CN116375962A - Polyurethane adhesive for alcohol-water soluble gravure printing ink and preparation method thereof - Google Patents
Polyurethane adhesive for alcohol-water soluble gravure printing ink and preparation method thereof Download PDFInfo
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- CN116375962A CN116375962A CN202211580032.4A CN202211580032A CN116375962A CN 116375962 A CN116375962 A CN 116375962A CN 202211580032 A CN202211580032 A CN 202211580032A CN 116375962 A CN116375962 A CN 116375962A
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- Prior art keywords
- alcohol
- parts
- polyurethane
- water soluble
- water
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 70
- 239000004814 polyurethane Substances 0.000 title claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000853 adhesive Substances 0.000 title claims abstract description 51
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 51
- 238000007646 gravure printing Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 30
- 229920000570 polyether Polymers 0.000 claims abstract description 30
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 29
- 150000002009 diols Chemical class 0.000 claims abstract description 24
- 229920000728 polyester Polymers 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000004970 Chain extender Substances 0.000 claims abstract description 11
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000003085 diluting agent Substances 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 44
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 28
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 22
- 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 17
- 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 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical group 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- -1 polypropylene adipate Polymers 0.000 claims description 8
- MEBJLVMIIRFIJS-UHFFFAOYSA-N hexanedioic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)CCCCC(O)=O MEBJLVMIIRFIJS-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 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
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- 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 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 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 2
- 238000001035 drying Methods 0.000 abstract description 13
- 239000012046 mixed solvent Substances 0.000 abstract description 7
- 125000003277 amino group Chemical group 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 73
- 239000000203 mixture Substances 0.000 description 14
- 238000007639 printing Methods 0.000 description 12
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- 210000003813 thumb Anatomy 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229920006267 polyester film Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920005586 poly(adipic acid) Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- VGHCVSPDKSEROA-UHFFFAOYSA-N 2-methyl-1,4-dioxecane-5,10-dione Chemical compound CC1COC(=O)CCCCC(=O)O1 VGHCVSPDKSEROA-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- BZNOBFUQYZPVBC-UHFFFAOYSA-N hexanedioic acid;3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO.OC(=O)CCCCC(O)=O BZNOBFUQYZPVBC-UHFFFAOYSA-N 0.000 description 2
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5072—Polyethers having heteroatoms other than oxygen containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a polyurethane adhesive for alcohol-water soluble gravure printing ink and a preparation method thereof, wherein the polyurethane adhesive comprises the following raw materials in parts by weight: 60-85 parts of polyester diol, 3-9 parts of sulfonate polyether diol, 10-30 parts of diisocyanate, 2-8 parts of amine chain extender, 0.01-0.1 part of catalyst, 80-120 parts of alcohol diluent and 80-120 parts of deionized water. The polyurethane adhesive for the alcohol-water soluble gravure printing ink and the preparation method thereof provided by the invention are soluble in a mixed solvent of alcohol and water, and can effectively solve the problems of low drying speed and low production efficiency of the existing water-based ink when being used in the ink.
Description
Technical Field
The invention belongs to the technical field of printing ink, and particularly relates to a polyurethane adhesive for alcohol-water soluble gravure printing ink and a preparation method thereof.
Background
The water-based ink emerging in the gravure printing market in recent years takes water as a solvent, so that the pollution of volatile organic compounds is reduced, the environment is protected, but the water has high volatilization latent heat and low drying speed, and the high-speed printing requirement of a gravure machine cannot be met; the drying speed can be partially improved by adding alcohol into the ink, and the machine speed reaches 150-180 m/min, but compared with the machine speed of 300-350 m/min of solvent type gravure printing ink, the printing speed is still lower, the production efficiency is low, and the product lacks market competitiveness.
The alcohol-water soluble polyurethane adhesive solves the problem, can be dissolved in a mixed solvent of ethanol and water, and the ink prepared by the adhesive has the advantages of high drying speed, high printing speed, small smell, low VOC emission and capability of greatly improving the workshop operation environment; meanwhile, the low volatility of water enables the ink to have the advantage of low combustibility, so that the fire hazard caused by static electricity and flammable solvents can be reduced, and the safety of the ink is greatly improved.
Disclosure of Invention
Based on the technical problems, the invention provides a polyurethane adhesive for alcohol-water soluble gravure printing ink and a preparation method thereof, wherein the polyurethane adhesive is soluble in a mixed solvent of alcohol and water, and can effectively solve the problems of low drying speed and low production efficiency of the existing water-based ink when being used in the ink.
The invention provides a polyurethane adhesive for alcohol-water soluble gravure printing ink, which comprises the following raw materials in parts by weight: 60-85 parts of polyester diol, 3-9 parts of sulfonate polyether diol, 10-30 parts of diisocyanate, 2-8 parts of amine chain extender, 0.01-0.1 part of catalyst, 80-120 parts of alcohol diluent and 80-120 parts of deionized water; wherein the polyester diol is polypropylene adipate with molecular weight of 500-4000.
In the invention, sulfonate polyether glycol is selected as a polyol monomer, and a water-tolerant group of sulfonate is introduced into a main chain structure of polyurethane molecules, so that the water solubility of the obtained polyurethane is improved; however, the existence of the monopure water capacitive group can reduce the alcohol solubility of polyurethane, and the alcohol capacitive group of the poly (propylene adipate) can be further introduced into the main chain structure of polyurethane molecules by selecting the poly (propylene adipate) with the molecular weight of 500-4000 as a polyol monomer, so that the alcohol solubility of the obtained polyurethane is obviously improved; according to the invention, the reasonable selection of the two polyol monomers is integrated, so that polyurethane which is soluble in an alcohol solvent and has good hydrophilicity is obtained, and the effective solubility of the alcohol-water mixed solvent is finally shown.
Preferably, the polyester diol is at least one of poly (1, 2-propanediol adipate) with molecular weight of 1000, 2000 or 3000.
In the invention, when the polyester diol is specifically poly (1, 2-propanediol adipate) with molecular weight of 1000, 2000 or 3000, besides the alcohol water solubility of the obtained polyurethane adhesive can be further improved, the ester group has stronger polarity, and the capability of forming hydrogen bonds is stronger, and the intermolecular acting force is larger, so that the obtained polyurethane adhesive has the advantages of good pigment dispersibility, large cohesive energy, strong adhesive force, higher wear resistance, good heat resistance and the like.
Preferably, the sulfonate polyether glycol is a SulfadiolGS-7Q polyether glycol.
In the invention, the Sulfadiol GS-7Q polyether glycol contains both a sulfonate hydrophilic group and an ether bond capable of promoting the solubility of polyurethane alcohol, so that the selective addition of GS-7Q can further promote the alcohol water solubility of the obtained polyurethane adhesive.
Preferably, the mass ratio of the polyester diol to the sulfonate polyether diol is 9-16:1.
In the invention, the alcohol water solubility of the polyurethane adhesive is not brought by a single water solubility or an alcohol solubility improving monomer, but is brought by the fact that the sulfonate polyether glycol and the polypropylene glycol adipate are compounded and meet a certain proportioning relationship, so that the whole polyurethane can just meet the solubility characteristic of the alcohol water solubility; the invention therefore defines a mass ratio of the polyester diol to the sulfonate polyether diol of 9-16:1, which further optimizes the alcohol water solubility of the polyurethane adhesive.
Preferably, the diisocyanate is at least one of isophorone diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane-4, 4' -diisocyanate, 1, 6-hexamethylene diisocyanate or tetramethylxylylene diisocyanate.
In the invention, the specific selection of diisocyanate can lead the polyurethane adhesive to have better yellowing resistance, water resistance and heat resistance.
Preferably, the amine chain extender is at least one of ethylenediamine, isophoronediamine, hexamethylenediamine or diethylenetriamine.
In the invention, the amine chain extender is used as a rear chain extender to improve the molecular weight, the thermal stability and the water resistance of the polyurethane to a certain extent.
Preferably, the catalyst is at least one of organobismuth, tetrabutyl titanate, stannous octoate or stannous chloride; the alcohol solvent is at least one of isopropanol, ethanol or n-propanol.
In the invention, the alcohol solvent is adopted as the diluent, so that the method has the advantages of easy treatment, safety, environmental protection, recycling and the like.
The invention also provides a preparation method of the polyurethane adhesive for the alcohol-water soluble gravure printing ink, which comprises the following steps:
s1, mixing polyester diol, sulfonate polyether diol, diisocyanate and a catalyst, and performing a prepolymerization reaction to obtain an NCO group-terminated polyurethane prepolymer;
s2, adding the NCO-terminated polyurethane prepolymer into a solution formed by mixing an amine chain extender, an alcohol diluent and deionized water for chain extension reaction, and obtaining the polyurethane adhesive for the alcohol-water soluble gravure printing ink.
According to the invention, the polyurethane prepolymer which is soluble in alcohol solvents and has good hydrophilicity is synthesized by selecting the raw materials of polyester diol, sulfonate polyether diol and diisocyanate, and then amine chain extender is added for post chain extension, so that the obtained polyurethane is ensured to have ordered structure and controllable reaction by the process method; the polyurethane adhesive is used for manufacturing alcohol-water ink, and the obtained alcohol-water ink has the advantages of small smell, low VOC emission, nonflammability, high drying speed, good adhesion to plastic substrates such as PET, OPP and the like, high composite strength, fresh and beautiful color of printed matters and strong layering sense.
Preferably, in the step S1, the temperature of the prepolymerization reaction is 80-90 ℃ and the time is 2-6h; in the step S2, the temperature of the chain extension reaction is 30-50 ℃ and the time is 2-4h.
Preferably, the NCO content of the NCO-terminated polyurethane prepolymer is 1.4-2.2%.
In the present invention, whether the prepared reaction product is acceptable or not is confirmed by limiting the NCO content in the terminal NCO-based polyurethane prepolymer.
Preferably, the polyurethane adhesive for alcohol-water soluble gravure ink has a rotational viscosity of 500-1500 mpa.s at 25 ℃ and a solid content of 34-36%.
In the invention, the viscosity and the solid content of the polyurethane adhesive are limited to ensure that an emulsion with uniform viscosity, uniform particle size and uniform distribution of the emulsion is formed, and meanwhile, the dispersion flow of the polyurethane adhesive is facilitated, and when the emulsion is used for ink, the emulsion is conducive to the drying of the ink, so that the drying time is shortened.
Compared with the prior art, the invention has the following advantages:
in the polyurethane adhesive, sulfonate polyether glycol is introduced, sulfonate groups contained in the sulfonate polyether glycol have strong hydrophilicity, and the polyurethane adhesive is well alcohol-water-soluble through reasonable selection of polyester polyol, so that the polyurethane adhesive can be used for preparing printing ink by using a mixed solvent of alcohol and water; the use of the alcohol-water mixed solvent in the obtained printing ink can reduce VOC emission and meet the requirement of high-speed gravure printing, thereby solving the problems of low speed, low production efficiency and poor drying easiness of a common gravure polyurethane ink printer.
Detailed Description
The present invention will be described in detail by way of specific examples, which should be clearly set forth for the purpose of illustration and are not to be construed as limiting the scope of the present invention.
Example 1
The polyurethane adhesive for the alcohol-water soluble gravure printing ink is prepared by the following method:
(1) NCO-terminated polyurethane prepolymer:
| raw materials | Parts by mass |
| Poly (1, 2-propanediol adipate) (Mn=2000) | 79.2 |
| Sulfonate polyether glycol Sulfadiol GS-7Q | 4.0 |
| Isophorone diisocyanate IPDI | 16.79 |
| Organobismuth catalysts | 0.01 |
Uniformly mixing poly (adipic acid) -1, 2-propylene glycol ester (Mn=2000), sulfonate polyether glycol Sulfadiol GS-7Q, isophorone diisocyanate (IPDI) and an organobismuth catalyst according to the formula, reacting at a constant temperature of 90 ℃ for 3 hours, and measuring NCO by a di-n-butylamine titration method to obtain an NCO-terminated polyurethane prepolymer with NCO% of 2.15;
(2) Polyurethane adhesive:
| raw materials | Parts by mass |
| NCO-terminated polyurethane prepolymer in step (1) | 33.2 |
| Ethanol | 32.5 |
| Deionized water | 32.5 |
| Isophorone diamine IPDA | 1.8 |
Uniformly mixing isophorone diamine IPDA, ethanol and deionized water according to the formula to form a mixed solution, adding the NCO-terminated polyurethane prepolymer obtained in the step (1) into the mixed solution in 25min under the stirring state, and reacting at the constant temperature of 40 ℃ for 3h to obtain the transparent and stable polyurethane adhesive, wherein the viscosity is 510mpa.s and the solid content is 35.1%.
Example 2
The polyurethane adhesive for the alcohol-water soluble gravure printing ink is prepared by the following method:
(1) NCO-terminated polyurethane prepolymer:
| raw materials | Parts by mass |
| Poly (1, 2-propanediol adipate) (Mn=1000) | 65.8 |
| Sulfonate polyether glycol Sulfadiol GS-7Q | 7.7 |
| Dicyclohexylmethane diisocyanate HMDI | 26.47 |
| Tetrabutyl titanate | 0.03 |
Uniformly mixing poly (adipic acid) -1, 2-propylene glycol ester (Mn=1000), sulfonate polyether glycol Sulfadiol GS-7Q, dicyclohexylmethane diisocyanate (HMDI) and tetrabutyl titanate according to the formula, reacting at a constant temperature of 80 ℃ for 4 hours, and measuring NCO% by adopting a di-n-butylamine titration method to obtain an NCO-terminated polyurethane prepolymer with NCO% of 1.43;
(2) Polyurethane adhesive:
| raw materials | Parts by mass |
| NCO-terminated polyurethane prepolymer in step (1) | 33.8 |
| Isopropyl alcohol | 32.5 |
| Deionized water | 32.5 |
| Isofur (Isofur)Ketone diamine IPDA | 1.2 |
Uniformly mixing isophorone diamine IPDA, isopropanol and deionized water according to the formula to form a mixed solution, adding the NCO-terminated polyurethane prepolymer obtained in the step (1) into the mixed solution in 20min under stirring, and reacting at a constant temperature of 50 ℃ for 2h to obtain the transparent and stable polyurethane adhesive, wherein the viscosity is 1490mpa.s and the solid content is 35.9%.
Example 3
The polyurethane adhesive for the alcohol-water soluble gravure printing ink is prepared by the following method:
(1) NCO-terminated polyurethane prepolymer:
| raw materials | Parts by mass |
| Poly (1, 2-propanediol adipate) (mn=3000) | 80.2 |
| Sulfonate polyether glycol Sulfadiol GS-7Q | 6.0 |
| Isophorone diisocyanate IPDI | 13.78 |
| Stannous chloride | 0.02 |
Uniformly mixing poly (adipic acid) -1, 2-propylene glycol ester (Mn=3000), sulfonate polyether glycol Sulfadiol GS-7Q, isophorone diisocyanate (IPDI) and stannous chloride according to the formula, reacting at a constant temperature of 90 ℃ for 3 hours, and measuring NCO by a di-n-butylamine titration method to obtain an NCO-terminated polyurethane prepolymer with NCO% of 1.74;
(2) Polyurethane adhesive:
uniformly mixing isophorone diamine IPDA, n-propanol and deionized water according to the formula to form a mixed solution, adding the NCO-terminated polyurethane prepolymer obtained in the step (1) into the mixed solution in 30min under the stirring state, and reacting at the constant temperature of 40 ℃ for 3h to obtain the transparent and stable polyurethane adhesive, wherein the viscosity is 1090mpa.s and the solid content is 35.4%.
Comparative example 1
A polyurethane adhesive, which is prepared by the following method:
(1) NCO-terminated polyurethane prepolymer:
| raw materials | Parts by mass |
| Poly (3-methyl-1, 5-pentanediol adipate) (Mn=2000) | 79.2 |
| Sulfonate polyether glycol Sulfadiol GS-7Q | 4.0 |
| Isophorone diisocyanate IPDI | 16.79 |
| Organobismuth catalysts | 0.01 |
Uniformly mixing poly (adipic acid-3-methyl-1, 5-pentanediol) (Mn=2000), sulfonate polyether glycol SulfadiolGS-7Q, isophorone diisocyanate (IPDI) and an organic bismuth catalyst according to the formula, reacting at a constant temperature of 90 ℃ for 3 hours, and determining NCO% by adopting a di-n-butylamine titration method to obtain an NCO-terminated polyurethane prepolymer with NCO% of 2.03;
(2) Polyurethane adhesive:
uniformly mixing isophorone diamine IPDA, ethanol and deionized water according to the formula to form a mixed solution, adding the NCO-terminated polyurethane prepolymer obtained in the step (1) into the mixed solution in 25min under the stirring state, reacting at the constant temperature of 40 ℃ for 3h to obtain a turbid opaque solution, and layering the solution after standing for two hours.
Comparative example 2
A polyurethane adhesive, which is prepared by the following method:
(1) NCO-terminated polyurethane prepolymer:
| raw materials | Parts by mass |
| Poly (1, 2-propanediol adipate) (Mn=2000) | 79.2 |
| DMPA (2, 2-Dimethylolpropionic acid) | 4.0 |
| Isophorone diisocyanate IPDI | 16.79 |
| Organobismuth catalysts | 0.01 |
| Triethylamine | 2.5 |
Uniformly mixing poly (adipic acid) -1, 2-propylene glycol ester (Mn=2000), 2-dimethylolpropionic acid DMPA, isophorone diisocyanate IPDI and an organic bismuth catalyst according to the formula, reacting at a constant temperature of 90 ℃ for 3 hours, and measuring NCO% by a di-n-butylamine titration method to obtain a polyurethane prepolymer with NCO% of 2.09; reducing the temperature of the polyurethane prepolymer to 25 ℃, adding triethylamine, and stirring and reacting for 15min to obtain the fully neutralized polyurethane prepolymer with the end NCO groups;
(2) Polyurethane adhesive:
| raw materials | Parts by mass |
| NCO-terminated polyurethane prepolymer in step (1) | 33.2 |
| Ethanol | 32.5 |
| Deionized water | 32.5 |
| Isophorone diamine IPDA | 1.8 |
Uniformly mixing isophorone diamine IPDA, ethanol and deionized water according to the formula to form a mixed solution, adding the NCO-terminated polyurethane prepolymer obtained in the step (1) into the mixed solution in 25min under the stirring state, reacting at the constant temperature of 40 ℃ for 3h to obtain a turbid opaque solution, and layering the solution after standing for two hours.
The polyurethane binders obtained in examples 1 to 3 were each formulated into printing inks according to the following formulation in which the raw materials were charged to a content of 250cm 3 In the sealed plastic bottle of (2) and mixing for 2-3h by using a fast hand to obtain the printing ink composition.
Table 1 working formulation for printing ink compositions
The following performance tests were performed on the above-described printing ink composition, and the test results are shown in table 2 below:
(1) The ink primary drying test method comprises the following steps:
scraping the ink composition on a 50u scraper fineness gauge, blowing with a blower with small cold air volume for 5 seconds, rapidly lightly pressing the ink surfaces of 0-15u, 16-35u and 36-50u of fineness gauge for 1-2 seconds by using the thumb surface, and observing the residual condition of the ink on the thumb surface;
evaluation criteria: o:0-15u, 16-35u and 36-50u are free from residual ink; delta: 0-15u of thumb surface is free from ink residue, 16-35u of thumb surface is free from ink residue, and 36-50u of thumb surface is free from ink residue; x: the 0-15u thumb surface has ink residue, or the 16-35u thumb surface has ink residue.
(2) Ink attachment fastness testing method:
the ink composition was coated on the surface-treated plastic film using a wire rod so that the solid content was 2 to 3um thick. After drying with a blower, a 3M adhesive tape was stuck on the coated surface, and the adhesive tape was peeled off rapidly in a direction perpendicular to the coated surface, and the state of the coated surface was observed.
Evaluation criteria: o: the ink residue is more than 90%; delta: 50-90% of ink residue; x: the ink residue was less than 50%.
(3) The ink viscosity test method comprises the following steps:
the ink composition was warmed to room temperature (about 25 ℃), a sample of ink was poured into the 3# enrobed cup until the ink was flush with the rim of the 13 # enrobed cup and the air bubbles were scraped off with a glass rod; the time required from the start of the test sample flowing out to the time when the sample flow wire is interrupted and the first drop appears is the viscosity of the ink, and the ink viscosity test method GB/T13217.4-91 is specifically referred to.
(4) The ink fineness test method comprises the following steps:
reference is made in particular to the ink fineness test method GB/T13217.3-91.
(5) The method for testing the composite strength of the ink printing product comprises the following steps:
coating an ink composition on a surface-treated polyester film (PET) using a wire rod to have a solid content of 2-3um thick; after being dried by a blower, the two-component polyurethane adhesive is coated by a silk stick, and the sizing amount is 2-2.5g/m 3 (XUA-5070A/XUA-5070B, 100:7 ratio) and then compounding with a CPP film surface-treated, inCuring at 50 ℃ for 48 hours; preparing a sample with the width of 15mm from the composite film, measuring the T peeling strength by using a universal electronic stretcher, and taking the T peeling strength as the composite strength; the larger the number, the higher the composite strength.
(6) The ink anti-blocking test method comprises the following steps:
coating the ink composition on a surface-treated polyester film (PET) by using a silk rod to enable the solid component to be 2-3 mu m thick, and fully drying by using a blower; the coated surface was superposed with the non-coated surface, and 2.0kgf/cm was applied at a temperature of 50 ℃ 2 After 2 hours, the surface state was observed, specifically with reference to the ink anti-blocking test method GB/T13217.8-91.
Evaluation criteria: o: no adhesion is caused during stripping; delta: adhesion during stripping; x: the ink is transferred.
(7) The ink re-solubility testing method comprises the following steps:
the ink composition was applied to a glass plate to a solid content of 2 to 3 μm, stored at room temperature (about 25 ℃) for 30 seconds, and then immersed in a mixed solvent having a weight ratio of ethanol to water of 1:1, and the resolubility of the ink film was observed.
Evaluation criteria: o: redissolving the coating film; x: the coating film remains undissolved on the glass plate.
(8) The ink stability test method comprises the following steps:
after the prepared ink composition was stored at room temperature (about 25 ℃) for 30 days, the ink was observed for delamination and sedimentation.
Evaluation criteria: o: the printing ink has no layering and no precipitation; delta: the ink has no layering and a small amount of precipitation; x: the ink delaminates, or has a large amount of sediment.
Table 2 test results of ink compositions obtained in examples and comparative examples
The composite strength test results are shown in table 3:
TABLE 3 results of composite Strength test of ink compositions obtained in examples and comparative examples
From the comparison example, the transparent and stable polyurethane solution cannot be obtained by adopting poly adipic acid-3-methyl-1, 5-pentanediol ester as polyester diol in the comparison example 1 and adopting 2, 2-dimethylolpropionic acid as hydrophilic chain extender in the comparison example 2; only when the poly adipic acid-1, 2 propylene glycol ester is adopted as dihydric alcohol and the sulfonate polyether glycol is compounded as dihydric alcohol in the embodiment, transparent and stable polyurethane solution can be obtained, and when the polyurethane adhesive is used for preparing alcohol water-soluble ink, various performances are better; meanwhile, compared with examples 1 and 2, although the sulfonate polyether glycol and the polypropylene glycol adipate are compounded to serve as glycol, when the ratio of the sulfonate polyether glycol to the polypropylene glycol adipate is not 9-16:1, and the ratio of the sulfonate polyether glycol to the polypropylene glycol is 9-16:1 in example 3, the obtained polyurethane adhesive is obviously more excellent in various performances when the polyurethane adhesive is used for manufacturing alcohol water-soluble ink.
Therefore, the ink prepared from the alcohol-water soluble polyurethane adhesive has the advantages of quick drying, good adhesion on PET, PE, OPP plastic substrates, high composite strength and suitability for high-speed gravure printing.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (11)
1. The polyurethane adhesive for the alcohol-water soluble gravure printing ink is characterized by comprising the following raw materials in parts by weight: 60-85 parts of polyester diol, 3-9 parts of sulfonate polyether diol, 10-30 parts of diisocyanate, 2-8 parts of amine chain extender, 0.01-0.1 part of catalyst, 80-120 parts of alcohol diluent and 80-120 parts of deionized water; wherein the polyester diol is polypropylene adipate with molecular weight of 500-4000.
2. The polyurethane binder for alcohol-water soluble gravure ink according to claim 1, wherein the polyester diol is at least one of poly (1, 2-propanediol adipate) having a molecular weight of 1000, 2000 or 3000.
3. Polyurethane binder for alcohol-water soluble gravure ink according to claim 1 or 2 characterized in that the sulfonate polyether glycol is a SulfadiolGS-7Q polyether glycol.
4. A polyurethane binder for alcohol-water soluble gravure ink according to any one of claims 1 to 3, characterized in that the mass ratio of the polyester diol and the sulfonate polyether diol is 9 to 16:1.
5. The polyurethane binder for alcohol-water-soluble gravure ink according to any one of claims 1 to 4, wherein the diisocyanate is at least one of isophorone diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane-4, 4' -diisocyanate, 1, 6-hexamethylene diisocyanate, or tetramethylxylylene diisocyanate.
6. Polyurethane binder for alcohol-water soluble gravure ink according to any of claims 1 to 5 characterized in that said amine chain extender is at least one of ethylenediamine, isophoronediamine, hexamethylenediamine or diethylenetriamine.
7. Polyurethane binder for alcohol-water soluble gravure ink according to any of claims 1 to 6 characterized in that the catalyst is at least one of organobismuth, tetrabutyl titanate, stannous octoate or stannous chloride; the alcohol solvent is at least one of isopropanol, ethanol or n-propanol.
8. The preparation method of the polyurethane adhesive for the alcohol-water soluble gravure printing ink is characterized by comprising the following steps of:
s1, mixing polyester diol, sulfonate polyether diol, diisocyanate and a catalyst, and performing a prepolymerization reaction to obtain an NCO group-terminated polyurethane prepolymer;
s2, adding the NCO-terminated polyurethane prepolymer into a solution formed by mixing an amine chain extender, an alcohol diluent and deionized water for chain extension reaction, and obtaining the polyurethane adhesive for the alcohol-water soluble gravure printing ink.
9. The method for preparing a polyurethane adhesive for alcohol-water soluble gravure ink according to claim 8, wherein in the step S1, the temperature of the prepolymerization is 80-90 ℃ for 2-6 hours; in the step S2, the temperature of the chain extension reaction is 30-50 ℃ and the time is 2-4h.
10. The method for preparing a polyurethane binder for alcohol-water soluble gravure printing ink according to claim 8 or 9, characterized in that the NCO content of the terminal NCO group polyurethane prepolymer is 1.4 to 2.2%.
11. The method for producing a polyurethane adhesive for alcohol-water-soluble gravure ink according to any one of claims 8 to 10, characterized in that the polyurethane adhesive for alcohol-water-soluble gravure ink has a rotational viscosity of 500 to 1500 mpa-s at 25 ℃ and a solid content of 34 to 36%.
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| CN202211580032.4A CN116375962A (en) | 2022-12-09 | 2022-12-09 | Polyurethane adhesive for alcohol-water soluble gravure printing ink and preparation method thereof |
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