CN103901719A - Quick-drying-type carboxyl-containing photosensitive resin and preparation method thereof - Google Patents
Quick-drying-type carboxyl-containing photosensitive resin and preparation method thereof Download PDFInfo
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- CN103901719A CN103901719A CN201410173380.9A CN201410173380A CN103901719A CN 103901719 A CN103901719 A CN 103901719A CN 201410173380 A CN201410173380 A CN 201410173380A CN 103901719 A CN103901719 A CN 103901719A
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- 238000002360 preparation method Methods 0.000 title claims description 21
- 239000011347 resin Substances 0.000 title abstract 6
- 229920005989 resin Polymers 0.000 title abstract 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title abstract 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 61
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 126
- 229920002120 photoresistant polymer Polymers 0.000 claims description 36
- 239000003112 inhibitor Substances 0.000 claims description 34
- 238000006116 polymerization reaction Methods 0.000 claims description 34
- 239000003822 epoxy resin Substances 0.000 claims description 22
- 229920000647 polyepoxide Polymers 0.000 claims description 22
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007795 chemical reaction product Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 13
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical group COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- -1 phenol compound Chemical class 0.000 claims description 6
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 5
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 claims description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000004843 novolac epoxy resin Substances 0.000 claims description 4
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 claims description 4
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 4
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 claims description 4
- 238000005530 etching Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000003384 imaging method Methods 0.000 abstract description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract description 2
- 230000036211 photosensitivity Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 8
- 229920000058 polyacrylate Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical group C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000011378 shotcrete Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Materials For Photolithography (AREA)
Abstract
The invention relates to a quick-drying-type carboxyl-containing photosensitive resin which is characterized in that an acid value of the photosensitive resin is 40-150KOH/g, the solid content is 40-70 weight percent, and the average molecular weight is 8000-15000. The invention also relates to a method for preparing the quick-drying-type carboxyl-containing photosensitive resin. The invention has the advantages that a coating formed by an alkaline imaging photosensitive resin compound of the quick-drying type carboxyl-containing photosensitive resin is high in finger touch dryness (tack-free property), and excellent photosensitivity and resolution can be obtained under low energy, so that the requirement on high-precision circuit etching can be met.
Description
Technical field
The present invention relates to a kind of carboxylic photoresist, relate in particular to carboxylic photoresist of a kind of quick-dry type and preparation method thereof.
Background technology
Traditionally, in the manufacture of printed-wiring board (PWB) (PCB) is produced, use circuit ink to reach the object that circuit forms.So-called circuit ink, refers on covered substrate copper face, utilizes exposure and alkaline video picture to carry out image transfer, and forms the film of special pattern, thereby reach the protective material of anti-etching formation specific circuit.
In recent years, along with miniaturization and, high performance and the high density actual load of electrical equipment, printed circuit board industry is constantly reducing live width and the line-spacing of its circuit, the analytic ability of traditional circuit ink cannot reach the requirement of product, improve exposure energy and can cause suction vacuum error, circuit can not resolved, and reduces exposure energy and can cause again the series of problems such as open circuit breach.Numerous PCB manufacturer is in the product that has high precision to require, and the dry film of use cost costliness replaces traditional circuit ink to reach the requirement of product; But in traditional circuit ink, increase the use amount of sensitization monomer and light trigger, though can improve its analytic ability, its dry to touch (tack-free property) is variation obviously, cannot carry out Industry Promotion.
Summary of the invention
For above-mentioned shortcoming, the object of the present invention is to provide the carboxylic photoresist of a kind of quick-dry type, it is good and can obtain excellent photonasty and resolution under low-yield that the alkaline video picture type Photosensitve resin composition that contains the carboxylic photoresist of this quick-dry type forms the dry to touch (tack-free property) of film, thereby can meet the requirement of high precision circuit etching.
Technology contents of the present invention is: the carboxylic photoresist of a kind of quick-dry type, and the acid value that it is characterized in that it is 40～150KOH/g, and solid content is 40～70wt%, and mean molecular weight is 8000～15000; Its preparation process is as follows:
(1), in organic solvent, add the compound (a) in molecule with more than 2 ring-type ether, then add unsaturated monocarboxylic (b) and catalyzer, at 100～160 ℃, react 8～36 hours to obtain reaction product (c);
The compound (a) wherein in molecule with more than 2 ring-type ether is Study On O-cresol Epoxy Resin, phenol novolac epoxy resins, bisphenol f type epoxy resin, bisphenol-s epoxy resin or united phenol-type epoxy resin;
Unsaturated monocarboxylic (b) is acrylic or methacrylic acid; The weight ratio in the addition of unsaturated monocarboxylic (b) and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Catalyzer is the trivalent organophosphorus compounds that carbon number is 1～12 alkyl or aryl that has of tertiary phosphine class, is specially triethyl phosphine, tributylphosphine or triphenylphosphine; The use amount of catalyzer be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.2～5.0%;
Organic solvent is the 1-Methoxy-2-propyl acetate of volatility excellence, and its use amount is 0.5～3 times of weight in molecule with the compound (a) of more than 2 ring-type ether;
(2) in the reaction product (c), making, add respectively polymerization inhibitor and after saturated or unsaturated multi-anhydride (d), at 80～150 ℃, react 6～12 hours to obtain reaction product (e) in step (1);
Saturated or unsaturated multi-anhydride (d) is maleic anhydride, phthalic anhydride, succinic anhydride, THPA or tetrabydrophthalic anhydride; The weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:1～1:3;
Polymerization inhibitor is the substituted phenol compound of phenol, is specially p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%;
(3) after adding respectively polymerization inhibitor in the reaction product (e), making in step (2) and thering is the compound (f) of olefinic unsaturated group and ring-type ether in molecule, react and within 6～12 hours, be the carboxylic photoresist of finished product quick-dry type at 80～150 ℃;
The compound (f) wherein in molecule with olefinic unsaturated group and ring-type ether is glycidyl methacrylate or acrylic acid 4-hydroxy butyl ester glycidol ether, and the weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Polymerization inhibitor is the substituted phenol compound of phenol, is specially p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%.
Another object of the present invention is to provide the preparation method of the carboxylic photoresist of above-mentioned quick-dry type.
A preparation method for the carboxylic photoresist of quick-dry type, its step is as follows:
(1), in organic solvent, add the compound (a) in molecule with more than 2 ring-type ether, then add unsaturated monocarboxylic (b) and catalyzer, at 100～160 ℃, react 8～36 hours to obtain reaction product (c);
The compound (a) wherein in molecule with more than 2 ring-type ether is Study On O-cresol Epoxy Resin, phenol novolac epoxy resins, bisphenol f type epoxy resin, bisphenol-s epoxy resin or united phenol-type epoxy resin;
Unsaturated monocarboxylic (b) is acrylic or methacrylic acid; The weight ratio in the addition of unsaturated monocarboxylic (b) and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Catalyzer is the trivalent organophosphorus compounds that carbon number is 1～12 alkyl or aryl that has of tertiary phosphine class, is specially triethyl phosphine, tributylphosphine or triphenylphosphine; The use amount of catalyzer be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.2～5.0%;
Organic solvent is the 1-Methoxy-2-propyl acetate of volatility excellence, and its use amount is 0.5～3 times of weight in molecule with the compound (a) of more than 2 ring-type ether;
(2) in the reaction product (c), making, add respectively polymerization inhibitor and after saturated or unsaturated multi-anhydride (d), at 80～150 ℃, react 6～12 hours to obtain reaction product (e) in step (1);
Saturated or unsaturated multi-anhydride (d) is maleic anhydride, phthalic anhydride, succinic anhydride, THPA or tetrabydrophthalic anhydride; The weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:1～1:3;
Polymerization inhibitor is the substituted phenol compound of phenol, is specially p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%;
(3) after adding respectively polymerization inhibitor in the reaction product (e), making in step (2) and thering is the compound (f) of olefinic unsaturated group and ring-type ether in molecule, react and within 6～12 hours, be the carboxylic photoresist of finished product quick-dry type at 80～150 ℃;
The compound (f) wherein in molecule with olefinic unsaturated group and ring-type ether is glycidyl methacrylate or acrylic acid 4-hydroxy butyl ester glycidol ether, and the weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Polymerization inhibitor is the substituted phenol compound of phenol, is specially p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%.
In the preparation method's of the carboxylic photoresist of above-mentioned quick-dry type step (1), the preferably Study On O-cresol Epoxy Resin of compound (a) in molecule with more than 2 ring-type ether, especially has 70 ℃ of above Study On O-cresol Epoxy Resins of high softening-point; The use amount of catalyzer, be preferably the compound (a) in molecule with more than 2 ring-type ether weight 0.5～3.0%, most preferably be 0.8～2.0%; Preferably 110～130 ℃ of temperature of reaction; Consumption of organic solvent is preferably 0.8～2 times of weight of the compound (a) in molecule with more than 2 ring-type ether, more preferably 1～1.5 times.
In the preparation method's of the carboxylic photoresist of above-mentioned quick-dry type step (2), the use amount of polymerization inhibitor be preferably the compound (a) in molecule with more than 2 ring-type ether weight 0.1～0.5%, more preferably 0.15～0.3%; Preferably 90～110 ℃ of temperature of reaction.
In the preparation method's of the carboxylic photoresist of above-mentioned quick-dry type step (3), the use amount of polymerization inhibitor be preferably the compound (a) in molecule with more than 2 ring-type ether weight 0.1～0.5%, more preferably 0.15～0.3%; Preferably 90～110 ℃ of temperature of reaction.
Contain the alkaline video picture type of one of the present invention Photosensitve resin composition, it comprises the component of following percentage by weight:
(1), the carboxylic photoresist 20～35 of quick-dry type
(2), quick-dry type acrylate polymer 5～25
(3), in molecule, contain the composition 5～15 of more than 2 compound of olefinic unsaturated group
(4), photoinitiator composite 3～10
(5), filler 35～50
The acid value of quick-dry type acrylate polymer is 40～150KOH/g, and solid content is 40～70wt%, and mean molecular weight is 5000～10000;
Quick-dry type acrylate polymer is prepared by following method, in organic solvent (I), add unsaturated monocarboxylic (b '), add again the acrylate that contains single olefinic unsaturated group in molecule (a ') and azo-initiator (c '), then at 80～160 ℃ of reactions quick-dry type acrylate polymer that gets product for 8～24 hours;
Wherein in the preparation method of above-mentioned quick-dry type acrylate polymer, and unsaturated monocarboxylic (b ') be acrylic or methacrylic acid;
Organic solvent (I) is 1-Methoxy-2-propyl acetate or the propylene glycol monomethyl ether organic solvent of volatility excellence, and the weight ratio of the addition of organic solvent (I) and unsaturated monocarboxylic (b ') is 2:1～8:1;
The acrylate (a ') that contains single olefinic unsaturated group in molecule is the potpourri in methyl methacrylate and butyl acrylate, methacrylic acid benzyl ester, Isooctyl acrylate monomer or hydroxyethyl methylacrylate; The percentage by weight that methyl methacrylate contains in the acrylate (a ') of single olefinic unsaturated group in molecule is 30～70; In molecule, contain single olefinic unsaturated group acrylate (a ') addition for the weight ratio of unsaturated monocarboxylic (b ') be 2:1～5:1;
Azo-initiator (c ') be oil-soluble azo-initiator, be specially azoisobutyronitrile or ABVN; The addition of azo-initiator (c ') be unsaturated monocarboxylic (b ') weight 1～20%;
In molecule, contain more than 2 olefinic unsaturated group compound composition be the composition of trimethylolpropane triacrylate and dipentaerythritol acrylate, the percentage by weight of trimethylolpropane triacrylate and dipentaerythritol acrylate is 1:1～1:2;
Photoinitiator composite is the component of following percentage by weight:
Tetraethyl michaelis ketone 1～5
Two 2, the luxuriant titanium 0.5～1.5 of the fluoro-3-pyrroles's phenyl two of 6-bis-
2-isopropyl thioxanthone 15～25
2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-(4-morpholinyl)-1-acetone 70～80
Filler is the component of following percentage by weight:
Silica 1～5
Porcelain earth 3～10
Talcum powder 85～95;
The mean grain size of silicon dioxide is 4～8um; Kaolinic mean grain size is 4～8um; Talcous mean grain size is 3～8um.
The advantage that the present invention has is: contain film that alkaline video picture type Photosensitve resin composition of the present invention forms in middle high temperature (80～130 ℃) prebake conditions after two minutes, dry to touch (tack-free property) excellence, under low-yield, excellent photonasty and resolution can be obtained, thereby the requirement of high precision circuit etching can be met.
Embodiment
Below, though utilize embodiments of the invention etc. can specific description, the present invention is limited by these embodiment not.
In the following example:
Study On O-cresol Epoxy Resin is that manufacture in South Asia, Kunshan, NPCN-703, epoxide number 0.45 equivalent/100g, 81 ℃ of softening points;
Tetraethyl michaelis ketone is that Jiu chemical company produces, JRCure EMK;
Two 2, the luxuriant titanium of the fluoro-3-pyrroles's phenyl two of 6-bis-is that Ciba company produces, IRGACURE 784;
2-isopropyl thioxanthone is that Jiu chemical company produces, JRCure ITX;
2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-(4-morpholinyl)-1-acetone is that Jiu chemical company produces, JRCure 907;
Silicon dioxide is that goldschmidt chemical corporation is produced, AEROSIL R974; Mean grain size is 4.5um;
Porcelain earth is that BASF AG produces, Satintone 5; Mean grain size is 5.0um;
Talcum powder is that talcum company of Fuji produces, LMS-200; Mean grain size is 6.0um.
Example 1,
(1), possessing thermometer, reflux condensing tube, in the removable flask of 2L of stirrer, add 360g Study On O-cresol Epoxy Resin, 125g acrylic acid, 2.5g is as the triphenylphosphine of catalyzer, 450g 1-Methoxy-2-propyl acetate is as solvent, then be warmed up to 115 ℃ of reactions 12 hours, after being cooled to again 60 ℃, add 250g phthalic anhydride, 0.8g is as the p methoxy phenol of polymerization inhibitor, be warmed up to 100 ℃ of reactions 8 hours, after cooling to again 60 ℃, add glycidyl methacrylate 100g, 0.6g is as the p-dihydroxy-benzene of polymerization inhibitor, control 95 ℃ of reactions of temperature 8 hours, obtain the carboxylic photoresist of a kind of quick-dry type of the present invention, the carboxylic photoresist solid content of this quick-dry type is 65wt%, and acid value is 55～65mgKOH/g, and mean molecular weight is 10000,
(2) in the removable flask of the 2L that possesses thermometer, reflux condensing tube, stirrer, add 90g acrylic acid, 480g 1-Methoxy-2-propyl acetate as solvent, add again potpourri and the 7g ABVN of 200g methyl methacrylate and 100g hydroxyethyl methylacrylate composition, be warmed up to 90 ℃ of reactions 10 hours, obtain the carboxylic photoresist of finished product quick-dry type; The carboxylic photoresist solid content of this quick-dry type is 45wt%, and acid value is 50～60mgKOH/g, and mean molecular weight is 6000;
(3), by the carboxylic photoresist of quick-dry type making in 450 g steps (1), the quick-dry type acrylate polymer making in 400g step (2), 100g trimethylolpropane triacrylate, 100g dipentaerythritol acrylate, 2.5g tetraethyl michaelis ketone, 1g two 2, the luxuriant titanium of the fluoro-3-pyrroles's phenyl two of 6-bis-, 25g2-isopropyl thioxanthone, 90g2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-(4-morpholinyl)-1-acetone, 25g silicon dioxide, after mixing, 50g porcelain earth and 800g talcum powder be finished product alkalescence video picture type Photosensitve resin composition.
Example 2, (1), possessing thermometer, reflux condensing tube, in the removable flask of 2L of stirrer, add 360g Study On O-cresol Epoxy Resin, 125g acrylic acid, 2.5g is as the triphenylphosphine of catalyzer, 450g 1-Methoxy-2-propyl acetate is as solvent, then be warmed up to 115 ℃ of reactions 12 hours, after being cooled to again 60 ℃, add 250g maleic anhydride, 0.8g is as the p methoxy phenol of polymerization inhibitor, be warmed up to 100 ℃ of reactions 8 hours, after cooling to again 60 ℃, add acrylic acid 4-hydroxy butyl ester glycidol ether 100g, 1.0g is as the p-dihydroxy-benzene of polymerization inhibitor, control 95 ℃ of reactions of temperature 8 hours, obtain the carboxylic photoresist of a kind of quick-dry type of the present invention, the carboxylic photoresist solid content of this quick-dry type is 65wt%, and acid value is 50～60mgKOH/g, and mean molecular weight is 14000,
(2) in the removable flask of the 2L that possesses thermometer, reflux condensing tube, stirrer, add 90g acrylic acid, 480g 1-Methoxy-2-propyl acetate as solvent, add again potpourri and the 7g ABVN of 200g methyl methacrylate and 100g EHMA composition, be warmed up to 90 ℃ of reactions 10 hours, obtain the carboxylic photoresist of finished product quick-dry type; The carboxylic photoresist solid content of this quick-dry type is 45wt%, and acid value is 50～60mgKOH/g, and mean molecular weight is 8000;
(3), by the carboxylic photoresist of quick-dry type making in 610 g steps (1), the quick-dry type acrylate polymer making in 200g step (2), 100g trimethylolpropane triacrylate, 100g dipentaerythritol acrylate, 2.5g tetraethyl michaelis ketone, 1g two 2, the luxuriant titanium of the fluoro-3-pyrroles's phenyl two of 6-bis-, 25g2-isopropyl thioxanthone, 90g2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-(4-morpholinyl)-1-acetone, 25g silicon dioxide, after mixing, 50g porcelain earth and 800g talcum powder be finished product alkalescence video picture type Photosensitve resin composition.
The properties of the film that the finished product alkalescence video picture type Photosensitve resin composition of preparation in embodiment 1 and 2 is formed is tested relatively, evaluates, respectively in result shown in table 1.
Table 1
From the result shown in table 1, according to Photosensitve resin composition of the present invention, can obtain dry to touch excellence, can obtain high photosensitivity and excellent resolution in 100 mJ/cm2 energy left and right, and can be by the Photosensitve resin composition of alkaline video picture.
The appraisal procedure of the performance test in above-mentioned table 1 illustrates as follows.
(1) dry to touch
Each test example is coated on copper face substrate, at 120 ℃ of temperature, toasts 2min, by the light film coated surface of pressing of finger, to specific viscosity chirality difference.Determinating reference is as shown in following.
◎: represent dry to touch excellence (not having sticky hand to occur).
Zero: represent dry to touch good (having slight sticky hand to occur).
△: represent dry to touch general (having serious sticky hand to occur).
(2) sensitivity
Use 21 lattice energy gages to cover on the dry coating that each test example forms, utilize respectively 50,100,150, the ultraviolet light of 200mJ/cm2 energy exposes, carry out again alkaline video picture, finally assess lattice after video picture and count the residual lattice number (residual lattice number is the almost lattice number of complete reservation virgin state of film) of table.
Wherein, the mode of alkaline video picture is gunite, and alkaline imaging liquid is the sodium carbonate alkaline aqueous solution of 1.0wt% concentration, and imaging liquid temperature is 30 ℃, and time of developing is 1min.
(3) resolution
With above-mentioned sensitivity method, use the resolution egative film of 1.5～3.5mil to cover on the dry coating that each test example forms, utilize respectively 50,100,150, the ultraviolet light of 200mJ/cm2 energy exposes, then carries out alkaline video picture, finally assesses complete minimum resolution after video picture.
(4) development point
Each test example is coated on copper face substrate, at 120 ℃ of temperature, toasts 2min, then carry out alkaline video picture, assess the pre-baked rear clean shortest time of painting film development.
Claims (4)
1. the carboxylic photoresist of quick-dry type, the acid value that it is characterized in that it is 40～150KOH/g, and solid content is 40～70wt%, and mean molecular weight is 8000～15000; Its preparation process is as follows:
(1), in organic solvent, add the compound (a) in molecule with more than 2 ring-type ether, then add unsaturated monocarboxylic (b) and catalyzer, at 100～160 ℃, react 8～36 hours to obtain reaction product (c);
The compound (a) wherein in molecule with more than 2 ring-type ether is Study On O-cresol Epoxy Resin, phenol novolac epoxy resins, bisphenol f type epoxy resin, bisphenol-s epoxy resin or united phenol-type epoxy resin;
Unsaturated monocarboxylic (b) is acrylic or methacrylic acid; The weight ratio in the addition of unsaturated monocarboxylic (b) and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Catalyzer is the trivalent organophosphorus compounds that carbon number is 1～12 alkyl or aryl that has of tertiary phosphine class, is specially triethyl phosphine, tributylphosphine or triphenylphosphine; The use amount of catalyzer be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.2～5.0%;
Organic solvent is 1-Methoxy-2-propyl acetate, and its use amount is 0.5～3 times of weight in molecule with the compound (a) of more than 2 ring-type ether;
(2) in the reaction product (c), making, add respectively polymerization inhibitor and after saturated or unsaturated multi-anhydride (d), at 80～150 ℃, react 6～12 hours to obtain reaction product (e) in step (1);
Saturated or unsaturated multi-anhydride (d) is maleic anhydride, phthalic anhydride, succinic anhydride, THPA or tetrabydrophthalic anhydride; The weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:1～1:3;
Polymerization inhibitor is the substituted phenol compound of phenol, is specially p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%;
(3) after adding respectively polymerization inhibitor in the reaction product (e), making in step (2) and thering is the compound (f) of olefinic unsaturated group and ring-type ether in molecule, react and within 6～12 hours, be the carboxylic photoresist of finished product quick-dry type at 80～150 ℃;
The compound (f) wherein in molecule with olefinic unsaturated group and ring-type ether is glycidyl methacrylate or acrylic acid 4-hydroxy butyl ester glycidol ether, and the weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Polymerization inhibitor is the substituted phenol compound of phenol, is specially p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%.
2. a preparation method for the carboxylic photoresist of quick-dry type, its step is as follows:
(1), in organic solvent, add the compound (a) in molecule with more than 2 ring-type ether, then add unsaturated monocarboxylic (b) and catalyzer, at 100～160 ℃, react 8～36 hours to obtain reaction product (c);
The compound (a) wherein in molecule with more than 2 ring-type ether is Study On O-cresol Epoxy Resin, phenol novolac epoxy resins, bisphenol f type epoxy resin, bisphenol-s epoxy resin or united phenol-type epoxy resin;
Unsaturated monocarboxylic (b) is acrylic or methacrylic acid; The weight ratio in the addition of unsaturated monocarboxylic (b) and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Catalyzer is the trivalent organophosphorus compounds that carbon number is 1～12 alkyl or aryl that has of tertiary phosphine class, is specially triethyl phosphine, tributylphosphine or triphenylphosphine; The use amount of catalyzer be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.2～5.0%;
Organic solvent is 1-Methoxy-2-propyl acetate, and its use amount is 0.5～3 times of weight in molecule with the compound (a) of more than 2 ring-type ether;
(2) in the reaction product (c), making, add respectively polymerization inhibitor and after saturated or unsaturated multi-anhydride (d), at 80～150 ℃, react 6～12 hours to obtain reaction product (e) in step (1);
Saturated or unsaturated multi-anhydride (d) is maleic anhydride, phthalic anhydride, succinic anhydride, THPA or tetrabydrophthalic anhydride; The weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:1～1:3;
Polymerization inhibitor is p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%;
(3) after adding respectively polymerization inhibitor in the reaction product (e), making in step (2) and thering is the compound (f) of olefinic unsaturated group and ring-type ether in molecule, react and within 6～12 hours, be the carboxylic photoresist of finished product quick-dry type at 80～150 ℃;
The compound (f) wherein in molecule with olefinic unsaturated group and ring-type ether is glycidyl methacrylate or acrylic acid 4-hydroxy butyl ester glycidol ether, and the weight ratio in its addition and molecule with the compound (a) of more than 2 ring-type ether is 1:2～1:5;
Polymerization inhibitor is p-dihydroxy-benzene, MEHQ or metoxyphenol; The use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.05～1.0%.
3. the preparation method of the carboxylic photoresist of quick-dry type according to claim 2, is characterized in that
In the preparation method's of the carboxylic photoresist of quick-dry type step (1), the compound (a) in molecule with more than 2 ring-type ether is Study On O-cresol Epoxy Resin; The use amount of catalyzer be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.5～3.0%; Temperature of reaction is 110～130 ℃; Consumption of organic solvent is 0.8～2 times of weight in molecule with the compound (a) of more than 2 ring-type ether;
In the preparation method's of the carboxylic photoresist of quick-dry type step (2), the use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.1～0.5%; Temperature of reaction is 90～110 ℃;
In the preparation method's of the carboxylic photoresist of quick-dry type step (3), the use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.1～0.5%; Temperature of reaction is 90～110 ℃.
4. the preparation method of the carboxylic photoresist of quick-dry type according to claim 3, is characterized in that
In the preparation method's of the carboxylic photoresist of quick-dry type step (1), the use amount of catalyzer be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.8～2.0%; Consumption of organic solvent is 1～1.5 times of weight in molecule with the compound (a) of more than 2 ring-type ether;
In the preparation method's of the carboxylic photoresist of quick-dry type step (2), the use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.15～0.3%;
In the preparation method's of the carboxylic photoresist of quick-dry type step (3), the use amount of polymerization inhibitor be in molecule, have the compound (a) of more than 2 ring-type ether weight 0.15～0.3%.
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| CN109791356A (en) * | 2016-11-11 | 2019-05-21 | 住友电木株式会社 | Photosensitive resin composition, resin film, cured film, method for producing semiconductor device, and semiconductor device |
| CN112859518A (en) * | 2021-01-04 | 2021-05-28 | 赣州西琦光学科技有限公司 | Photosensitive dry film and preparation method thereof |
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