CN1550892A - Photosensitive resin composition for image forming - Google Patents
Photosensitive resin composition for image forming Download PDFInfo
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- CN1550892A CN1550892A CNA2004100369845A CN200410036984A CN1550892A CN 1550892 A CN1550892 A CN 1550892A CN A2004100369845 A CNA2004100369845 A CN A2004100369845A CN 200410036984 A CN200410036984 A CN 200410036984A CN 1550892 A CN1550892 A CN 1550892A
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- epoxy acrylate
- epoxy
- reaction
- triphenyl phosphonium
- acid
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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
- G03F7/004—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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- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A photosensitive resin composition for the formation of image is provided, to prevent the aging of viscosity of a resin solution, to obtain a good developing property of an unexposed region and to improve storage stability. The photosensitive resin composition comprises a carboxyl group-containing epoxy acrylate which can be obtained by reacting an epoxy resin having at least two epoxy groups in a molecule and an unsaturated monobasic acid in the presence of an esterification catalyst to prepare an epoxy acrylate and reacting the hydroxyl group of the epoxy acrylate with a dibasic acid anhydride, wherein the esterification catalyst is a quaternary phosphonium salt represented by the formula 1. In the formula 1, R1, R2, R3 and R4 are identical or different one another and are an aromatic organic group capable of having a substituent; and X- is a corresponding anion.
Description
Technical field
The present invention relates to a kind of photosensitive polymer combination that image forms that is used for.
Background technology
Make the reaction of epoxy resin and unsaturated monoacid and the epoxy acrylate (vinyl acetate) that obtains can be heated or be subjected to light and be cured,, therefore be used in the various uses such as anticorrosive additive material relevant with electronic unit because of the function admirables such as chemical resistance of solidfied material.In addition, knownly introduce carboxyl, can obtain to carry out the photoresist (for example the spy opens clear 61-243869 communique and the clear 63-258975 communique of Te Kai) that alkali develops by hydroxyl that epoxy acrylate has and multi-anhydride are reacted.
; the inventor is through discovering; when the synthesizing epoxy acrylate; if use known in the past tertiary amine or tertiary phosphine class etc. as epoxy resin and unsaturated monacid catalyst for esterification reaction; just there is the resin solution (resin combination) that contains epoxy acrylate, during preservation the problem that increases in time of its viscosity.
On the other hand, form when using photosensitive polymer combination,, often cooperate epoxy resin in order to improve the cross-linking density of the cured coating film after the exposure at the image that carboxylic epoxy acrylate is used for scolder resist etc.Filming of this photosensitive polymer combination that has cooperated epoxy resin, in case carry out heat drying before exposure, it is insufficient that its alkali-developable often will become.Can think that this is because when the synthesizing epoxy acrylate, the esterification catalyst of tertiary amine or tertiary phosphine class etc. makes carboxylic epoxy acrylate and epoxy resin carry out cross-linking reaction, thereby makes the cause of the alkali dissolution reduction of unexposed portion.
The viscosity of resin solution in the preservation process increases or the problem of the development reduction of unexposed portion in order to solve, and discloses the technology of a kind of lithium as esterification catalyst use naphthenic acid, lauric acid, stearic acid, oleic acid, octenoic acid etc., chromium, zirconium, potassium, sodium salt in for example special fair 6-123233 communique.Though this technology has been improved the storage stability of resin solution considerably, generate easily insolubles during esterification, and this insolubles can not adopt filter operation to remove fully, therefore, on industrial implementation, must improve.In addition, for the nearest environmental requirement of correspondence, the kind of the compound that can use as catalyzer also is restricted.
And then the spy opens and also discloses a kind of like this technology in the flat 14-293876 communique, wherein, uses known in the past tertiary phosphine as esterification catalyst, and carries out the synthetic of epoxy acrylate under oxygen atmosphere, makes the catalytic activity forfeiture of tertiary phosphine thus.But, the inventor is through discovering, make this technology reactive stably and when unexposed portion presented good development in building-up process performance, temperature, humidity at building-up process need be carried out strict control at temperature, the humidity of catalyst activity forfeiture process in addition, and viscosity increases and the problem of the development reduction of unexposed portion yet produce in resin solution preservation process.
Summary of the invention
Under above-mentioned condition, the objective of the invention is to, provide the development preferable image of the good and unexposed portion of a kind of storage stability to form and use photosensitive polymer combination, the viscosity that can reduce resin solution changes in time.In addition, the present invention also aims to, provide a kind of image to form and use photosensitive polymer combination, use makes the little catalyzer of environmental impact.
Can realize the image formation photosensitive polymer combination of the present invention of above-mentioned purpose, be a kind of resin combination that contains carboxylic epoxy acrylate, this carboxylic epoxy acrylate is by making the reaction of the epoxy resin that has 2 above epoxy radicals in 1 molecule and unsaturated monoacid and then make hydroxyl in the epoxy acrylate that obtains in this reaction and multi-anhydride reacts and obtains in the presence of esterification catalyst; It is characterized in that,, use following general formula (1) expression De quaternary alkylphosphonium salt as esterification catalyst.
(in the formula: R
1, R
2, R
3, R
4Identical or different, each expression has the organic group that can have substituent aromatic rings, X
-Expression is to negative ion (counter anion).)
Above-mentioned R
1, R
2, R
3, R
4Identical or different, be preferably each and can have substituent aryl or can have substituent aralkyl, more preferably each can have substituent phenyl or can have substituent benzyl.
Image of the present invention forms use photosensitive polymer combination, owing to be using epoxy acrylate that special catalyst synthesizes as major component, therefore, resin combination does not show the tackify behavior in the preservation process, have good storage stability.In addition, during dried coating film before exposure,, also be good with the development of weak base aqueous solution even drying time is long.
Image of the present invention forms uses photosensitive polymer combination, can be used for various uses, except the matrix resin that is used for fibre reinforced plastics (FRP), coating, bonding agent etc., form owing to can carry out microfabrication or image, therefore also can be used for printing plate or various anticorrosive additive material.
Embodiment
Main points of the present invention are,, as esterification catalyst, use to have 4 organic group De quaternary alkylphosphonium salts that have aromatic rings when forming epoxy acrylate with the photosensitive polymer combination major component as image when synthetic.By using this catalyzer, can carry out esterification effectively, thereby the viscosity of the solution of the photoresist that can suppress to obtain when preserving rises.And then, even, also can suppress the cross-linking reaction of the carboxyl of this epoxy resin and photoresist (epoxy acrylate), therefore, can guarantee the alkali-developable of unexposed portion owing in photosensitive polymer combination, cooperate the situation of epoxy resin.According to the present invention, worryingly reacting balance ground is carried out even do not use to the influential compound of environment, at this moment, just can remove insolubles owing to finish the back by easy filter operation in reaction, therefore and the prior art of the acylate of use metal compare, the present invention industrial be favourable.Below describe the present invention in detail.
Image of the present invention forms and uses photosensitive polymer combination, is that a kind of containing with the epoxy acrylate as photoresist is the resin combination of major component.As the epoxy resin that constitutes the epoxy acrylate initiation material, so long as the epoxy resin that has 2 above epoxy radicals in 1 molecule can be used with regard to there is no particular limitation.Can enumerate particularly: bisphenol-type epoxy resin; Biphenyl type epoxy resin; Alicyclic epoxy resin; Multi-functional glycidyl polyimide resins such as four glycidyl group ADP methylmethane; Multi-functional glycidyl ether resins such as tetraphenyl glycidyl ether ethane; Line style phenol novolac epoxy resins or line style cresol novolak epoxy; The polyphenolic substance that phenolic compounds such as phenol, orthoresol, metacresol, naphthols and the aromatic aldehyde with phenolic hydroxyl group obtain through condensation reaction and the reactant of chloropropylene oxide; The polyphenolic substance that double olefin compounds such as phenolic compounds and divinylbenzene or dicyclopentadiene obtain through addition reaction and the reactant of chloropropylene oxide; With the ring-opening polymerization polymer epoxidised product of peracid with 4 vinyl cyclohexene-1-oxide; Triglycidyl group chlorinated isocyanurates etc. has the epoxy resin of heterocycle; Phenol aralkyl-type epoxy resin etc.In addition, also can use by more than 2 molecules that make these each epoxy resin with chain elongation agent reaction such as polyprotonic acid, polyphenolic substance, multifunctional amino-compound or multi-thiol bonding, thereby the product that strand is prolonged.In addition, also can be homopolymer or the multipolymer that glycidyl acrylate, glycidyl methacrylate etc. have the monomer of glycidyl.Above-mentioned substance can use separately or multiple being used in combination.
When the synthesizing epoxy acrylate,, be meant to have 1 carboxyl and the monoacid of free-radical polymerised pair of key more than 1 with the so-called unsaturated monoacid of epoxy resin reaction.As concrete example, can enumerate: the reactant of the reactant of the reactant of acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, β-acryloxy propionic, hydroxyalkyl acrylates and dibasic acid anhydride, hydroxyalkyl methacrylates and dibasic acid anhydride, polyfunctional acrylic ester and dibasic acid anhydride, multifunctional methacrylate and the reactant of dibasic acid anhydride etc. with 1 hydroxyl and 2 above methacryls with 1 hydroxyl and 2 above acryloyl groups with 1 hydroxyl and 1 methacryl with 1 hydroxyl and 1 acryloyl group.Wherein, be preferably the material that acrylic acid etc. has acryloyl group, and methacrylic acid etc. has the material of methacryl.Above-mentioned monoacid can use separately or multiple being used in combination.
Above-mentioned epoxy resin and unsaturated monacid esterification have been well-known, except catalyzer uses quaternary alkylphosphonium salt, can adopt usual method.The present invention is specially, make unsaturated monacid consumption with respect to 1 chemical equivalent of the epoxy radicals in the epoxy resin (equivalent of chemical reaction, at this moment refer to 1 mole) be 0.8～1.1 mole, in the existence of free radical polymerization monomer described later or not, or the existence of thinning agent or do not exist down, under the existence of polymerization inhibitor and catalysts, under 80～130 ℃, carry out esterification usually, can obtain epoxy acrylate thus.Above-mentioned thinning agent for example has solvent.Above-mentioned polymerization inhibitor for example has: quinones such as quinhydrones; Alkyl benzene phenols such as 2,6 di t butyl phenol; Phenothiazine, 4-hydroxyl-2,2,6, the N-oxyl class of 6-tetramethyl piperidine-N-oxyl etc.; Oxygen etc.Above-mentioned catalysts is the You quaternary alkylphosphonium salt for example.
In addition, when the reaction of above-mentioned epoxy resin and unsaturated monoacid, also can be used in combination with unsaturated monoacid: specific phenolic compounds has chain alkyl or has the substituting group that contains aromatic rings or have alcoholic extract hydroxyl group etc.; Specific monoacid does not have free-radical polymerised.This does not have free-radical polymerised monoacid and for example has, acetate, propionic acid, dihydromethyl propionic acid etc.The kind of the material that combinations thereof is used and consumption can suit according to the various requirement characteristics such as rerum natura of solidfied material to select.Material and the unsaturated monoacid that combinations thereof is used and being used for obtains having the situation of the curable resin of free-radical polymerised pair of key and hydroxyl, with respect to 1 chemical equivalent of the epoxy radicals in the epoxy resin, unsaturated monacid consumption is preferably more than 0.4 mole, more preferably more than 0.5 mole, as unsaturated monoacid and phenolic compounds and do not have free-radical polymerised monacid total amount, with respect to epoxy radicals 1 chemical equivalent, be preferably 0.8～1.1 mole.If unsaturated monacid consumption is few, then the optical polymerism of epoxy acrylate becomes not enough.In addition, if should the total amount surpass 1.1 moles, then increase such as the amount of remaining unsaturated monoacid etc. owing to unreacted, these low molecular weight compounds can cause the characteristic of solidfied material to reduce, and are not preferred therefore.
For above-mentioned esterification, in the conventional method,, for example have: tertiary amines such as triethylamine as esterification catalyst; Quaternary ammonium salts such as triethyl benzyl ammonia chloride; The imidazolium compounds of 2-ethyl-4-methylimidazole etc.; The tertiary phosphine of triphenylphosphine etc.; The acylate of metal.But among the present invention, do not use above-mentioned esterification catalyst, and use the specific De quaternary alkylphosphonium salt of following general formula (1) expression.
(in the formula: R
1, R
2, R
3, R
4Identical or different, each expression has the organic group that can have substituent aromatic rings, X
-Expression is to negative ion.)
Above-mentioned quaternary alkylphosphonium salt is characterised in that, with the organic group R of phosphorus atoms bonding
1, R
2, R
3, R
4All has aromatic rings.From embodiment described later also as can be seen, when adopting quaternary alkylphosphonium salt, if the organic group R of bonding on the phosphorus atoms of Gai quaternary alkylphosphonium salt
1, R
2, R
3, R
4In one be the alkyl De quaternary alkylphosphonium salt that does not have aromatic rings, rise at the viscosity of resin combination in the preservation process, it is insufficient that it suppresses effect.Therefore, the present invention as esterification catalyst De quaternary alkylphosphonium salt is, all organic groups be bonded directly on the phosphorus atoms or between alkyl etc. other organic group and organic group with aromatic rings is bonded on the phosphorus atoms.Though have only the just useful reason of this specific De quaternary alkylphosphonium salt still indeterminate, the inventor thinks the influence of the aromatic rings that quaternary alkylphosphonium salt has.Specific as follows: since above-mentioned specific De quaternary alkylphosphonium salt than in the past esterification catalyst such as more known tertiary amine or tertiary phosphine class, catalytic activity with height, epoxy radicals remaining in the epoxy acrylate is reduced, between the photosensitive polymer combination storage life, the reaction probability of epoxy radicals that this is remaining and carboxyl (by the carboxyl that is imported into reaction from unreacted unsaturated monacid carboxyl and/or multi-anhydride) reduces, therefore, suppressed the viscosity rising.Also think in addition, because above-mentioned specific De quaternary alkylphosphonium salt is carrying out among the esterification, lose its catalytic activity lentamente, perhaps, owing to just do not demonstrate its catalytic activity under the temperature when cured coating film predrying, therefore, even, also can suppress the reduction of alkali-developable cooperating under the situation of epoxy resin in addition.
In the above-mentioned general formula (1), R
1, R
2, R
3, R
4Be preferably aryl or aralkyl, they can have substituting group, and also there is no particular limitation for the carbon number of the alkyl of aralkyl (alkyl between phosphorus atoms and the aromatic rings).R most preferably
1, R
2, R
3, R
4Be phenyl or benzyl De quaternary alkylphosphonium salt.X
-Expression specifically has halide ion, acetic acid ion, borate ion etc. to negative ion.
Concrete example as above-mentioned general formula (1) expression De quaternary alkylphosphonium salt, for example can enumerate: benzyl triphenyl phosphonium bromide, Bian base triphenyl phosphonium chloride, benzyl triphenyl phosphonium hydroxides, 4-benzyl chloride base triphenyl phosphonium chloride, cinnamyl triphenyl phosphonium chloride, 4-ethoxy benzyl triphenyl phosphonium bromide, phenacyl triphenyl phosphonium bromide, 4-phenyl phosphonium bromide, tetraphenyl phosphonium chloride, tetraphenyl phosphonium iodide, tetraphenylphosphoniphenolate tetraphenyl borate salts etc., can use a kind or multiple.Wherein, preferably use benzyl triphenyl phosphonium bromide, Bian base triphenyl phosphonium chloride, 4-benzyl chloride base triphenyl phosphonium chloride etc.
In addition; also can with meet above-mentioned general formula (1) De quaternary alkylphosphonium salt with above-mentioned general formula (1) expression De quaternary alkylphosphonium salt as esterification catalyst; described general formula (the 1) De quaternary alkylphosphonium salt that do not meet; for example have; the acetonyl triphenyl phosphonium chloride; allyl triphenyl phosphonium bromide; the allyl triphenyl phosphonium chloride; n-pentyl triphenyl phosphonium bromide; bromomethyl triphenyl phosphonium bromide; 3-bromopropyl triphenyl phosphonium bromide; normal-butyl triphenyl phosphonium bromide; 4-carboxybutyl triphenyl phosphonium bromide; the triphenyl phosphonium bromide; 3-carboxyl propyl group triphenyl phosphonium bromide; the chloromethyl triphenyl phosphonium chloride; cyano methyl three normal-butyl chlorination Phosphonium; cyclopropyl triphenyl phosphonium bromide; 2-ethyl triphenyl phosphonium bromide; 2-1; 3-diox-2-base ethyl triphenyl phosphonium bromide; 2-ethyl triphenyl phosphonium bromide; 2-1; 3-dioxolanes-2-base ethyl triphenyl phosphonium bromide; 2-Jia base triphenyl phosphonium bromide; 2-1,3-dioxolanes-2-ylmethyl triphenyl phosphonium bromide; ethoxy carbonyl methyl phosphonium bromide; ethoxy carbonyl Jia base triphenyl phosphonium bromide; the ethyl triphenyl phosphonium bromide; triphenyl phosphonium chloride; formoxyl methyl triphenyl phosphonium chloride; n-heptyl triphenyl phosphonium bromide; n-hexyl triphenyl phosphonium bromide; isopropyl triphenyl phosphonium iodide; methoxycarbonyl methyl phosphonium bromide; methoxycarbonyl Jia base triphenyl phosphonium bromide; triphenyl phosphonium chloride; the methoxy triphenyl phosphonium chloride; Jia base triphenyl phosphonium bromide; the methyl triphenyl phosphonium iodide; n-pro-pyl triphenyl phosphonium bromide; the tetra-n-butyl phosphonium bromide; the tetra-n-butyl phosphonium chloride; n-tetradecane base triphenyl phosphonium bromide; the tetraethyl phosphonium bromide; Si Yi Ji Phosphonium hexafluorophosphate; Si Yi Ji Phosphonium tetrafluoroborate; the Si phosphonium chloride; tetrakis hydroxymethyl phosphonium chloride; four Liu Suan Phosphonium; tetra methylol sulfuric acid phosphonium; four n-octyl bromination Phosphonium; 2-ethoxyl methyl triphenyl phosphonium chloride; 2-trimethylsilylethoxymethyl triphenyl phosphonium chloride; 2-triphenyl phosphonium iodide; 2-trimethyl silyl ethyl triphenyl phosphonium iodide; the triphenyl phosphonium bromide; 3-trimethyl silyl-2-propynyl triphenyl phosphonium bromide; triphenyl vinyl bromination Phosphonium etc.
And then, also can a part be used in combination known in the past esterification catalyst.Known in the past esterification catalyst for example has: tertiary amines such as triethylamine; Quaternary ammonium salts such as triethyl benzyl ammonia chloride; Imidazolium compoundss such as 2-ethyl-4-methylimidazole; Tertiary phosphines such as triphenylphosphine; The acylate of metal; The inorganic salts of metal; Metal chelate compound etc.
The consumption of above-mentioned general formula (1) expression De quaternary alkylphosphonium salt with respect to epoxy resin and unsaturated monacid total amount, is generally 0.01～10 quality %, is preferably 0.05～5 quality %.If consumption less than 0.01 quality %, then can not fully carry out epoxy resin and unsaturated monacid esterification, and if consumption surpasses 10 quality %, then not only waste, and the storage stability of resin combination is reduced.
As the solvent (thinning agent) that can use when the synthesizing epoxy acrylate, can enumerate: hydro carbons such as toluene, dimethylbenzene; Match fine jade Suo Fu classes such as match fine jade Suo Fu (Cellosolve), butyl match fine jade Suo Fu; Carbitol such as carbitol, butyl carbitol class; Ester classes such as match fine jade Suo Fu acetic acid esters, carbitol acetic acid esters, propylene glycol monomethyl ether, DPGME acetic acid esters, glutaric acid methyl esters, dimethyl glutarate, methyl succinate, dimethyl succinate, hexane diacid methyl esters, dimethyl adipate; Ketone such as methyl isobutyl ketone, methyl ethyl ketone; Ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether etc., these solvents can use separately or multiple mixing is used.
In the epoxy acrylate that obtains by above-mentioned esterification, owing to epoxy radicals generation ring-opening reaction generates hydroxyl.Because, therefore unexposed portion is dissolved in the aqueous alkali, develop thereby when adopting photoetching process to carry out microfabrication or image formation, can carry out alkali by in the epoxy acrylate that this hydroxyl and multi-anhydride addition are obtained, importing carboxyl.
As can with the multi-anhydride of hydroxyl reaction, can enumerate: phthalic anhydride, succinic anhydride, octenyl succinic acid anhydride, five succinic anhydrides, five [dodecenyl succinic] succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydro phthalic anhydride, methyltetrahydro phthalic anhydride, 3,6-nadic anhydride, methyl nadic anhydride, tetrabromophthalic anhydride, 9, the 10-dihydro-9-oxy is assorted-dibasic acid anhydrides such as reactant of 10-phospho hetero phenanthrene-10-oxide and itaconic anhydride or maleic anhydride; Trimellitic anhydride; The aliphatics of biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic dianhydride, PMA, benzophenone tetracarboxylic dianhydride etc. or aromatic series tetra-atomic acid dianhydride etc., above-mentioned multi-anhydride can use separately or multiple being used in combination.
For the reaction by epoxy acrylate and multi-anhydride, resultant carboxylic epoxy acrylate is preferably adjusted the reactive ratio of epoxy acrylate and multi-anhydride, so that the acid number of this carboxylic epoxy acrylate reaches more than the 30mgKOH/g.More preferably make the following 50mgKOH/g of being limited to of described acid number.In addition, be limited to 120mgKOH/g on preferred, be limited to 100mgKOH/g on further preferred.In order to satisfy these acid number scopes, making the anhydride group in the multi-anhydride is that 0.1～1.1 mole scope ground reacts and gets final product with respect to 1 chemical equivalent of the hydroxyl in the epoxy acrylate.More preferably 0.2～0.9 mole.This reaction is carried out under 50～130 ℃ usually.During reaction, the polymerization inhibitor of above-mentioned solvent or quinhydrones or oxygen etc. is existed, also can add known catalyzer as required.
It is a kind ofly to contain the resin combination of above-mentioned carboxylic epoxy acrylate as the photoresist composition that image of the present invention forms with photosensitive polymer combination, in the said composition, also can contain known free-radical polymerised compound.There is no particular limitation for the ratio of carboxylic epoxy acrylate and free-radical polymerised compound, is preferably 100: 5～500 (mass ratioes).In this free-radical polymerised compound, comprise oligomer and monomer.
As the free radical polymerization oligomers, can use unsaturated polyester (UP), urethane acrylate, polyester acrylate etc.
As free radical polymerization monomer, can enumerate: aromatic vinyl base system monomers such as styrene, α-Jia Jibenyixi, α-chlorostyrene, vinyltoluene, divinylbenzene, diallyl phthalate, phenyl-phosphonic acid diallyl; Vinyl acetate monomer such as vinyl acetate, hexanedioic acid vinyl ester; Propylene base system monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, beta-hydroxy ethyl propylene acid esters, ethylene glycol diacrylate, diacrylate binaryglycol ester, diacrylate propylene glycol ester, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol tetracrylate, six acrylic acid dipentaerythritol ester, three [2-acryloxy ethyl] triazine; Methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, beta-hydroxy ethyl-methyl acrylate, methacrylate, the methyl acrylate, 2-oxo-1,3-dioxolanes-4-ylmethyl acrylate, 2-oxo-1,3-dioxolanes-4-ylmethyl methacrylate, Ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate, the dimethyl allene acid propylene glycol ester, the trimethylolpropane dimethylacrylate, trimethylol-propane trimethacrylate, pentaerythritol tetramethacrylate, hexamethyl acrylic acid dipentaerythritol ester, metering system base system monomers such as three [2-methacryloxyethyl] triazine; Acrylic acid-2-ethyl ester, methacrylic acid-2-ethyl ester, acrylic acid-2-ethyleneoxy ethoxy ethyl ester, methacrylic acid-2-ethyleneoxy ethoxy ethyl ester, acrylic acid-2-ethyl ester, methacrylic acid-2-ethyl ester, the different propenyloxy group ethoxy ethoxy of acrylic acid-2-ethyl ester, the different propenyloxy group ethoxy ethoxy of methacrylic acid-2-ethyl ester, methacrylic acid-2-ethyl ester, the different propenyloxy group ethoxy ethoxy ethoxy of acrylic acid-2-ethyl ester, the different propenyloxy group ethoxy ethoxy ethoxy of methacrylic acid-2-ethyl ester, methacrylic acid-2-ethyl ester, the different propenyloxy group ethoxy ethoxy ethoxy of acrylic acid-2-ethoxy ethyl ester, the vinyl ether compound with free-radical polymerised pair of key of the different propenyloxy group ethoxy ethoxy ethoxy of methacrylic acid-2-ethoxy ethyl ester etc.; Acrylic acid-2-sulfo-ethyleneoxy ethoxy ethyl ester, methacrylic acid-2-sulfo-ethyleneoxy ethoxy ethyl ester, acrylic acid-2-ethyleneoxy thio ethoxy ethyl ester, methacrylic acid-2-ethyleneoxy thio ethoxy ethyl ester etc. have the vinyl sulfide compound of free-radical polymerised pair of key; Triallyl cyanurate etc.
In order to improve the cross-linking density of the cured coating film after the exposure, image of the present invention forms with also cooperating epoxy resin in the photosensitive polymer combination.As epoxy resin, can use in the initiation material example of above-mentioned epoxy acrylate any.At this moment, also can cooperate epoxy hardeners such as dicyandiamide, imidazolium compounds.
In addition, image of the present invention forms with in the photosensitive polymer combination, also can add known adjuvant as required, for example has: the filling agent of talcum, clay, barium sulphate etc.; The painted pigment of using; Defoamer; Coupling agent; Levelling agent; Photosensitizer; Release agent; Lubricant; Plastifier; Antioxidant; Ultraviolet light absorber; Fire retardant; Polymerization inhibitor; Tackifier etc.And, also Ke Yi Pei He oxazoline compound, oxetane compound etc.And then above-mentioned composition is that matrix resin can be made for fiber reinforced composite material with various reinforcing fibers as the reinforcement fiber.
Image of the present invention forms and uses photosensitive polymer combination, also can come heat curing by using known thermal polymerization, but in order to adopt photoetching process to carry out microfabrication or image formation, preferably adds Photoepolymerizationinitiater initiater and make its photocuring.
As Photoepolymerizationinitiater initiater, can use known Photoepolymerizationinitiater initiater, can enumerate: benzoin and alkyl ethers thereof such as benzoin, benzoin methylether, benzoin ethyl ether; Acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone, 4-acetophenone, 4-[1-tert-butyl group dioxy base-1-Methylethyl] acetophenones such as acetophenone; Anthraquinone classes such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone; 2,4-dimethyl thioxanthones, 2, thioxanthene ketones such as 4-diisopropyl thioxanthones, 2-clopenthixal ketone; Ketals such as acetophenone dimethyl ketone acetal, benzyl dimethyl ketal; Benzophenone, 4-benzophenone, 4-[1-tert-butyl group dioxy base-1-Methylethyl] benzophenone, 3,3 ', 4,4 '-four benzophenone, 3,3 ', 4, benzophenones such as 4 '-four [tert-butyl group dioxy base carbonyl] benzophenone; 2-methyl isophthalic acid-[4-phenyl]-2-morpholino propane-1-ketone or 2-benzyl-2-dimethylamino-1--butanone-1,2-methyl isophthalic acid-[4-methyl mercapto phenyl]-2-morpholino propane-1-ketone or 2-benzyl-2-dimethylamino-1-butanone-1,2-methyl isophthalic acid-[4-phenyl]-2-morpholino propane-1-ketone or 2-benzyl-2-dimethylamino-1-4-morpholino phenyl-butanone-1,2-methyl isophthalic acid-[4-methyl mercapto phenyl]-2-morpholino propane-1-ketone or 2-benzyl-2-dimethylamino-1-4-morpholino phenyl-butanone-1; Acylphosphine oxide (acyl phosphine oxide) class; Xanthene ketone etc.
These Photoepolymerizationinitiater initiaters can use a kind or use as multiple potpourri, form with photoresist (total of carboxylic epoxy acrylate and the free-radical polymerised compound that uses as required) 100 mass parts with respect to image, preferably contain 0.5～30 mass parts.When the amount of Photoepolymerizationinitiater initiater was less than 0.5 mass parts, needing increased light application time, also is difficult to cause polymerization even perhaps carry out illumination, therefore, under usual conditions, can not get suitable skin hardness.Should illustrate, also do not have a large amount of relatively advantages of using even cooperate the Photoepolymerizationinitiater initiater that surpasses 30 weight portions.
Image is being formed when being applied on the base material, considering, forming when using photosensitive polymer combination, preferably preserving with solution state when preserving image from the viewpoint of manufacturability etc. with photosensitive polymer combination.As solvent, can use any solvent that can when epoxy acrylate is synthetic, use.When being coated with, also can further diluting or concentrate so that reach optimum concentration.
When image formation of the present invention is used with the photosensitive polymer combination photocuring,, therefore can carry out alkali and develop because unexposed portion is dissolved in the aqueous alkali.As the concrete example of operable alkali, can enumerate: alkali metal compounds such as sodium carbonate, sal tartari, NaOH, potassium hydroxide; Alkaline earth metal compounds such as calcium hydroxide; Ammonia; Water-soluble organic amines such as single methylamine, dimethylamine, trimethylamine, mono aminoethane, diethylamine, triethylamine, single propylamine, dimethyl propylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylene triamine, dimethyl amino ethyl methacrylate, polyethyleneimine.Above-mentioned alkaloid substance can use separately or multiple being used in combination.
[embodiment]
Below, illustrate in greater detail the present invention with embodiment, but following embodiment not limiting the present invention, change is implemented in the scope that does not break away from above-mentioned and aftermentioned scope, all is included in the technical scope of the present invention.Should illustrate that " part " among the embodiment and " % " all are benchmark with the quality.In addition, in instructions " more than " and " following " all comprise given figure, that is, " more than the X " refers to " equal X or greater than X ", " X following " refers to " equal X or less than X ", " surpassing ", " exceeding ", " less than " and " deficiency " neither given figure that comprises.
Synthesis example 1
To line style cresol novolak epoxy " ESCN195XHH " (SUMITOMO CHEMICAL chemical company system, epoxide equivalent (epoxy equivalent) 200) in 400 part, add 0.5 part of 145 parts in acrylic acid, 293 parts of ethyl carbitol acetic acid esters, 2.2 parts of benzyl triphenyl phosphonium bromides and methylnaphthohydroquinone, under 115 ℃, make its reaction 10 hours, when the acid number of reactant reaches 1.7, finish reaction.Obtain containing the ethyl carbitol acetate solution of 65% epoxy acrylate.
Secondly, in 200 parts of this solution, add 23 parts of 43 parts of tetrahydrophthalic anhydrides and ethyl carbitol acetic acid esters, under 100 ℃, make its reaction 6 hours.Obtain the ethyl carbitol acetate solution A-1 that contains 65% carboxylic epoxy acrylate of acid number 94.
Synthesis example 2
The benzyl triphenyl phosphonium bromide that uses in the synthesis example 1 is changed into 2.2 parts of 4-phenyl phosphonium bromides for 2.2 parts, in addition, similarly under 115 ℃, make its reaction 10 hours, when the acid number of reactant reaches 2.5, finish reaction with synthesis example 1.Obtain containing the ethyl carbitol acetate solution of 65% epoxy acrylate.
Secondly, in 200 parts of this solution, add 23 parts of 43 parts of tetrahydrophthalic anhydrides and ethyl carbitol acetic acid esters, under 100 ℃, make its reaction 6 hours.Obtain the ethyl carbitol acetate solution A-2 that contains 65% carboxylic epoxy acrylate of acid number 96.
Synthesis example 3
To with synthesis example 1 in 400 parts of the used identical line style cresol novolak epoxy resins " ESCN195XHH ", add p-hydroxybenzene-83 parts of 2-ethanol, 315 parts of ethyl carbitol acetic acid esters, 0.6 part of tetrabutylammonium chloride, make its reaction after 4 hours under 120 ℃, add 0.6 part of 102 parts in acrylic acid, 2.3 parts of Bian base triphenyl phosphonium chlorides and methylnaphthohydroquinone, and then under 115 ℃, make its reaction 10 hours, when reaching 1.5, finishes the acid number of reactant reaction.Obtain containing the ethyl carbitol acetate solution of 65% epoxy acrylate.
Secondly, in 200 parts of this solution, add 18 parts of 34 parts of tetrahydrophthalic anhydrides and ethyl carbitol acetic acid esters, under 100 ℃, make its reaction 6 hours.Obtain the ethyl carbitol acetate solution A-3 that contains 65% carboxylic epoxy acrylate of acid number 79.
Compare synthesis example 1
The benzyl triphenyl phosphonium bromide that uses in the synthesis example 1 is changed into 2.2 parts of triphenylphosphines for 2.2 parts, in addition, similarly under 115 ℃, make its reaction 10 hours, when the acid number of reactant reaches 6.6, finish reaction with synthesis example 1.Obtain containing the ethyl carbitol acetate solution of 65% epoxy acrylate.
Secondly, in 200 parts of this solution, add 23 parts of 43 parts of tetrahydrophthalic anhydrides and ethyl carbitol acetic acid esters, under 100 ℃, make its reaction 6 hours.Obtain the ethyl carbitol acetate solution B-1 that contains 65% carboxylic epoxy acrylate that is used for comparison of acid number 100.
Compare synthesis example 2
The benzyl triphenyl phosphonium bromide that uses in the synthesis example 1 is changed into 2.2 parts of tetra-n-butyl ammonium bromides for 2.2 parts, in addition, similarly under 115 ℃, make its reaction 10 hours, when the acid number of reactant reaches 4.0, finish reaction with synthesis example 1.Obtain containing the ethyl carbitol acetate solution of 65% epoxy acrylate.
Secondly, in 200 parts of this solution, add 23 parts of 43 parts of tetrahydrophthalic anhydrides and ethyl carbitol acetic acid esters, under 100 ℃, make its reaction 6 hours.Obtain the ethyl carbitol acetate solution B-2 that contains 65% carboxylic epoxy acrylate that is used for comparison of acid number 99.
Compare synthesis example 3
The benzyl triphenyl phosphonium bromide that uses in the synthesis example 1 is changed into 2.2 parts of ethyl triphenyl phosphonium bromides for 2.2 parts, in addition, similarly under 115 ℃, make its reaction 10 hours, when the acid number of reactant reaches 3.9, finish reaction with synthesis example 1.Obtain containing the ethyl carbitol acetate solution of 65% epoxy acrylate.
Secondly, in 200 parts of this solution, add 23 parts of 43 parts of tetrahydrophthalic anhydrides and ethyl carbitol acetic acid esters, under 100 ℃, make its reaction 6 hours.Obtain the ethyl carbitol acetate solution B-3 that contains 65% carboxylic epoxy acrylate that is used for comparison of acid number 97.
Embodiment 1～3 and comparative example 1～3
[storage stability]
Estimate synthesis example 1～3 and the storage stability that compares the resin solution that obtains in the synthesis example 1～3, the results are shown in the table 1.Should illustrate, storage stability is, each resin solution joined in the Pyrex glass system test tube of φ 18mm, remains in 80 ℃ the oil bath, use E type viscometer determining viscosity over time, estimate tackify rate (multiplying power) with respect to initial stage viscosity (=1.0).
The storage stability of table 1. resin solution (with respect to the tackify rate of initial stage viscosity)
| Embodiment | Comparative example | |||||
| ????1 | ????2 | ????3 | ????1 | ????2 | ????3 | |
| The numbering that contains the resin solution of carboxylic epoxy acrylate | ???A-1 | ????A-2 | ????A-3 | ????B-1 | ????B-2 | ????B-3 |
| Holding time: 80 ℃ * 2 hours 80 ℃ * 4 hours 80 ℃ * 6 hours 80 ℃ * 8 hours | ???1.0 ???1.0 ???1.0 ???1.1 | ????1.0 ????1.0 ????1.1 ????1.2 | ????1.0 ????1.0 ????1.0 ????1.1 | ????1.0 ????1.1 ????1.3 ????1.6 | ????1.0 ????1.0 ????1.2 ????1.4 | ????1.0 ????1.0 ????1.2 ????1.4 |
As seen from Table 1, compare with each solution of comparative example, the viscosity that each solution of the embodiment of the invention can suppress in time rises the storage stability that oblatio is good.
Embodiment 4～6 and comparative example 4～6
Use synthesis example 1～3 and compare the resin solution that obtains in the synthesis example 1～3, the photosensitive polymer combination that cooperates shown in the preparation table 2 adopts following method to estimate.The results are shown in the table 3.
[alkali-developable]
Each photosensitive polymer combination is applied on the thick copper-clad laminate sheet of 1.6mm that cleaning by degreasing in advance crosses, and making its thickness is 20～30 μ m, carries out drying in the heated air circulation type drying oven, under 80 ℃, is filmed.Then, each uses 1%Na
2CO
3Aqueous solution is under 30 ℃ temperature and at 2.1kg/cm
2Pressure under, carried out for 60 seconds and develop, with the visual method evaluation film have or not remaining.Benchmark is as follows, develop fully: film no remaining and can develop fully, residual a little: film have remaining a little and can develop, part is residual: filmed remaining and development effect is poor, all residual: film comprehensive remaining and development effect is poor, develop fully, residual a little be qualified, part residual, whole residual be bad.
[photo-curable]
Each photosensitive polymer combination is applied on the thick copper-clad laminate sheet of 1.6mm that cleaning by degreasing in advance crosses, and making its thickness is 20～30 μ m, in the heated air circulation type drying oven, 80 ℃ dry 30 minutes down, filmed.Then, each carries out 500mJ/cm with ultraviolet exposure apparatus according
2After the exposure, use 1%Na
2CO
3Aqueous solution is under 30 ℃ temperature and at 2.1kg/cm
2Pressure under, carried out for 90 seconds and develop, with the visual method evaluation film have or not remaining.Benchmark is as follows, zero: film no remaining, *: it is remaining to have filmed, and zero is qualified, * be bad.
Table 2 photosensitive polymer combination (numeral is a umber)
| Embodiment | Comparative example | |||||
| ????1 | ????2 | ????3 | ????1 | ????2 | ????3 | |
| The numbering that contains the resin solution of carboxylic epoxy acrylate | ||||||
| A-1 | ????100 | |||||
| A-2 | ????100 | |||||
| A-3 | ????100 | |||||
| B-1 | ????100 | |||||
| B-2 | ????100 | |||||
| B-3 | ????100 | |||||
| Polyfunctional monomer: dipentaerythritol base six acrylate | ????7 | ????7 | ????7 | ????7 | ????7 | ????7 |
| Photoepolymerizationinitiater initiater: Irugacure 907 1) | ????5 | ????5 | ????5 | ????5 | ????5 | ????5 |
| Epoxy resin: YDPN-638P 2) | ????21 | ????21 | ????21 | ????21 | ????21 | ????21 |
| Epoxy hardener: dicyandiamide | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 |
Note: 1) the vapour Bart plants the photopolymerization of chemical company (Ciba Specialty Chemicals) system
Initiating agent.
2) Japanese Dongdu changes into the novolac epoxy resin of corporate system.
The alkali-developable of table 3 resin and photo-curable
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Alkali-developable drying time: 80 ℃ * 30 minutes 80 ℃ * 60 minutes 80 ℃ * 90 minutes | Developing fully develops fully develops fully | Developing fully, it is residual a little to develop fully | Developing fully develops fully develops fully | It is all residual all residual to develop fully | The part of developing fully is residual all residual | The part of developing fully is residual all residual |
| Photo-curable | ○ | ○ | ○ | ○ | ○ | ○ |
As seen from Table 3, the good alkali-developable of the embodiment of the invention (each solution) oblatio even drying time is long, also can be kept development.And the comparative example oblatio in case prolong drying time, then reduces its development significantly.In addition, the embodiment of the invention (each solution) is oblatio all, good photo-curable.
Claims (3)
1. an image forms and uses photosensitive polymer combination, be a kind of resin combination that contains carboxylic epoxy acrylate, described carboxylic epoxy acrylate is by making the reaction of the epoxy resin that has 2 above epoxy radicals in 1 molecule and unsaturated monoacid and then make hydroxyl in the epoxy acrylate that obtains in this reaction and multi-anhydride reacts and obtains in the presence of esterification catalyst; It is characterized in that,, use following general formula to represent the De quaternary alkylphosphonium salt as esterification catalyst,
In the formula: R
1, R
2, R
3, R
4Identical or different, each expression has the organic group that can have substituent aromatic rings, and X-represents negative ion.
2. image according to claim 1 forms and uses photosensitive polymer combination, wherein, and above-mentioned R
1, R
2, R
3, R
4Identical or different, respectively be can have substituent aryl or can have substituent aralkyl.
3. image according to claim 2 forms and uses photosensitive polymer combination, wherein, and above-mentioned R
1, R
2, R
3, R
4Identical or different, respectively be can have substituent phenyl or can have substituent benzyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003122063 | 2003-04-25 | ||
| JP2003122063 | 2003-04-25 |
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| Publication Number | Publication Date |
|---|---|
| CN1550892A true CN1550892A (en) | 2004-12-01 |
| CN1278184C CN1278184C (en) | 2006-10-04 |
Family
ID=34362580
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100369845A Expired - Fee Related CN1278184C (en) | 2003-04-25 | 2004-04-26 | Photosensitive resin composition for image forming |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100682711B1 (en) |
| CN (1) | CN1278184C (en) |
| TW (1) | TW200504101A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101639649B (en) * | 2008-07-29 | 2012-08-08 | 佳能株式会社 | Developer bearing member and process for producing same, development apparatus and development method |
| CN103045015A (en) * | 2013-01-25 | 2013-04-17 | 深圳市万佳原丝印器材有限公司 | Liquid photo-imageable alkali developable and anodizing resistant ink and preparation method thereof |
| CN104109228A (en) * | 2013-04-18 | 2014-10-22 | 日本化药株式会社 | Manufacture method of reactive epoxy carboxylate compound, resin composition containing same and cured product thereof |
| CN106886128A (en) * | 2017-03-28 | 2017-06-23 | 深圳市道尔顿电子材料有限公司 | A kind of negative photoresist |
| US9695333B2 (en) | 2014-12-31 | 2017-07-04 | Industrial Technology Research Institute | Resin composition and coating material using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI756879B (en) * | 2020-10-26 | 2022-03-01 | 南亞塑膠工業股份有限公司 | Unsaturated polyester resin composition and molding product thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4175973A (en) | 1974-05-02 | 1979-11-27 | General Electric Company | Curable compositions |
| US4632891A (en) | 1984-10-04 | 1986-12-30 | Ciba-Geigy Corporation | Process for the production of images |
| JPH06135869A (en) * | 1992-10-28 | 1994-05-17 | Sagami Chem Res Center | Production of compound having perfluoroalkyl group |
| JP4894093B2 (en) * | 2001-03-30 | 2012-03-07 | Ｄｉｃ株式会社 | Method for producing active energy ray-curable resin |
-
2004
- 2004-04-02 KR KR1020040022862A patent/KR100682711B1/en not_active IP Right Cessation
- 2004-04-20 TW TW093110928A patent/TW200504101A/en not_active IP Right Cessation
- 2004-04-26 CN CNB2004100369845A patent/CN1278184C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101639649B (en) * | 2008-07-29 | 2012-08-08 | 佳能株式会社 | Developer bearing member and process for producing same, development apparatus and development method |
| CN103045015A (en) * | 2013-01-25 | 2013-04-17 | 深圳市万佳原丝印器材有限公司 | Liquid photo-imageable alkali developable and anodizing resistant ink and preparation method thereof |
| CN103045015B (en) * | 2013-01-25 | 2016-05-11 | 深圳市万佳原丝印器材有限公司 | Anti-anodic oxidation ink of liquid photosensitive imaging and developing with alkali and preparation method thereof |
| CN104109228A (en) * | 2013-04-18 | 2014-10-22 | 日本化药株式会社 | Manufacture method of reactive epoxy carboxylate compound, resin composition containing same and cured product thereof |
| US9695333B2 (en) | 2014-12-31 | 2017-07-04 | Industrial Technology Research Institute | Resin composition and coating material using the same |
| CN106886128A (en) * | 2017-03-28 | 2017-06-23 | 深圳市道尔顿电子材料有限公司 | A kind of negative photoresist |
| CN106886128B (en) * | 2017-03-28 | 2021-02-19 | 深圳市道尔顿电子材料有限公司 | Negative photoresist |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100682711B1 (en) | 2007-02-15 |
| TWI302917B (en) | 2008-11-11 |
| KR20040092408A (en) | 2004-11-03 |
| TW200504101A (en) | 2005-02-01 |
| CN1278184C (en) | 2006-10-04 |
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