anhydrosorbitol acid, acrylic acid dimer, (methyl) 2-Hydroxy ethyl acrylate etc.Particularly, preferably use the succinyl oxide affixture of vinylformic acid, 2-Hydroxy ethyl acrylate in order to obtain high reactivity energy light solidified.(d) unsaturated monoprotic acid can more than 2 kinds and be used.
(e) having the saturated monoprotic acid of primary hydroxyl group, is the monoprotic acid with polymerizability unsaturated group.Specifically, can enumerate the monoprotic acid that oxyacetic acid, hydroxy-propionic acid, R-Glyceric acid, dimethylol propionic acid, dimethylolpropionic acid etc. have 1 above primary hydroxyl group.Among them, preferably use oxyacetic acid, dimethylolpropionic acid, dimethylol propionic acid.These compounds can use a kind, or also use more than 2 kinds.
Have in use under the saturated monacid situation of primary hydroxyl group; Because compare with the common secondary hydroxyl that generates through epoxy group(ing) and monoprotic acid reaction; Higher with the mobility reactive higher, carboxyl that addition produces of multi-anhydride among the operation II, so the raising of alkali dissolution property.Therefore, compare, can realize same alkali dissolution property with lower acid value with phenolic varnish type epoxy (methyl) propenoate such shown in the fair 1-54390 communique of spy, that side chain has carboxyl.Therefore, owing to can increase the addition amount of the mono-epoxy compounds that in operation III, reacts among the present invention with free-radical polymerised unsaturated group, so can be with the further highly sensitiveization of photoresist (A).
Reactant II of the present invention makes the hydroxyl of the reactant I that operation I generated, further obtains with the reaction of (f) multi-anhydride.As such multi-anhydride; 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; Trimellitic acid 1,2-anhydride, 1,2,4; Multi-anhydrides such as 5-pyromellitic anhydride, UVNUL MS-40 tetracarboxylic acid anhydride, biphenyl tetracarboxylic acid anhydrides especially preferably use Tetra Hydro Phthalic Anhydride acid anhydride, succinyl oxide, hexahydrophthalic anhydride.
In operation III of the present invention, make reactant II and (g) have the mono-epoxy compounds of free-radical polymerised unsaturated group and (h) water-soluble mono epoxy compounds reaction.The mono-epoxy compounds that has free-radical polymerised unsaturated group as (g); Can use known compound; For example can enumerate, SY-Monomer G, glycidyl acrylate, glycidyl allyl ether, vinylbenzene to glycidyl ether, have (methyl) propenoate (trade(brand)name: サ イ Network ロ マ one (registered trademark) A200, M100 (ダ イ セ Le chemical industry (strain) system)) of ester ring type epoxy group(ing) etc.Wherein preferably use (methyl) glycidyl acrylate.On the other hand, as (h) water-soluble mono epoxy compounds, can be compound (n=4～6, for example trade(brand)name: デ Na コ one Le (registered trademark) EX-145 (Na ガ セ ケ system テ Star Network ス (strain) system) such shown in the formula.
Mono-epoxy compounds with free-radical polymerised unsaturated group, owing to be positioned at the most external of photoresist (A) skeleton, therefore the mobility of free-radical polymerised unsaturated group is high, so can highly sensitiveization.On the other hand; The water-soluble mono epoxy compounds is positioned at the most external of resin matrix too; When the mobility that suppresses the unsaturated group of above-mentioned mono-epoxy compounds with free-radical polymerised unsaturated group through appropriateness helps to improve storage or the stability during operation sequence, and make resin matrix have the wetting ability of appropriateness and improve solvability alkaline solution.
Then, the method for manufacture for photoresist (A) describes.In operation I during building-up reactions thing I, make (c) phenolic resin varnish type epoxy resin with (d) unsaturated monoprotic acid and (e) have the saturated monoprotic acid reaction of primary hydroxyl group through known method.At epoxy resin is under the situation of liquid, can under condition of no solvent, react, and be under the solid situation at (c) phenolic resin varnish type epoxy resin, preferably in solvent, reacts.
As employed solvent; Can use known solvent, for example can enumerate ketones such as methylethylketone, pimelinketone; Arene such as toluene, YLENE; Divalent alcohol ethers such as dipropylene glycol dimethyl ether, ester classes such as ETHYLE 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 etc.
In addition, the temperature of reaction among the operation I is preferably 60 ℃～150 ℃.Reaction times is preferably 5～20 hours.
The preferred epoxy group(ing) in (c) phenolic resin varnish type epoxy resin with respect to 1 mole, (d) saturated monoprotic acid is preferably 0.9～1.1 mole with the saturated monacid total amount that (e) has primary hydroxyl group and adds suchly.
In addition, if unsaturated monoprotic acid is 1 mole with the saturated monacid total amount with primary hydroxyl group, the saturated monacid consumption that then has primary hydroxyl group is preferably 0.05～0.4 mole.Be less than 0.05 mole if having the saturated monacid consumption of primary hydroxyl group; The effect of then using is low; If more than 0.4 mole; Then the concentration from unsaturated monacid polymerizability unsaturated group reduces, even the compound of stating among the operation II after adding sometimes with free-radical polymerised unsaturated group and epoxy group(ing) also is difficult to realize highly sensitiveization, can not give full play to effect of the present invention.
Operation III is through making the carboxyl of the reactant II among the above-mentioned operation II, with (g) have the mono-epoxy compounds of free-radical polymerised unsaturated group and (h) reaction of water-soluble mono epoxy compounds obtain.Employed identical catalyzer when catalysts uses with building-up reactions thing I after building-up reactions thing II, both can directly carry out the synthetic of operation III under the state of not adding new catalyzer, also can add new catalyzer.
Consumption with compound of free-radical polymerised unsaturated group and epoxy group(ing); Preferably with respect to the carboxyl among 1 mole of above-mentioned reactant II, (g) having the mono-epoxy compounds of free-radical polymerised unsaturated group is 0.15～0.4 mole with (h) total amount of water-soluble mono epoxy compounds.If be lower than 0.15 mole, then improve the effect of luminous sensitivity and tend to variation, if be more than 0.4 mole, then the quantitative change of the carboxyl in the resin gets very fewly, alkali-developable tends to variation.On the other hand, the consumption of water-soluble mono epoxy compounds is 0.01～0.1 mole with respect to the carboxyl of 1 mole of above-mentioned reactant II.If be below 0.01 mole; Then can not get effect of sufficient,, then not only can not get and add corresponding effects if be more than 0.1 mole; And excessively suppressing above-mentioned mobility with mono-epoxy compounds of free-radical polymerised unsaturated group, the result causes luminous sensitivity to reduce.Temperature of reaction is preferably 60～150 ℃.In addition, the reaction times is preferably 0.5～20 hour.
The invention further relates to a kind of photosensitive polymer combination, it is characterized in that, contain above-mentioned photoresist (A), epoxy resin (B), Photoepolymerizationinitiater initiater (C) and reactive diluent (D).This photosensitive polymer combination can be used as the alkali developable photosensitive polymer combination and uses.
As the epoxy resin (B) that uses in the alkali developable photosensitive polymer combination of the present invention, for example can enumerate (c) phenolic resin varnish type epoxy resin that uses among triglycidyl isocyanurate, the above-mentioned operation I.These epoxy resin can use a kind, or also use more than 2 kinds.In addition, in order to guarantee to improve toughness on the basis of Tg, using isocyanate modified epoxy resin is effectively, and from giving the viewpoint of flame retardant resistance, use phosphorous epoxy resin etc. is effective.
In order to improve the various characteristics as solder resist such as adhesivity, thermotolerance, anti-plating property, above-mentioned epoxy resin (B) can be used as the thermofixation components matching in compsn.When making printed wiring board etc., after developing, make resin solidification through heating with dilute alkaline aqueous solution, can realize the more excellent adhesivity of running board, thermotolerance, anti-plating property etc.
Epoxy resin (B) can use separately, or uses as the mixture more than 2 kinds.The consumption of epoxy resin of the present invention (B) is 5～100 mass parts with respect to the photoresist (A) of 100 mass parts.If be less than 5 mass parts, then be difficult to obtain good cured coating film characteristic, if more than 100 mass parts, then the alkali dissolution sexual orientation is in variation.
For characteristics such as the adhesivity that further improves above-mentioned epoxy resin (B), chemical resistant properties, thermotolerances, preferred and use epoxy hardener.As such epoxy curing agent, can enumerate imdazole derivatives, phenol derivatives, Dyhard RU 100, cyanoguanidine derivative, melamine, melamine resin, hydrazide derivatives, amine, acid anhydrides etc.Above-mentioned solidifying agent can use a kind, or mixes more than 2 kinds and use.The consumption of above-mentioned solidifying agent, preferably with respect to the epoxy group(ing) of 1 mole of this epoxy resin, the active hydrogen amount of solidifying agent is 0.5～1.2 mole a ratio.
As the concrete example of the Photoepolymerizationinitiater initiater that uses in the photosensitive polymer combination of the present invention (C), can enumerate bitter almond oil camphor class, acetophenones, anthraquinone class, thioxanthene ketone, benzophenone etc., for example; In the bitter almond oil camphor class, verivates such as bitter almond oil camphor, benzoin methylether, benzoin iso-propylether are arranged, in acetophenones; Methyl phenyl ketone, 2 is arranged, and 2-dimethoxy-verivates such as 2-phenyl methyl phenyl ketone is in the anthraquinone class; Verivates such as 2-methylanthraquinone, 2-chloroanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone are arranged, in the thioxanthene ketone, thioxanthone, 2 is arranged; Verivates such as 4-dimethyl-thioxanthone, in benzophenone, have UVNUL MS-40,4-benzoyl--4 '-methyldiphenyl thioether, 4; 4 '-dichloro benzophenone, N, verivates, 2,4 such as N-dimethylamino UVNUL MS-40; 6-trimethylbenzoyl diphenyl phosphine oxides etc. can use separately, or combination is used more than 2 kinds.In addition, in the Photoepolymerizationinitiater initiater (C) can and with the so known photosensitizers of tertiary amines.Specifically, can enumerate trolamine, tripropanol amine, triethylamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid pentyl ester etc.
Above-mentioned Photoepolymerizationinitiater initiater (C) can use a kind, or mixes more than 2 kinds and use, and then can also and use with known photosensitizers.The usage ratio of Photoepolymerizationinitiater initiater (C) is 0.5～30 mass parts with respect to 100 mass parts photoresists (A).If be below 0.5 mass parts, the effect of then using is low, causes luminous sensitivity to reduce.Even use more than 30 mass parts, corresponding effects is also low with adding.
Use reactive diluent (D) in the photosensitive polymer combination of the present invention.Reactive diluent (D) mainly uses in order when using to the solidified nature of active-energy light and/or photosensitive polymer combination as impedance printing ink, to improve coating.
As such polymerizable unsaturated compound; The monomer class that preferably has active-energy light-cured property; Can enumerate 2-Hydroxy ethyl acrylate, vinylformic acid-2-hydroxy propyl ester, N-pyrrolidone, N-acryloyl morpholine, N; N-DMAA, N; N-diethylammonium acrylic amide, vinylformic acid-N; N-dimethylamino ethyl ester, vinylformic acid (N, N-dimethylamino) propyl ester, methoxy poly (ethylene glycol) propenoate, oxyethyl group polyethylene glycol acrylate, melamine acrylate, vinylformic acid phenoxy ethyl, vinylformic acid phenoxy propyl ester, glycol diacrylate, dipropylene glycol diacrylate, gather dipropylene glycol diacrylate, Viscoat 295, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, glycerine diacrylate, IBOA, vinylformic acid (dicyclopentenyl oxygen base) ethyl ester and the various methacrylic esters corresponding with these compounds.These polymerizable unsaturated compounds can use a kind, or also use more than 2 kinds.
Reactive diluent (D) can use separately, or uses as the mixture more than 2 kinds.Consumption is 10～200 mass parts with respect to the above-mentioned photoresist (A) of 100 mass parts, is preferably 20～150 mass parts.If consumption is lower than 10 mass parts, then luminous sensitivity became low sometimes, and viscosity height and coating is poor.On the other hand, if consumption surpasses 200 mass parts, then sometimes under the situation of usability photosensitive resin composition as impedance printing ink, it is low that viscosity became, and becomes insufficient as the characteristic of cured coating film.
In addition, in order to adjust coating, can and use and the use solvent with above-mentioned reactive diluent (D).As these solvents; Can enumerate ketones such as methylethylketone, MIBK, pimelinketone; Trivalin SF classes such as aromatic hydrocarbon such as toluene, YLENE, ethyl cellosolve, ethylene glycol butyl ether, Trivalin SF, diethylene glycol monobutyl ether, ETHYLE ACETATE, butylacetate, cellosolve acetic ester, butyl cellosolve acetate, ethyl carbitol acetic ester etc.These solvents can use a kind, or also use more than 2 kinds.
In addition; Under the situation of photosensitive polymer combination of the present invention being processed the use of fluid impedance printing ink; Can further use inorganic fillers such as silicon-dioxide, lime carbonate, permanent white, clay, talcum as required; Painted pigment such as phthalocyanine green, phthalocyanine blue, titanium oxide, carbon black, various additives such as skimmer, levelling agent, and stopper such as quinhydrones, Resorcinol, pyrocatechol, pyrogallol, hydroquinone monomethyl ether, tert-butyl catechol, phenothiazine.
Photosensitive polymer combination of the present invention is through above-mentioned each gradation composition is preferably cooperated with aforementioned proportion, with uniform mixing such as 3 roller mills, thereby obtain.In addition, photosensitive polymer combination of the present invention is the compsn of liquid, and can obtain cured article through for example following being cured suchly.That is, be coated with compsn of the present invention through method thickness with 10～160 μ m on printed wiring board such as silk screen print method, gunite, rolling method, electrostatic coating method, curtain-type curtain coatings.Then, this is filmed under 60～110 ℃, carry out drying.Egative film is filmed with this directly contact, perhaps on discontiguous state held is being filmed, irradiation ultraviolet radiation and make the compsn exposure then.Unexposed portion dissolving is removed and develop with dilute alkaline aqueous solution, further solidify fully through uviolizing and/or heating (for example heating 0.5～1.0 hour) then, thereby obtain cured coating film at 100～200 ℃ in order to improve various rerum naturas.
Embodiment
Below, illustrating in greater detail the present invention through embodiment, comparative example, " part " in each example and " % " they then are quality criterias only otherwise specify.The present invention is not limited in these embodiment.
Synthetic example 1 (the synthetic example of resin 1)
In the flask that has stirrer, gas introduction tube, return line; Add 92 parts of ethyl carbitol acetic ester; Dissolve the o-cresol phenolic epoxy varnish (trade(brand)name: エ Port ト one ト (registered trademark) YDCN704 of 210 parts (1.0 equivalents) therein; Toto Kasei KK's system, epoxy equivalent (weight) 210).Further add 69.84 parts of (0.97 mole) vinylformic acid, 2.16 parts of (0.03 mole) oxyacetic acids, 2.17 parts of stoppers 2,6-di-t-butyl-4-methoxyphenol and 0.45 part of triphenylphosphine, 0.85 part of chromium naphthenate (metal content 3%).When the gas introduction tube from the liquid level bottom is blown into air, be heated to 130 ℃ and sustained reaction 10 hours, and obtained the reactant that acid value is 0.5mg KOH/g (reactant I).Add 98 parts of ethyl carbitol acetic ester, 106.4 parts of (0.7 mole) Tetra Hydro Phthalic Anhydrides therein, further reacted 2 hours down, obtain the reactant that the solids component acid value is 101.1mg KOH/g (reactant II) at 120 ℃.Further add 21.3 parts of (0.15 mole) SY-Monomer Gs, 13.5 parts of (0.03 mole) デ Na コ one Le (registered trademark) EX-145 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system, epoxy equivalent (weight) 450: phenol (EO)
5Glycidyl ether), further reacted 3 hours down at 120 ℃, obtaining the solids component acid value is the resin 1 of 68.9mg KOH/g.
Synthetic example 2 (the synthetic examples of resin 2)
In the flask that has stirrer, gas introduction tube, return line; Add 92 parts of ethyl carbitol acetic ester; Dissolve the o-cresol phenolic epoxy varnish (trade(brand)name: エ Port ト one ト (registered trademark) YDCN704 of 210 parts (1.0 equivalents) therein; Toto Kasei KK's system, epoxy equivalent (weight) 210).Further add 69.84 parts of (0.97 mole) vinylformic acid, 2.16 parts of (0.03 mole) oxyacetic acids, 2.17 parts of stoppers 2; 6-di-t-butyl-4-methoxyphenol and 0.45 part of triphenylphosphine, 0.85 part of zirconium naphthenate (metal content 6%); When the gas introduction tube from the liquid level bottom is blown into air, be heated to 130 ℃ and sustained reaction 10 hours, and obtained the reactant that acid value is 0.5mg KOH/g (reactant I).Add 98 parts of ethyl carbitol acetic ester, 106.4 parts of (0.7 mole) Tetra Hydro Phthalic Anhydrides therein, further reacted 2 hours down, obtain the reactant that the solids component acid value is 101.1mg KOH/g (reactant II) at 120 ℃.Further add 21.3 parts of (0.15 mole) SY-Monomer Gs, 13.5 parts of (0.03 mole) デ Na コ one Le (registered trademark) EX-145 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system, epoxy equivalent (weight) 450: phenol (EO)
5Glycidyl ether), further reacted 3 hours down at 120 ℃, obtaining the solids component acid value is the resin 2 of 68.9mg KOH/g.
Synthetic example 3 (the synthetic examples of resin 3)
In the flask that has stirrer, gas introduction tube, return line; Add 92 parts of ethyl carbitol acetic ester; Dissolve the o-cresol phenolic epoxy varnish (trade(brand)name: エ Port ト one ト (registered trademark) YDCN704 of 210 parts (1.0 equivalents) therein; Toto Kasei KK's system, epoxy equivalent (weight) 210).Further add 69.84 parts of (0.97 mole) vinylformic acid, 2.16 parts of (0.03 mole) oxyacetic acids, 2.17 parts of stoppers 2; 6-di-t-butyl-4-methoxyphenol and 0.45 part of triphenylphosphine, 0.85 part of zirconium caprylate (metal content 12%); When the gas introduction tube from the liquid level bottom is blown into air, be heated to 130 ℃ and sustained reaction 10 hours, and obtained the reactant that acid value is 0.5mg KOH/g (reactant I).Add 98 parts of ethyl carbitol acetic ester, 106.4 parts of (0.7 mole) Tetra Hydro Phthalic Anhydrides therein, further reacted 2 hours down, obtain the reactant that the solids component acid value is 101.1mg KOH/g (reactant II) at 120 ℃.Further add 21.3 parts of (0.15 mole) SY-Monomer Gs, 13.5 parts of (0.03 mole) デ Na コ one Le (registered trademark) EX-145 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system, epoxy equivalent (weight) 450: phenol (EO)
5Glycidyl ether), further reacted 3 hours down at 120 ℃, obtaining the solids component acid value is the resin 3 of 68.9mg KOH/g.
Synthetic example 4 (the synthetic examples of resin 4)
In the flask that has stirrer, gas introduction tube, return line; Add 92 parts of ethyl carbitol acetic ester; Dissolve the o-cresol phenolic epoxy varnish (trade(brand)name: エ Port ト one ト (registered trademark) YDCN704 of 210 parts (1.0 equivalents) therein; Toto Kasei KK's system, epoxy equivalent (weight) 210).Further add 69.84 parts of (0.97 mole) vinylformic acid, 2.16 parts of (0.03 mole) oxyacetic acids, 2.17 parts of stoppers 2; 6-di-t-butyl-4-methoxyphenol and 0.12 part of triphenylphosphine, 0.85 part of chromium naphthenate (metal content 3%); When the gas introduction tube from the liquid level bottom is blown into air, be heated to 130 ℃ and sustained reaction 10 hours, and obtained the reactant that acid value is 0.5mg KOH/g (reactant I).Add 98 parts of ethyl carbitol acetic ester, 106.4 parts of (0.7 mole) Tetra Hydro Phthalic Anhydrides therein, further reacted 2 hours down, obtain the reactant that the solids component acid value is 101.1mg KOH/g (reactant II) at 120 ℃.Further add 21.3 parts of (0.15 mole) SY-Monomer Gs, 13.5 parts of (0.03 mole) デ Na コ one Le (registered trademark) EX-145 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system, epoxy equivalent (weight) 450: phenol (EO)
5Glycidyl ether), further reacted 3 hours down at 120 ℃, obtaining the solids component acid value is the resin 4 of 68.9mg KOH/g.
Synthetic example 5 (the synthetic examples of resin 5)
In the flask that has stirrer, gas introduction tube, return line; Add 92 parts of ethyl carbitol acetic ester; Dissolve the o-cresol phenolic epoxy varnish (trade(brand)name: エ Port ト one ト (registered trademark) YDCN704 of 210 parts (1.0 equivalents) therein; Toto Kasei KK's system, epoxy equivalent (weight) 210).Further add 69.84 parts of (0.97 mole) vinylformic acid, 2.16 parts of (0.03 mole) oxyacetic acids, 2.17 parts of stoppers 2; 6-di-t-butyl-4-methoxyphenol and 1.5 parts of triphenylphosphines, 0.85 part of chromium naphthenate (metal content 12%); When the gas introduction tube from the liquid level bottom is blown into air, be heated to 130 ℃ and sustained reaction 10 hours, and obtained the reactant that acid value is 0.5mg KOH/g (reactant I).Add 98 parts of ethyl carbitol acetic ester, 106.4 parts of (0.7 mole) Tetra Hydro Phthalic Anhydrides therein, further reacted 2 hours down, obtain the reactant that the solids component acid value is 101.1mg KOH/g (reactant II) at 120 ℃.Further add 21.3 parts of (0.15 mole) SY-Monomer Gs, 13.5 parts of (0.03 mole) デ Na コ one Le (registered trademark) EX-145 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system, epoxy equivalent (weight) 450: phenol (EO)
5Glycidyl ether), further reacted 3 hours down at 120 ℃, obtaining the solids component acid value is the resin 5 of 68.9mg KOH/g.
Synthetic example 6 (the synthetic examples of resin 6)
In the flask that has stirrer, gas introduction tube, return line; Add 92 parts of ethyl carbitol acetic ester; Dissolve the o-cresol phenolic epoxy varnish (trade(brand)name: エ Port ト one ト (registered trademark) YDCN704 of 210 parts (1.0 equivalents) therein; Toto Kasei KK's system, epoxy equivalent (weight) 210).Further add 69.84 parts of (0.97 mole) vinylformic acid, 2.16 parts of (0.03 mole) oxyacetic acids, 2.17 parts of stoppers 2; 6-di-t-butyl-4-methoxyphenol and 0.45 part of triphenylphosphine, 0.4 part of chromium naphthenate (metal content 12%); When the gas introduction tube from the liquid level bottom is blown into air, be heated to 130 ℃ and sustained reaction 10 hours, and obtained the reactant that acid value is 0.5mg KOH/g (reactant I).Add 98 parts of ethyl carbitol acetic ester, 106.4 parts of (0.7 mole) Tetra Hydro Phthalic Anhydrides therein, further reacted 2 hours down, obtain the reactant that the solids component acid value is 101.1mg KOH/g (reactant II) at 120 ℃.Further add 21.3 parts of (0.15 mole) SY-Monomer Gs, 13.5 parts of (0.03 mole) デ Na コ one Le (registered trademark) EX-145 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system, epoxy equivalent (weight) 450: phenol (EO)
5Glycidyl ether), further reacted 3 hours down at 120 ℃, obtaining the solids component acid value is the resin 6 of 68.9mg KOH/g.
Synthetic example 7 (the synthetic examples of resin 7)
In the flask that has stirrer, gas introduction tube, return line; Add 92 parts of ethyl carbitol acetic ester; Dissolve the o-cresol phenolic epoxy varnish (trade(brand)name: エ Port ト one ト (registered trademark) YDCN704 of 210 parts (1.0 equivalents) therein; Toto Kasei KK's system, epoxy equivalent (weight) 210).Further add 69.84 parts of (0.97 mole) vinylformic acid, 2.16 parts of (0.03 mole) oxyacetic acids, 2.17 parts of stoppers 2; 6-di-t-butyl-4-methoxyphenol and 0.45 part of triphenylphosphine, 5.0 parts of chromium naphthenates (metal content 12%); When the gas introduction tube from the liquid level bottom is blown into air, be heated to 130 ℃ and sustained reaction 10 hours, and obtained the reactant that acid value is 0.5mg KOH/g (reactant I).Add 98 parts of ethyl carbitol acetic ester, 106.4 parts of (0.7 mole) Tetra Hydro Phthalic Anhydrides therein, further reacted 2 hours down, obtain the reactant that the solids component acid value is 101.1mg KOH/g (reactant II) at 120 ℃.Further add 21.3 parts of (0.15 mole) SY-Monomer Gs, 13.5 parts of (0.03 mole) デ Na コ one Le (registered trademark) EX-145 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system, epoxy equivalent (weight) 450: phenol (EO)
5Glycidyl ether), further reacted 3 hours down at 120 ℃, obtaining the solids component acid value is the resin 7 of 68.9mg KOH/g.
Relatively more synthetic example 1 (the synthetic example of resin 8)
In the flask that has stirrer, gas introduction tube, return line; Add 92 parts of ethyl carbitol acetic ester; Dissolve the o-cresol phenolic epoxy varnish (trade(brand)name: エ Port ト one ト (registered trademark) YDCN704 of 210 parts (1.0 equivalents) therein; Toto Kasei KK's system, epoxy equivalent (weight) 210).Further add 69.84 parts of (0.97 mole) vinylformic acid, 2.16 parts of (0.03 mole) oxyacetic acids, 2.17 parts of stoppers 2; 6-di-t-butyl-4-methoxyphenol and 0.85 part of triphenylphosphine; When the gas introduction tube from the liquid level bottom is blown into air, be heated to 130 ℃ and sustained reaction 10 hours, and obtained the reactant that acid value is 0.5mg KOH/g (reactant I).Add 98 parts of ethyl carbitol acetic ester, 106.4 parts of (0.7 mole) Tetra Hydro Phthalic Anhydrides therein, further reacted 2 hours down, obtain the reactant that the solids component acid value is 101.1mg KOH/g (reactant II) at 120 ℃.Further add 21.3 parts of (0.15 mole) SY-Monomer Gs, 13.5 parts of (0.03 mole) デ Na コ one Le (registered trademark) EX-145 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system, epoxy equivalent (weight) 450: phenol (EO)
5Glycidyl ether), further reacted 3 hours down at 120 ℃, obtaining the solids component acid value is the resin 8 of 68.9mgKOH/g.
Relatively more synthetic example 2 (the synthetic examples of resin 9)
In the flask that has stirrer, gas introduction tube, return line; Add 92 parts of ethyl carbitol acetic ester; Dissolve the o-cresol phenolic epoxy varnish (trade(brand)name: エ Port ト one ト (registered trademark) YDCN704 of 210 parts (1.0 equivalents) therein; Toto Kasei KK's system, epoxy equivalent (weight) 210).Further add 69.84 parts of (0.97 mole) vinylformic acid, 2.16 parts of (0.03 mole) oxyacetic acids, 2.17 parts of stoppers 2; 6-di-t-butyl-4-methoxyphenol and 1.4 parts of chromium naphthenates (metal content 3%); When the gas introduction tube from the liquid level bottom is blown into air, be heated to 130 ℃ and sustained reaction 10 hours, and obtained the reactant that acid value is 0.5mg KOH/g (reactant I).Add 98 parts of ethyl carbitol acetic ester, 106.4 parts of (0.7 mole) Tetra Hydro Phthalic Anhydrides therein, further reacted 2 hours down, obtain the reactant that the solids component acid value is 101.1mg KOH/g (reactant II) at 120 ℃.Further add 21.3 parts of (0.15 mole) SY-Monomer Gs, 13.5 parts of (0.03 mole) デ Na コ one Le EX-145 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system, epoxy equivalent (weight)s 450: phenol (EO)
5Glycidyl ether), further reacted 3 hours down at 120 ℃, obtaining the solids component acid value is the resin 9 of 68.9mgKOH/g.
Relatively more synthetic example 3 (the synthetic examples of resin 10)
In the flask that has stirrer, gas introduction tube, return line; Add 92 parts of ethyl carbitol acetic ester; Dissolve the o-cresol phenolic epoxy varnish (trade(brand)name: エ Port ト one ト (registered trademark) YDCN704 of 210 parts (1.0 equivalents) therein; Toto Kasei KK's system, epoxy equivalent (weight) 210).Further add 69.84 parts of (0.97 mole) vinylformic acid, 2.16 parts of (0.03 mole) oxyacetic acids, 2.17 parts of stoppers 2; 6-di-t-butyl-4-methoxyphenol and 0.85 part of benzyldimethylamine; When the gas introduction tube from the liquid level bottom is blown into air, be heated to 130 ℃ and sustained reaction 10 hours, and obtained the reactant that acid value is 0.5mg KOH/g (reactant I).Add 98 parts of ethyl carbitol acetic ester, 106.4 parts of (0.7 mole) Tetra Hydro Phthalic Anhydrides therein, further reacted 2 hours down, obtain the reactant that the solids component acid value is 101.1mg KOH/g (reactant II) at 120 ℃.Further add 21.3 parts of (0.15 mole) SY-Monomer Gs, 13.5 parts of (0.03 mole) デ Na コ one Le (registered trademark) EX-145 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system, epoxy equivalent (weight) 450: phenol (EO)
5Glycidyl ether), further reacted 3 hours down at 120 ℃, obtaining the solids component acid value is the resin 10 of 68.9mgKOH/g.
Relatively more synthetic example 4 (the synthetic examples of resin 11)
In the flask that has stirrer, gas introduction tube, return line; Add 92 parts of ethyl carbitol acetic ester; Dissolve 210 parts of (1.0 equivalent) o-cresol phenolic epoxy varnish (trade(brand)name: エ Port ト one ト (registered trademark) YDCN704 therein; Toto Kasei KK's system; Epoxy equivalent (weight) 210), further adds 69.84 parts of (0.97 mole) vinylformic acid, 2.16 parts of (0.03 mole) oxyacetic acids, 2.17 parts of stoppers 2,6-di-t-butyl-4-methoxyphenol and 0.45 part of benzyldimethylamine, 0.85 part of chromium naphthenate (amount of metal 3%); When the gas introduction tube from the liquid level bottom is blown into air, be heated to 130 ℃ and sustained reaction 10 hours, and obtained the reactant that acid value is 0.5mg KOH/g (reactant I).Add 98 parts of ethyl carbitol acetic ester, 106.4 parts of (0.7 mole) Tetra Hydro Phthalic Anhydrides therein, further reacted 2 hours down, obtain the reactant that the solids component acid value is 101.1mg KOH/g (reactant II) at 120 ℃.Further add 21.3 parts of (0.15 mole) SY-Monomer Gs, 13.5 parts of (0.03 mole) デ Na コ one Le (registered trademark) EX-145 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system, epoxy equivalent (weight) 450: phenol (EO)
5Glycidyl ether), further reacted 3 hours down at 120 ℃, obtaining the solids component acid value is the resin 11 of 68.9mg KOH/g.
Relatively more synthetic example 5 (the synthetic examples of resin 12)
In the flask that has stirrer, gas introduction tube, return line; Add 92 parts of ethyl carbitol acetic ester; Dissolve the o-cresol phenolic epoxy varnish (trade(brand)name: エ Port ト one ト (registered trademark) YDCN704, Toto Kasei KK's system, epoxy equivalent (weight) 210) of 210 parts (1.0 equivalents) therein; Further add 72 parts of (1.0 moles) vinylformic acid, 2.17 parts of stoppers 2; 6-di-t-butyl-4-methoxyphenol and 0.85 part of triphenylphosphine were heated to 130 ℃ and sustained reaction 10 hours when the gas introduction tube from the liquid level bottom is blown into air, obtain the reactant that acid value is 0.5mg KOH/g (reactant I).Add 98 parts of ethyl carbitol acetic ester, 72.0 parts of (0.5 mole) Tetra Hydro Phthalic Anhydrides therein, further reacted 2 hours down at 120 ℃, obtaining the solids component acid value is the resin 12 of 78.4mg KOH/g.
Relatively more synthetic example 6 (the synthetic examples of resin 13)
In the flask that has stirrer, gas introduction tube, return line; Add 92 parts of ethyl carbitol acetic ester; Dissolve the o-cresol phenolic epoxy varnish (trade(brand)name: エ Port ト one ト (registered trademark) YDCN704 of 210 parts (1.0 equivalents) therein; Toto Kasei KK's system, epoxy equivalent (weight) 210).Further add 72 parts of (1.0 moles) vinylformic acid, 2.17 parts of stoppers 2; 6-di-t-butyl-4-methoxyphenol and 0.85 part of triphenylphosphine; When the gas introduction tube from the liquid level bottom is blown into air, be heated to 130 ℃ and sustained reaction 10 hours, and obtained the reactant that acid value is 0.5mg KOH/g (reactant I).Add 98 parts of ethyl carbitol acetic ester, 106.4 parts of (0.7 mole) Tetra Hydro Phthalic Anhydrides therein, further reacted 2 hours down, obtain the reactant that the solids component acid value is 101.1mg KOH/g (reactant II) at 120 ℃.Further add 21.3 parts of (0.15 mole) SY-Monomer Gs, 13.5 parts of (0.03 mole) デ Na コ one Le (registered trademark) EX-145 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system, epoxy equivalent (weight) 450: phenol (EO)
5Glycidyl ether), further reacted 3 hours down at 120 ℃, obtaining the solids component acid value is the resin 13 of 68.9mg KOH/g.
Relatively more synthetic example 7 (the synthetic examples of resin 14)
In the flask that has stirrer, gas introduction tube, return line; Add 92 parts of ethyl carbitol acetic ester; Dissolve the o-cresol phenolic epoxy varnish (trade(brand)name: エ Port ト one ト (registered trademark) YDCN704, Toto Kasei KK's system, epoxy equivalent (weight) 210) of 210 parts (1.0 equivalents) therein; Further add 72 parts of (1.0 moles) vinylformic acid, 2.17 parts of stoppers 2; 6-di-t-butyl-4-methoxyphenol and 0.85 part of benzyldimethylamine were heated to 130 ℃ and sustained reaction 10 hours when the gas introduction tube from the liquid level bottom is blown into air, obtain the reactant that acid value is 0.5mg KOH/g (reactant I).Add 98 parts of ethyl carbitol acetic ester, 106.4 parts of (0.7 mole) Tetra Hydro Phthalic Anhydrides therein, further reacted 2 hours down, obtain the reactant that the solids component acid value is 101.1mg KOH/g (reactant II) at 120 ℃.Further add 21.3 parts of (0.15 mole) SY-Monomer Gs, further reacted 3 hours down at 120 ℃, obtaining the solids component acid value is the resin 14 of 75.3mg KOH/g.
Relatively more synthetic example 8 (synthetic failure example)
In the device identical with relatively synthetic example 6, do not use stopper and synthetic catalyst, be not blown into air, in addition, likewise react, but gelation has taken place the 4th hour of the operation of reactant I with relatively more synthetic example 3.Confirm once more, but the acid value in the reaction reduces hardly, and likewise gelation has taken place.
Embodiment 1～7 and comparative example 1～7
Cooperation ratio according to shown in the table 1 cooperates each composition, and is fully mixing with 3 roller mills, thereby obtains photosensitive polymer combination of the present invention.In addition, the quality of the resin in the table 1 is to represent with the value of resin solid composition.
Then,, be coated with above-mentioned photosensitive polymer combination, make that dry coating is 30～40 μ m through silk screen print method having accomplished in advance on the surface-treated printed wiring board.80 ℃ dry 20 minutes down, be cooled to room temperature then and obtain dry coating (below be referred to as " predrying filming ").Should predryingly film with extra-high-pressure mercury vapour lamp with 250mJ/cm
2Make public.Then, under 150 ℃, carry out 30 minutes after fixing, thereby obtain cured coating film.Carry out the various evaluation of physical property of the following stated for resulting cured coating film and predrying filming.Table 2 shows their evaluation result.
Sensitivity
Sensitivity determination is set with GTG (step tablet, 14 grades of Kodak) on predrying filming, uses extra-high-pressure mercury vapour lamp with 250mJ/cm
2Make public.Then, use 1% aqueous sodium carbonate, press 2.0kgf/mm to spray
2Carry out developing in 60 seconds, measure the progression that exposed portion is not removed after developing.
Touch dry property
When measuring above-mentioned sensitivity, estimate the easy degree of peeling off when peeling off the GTG that makes public afterwards.
◎: can peel off when peeling off out of questionly.
Zero: have adhesion a little when peeling off but can peel off out of questionly.
*: there is the adhesion of GTG when peeling off.
Dry control latitude
Become 20 minutes respectively and 40 minutes, 50 minutes, 60 minutes, 70 minutes predrying time of drying of filming under 80 ℃, then predrying filming used 1% aqueous sodium carbonate, press 2.0kgf/mm with spraying
2Develop, observe filming after developing, estimate with following benchmark.
◎: after the development time 60 seconds, range estimation does not have and films.
Zero: after the development time 120 seconds, range estimation does not have and films.
*: after the development time 120 seconds, range estimation has residual film.
Solder heat resistance property
According to JIS C6481, cured coating film, 260 ℃ scolder was suspended for 10 seconds in bathing, suspends altogether 3 times, observe the state of appearance of films such as taking out the expansion of filming afterwards or peel off, estimate with following benchmark.
◎: outward appearance no change.
Zero: outward appearance changes slightly.
*: outward appearance changes.
Solvent resistance
Cured coating film was flooded in methylene dichloride 30 minutes, estimate the membrane stage that is coated with after flooding.
◎: outward appearance no change.
Zero: outward appearance changes slightly.
*: outward appearance changes.
Anti-PCT (pressure kettle test) property
Cured coating film 121 ℃, 2 normal atmosphere, saturated vapo(u)r atmosphere held 50 hours, 100 hours, is estimated the membrane stage that is coated with after placing.
◎: outward appearance no change.
Zero: outward appearance changes slightly.
*: outward appearance changes.
Anti-gold-plated property
As pre-treatment, cured coating film is carried out following operation, promptly be immersed in 30 ℃ the acid degreasing fluid → dipping washing → soft etch processes → dipping washing → interpolation catalyzer (in 30 ℃ nickel plating catalyst liquid, flooding 7 minutes) → flood the operation of washing.Then carry out the chemical nickel plating operation, that is, (85 ℃, pH=4.6) middle dipping 20 minutes → acid dipping 1 minute (10 volume % aqueous sulfuric acids of room temperature) → dipping is washed at nickel-plating liquid.Carry out the chemical gilding operation at last, that is, and 10 minutes → dipping of dipping washing in the gold plating liquid (95 ℃, pH=6, the potassium auric cyanide 3 volume % aqueous solution) → with 60 ℃ warm water immersions washings → fully washing, drying after abundant draining then.Utilize visual assessment to be coated with membrane stage, and use cellophane tape to carry out stripping test, thereby estimate filming after this processing.
◎: the outward appearance no change, do not have fully and peel off.
Zero: the outward appearance no change, peel off but observe a little.
△: outward appearance changes, and observes a little and peel off.
Thermostability
With respect to resin 1, resin 13, resin 14,10 parts of Viscoat 295s of thorough mixing are put into test tube.To estimate as gelation time in the time of 120 ℃ of following lost flowability.Table 3 display result.
[table 3]
| Resin | Resin 1 | Resin 13 | Resin 14 |
| Gelation time | More than 450 minutes | 360 minutes | 190 minutes |
Claims (7)
1. the method for manufacture of photoresist (A) is characterized in that, comprises following operation I, operation II, operation III,
Operation I is containing in the presence of following (a) and the mixture (b), makes following (c), (d) and (e) reaction, thereby obtains resin, be the operation of reactant I,
(a) 3 valency organo phosphorous compoundss,
(b) be selected from the catalyst compound more than a kind or 2 kinds of chromium naphthenate, zirconium naphthenate or zirconium caprylate,
(c) phenolic resin varnish type epoxy resin,
(d) unsaturated monoprotic acid,
(e) has the saturated monoprotic acid of primary hydroxyl group;
Operation II makes this reactant I further obtain resin with the reaction of (f) multi-anhydride, be the operation of reactant II;
Operation III further reacts this reactant II with (g) with (h), thereby obtains the operation of photoresist (A),
(g) have the mono-epoxy compounds of free-radical polymerised unsaturated group,
(h) water-soluble mono epoxy compounds.
2. method of manufacture according to claim 1 is characterized in that, in said operation I, further contains stopper (i).
3. method of manufacture according to claim 1 and 2 is characterized in that, said (a) 3 valency organo phosphorous compoundss are triphenylphosphines, and in said operation I, is blown into air and reacts.
4. the method for manufacture of photoresist according to claim 1 and 2; It is characterized in that; With respect to the said photoresist of 100 mass parts (A); The consumption of said (a) 3 valency organo phosphorous compoundss is 0.03～0.33 mass parts, and the consumption of said (b) catalyst compound is 0.1～1.0 mass parts.
5. the method for manufacture of photoresist according to claim 3; It is characterized in that; With respect to the said photoresist of 100 mass parts (A), the consumption of said (a) 3 valency organo phosphorous compoundss is 0.03～0.33 mass parts, and the consumption of said (b) catalyst compound is 0.1～1.0 mass parts.
6. the photoresist of making through each described method of manufacture of claim 1～5 (A).
7. a photosensitive polymer combination is characterized in that, contains the described photoresist of claim 6 (A), epoxy resin (B), Photoepolymerizationinitiater initiater (C) and reactive diluent (D).
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2007/053030 WO2008102431A1 (en) | 2007-02-20 | 2007-02-20 | Process for producing photosensitive resin, photosensitive resin obtained by the process, and photosensitive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101611068A CN101611068A (en) | 2009-12-23 |
| CN101611068B true CN101611068B (en) | 2012-07-04 |
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| CN2007800514380A Expired - Fee Related CN101611068B (en) | 2007-02-20 | 2007-02-20 | Process for producing photosensitive resin, photosensitive resin obtained by the process, and photosensitive resin composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5356211B2 (en) |
| KR (1) | KR101387796B1 (en) |
| CN (1) | CN101611068B (en) |
| WO (1) | WO2008102431A1 (en) |
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| 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 |
| CN105669892B (en) * | 2016-03-17 | 2019-07-26 | 上海昭和高分子有限公司 | A kind of solvent type copolymer resins and combinations thereof |
| JP2021192069A (en) * | 2018-08-30 | 2021-12-16 | 昭和電工株式会社 | Photosensitive resin composition for black column spacer formation, black column spacer and image display device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1433532A (en) * | 2000-01-17 | 2003-07-30 | 昭和高分子株式会社 | Photosensitive resin composition |
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|---|---|---|---|---|
| JP2000321765A (en) * | 1999-05-13 | 2000-11-24 | Showa Highpolymer Co Ltd | Photosensitive resin composition |
| JP4316093B2 (en) * | 2000-03-21 | 2009-08-19 | 昭和高分子株式会社 | Photosensitive resin composition |
| JP2003057821A (en) * | 2001-08-13 | 2003-02-28 | Showa Highpolymer Co Ltd | Photosensitive resin and photosensitive resin composition |
| JP4682340B2 (en) * | 2003-07-25 | 2011-05-11 | 昭和電工株式会社 | Method for producing photosensitive resin |
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- 2007-02-20 CN CN2007800514380A patent/CN101611068B/en not_active Expired - Fee Related
- 2007-02-20 JP JP2009500028A patent/JP5356211B2/en active Active
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|---|---|---|---|---|
| CN1433532A (en) * | 2000-01-17 | 2003-07-30 | 昭和高分子株式会社 | Photosensitive resin composition |
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| Title |
|---|
| JP特开2000-321765A 2000.11.24 |
| JP特开2001-264977A 2001.09.28 |
| JP特开2003-57821A 2003.02.28 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2008102431A1 (en) | 2010-05-27 |
| WO2008102431A1 (en) | 2008-08-28 |
| KR101387796B1 (en) | 2014-04-21 |
| CN101611068A (en) | 2009-12-23 |
| JP5356211B2 (en) | 2013-12-04 |
| KR20100014472A (en) | 2010-02-10 |
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