CN115304703B - 一种改性油墨树脂及其制备方法 - Google Patents
一种改性油墨树脂及其制备方法 Download PDFInfo
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- CN115304703B CN115304703B CN202210853046.2A CN202210853046A CN115304703B CN 115304703 B CN115304703 B CN 115304703B CN 202210853046 A CN202210853046 A CN 202210853046A CN 115304703 B CN115304703 B CN 115304703B
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- resin
- methacrylate
- acrylate
- monomer
- ink resin
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- 229920005989 resin Polymers 0.000 title claims abstract description 62
- 239000011347 resin Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 239000004593 Epoxy Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 30
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 22
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 22
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- -1 2-dimethyl oxetane Chemical compound 0.000 claims description 10
- 235000007586 terpenes Nutrition 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 8
- 150000003505 terpenes Chemical class 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 6
- 229940011051 isopropyl acetate Drugs 0.000 claims description 6
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 4
- KPPWZEMUMPFHEX-UHFFFAOYSA-N 2,4-dimethyloxetane Chemical compound CC1CC(C)O1 KPPWZEMUMPFHEX-UHFFFAOYSA-N 0.000 claims description 3
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 3
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 claims description 3
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
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- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 2
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- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- RVGLUKRYMXEQAH-UHFFFAOYSA-N 3,3-dimethyloxetane Chemical compound CC1(C)COC1 RVGLUKRYMXEQAH-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 240000000972 Agathis dammara Species 0.000 claims description 2
- 229920002871 Dammar gum Polymers 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
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- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 2
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- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 claims description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 2
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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Abstract
本发明提供了一种改性油墨树脂及其制备方法。该油墨树脂采用活性基团引发环氧单体聚合的方式，在树脂主链上接枝聚醚树脂，有效改善了油墨树脂对颜料的润湿分散效果，使得该油墨树脂广泛适用于BOPP、PE、PVC、CPP、PET等多种基材的印刷，具有附着牢度强、抗粘连性好、高光泽等优异性能。
Description
技术领域
本发明涉及油墨树脂技术领域，具体涉及一种改性油墨树脂及其制备方法。
技术背景
近年来，随着人民生活水平的提高，带动了包装工业的飞速增长，也促进了凹版油墨技术及市场的不断发展。油墨树脂是用于塑料包装印刷油墨的主体材料，其性能决定油墨的印刷适性、颜料分散性、附着牢度、油墨的毒性以及环保性能等。长期以来，我国的塑料凹印油墨以聚酰胺类苯溶型树脂为主体，油墨中含有大量的苯类溶剂，在油墨的制造、使用过程中存在着苯溶剂的挥发污染，危害生产者及消费者的健康。
目前，塑料凹版油墨逐渐从苯溶性油墨过渡到酯溶性油墨和醇酯溶性油墨。近年来出现的聚氨酯油墨和其它类型的油墨，普遍存在对颜料润湿分散性差，干燥慢等问题，影响了该类产品的推广使用。对丙烯酸酯类油墨而言，其仅在国内少数一些产品得到应用，全色谱的聚丙烯酸酯塑料凹版油墨尚无此类树脂供应。专利CN101747475B公开了一种采用丙烯酸酯、叔碳酸乙烯酯、乙酸乙烯酯、活性官能团单体为原料，制得丙烯酸预聚体，然后与环己酮与甲醛的缩聚物混合而成的油墨树脂。专利CN102241795B公开了一种采用甲基丙烯酸酯、丙烯酸酯、活性官能团单体、叔碳酸缩水甘油酯、N，N-二甲氨基丙烯酸乙酯、松香加成聚合物反应制备而成的油墨树脂。通过在聚合物上接枝松香树脂的方法，来提高油墨树脂对颜料的润湿分散性。专利CN101962481B公开了一种适合用作溶剂型颜料分散剂的高分子组合物。该树脂以环氧丙烯酸酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯制备带有环氧基团的丙烯酸共聚物为主链，将带有氨基的直链聚酯、芳环或杂环胺类化合物与主链上的环氧基团反应，实现在树脂主链上的接枝，以达到良好分散颜料的效果。专利CN102134311B公开了一种萜烯聚酯丙烯酸酯的制备方法。以萜烯马来酐、二元醇、不饱和二元酸，制得萜烯不饱和聚酯，再与含有丙烯酸基团的羧酸反应，制得萜烯聚酯丙烯酸酯。
虽然凹版油墨树脂蓬勃发展，种类繁多，但是多数树脂对颜料的分散作用较差，需要在油墨制备过程中加入助剂来提高对颜料的分散性。
发明内容
本发明要解决的技术问题是克服现有油墨树脂的缺陷，提供一种改性塑料凹版油墨树脂及其制备方法，扩宽油墨树脂的应用范围。
为了解决上述技术问题，本发明提供了如下的技术方案：
一种改性油墨树脂，以重量百分比计，由如下组分制备而成：
引发剂 0.1～0.5wt%
溶剂 40～60wt%
硬单体 5～20wt%
软单体 5～20wt%
功能单体 1～10wt%
催化剂 0.05～0.5wt%
环氧单体 5～15wt%
中和剂 0.05～0.5wt%
增粘树脂 1～10wt%；
该油墨树脂的制备方法如下：
（1）将10～30wt％的引发剂和90wt％的溶剂加入反应釜，搅拌均匀后，升温至60～85℃；
（2）待温度稳定后，将硬单体、软单体、功能单体混合均匀，在2～4小时内均匀滴入反应釜，同时滴加余量的引发剂和余量的溶剂；
（3）滴加完毕后，保持温度60～85℃，继续搅拌反应2～4小时；
（4）将催化剂加入上述反应釜中，通入环氧单体，温度70～100℃，保持反应釜压力0.1～0.3MPa，搅拌反应2～4小时；
（5）降至室温，加入中和剂，调整pH值为7～8后加入增粘树脂，搅拌均匀后出料，制得油墨树脂。
需要说明的是，上述制备步骤中，反应溶剂按照重量被分为10～30wt%的第一份，余量为第二份，步骤（1）中 “10～30wt％的引发剂”即引发剂总重量10～30％的引发剂；溶剂按照重量被分为90wt％、10wt％，步骤（1）中“90wt％的溶剂”即溶剂总重量90%的去离子水，步骤（2）中“余量的溶剂”即溶剂总重量10%的去离子水。
进一步的，所述引发剂选自偶氮二异丁腈、偶氮二异庚腈、过氧化二苯甲酰、过氧化苯甲酸特丁酯、过氧化二碳酸二异丙酯中任一种或多种。
进一步的，所述溶剂选自乙酸乙酯、乙酸正丙酯、乙酸异丙酯、乙酸丁酯、乙酸仲丁酯中任一种或多种。
进一步的，所述硬单体选自甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异丙酯、甲基丙烯酸丁酯、甲基丙烯酸异丁酯、甲基丙烯酸环己酯、甲基丙烯酸苯酯、甲基丙烯酸苄酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、苯乙烯、α-甲基苯乙烯、丙烯腈中任一种或多种。
进一步的，所述软单体选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸正辛酯、丙烯酸异辛酯、甲基丙烯酸甲氧基乙酯中任一种或多种。
进一步的，所述功能单体选自丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸-2-羟丙酯、甲基丙烯酸-2-羟丁酯、丙烯酸-4-羟丁酯中任一种或多种。
进一步的，所述催化剂选自氢氧化钠、氢氧化钾、氢氧化镁中任一种或多种。
进一步的，所述环氧单体选自环氧乙烷、环氧丙烷、氧杂环丁烷、甲基氧杂环丁烷、2，2-二甲基氧杂环丁烷、2，4-二甲基氧杂环丁烷、3，3-二甲基氧杂环丁烷中任一种或多种。
进一步的，所述中和剂选自醋酸、乳酸、磷酸、柠檬酸中任一种或多种。
进一步的，所述增粘树脂选自松香、聚合松香、松香甲酯、松香甘油酯、松香二甘醇酯、松香季戊四醇酯、松香酚醛树脂、松香萜烯酚醛树脂、萜烯树脂、达玛树脂、酚醛树脂中任一种或多种。
与现有技术相比，本发明具有以下有益效果：
本发明通过在油墨树脂主链上引入羧基、聚醚等结构，改善了油墨树脂对颜料的润湿分散作用，提高了油墨的展色性和存储稳定性。
具体实施方式
下面通过具体实施例对本发明做进一步的详述，但不应理解为是对本发明保护范围的限制。凡基于上述技术思想，利用本领域普通技术知识和惯用的技术手段所做的修改、替换、变更，均属于本发明的范围。
实施例1
改性油墨树脂的制备：
（1）将0.01公斤偶氮二异丁腈和54公斤乙酸乙酯加入反应釜，搅拌均匀后，升温至60℃；
（2）待温度稳定后，将5公斤甲基丙烯酸甲酯、14.3公斤丙烯酸甲酯和5.5公斤丙烯酸羟乙酯混合均匀，在2小时内均匀滴入反应釜，同时滴加由0.09公斤过氧化二苯甲酰和6公斤乙酸丁酯混合组成的引发剂溶液；
（3）滴加完毕后，保持温度60℃，继续搅拌反应4小时；
（4）将0.05公斤氢氧化钠加入上述反应釜中，通入10公斤环氧乙烷，温度70℃，保持反应釜压力0.1MPa，搅拌反应2小时；
（5）降至室温，加入0.05公斤醋酸，调整pH值为7后加入5公斤松香，搅拌均匀后出料，制得改性油墨树脂。
实施例2
改性油墨树脂的制备：
（1）将0.1公斤过氧化二碳酸二异丙酯和36公斤乙酸丁酯加入反应釜，搅拌均匀后，升温至85℃；
（2）待温度稳定后，将12.5公斤甲基丙烯酸乙酯、5公斤丙烯酸正丁酯、15公斤丙烯酸异辛酯和1公斤丙烯酸羟丙酯混合均匀，在3小时内均匀滴入反应釜，同时滴加由0.4公斤偶氮二异庚腈和4公斤乙酸异丙酯混合组成的引发剂溶液；
（3）滴加完毕后，保持温度72.5℃，继续搅拌反应3小时；
（4）将0.5公斤氢氧化钾加入上述反应釜中，通入15公斤氧杂环丁烷，温度85℃，保持反应釜压力0.3MPa，搅拌反应3小时；
（5）降至室温，加入0.5公斤柠檬酸，调整pH值为7.5后加入10公斤松香甘油酯，搅拌均匀后出料，制得改性油墨树脂。
实施例3
改性油墨树脂的制备：
（1）将0.09公斤过氧化二苯甲酰和45公斤乙酸正丙酯加入反应釜，搅拌均匀后，升温至72.5℃；
（2）待温度稳定后，将20公斤甲基丙烯酸环己酯、13.15公斤丙烯酸异丁酯和10公斤丙烯酸-2-羟丙酯混合均匀，在4小时内均匀滴入反应釜，同时滴加由0.21公斤过氧化二苯甲酰和5公斤乙酸正丙酯混合组成的引发剂溶液；
（3）滴加完毕后，保持温度85℃，继续搅拌反应2小时；
（4）将0.275公斤氢氧化镁加入上述反应釜中，通入2公斤环氧乙烷和3公斤2，4-二甲基氧杂环丁烷，温度100℃，保持反应釜压力0.2MPa，搅拌反应4小时；
（5）降至室温，加入0.275公斤磷酸，调整pH值为8后加入1公斤松香酚醛树脂，搅拌均匀后出料，制得改性油墨树脂。
实施例4
改性油墨树脂的制备：
（1）将0.06公斤偶氮二异庚腈和52.2公斤乙酸异丙酯加入反应釜，搅拌均匀后，升温至75℃；
（2）待温度稳定后，将15公斤甲基丙烯酸异冰片酯、5公斤丙烯酸异辛酯和8公斤丙烯酸-4-羟丁酯混合均匀，在2.5小时内均匀滴入反应釜，同时滴加由0.34公斤偶氮二异庚腈和5.8公斤乙酸异丙酯混合组成的引发剂溶液；
（3）滴加完毕后，保持温度65℃，继续搅拌反应2.5小时；
（4）将0.3公斤氢氧化钾加入上述反应釜中，通入7公斤氧杂环丁烷，温度80℃，保持反应釜压力0.15MPa，搅拌反应2.5小时；
（5）降至室温，加入0.3公斤乳酸，调整pH值为7.2后加入2公斤萜烯树脂和4公斤酚醛树脂，搅拌均匀后出料，制得改性油墨树脂。
实施例5
改性油墨树脂的制备：
（1）将0.05公斤过氧化二苯甲酰和38.7公斤乙酸丁酯加入反应釜，搅拌均匀后，升温至80℃；
（2）待温度稳定后，将8公斤甲基丙烯酸环己酯、20公斤甲基丙烯酸甲氧基乙酯和7公斤丙烯酸-4-羟丁酯混合均匀，在3.5小时内均匀滴入反应釜，同时滴加由0.15公斤过氧化二苯甲酰和4.3公斤乙酸丁酯混合组成的引发剂溶液；
（3）滴加完毕后，保持温度80℃，继续搅拌反应3.5小时；
（4）将0.35公斤氢氧化钾加入上述反应釜中，通入14公斤环氧丙烷，温度90℃，保持反应釜压力0.25MPa，搅拌反应3.5小时；
（5）降至室温，加入0.45公斤醋酸，调整pH值为7.6后加入7公斤松香甘油酯，搅拌均匀后出料，制得油墨树脂。
实施例6
凹版塑料油墨的制备：
将27公斤实施例1的改性油墨树脂、12公斤乙酸乙酯、11公斤钛白粉加入配料器，用高速分散机搅拌30分钟，使其混合均匀；将混合均匀的物料取出，送入砂磨机进行砂磨，待细度低于 10μm后取出，过滤；经检验合格后，包装，制得凹版塑料油墨。
对制备的凹版塑料油墨进行性能检测，主要技术指标如表1所示：
表1
。
以上检测结果依据 QB/T2024-2012标准测试。
对比例1
（1）将0.06公斤偶氮二异丁腈和44.73公斤乙酸乙酯加入反应釜，搅拌均匀后，升温至75℃；
（2）待温度稳定后，将22公斤甲基丙烯酸甲酯、23公斤丙烯酸异辛酯和5公斤丙烯酸羟乙酯混合均匀，在3小时内均匀滴入反应釜，同时滴加由0.24公斤偶氮二异庚腈和4.97公斤乙酸异丙酯混合组成的引发剂溶液；
（3）滴加完毕后，保持温度75℃，继续搅拌反应3小时，制得油墨树脂。
将27公斤上述所制油墨树脂、12公斤乙酸乙酯、11公斤钛白粉加入配料器，用高速分散机搅拌30分钟，使其混合均匀；将混合均匀的物料取出，送入砂磨机进行砂磨，待细度低于 10μm后取出，过滤，制得凹版塑料油墨。
对制备的凹版塑料油墨进行性能检测，主要技术指标如表2所示：
表2
。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，但本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (6)
1.一种改性油墨树脂，其特征在于，以重量百分比计，由如下组分制备而成：
引发剂 0.1～0.5wt%
溶剂 40～60wt%
硬单体 5～20wt%
软单体 5～20wt%
功能单体 1～10wt%
催化剂 0.05～0.5wt%
环氧单体 5～15wt%
中和剂 0.05～0.5wt%
增粘树脂 1～10wt%；
该油墨树脂的制备方法如下：
（1）将10～30wt％的引发剂和90wt％的溶剂加入反应釜，搅拌均匀后，升温至60～85℃；
（2）待温度稳定后，将硬单体、软单体、功能单体混合均匀，在2～4小时内均匀滴入反应釜，同时滴加余量的引发剂和余量的溶剂；
（3）滴加完毕后，保持温度60～85℃，继续搅拌反应2～4小时；
（4）将催化剂加入上述反应釜中，通入环氧单体，温度70～100℃，保持反应釜压力0.1～0.3MPa，搅拌反应2～4小时；
（5）降至室温，加入中和剂，调整pH值为7～8后加入增粘树脂，搅拌均匀后出料，制得油墨树脂；
其中，所述硬单体选自甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异丙酯、甲基丙烯酸丁酯、甲基丙烯酸异丁酯、甲基丙烯酸环己酯、甲基丙烯酸苯酯、甲基丙烯酸苄酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、苯乙烯、α-甲基苯乙烯、丙烯腈中任一种或多种；
所述软单体选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸正辛酯、丙烯酸异辛酯、甲基丙烯酸甲氧基乙酯中任一种或多种；
所述功能单体选自丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸-2-羟丙酯、甲基丙烯酸-2-羟丁酯、丙烯酸-4-羟丁酯中任一种或多种；
所述环氧单体选自环氧乙烷、环氧丙烷、氧杂环丁烷、甲基氧杂环丁烷、2，2-二甲基氧杂环丁烷、2，4-二甲基氧杂环丁烷、3，3-二甲基氧杂环丁烷中任一种或多种。
2.根据权利要求1所述的改性油墨树脂，其特征在于，所述引发剂选自偶氮二异丁腈、偶氮二异庚腈、过氧化二苯甲酰、过氧化苯甲酸特丁酯、过氧化二碳酸二异丙酯中任一种或多种。
3.根据权利要求1所述的改性油墨树脂，其特征在于，所述溶剂选自乙酸乙酯、乙酸正丙酯、乙酸异丙酯、乙酸丁酯、乙酸仲丁酯中任一种或多种。
4.根据权利要求1所述的改性油墨树脂，其特征在于，所述催化剂选自氢氧化钠、氢氧化钾、氢氧化镁中任一种或多种。
5.根据权利要求1所述的改性油墨树脂，其特征在于，所述中和剂选自醋酸、乳酸、磷酸、柠檬酸中任一种或多种。
6.根据权利要求1所述的改性油墨树脂，其特征在于，所述增粘树脂选自松香、聚合松香、松香甲酯、松香甘油酯、松香二甘醇酯、松香季戊四醇酯、松香酚醛树脂、松香萜烯酚醛树脂、萜烯树脂、达玛树脂、酚醛树脂中任一种或多种。
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