CN102746735A - Alcohol soluble polyurethane ink binder - Google Patents
Alcohol soluble polyurethane ink binder Download PDFInfo
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- CN102746735A CN102746735A CN2011100971755A CN201110097175A CN102746735A CN 102746735 A CN102746735 A CN 102746735A CN 2011100971755 A CN2011100971755 A CN 2011100971755A CN 201110097175 A CN201110097175 A CN 201110097175A CN 102746735 A CN102746735 A CN 102746735A
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- alcohol
- component
- soluble polyurethane
- gram
- polyurethane ink
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 37
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims description 42
- 239000011230 binding agent Substances 0.000 title abstract 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 15
- 229920000570 polyether Polymers 0.000 claims abstract description 15
- 229920000768 polyamine Polymers 0.000 claims abstract description 7
- 239000000853 adhesive Substances 0.000 claims description 33
- 230000001070 adhesive effect Effects 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 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 16
- 239000012895 dilution Substances 0.000 claims description 16
- 238000010790 dilution Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- -1 polyoxytrimethylene Polymers 0.000 claims description 11
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 5
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 4
- KSGWLNWYCHAFIX-UHFFFAOYSA-N triazine-4,5-diamine Chemical compound NC1=CN=NN=C1N KSGWLNWYCHAFIX-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical group CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 3
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical class CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 claims description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 235000013305 food Nutrition 0.000 abstract description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012948 isocyanate Substances 0.000 abstract description 3
- 150000002513 isocyanates Chemical class 0.000 abstract description 3
- 229920005862 polyol Polymers 0.000 abstract description 3
- 239000004593 Epoxy Substances 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 150000003077 polyols Chemical class 0.000 abstract 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- VYSYZMNJHYOXGN-UHFFFAOYSA-N ethyl n-aminocarbamate Chemical compound CCOC(=O)NN VYSYZMNJHYOXGN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
本发明属于食品包装所用的油墨连接料领域，具体涉及一种醇溶性聚氨酯油墨连接料。本发明的醇溶性聚氨酯油墨连接料包括甲组分和乙组分，甲组分是由聚醚多元醇、异氰酸酯和多元胺反应生成的端氨基聚氨酯，乙组分是由聚醚多元醇、异氰酸酯和环氧树脂反应生成的环氧树脂改性的聚氨酯。使用时，按照甲组分∶乙组分的质量比为10∶1～3混合，得到所述的醇溶性聚氨酯油墨连接料。本发明的油墨连接料中不含未反应的异氰酸酯基团，降低了其在使用过程中产生的毒性的可能，且对水气不敏感，环境适应性强。The invention belongs to the field of ink binders used in food packaging, and in particular relates to an alcohol-soluble polyurethane ink binder. The alcohol-soluble polyurethane ink binder of the present invention comprises a component and a component B. The component A is an amino-terminated polyurethane formed by the reaction of polyether polyol, isocyanate and polyamine, and component B is composed of polyether polyol, isocyanate Epoxy modified polyurethane produced by reacting with epoxy resin. When in use, the mass ratio of component A: component B is 10:1-3 and mixed to obtain the alcohol-soluble polyurethane ink binder. The ink binder of the invention does not contain unreacted isocyanate groups, which reduces the possibility of toxicity during use, is insensitive to moisture, and has strong environmental adaptability.
Description
Technical field
The invention belongs to the used ink adhesive field of food product pack, be specifically related to a kind of alcohol-soluble polyurethane ink adhesive.
Background technology
In the ester soluble polyurethane ink adhesive that uses at present, there is the free polyisocynate monomer of higher isocyanate groups of content and severe toxicity, makes this type ink adhesive in use great injury arranged human body.Use the made food pack of this type of ink adhesive simultaneously in storage and use, the hydrolysis of tolylene diisocyanate also might take place, discharge tolylene diamine and get in the food, human body is had potential harm.In addition, esters solvent has certain toxicity and pungency, and is very big to human harm, also can pollute environment.
The host of alcohol-soluble polyurethane ink adhesive and solidifying agent all do not contain isocyano group and free isocyanate-monomer; Use industrial alcohol to make solvent and just can satisfy request for utilization; Thereby be a kind of environmentfriendly products; Represent the developing direction of polyurethane oil ink connecting material, causing people's extensive concern.A kind of epoxide modified monocomponent polyurethane adhesive is disclosed in CN101358122.Hydroxyl through polyol compound makes epoxy ring-opening under high temperature, catalyzer existence condition, generate the epoxy resin modification polyvalent alcohol that has hydroxyl, again with isocyanate reaction generate need not solidifying agent can solidified modification monocomponent polyurethane adhesive.This method inserts epoxy resin in the polymer molecular chain, has improved the cohesive strength of tackiness agent, but this tackiness agent second-order transition temperature is high, and snappiness is not enough.A kind of pure dissolubility dual-component polyurethane adhesive is disclosed in CN1970672.This tackiness agent reacts the amino urethane of the end that generates as host by polyether glycol, isocyanic ester and polyamine, and epoxy resin is as solidifying agent.Because epoxy resin is insoluble to alcoholic solvent, has influenced the curing of this tackiness agent.
Summary of the invention
The purpose of this invention is to provide the used alcohol-soluble polyurethane ink adhesive of a kind of food product pack.
The used alcohol-soluble polyurethane ink adhesive of food product pack of the present invention comprises first component and second component; The first component is the amino urethane of end that is generated by polyether glycol, isocyanic ester and polyamine reaction, and the second component is the urethane by the epoxy resin modification of polyether glycol, isocyanic ester and epoxy resin reaction generation.Weight part with polyether glycol is a benchmark, specifically is to be prepared by following method:
Under the room temperature, the polyether glycol of 20～35 weight parts, the isocyanic ester of 1～10 weight part and the catalyzer of 0.01～0.05 weight part are stirred, be warming up to 60～100 ℃ of reactions 1～4 hour; Be cooled to room temperature; After adding the isopropanol of 20～30 weight parts, the polyamine that adds 0.2～2 weight part reacted 0.5～2 hour, added ethanol then and diluted; Making the solid content in the solution that obtains after the dilution is 20wt%～50wt%, obtains described first component;
Under the room temperature; The polyether glycol of 20～35 weight parts, the isocyanic ester of 1～10 weight part and the catalyzer of 0.01～0.05 weight part are stirred, be warming up to 60～100 ℃ of reactions 1～4 hour, add 1～5 parts by weight of epoxy resin and continue reaction 2～5 hours; Reduce to room temperature; Add ethanol then and dilute, making the solid content in the solution that obtains after the dilution is 20wt%～50wt%, obtains described second component;
During use, according to the first component: the mass ratio of second component is 10: 1～3 to mix, and obtains described alcohol-soluble polyurethane ink adhesive.
The number-average molecular weight scope of described polyether glycol is 1000～8000.
Described polyether glycol is polyoxytrimethylene polyvalent alcohol or THF homopolymer ethoxylated polyhydric alcohol.
Described isocyanic ester is selected from one or more in tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, the isophorone diisocyanate.
Described catalyzer is selected from one or more in stannous octoate, dibutyl tin laurate, Dibutyltin oxide, tetrabutyl tin, tin protochloride, titanium ethanolate, tetrabutyl titanate, metatitanic acid four isobutylates, the metatitanic acid four Virahol esters.
Described polyamine is selected from quadrol, hexanediamine, isophorone diamine, 4, one or more in 4 '-ditan diamines, benzidine, the triazinediamine.
Described epoxy resin is selected from one or more in bisphenol A type epoxy resin, bisphenol f type epoxy resin, the dihydroxyphenyl propane D type epoxy resin.
Alcohol-soluble polyurethane ink adhesive of the present invention has been compared following advantage with ester soluble polyurethane ink adhesive:
(1) do not contain unreacted isocyanate groups (in feeding intake in this alcohol-soluble polyurethane ink adhesive; The content of reactive hydrogen is greater than the amount of isocyanate group; Even moreover unreacted isocyanate group arranged; Because solvent is an ethanol, isocyanate group also can fall with the alcoholic acid hydroxyl reaction), reduced its in use toxigenous possibility.
(2) this alcohol-soluble polyurethane ink adhesive is insensitive to aqueous vapor, and is strong to the flexibility of environment.
(3) the used solvent of this alcohol-soluble polyurethane ink adhesive is an alcoholic solvent, than esters solvent, helps the reduction of product cost, reduces environmental pollution.
Embodiment
Embodiment 1
The preparation of first component: under the room temperature, 20 gram polyoxypropyleneglycols (number-average molecular weight is 1000), 1 gram tolylene diisocyanate and 0.01 gram dibutyl tin laurate are stirred, be warming up to 60 ℃ of reactions 1 hour; Reduce to room temperature; After adding 20 gram isopropanol, added 0.2 gram reacting ethylenediamine 0.5 hour, add ethanol then and dilute; Making the solid content in the solution that obtains after the dilution is 20wt%, obtains the first component.
The preparation of second component: under the room temperature, 20 gram polyoxypropyleneglycols (number-average molecular weight is 1000), 1 gram tolylene diisocyanate and 0.01 gram dibutyl tin laurate are stirred, be warming up to 60 ℃; Reacted 1 hour; Add 1 gram bisphenol A type epoxy resin and continue reaction 2 hours, reduce to room temperature, add ethanol then and dilute; Making the solid content in the solution that obtains after the dilution is 20wt%, obtains the second component.
During use, according to the first component: the mass ratio of second component is to mix at 10: 1, obtains the alcohol-soluble polyurethane ink adhesive.
Embodiment 2
The preparation of first component: under the room temperature, 27.5 gram PTMGs (number-average molecular weight is 4500), 5.5 gram isophorone diisocyanates and 0.03 gram stannous octoate are stirred, be warming up to 80 ℃ of reactions 2.5 hours; Reduce to room temperature; After adding 25 gram isopropanol, add 1.1 restrain oneself diamine reactants 1.25 hours, add ethanol then and dilute; Making the solid content in the solution that obtains after the dilution is 35wt%, obtains the first component.
The preparation of second component: under the room temperature, 27.5 gram PTMGs (number-average molecular weight is 4500), 5.5 gram isophorone diisocyanates and 0.03 gram stannous octoate are stirred, be warming up to 80 ℃; Reacted 2.5 hours; Add 3 gram bisphenol f type epoxy resins and continue reaction 3.5 hours, reduce to room temperature, add ethanol then and dilute; Making the solid content in the solution that obtains after the dilution is 35wt%, obtains the second component.
During use, according to the first component: the mass ratio of second component is to mix at 10: 2, obtains the alcohol-soluble polyurethane ink adhesive.
Embodiment 3
The preparation of first component: under the room temperature, 35 gram PTMGs (number-average molecular weight is 8000), 10 gram diphenylmethanediisocyanates and 0.05 gram Dibutyltin oxide are stirred, be warming up to 100 ℃ of reactions 4 hours; Reduce to room temperature; After adding 30 gram isopropanol, add 2 gram isophorone diamine reactions 2 hours, add ethanol then and dilute; Making the solid content in the solution that obtains after the dilution is 50wt%, obtains the first component.
The preparation of second component: under the room temperature; 35 gram PTMGs (number-average molecular weight is 8000), 10 gram diphenylmethanediisocyanates and 0.05 gram Dibutyltin oxide are stirred, be warming up to 100 ℃ of reactions 4 hours, add 5 gram dihydroxyphenyl propane D type epoxy resin and continue reaction 5 hours; Reduce to room temperature; Add ethanol then and dilute, making the solid content in the solution that obtains after the dilution is 50wt%, obtains the second component.
During use, according to the first component: the mass ratio of second component is to mix at 10: 3, obtains the alcohol-soluble polyurethane ink adhesive.
Embodiment 4
The preparation of first component: under the room temperature; 10 gram polyoxytrimethylene divalent alcohol (number-average molecular weight is 1000), 10 gram PTMGs (number-average molecular weight is 1000), 0.5 gram tolylene diisocyanate, 0.5 gram diphenylmethanediisocyanate, 0.005 gram stannous octoate and 0.005 gram Dibutyltin oxide are stirred; Be warming up to 60 ℃ of reactions 1 hour, reduce to room temperature, after the adding 20 gram isopropanol; Add 0.1 gram quadrol, 0.1 gram isophorone diamine reaction 0.5 hour; Add ethanol then and dilute, making the solid content in the solution that obtains after the dilution is 20wt%, obtains the first component.
The preparation of second component: under the room temperature; 5 gram polyoxytrimethylene trivalent alcohols (number-average molecular weight is 1000), 15 gram PTMGs (number-average molecular weight is 1000), 0.5 gram isophorone diisocyanate, 0.5 gram diphenylmethanediisocyanate, 0.005 gram Dibutyltin oxide and 0.005 gram tetrabutyl titanate are stirred; Be warming up to 60 ℃ of reactions 1 hour; Add 0.5 gram bisphenol A type epoxy resin and 0.5 gram dihydroxyphenyl propane D type epoxy resin continuation reaction 2 hours, reduce to room temperature, add ethanol then and dilute; Making the solid content in the solution that obtains after the dilution is 20wt%, obtains the second component.
During use, according to the first component: the mass ratio of second component is to mix at 10: 1, obtains the alcohol-soluble polyurethane ink adhesive.
Embodiment 5
The preparation of first component: under the room temperature; 10 gram polyoxytrimethylene divalent alcohol (number-average molecular weight is 4500), 17.5 gram PTMG triols (number-average molecular weight is 4500), 3 gram hexamethylene diisocyanates, 2.5 gram isophorone diisocyanates, 0.01 gram Dibutyltin oxide, 0.02 gram tetrabutyl titanate are stirred; Be warming up to 80 ℃ of reactions 2.5 hours, reduce to room temperature, after the adding 25 gram isopropanol; Add 0.5 gram benzidine, 0.6 gram triazinediamine reaction 1.25 hours; Add ethanol then and dilute, making the solid content in the solution that obtains after the dilution is 35wt%, obtains the first component.
The preparation of second component: under the room temperature; 15 gram polyoxytrimethylene trivalent alcohols (number-average molecular weight is 4500), 12.5 gram PTMGs (number-average molecular weight is 4500), 2.5 gram diphenylmethanediisocyanates, 3 gram isophorone diisocyanates, 0.02 gram tin protochloride and 0.01 gram metatitanic acid, four isobutylates are stirred; Be warming up to 80 ℃ of reactions 2.5 hours; Add 1 gram bisphenol A type epoxy resin, 2 gram dihydroxyphenyl propane D type epoxy resin continuation reactions 3.5 hours, reduce to room temperature, add ethanol then and dilute; Making the solid content in the solution that obtains after the dilution is 35wt%, obtains the second component.
During use, according to the first component: the mass ratio of second component is to mix at 10: 2, obtains the alcohol-soluble polyurethane ink adhesive.
Embodiment 6
The preparation of first component: under the room temperature; 15 gram polyoxytrimethylene divalent alcohol (number-average molecular weight is 8000), 20 gram PTMGs (number-average molecular weight is 8000), 6 gram diphenylmethanediisocyanates, 4 gram hexamethylene diisocyanates, 0.03 gram tetrabutyl tin and 0.02 gram tin protochloride are stirred, be warming up to 100 ℃ of reactions 4 hours, reduce to room temperature; After adding 30 gram isopropanol; Add 1 gram 4,4 '-ditan diamines, 1 gram triazinediamine reaction 2 hours add ethanol then and dilute; Making the solid content in the solution that obtains after the dilution is 50wt%, obtains the first component.
The preparation of second component: under the room temperature; 20 gram polyoxytrimethylene triols (number-average molecular weight is 8000), 15 gram PTMG triols (number-average molecular weight is 8000), 3 gram tolylene diisocyanates, 5 gram diphenylmethanediisocyanates, 2 gram isophorone diisocyanates, 0.01 gram dibutyl tin laurate, 0.01 gram Dibutyltin oxide, 0.03 gram titanium ethanolate are stirred; Be warming up to 100 ℃ of reactions 4 hours; Add 2 gram bisphenol A type epoxy resins, 1 gram bisphenol f type epoxy resin and 2 gram dihydroxyphenyl propane D type epoxy resin and continue reaction 5 hours; Reduce to room temperature; Add ethanol then and dilute, making the solid content in the solution that obtains after the dilution is 50wt%, obtains the second component.
During use, according to the first component: the mass ratio of second component is to mix at 10: 3, obtains the alcohol-soluble polyurethane ink adhesive.
Claims (7)
1. an alcohol-soluble polyurethane ink adhesive comprises first component and second component, it is characterized in that, and be benchmark with the weight part of polyether glycol, described alcohol-soluble polyurethane ink adhesive is to be prepared by following method:
Under the room temperature, the polyether glycol of 20～35 weight parts, the isocyanic ester of 1～10 weight part and the catalyzer of 0.01～0.05 weight part are stirred, be warming up to 60～100 ℃ of reactions 1～4 hour; Be cooled to room temperature; After adding the isopropanol of 20～30 weight parts, the polyamine that adds 0.2～2 weight part reacted 0.5～2 hour, added ethanol then and diluted; Making the solid content in the solution that obtains after the dilution is 20wt%～50wt%, obtains described first component;
Under the room temperature; The polyether glycol of 20～35 weight parts, the isocyanic ester of 1～10 weight part and the catalyzer of 0.01～0.05 weight part are stirred, be warming up to 60～100 ℃ of reactions 1～4 hour, add 1～5 parts by weight of epoxy resin and continue reaction 2～5 hours; Reduce to room temperature; Add ethanol then and dilute, making the solid content in the solution that obtains after the dilution is 20wt%～50wt%, obtains described second component;
During use, according to the first component: the mass ratio of second component is 10: 1～3 to mix, and obtains described alcohol-soluble polyurethane ink adhesive.
2. according to right 1 described alcohol-soluble polyurethane ink adhesive, it is characterized in that: the number-average molecular weight scope of described polyether glycol is 1000～8000.
3. alcohol-soluble polyurethane ink adhesive according to claim 1 and 2 is characterized in that: described polyether glycol is polyoxytrimethylene polyvalent alcohol or THF homopolymer ethoxylated polyhydric alcohol.
4. alcohol-soluble polyurethane ink adhesive according to claim 1 is characterized in that: described isocyanic ester is selected from one or more in tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, the isophorone diisocyanate.
5. alcohol-soluble polyurethane ink adhesive according to claim 1 is characterized in that: described catalyzer is selected from one or more in stannous octoate, dibutyl tin laurate, Dibutyltin oxide, tetrabutyl tin, tin protochloride, titanium ethanolate, tetrabutyl titanate, metatitanic acid four isobutylates, the metatitanic acid four Virahol esters.
6. alcohol-soluble polyurethane ink adhesive according to claim 1 is characterized in that: described polyamine is selected from quadrol, hexanediamine, isophorone diamine, 4, one or more in 4 '-ditan diamines, benzidine, the triazinediamine.
7. alcohol-soluble polyurethane ink adhesive according to claim 1 is characterized in that: described epoxy resin is selected from one or more in bisphenol A type epoxy resin, bisphenol f type epoxy resin, the dihydroxyphenyl propane D type epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110097175.5A CN102746735B (en) | 2011-04-18 | 2011-04-18 | Alcohol soluble polyurethane ink binder |
Applications Claiming Priority (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085862A (en) * | 2015-09-14 | 2015-11-25 | 中山市新辉化学制品有限公司 | Curing agent and preparation method of two-component alcohol-soluble polyurethane adhesive for composite film |
| CN105255256A (en) * | 2015-11-13 | 2016-01-20 | 南雄市星辉化工新材料有限公司 | Environment-friendly one-component high-temperature-steaming-resisting table printing ink and preparation method thereof |
| CN108840984A (en) * | 2018-07-09 | 2018-11-20 | 广州茵诺威化工有限公司 | Polyurethane modified epoxy resin and solvent-free PET film ink special and preparation method thereof |
| CN112279989A (en) * | 2020-10-30 | 2021-01-29 | 南通高盟新材料有限公司 | Alcohol-soluble polyurethane ink binder and preparation method thereof |
| CN113444219A (en) * | 2021-08-31 | 2021-09-28 | 苏州高泰电子技术股份有限公司 | Polyisocyanate prepolymer, rosin modified epoxy resin and conductive ink |
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| US4000214A (en) * | 1973-05-29 | 1976-12-28 | Reichhold Chemicals, Inc. | Urethane additive to a standard epoxy resin to improve adhesion to vinyl materials |
| CN101914362A (en) * | 2010-08-10 | 2010-12-15 | 上海材料研究所 | A kind of normal temperature curable two-component adhesive and its synthesis method |
| CN101993628A (en) * | 2009-08-12 | 2011-03-30 | 成都市新津托展油墨有限公司 | Method for preparing alcohol-soluble bi-component thermophilic digestion-resistant plastic composite gravure printing ink |
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| US4000214A (en) * | 1973-05-29 | 1976-12-28 | Reichhold Chemicals, Inc. | Urethane additive to a standard epoxy resin to improve adhesion to vinyl materials |
| CN101993628A (en) * | 2009-08-12 | 2011-03-30 | 成都市新津托展油墨有限公司 | Method for preparing alcohol-soluble bi-component thermophilic digestion-resistant plastic composite gravure printing ink |
| CN101914362A (en) * | 2010-08-10 | 2010-12-15 | 上海材料研究所 | A kind of normal temperature curable two-component adhesive and its synthesis method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085862A (en) * | 2015-09-14 | 2015-11-25 | 中山市新辉化学制品有限公司 | Curing agent and preparation method of two-component alcohol-soluble polyurethane adhesive for composite film |
| CN105255256A (en) * | 2015-11-13 | 2016-01-20 | 南雄市星辉化工新材料有限公司 | Environment-friendly one-component high-temperature-steaming-resisting table printing ink and preparation method thereof |
| CN108840984A (en) * | 2018-07-09 | 2018-11-20 | 广州茵诺威化工有限公司 | Polyurethane modified epoxy resin and solvent-free PET film ink special and preparation method thereof |
| CN108840984B (en) * | 2018-07-09 | 2021-08-13 | 广州茵诺威化工有限公司 | Special ink for polyurethane modified epoxy resin and solvent-free PET (polyethylene terephthalate) film and preparation method thereof |
| CN112279989A (en) * | 2020-10-30 | 2021-01-29 | 南通高盟新材料有限公司 | Alcohol-soluble polyurethane ink binder and preparation method thereof |
| CN113444219A (en) * | 2021-08-31 | 2021-09-28 | 苏州高泰电子技术股份有限公司 | Polyisocyanate prepolymer, rosin modified epoxy resin and conductive ink |
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| CN102746735B (en) | 2014-03-12 |
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