CN115403725A - Polyurethane binder for high-solid low-viscosity ink, and preparation method and device thereof - Google Patents
Polyurethane binder for high-solid low-viscosity ink, and preparation method and device thereof Download PDFInfo
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- CN115403725A CN115403725A CN202210975734.6A CN202210975734A CN115403725A CN 115403725 A CN115403725 A CN 115403725A CN 202210975734 A CN202210975734 A CN 202210975734A CN 115403725 A CN115403725 A CN 115403725A
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- Prior art keywords
- kettle
- amine
- polyurethane
- amine material
- ink
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Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 63
- 239000004814 polyurethane Substances 0.000 title claims abstract description 63
- 239000007787 solid Substances 0.000 title claims abstract description 46
- 239000011230 binding agent Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 151
- 238000007639 printing Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001412 amines Chemical group 0.000 claims description 98
- 239000000976 ink Substances 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 61
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 51
- 238000010438 heat treatment Methods 0.000 claims description 48
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 32
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 20
- 229920005862 polyol Polymers 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 16
- -1 alcohol ester Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000004970 Chain extender Substances 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 229920005749 polyurethane resin Polymers 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000007246 mechanism Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000012546 transfer Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 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 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
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 125000004427 diamine group Chemical group 0.000 claims description 4
- 238000007646 gravure printing Methods 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 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 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 3
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 210000001503 joint Anatomy 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 18
- 230000000052 comparative effect Effects 0.000 description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 2
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 101100298225 Caenorhabditis elegans pot-2 gene Proteins 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- MEBJLVMIIRFIJS-UHFFFAOYSA-N hexanedioic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)CCCCC(O)=O MEBJLVMIIRFIJS-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- ZQBVUULQVWCGDQ-UHFFFAOYSA-N propan-1-ol;propan-2-ol Chemical compound CCCO.CC(C)O ZQBVUULQVWCGDQ-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Images
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- 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
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
-
- 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
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 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
- C08G18/6651—Compounds of group C08G18/42 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
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a polyurethane binder for high-solid low-viscosity ink, and a preparation method and a device thereof. The polyurethane binder disclosed by the invention is mainly applied to high-solid low-viscosity polyurethane ink, has the characteristics of high performance, low viscosity, better printing adaptability and the like, and has excellent product performance. Because of the high-solid low-viscosity ink system, although the connecting material is a solvent type, the solid content of the applied ink is higher, and the added solvent is less, so the ink is more environment-friendly and economical compared with the traditional alcohol ester-soluble polyurethane ink.
Description
Technical Field
The invention relates to the technical field of gravure printing, in particular to a polyurethane binder for high-solid low-viscosity ink, and a preparation method and a device thereof.
Background
At present, the domestic flexible package polyurethane system gravure printing ink mainly comprises a composite printing ink consisting of a pigment, a dispersing agent, vinyl chloride-vinyl acetate copolymer, a polyurethane printing ink binder, n-propyl acetate, ethyl acetate, isopropanol and other solvents, and a printing base material is mainly a PET, BOPP and other film materials. The polyurethane ink binder mainly comprises polyurethane resin, an ester solvent and an alcohol solvent, wherein the polyurethane resin is generated by carrying out polymerization reaction on isocyanate, polyester or polyether polyol and a micromolecular chain extender, in addition to a carbamate group, a macromolecular chain also often contains groups such as an ether bond, an ester bond and a urea bond, hydrogen bonds are easily generated among the groups, and the polyurethane ink binder is more and more widely applied due to the excellent performances such as adhesion, wear resistance and scratch resistance on a substrate and the advantages of adjustable hardness.
At present, the solid content of the conventional white ink of polyurethane system is about 40-45%, the solid content of the ink is about 22-25%, and the rest is solvent. The recovery of large amounts of solvent after printing requires reprocessing by fractionation or combustion, which increases costs and is also not environmentally friendly. Although the development of the water-based ink system has been advanced, the improvement of the printing machine speed is restricted due to the problem of the drying speed. The high-solid low-viscosity ink system is characterized in that although the binder is a solvent type, the solid content of the applied ink is higher, and the added solvent is less, so that the ink is more environment-friendly and economical compared with the traditional alcohol ester-soluble polyurethane ink. However, when the conventional polyurethane ink binder is applied to a high-solid low-viscosity system, the viscosity of the original ink is too high, and a large amount of solvent is still required for dilution. There is therefore a need to develop a polyurethane ink vehicle suitable for high solids, low viscosity systems.
Disclosure of Invention
The present invention is directed to a polyurethane binder, a method and an apparatus for preparing the same, and a high solid content and low viscosity ink, which solve the above problems of the background art.
In order to solve the technical problems, the invention provides the following technical scheme: a polyurethane binder for a high-solid low-viscosity ink, the polyurethane binder having a viscosity of 500 to 600mPa · s at 25 ℃, characterized in that: the preparation raw materials comprise raw materials for preparing the alcohol ester-soluble polyurethane resin and an organic solvent; wherein the content of the first and second substances,
the polyurethane binder comprises the following raw materials in percentage by total weight of the preparation raw materials of the polyurethane binder:
preferably, the raw materials for preparing the alcohol ester-soluble polyurethane resin comprise the following components in parts by weight:
preferably, the polyester polyol is one or more of poly adipic acid-1,2 propylene glycol polyol, poly adipic acid-2 methyl 1,3 propylene glycol polyol, poly adipic acid-butanediol polyol, poly adipic acid-3 methyl 1,5 pentanediol polyol, and the polyol average molecular weight is 500-1000.
Preferably, the diisocyanate comprises one or more of isophorone diisocyanate, toluene diisocyanate, 4,4' -diphenylmethane diisocyanate and hexamethylene diisocyanate.
Preferably, the first locating pin is arranged at the output end of the manual telescopic mechanism.
Preferably, one side of the output end of the manual telescopic mechanism is further connected with a guide block, and the guide block is used for positioning the position of a hinge connecting hole of the vehicle body and the back door.
Preferably, the branched chain extender comprises one of pentaerythritol, glycerol and trimethylolpropane.
Preferably, the catalyst comprises one of dibutyltin dilaurate, tetraisobutyl titanate and triethylamine.
Preferably, the amine chain extender comprises one or more of diethylenetriamine, 2-methylpentamethylenediamine, 1,3-cyclohexyldimethylamine and isophoronediamine.
Preferably, the blocking agent comprises one or a mixture of more of monoethanolamine, tert-butylamine, benzylamine and octadecylamine. The primary amine end capping agents such as monoethanolamine, benzylamine, tert-butylamine and octadecylamine are adopted, and are combined with diamine chain extenders, the molecular weight distribution of the synthesized polyurethane resin is more average, the stability of the prepared ink is better, and in addition, the end capping agents are used for introducing structures such as hydroxyl, benzene rings, nonpolar long carbon chains and the like on end groups, so that the dispersion of pigments and the attachment of the pigments to nonpolar base material films such as BOPP and PE are facilitated.
The gravure printing high-solid low-viscosity ink is prepared by adopting the polyurethane binder for the high-solid low-viscosity ink.
A preparation method of a polyurethane binder for high-solid low-viscosity ink adopts a two-step branched chain extension method:
(a) Prepolymerization reaction: weighing polyalcohol raw materials according to a selected proportion, heating to 60 ℃, continuously adding the isocyanate raw materials with the selected proportion, uniformly stirring, heating to 85-110 ℃ and reacting for 4 hours;
(b) Reacting by a two-step stepped branched chain extension method: the first step of branching chain extension reaction: after the prepolymerization reaction is finished, closing heating, starting reflux water to cool the materials to 80 ℃, adding n-propyl acetate with a selected proportion into the reaction material in the step a, controlling the temperature of a reaction system to 65 ℃, adding a branched chain extender and a catalyst, uniformly stirring, then uniformly heating to 85 ℃, and continuing to react for 2 hours; second step carbamidation chain extension reaction: the reaction mass was cooled to 50-60 ℃. Simultaneously adding a diamine chain extender, an amine end-capping agent, ethyl acetate and isopropanol in a certain proportion into the other amine material kettle, uniformly stirring at 35 ℃, and transferring the material subjected to the second-step chain extension reaction into the amine material kettle at a constant speed;
(c) After the transfer, the material is heated to 50-60 ℃ and reacts for 1h, and then the material is discharged, thus obtaining the product.
A preparation device of a polyurethane connecting material for high-solid low-viscosity ink comprises a heating cavity, a cooling cavity, a first amine material kettle and a second amine material kettle which are arranged in a shell, wherein the heating cavity is positioned at the front end of the cooling cavity;
the second amine material kettle is fixedly arranged in the cooling cavity and positioned on one side of a pushing path of the first amine material kettle;
the pushing mechanism comprises a rotating shaft driven by a motor, two sliding rods are mounted at the tail end of the rotating shaft to form a sliding groove structure, an extending end is arranged on one side of the first amine material kettle, the rotating shaft extends into the extending end through a shell, a guide rod is fixedly mounted on the inner wall of the extending end and is connected in the sliding groove structure in a sliding mode, when the rotating shaft rotates, the sliding groove and the guide rod form a crank sliding rod structure, the first amine material kettle is driven to rotate and perform horizontal displacement at the same time, and therefore switching between the heating cavity and the cooling cavity is achieved;
the first amine material kettle is provided with a material guide pipe, the material guide pipe is communicated with a feeding opening of the kettle body and extends into the kettle body from the opening, and when the first amine material kettle rotates to the cooling cavity, the feeding opening of the first amine material kettle is in butt joint with the feeding opening of the second amine material kettle; in this state, because the first amine material kettle is not in a full state, the tail end of the material guide pipe is not in contact with the material, air in the first amine material kettle can be discharged to the second amine material kettle, heat is transferred to the second amine material kettle, and the first amine material kettle is not only suitable for cooling, but also used for helping the second amine material kettle to be heated;
a valve is arranged at the gap between the material guide pipe and the feeding opening of the first amine material kettle, and when the valve is opened, the first amine material kettle can directly convey materials into the second amine material kettle.
Compared with the prior art, the invention has the beneficial effects that:
1. a two-step stepped branching chain extension method is adopted, amino chain extension is carried out in addition to branching chain extension by using a polyhydroxy compound, so that the hyperbranched polyurethane resin containing more carbamido groups is synthesized, the structure contains enough harder polyurea bonds, and meanwhile, the resin has short main chain and more branched chains, so that the resin is ensured to have higher hardness when having better solubility in an alcohol ester solvent system, the ink prepared by the resin has lower printing viscosity and better strength, and adverse factors such as anti-sticking, sticking to a guide roller and the like can not occur when printing and rolling;
2. isopropanol in polyurethane ink vehicle solvent: n-propyl acetate: the ethyl acetate ratio was about 2:2: about 3, the ratio can enable the downstream printing ink to have good solvent volatilization speed, and if the amounts of isopropanol and n-propyl acetate are too much, the solvent residue is too much, the volatilization speed is too slow, and the conditions of poor drying and adhesion of the printing ink layer can occur; if the amount of the ethyl acetate is too much, powder aggregation caused by too fast drying is easy to occur, printing faults such as knife lines and silk forming are easy to occur, and in addition, the n-propyl acetate has a high boiling point and can be used as a solvent in the first-step branching chain extension process, so that the condition of insufficient stirring caused by too high viscosity in the first-step branching chain extension process is avoided.
Drawings
FIG. 1 is a schematic view of a production apparatus of the present invention;
FIG. 2 is a schematic view of the pushing mechanism of the present invention;
fig. 3 is a schematic view illustrating the installation of the guide tubes.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1:
the polyurethane binder for the high-solid low-viscosity ink is prepared from 30wt% of alcohol ester-soluble polyurethane, 30.2wt% of ethyl acetate, 20.5wt% of n-propyl acetate and 19.3wt% of isopropanol, and the viscosity of the polyurethane binder is 512.5mPa · s (25 ℃) through detection.
The preparation method of the polyurethane vehicle for the high-solid low-viscosity ink includes:
(a) Prepolymerization reaction: weighing 100g of 500-molecular-weight poly (adipic acid-1,2-propylene glycol) polyol according to the selected proportion, heating to 60 ℃, continuously adding 88.8g of isophorone diisocyanate, stirring uniformly, heating to 110 ℃ and reacting for 4 hours;
(b) Reacting by a two-step stepped branched chain extension method: the first step of branching chain extension reaction: after the prepolymerization reaction is finished, closing heating, starting reflux water to cool the materials to 80 ℃, taking 150.7g of n-propyl acetate to add into the reaction material in the step a, controlling the temperature of the reaction system to 65 ℃, adding 6.8g of pentaerythritol and 0.05g of dibutyltin dilaurate, uniformly stirring, then uniformly heating to 85 ℃, and continuing to react for 2 hours; second step carbamidation chain extension reaction: the reaction mass was cooled to 50-60 ℃. Meanwhile, adding 7.3g of isophorone diamine, 3.9g of monoethanolamine, 13.5g of octadecylamine, 220g of ethyl acetate and 141.9g of isopropanol into another amine material kettle, uniformly stirring at 35 ℃, and transferring the material after the second-step chain extension reaction into the amine material kettle at a constant speed;
(c) After the transfer, the temperature of the materials is raised to 50-60 ℃, the materials are discharged after the reaction for 1 hour, and then the product is obtained.
Example 2:
the polyurethane binder for the high-solid low-viscosity ink is prepared from 31wt% of alcohol ester-soluble polyurethane, 35wt% of ethyl acetate, 18wt% of n-propyl acetate and 16wt% of isopropanol, and the viscosity of the polyurethane binder is 525mPa · s (25 ℃) through detection.
The preparation method of the polyurethane vehicle for the high-solid low-viscosity ink includes:
(a) Prepolymerization reaction: weighing 50g of 1000 molecular weight poly adipic acid-2 methyl 1,3 propylene glycol polyol and 50g of 1000 molecular weight poly adipic acid-butanediol polyol according to the selected proportion, heating to 60 ℃, continuously adding 34.8g of toluene diisocyanate, stirring uniformly, heating to 85 ℃ and reacting for 4 hours;
(b) Reacting by a two-step stepped branched chain extension method: the first step of branching chain extension reaction: after the prepolymerization reaction is finished, closing heating, starting reflux water to cool the materials to 80 ℃, taking 84.6g of n-propyl acetate to add into the reaction materials in the step a, controlling the temperature of the reaction system to 65 ℃, adding 3.1g of glycerol and 0.05g of tetraisobutyl titanate, uniformly stirring, then uniformly heating to 85 ℃ and continuing the reaction for 2 hours; second step carbamidation chain extension reaction: the reaction mass was cooled to 50-60 ℃. Simultaneously adding 4.1g of 1,3 cyclohexyldimethylamine, 1.3g of monoethanolamine, 2.3g of benzylamine, 164.5g of ethyl acetate and 75.2g of isopropanol into another amine material kettle, uniformly stirring at 35 ℃, and transferring the material after the second-step chain extension reaction into the amine material kettle at a constant speed;
(c) After the transfer, the temperature of the materials is raised to 50-60 ℃, the materials are discharged after the reaction for 1 hour, and then the product is obtained.
Example 3:
the polyurethane binder for the high-solid low-viscosity ink is prepared from 29wt% of alcohol-soluble polyurethane, 27wt% of ethyl acetate, 22wt% of n-propyl acetate and 22wt% of isopropanol, and the viscosity of the polyurethane binder is 525mPa · s (25 ℃) through detection.
The preparation method of the polyurethane vehicle for the high-solid low-viscosity ink described in this embodiment includes:
(a) Prepolymerization reaction: weighing 50g of 800 molecular weight poly (adipic acid-butanediol) polyol, 50g of 800 molecular weight poly (adipic acid-3-methyl 1,5 pentanediol polyol) according to the selected proportion, heating to 60 ℃, continuously adding 31.2g of 4,4' -diphenylmethane diisocyanate and 21g of hexamethylene diisocyanate, stirring uniformly, heating to 85 ℃ and reacting for 4 hours;
(b) Reacting by a two-step stepped branched chain extension method: the first step of branching chain extension reaction: after the prepolymerization reaction is finished, closing heating, starting reflux water to cool the materials to 80 ℃, taking 125.4g of n-propyl acetate to add into the reaction material in the step a, controlling the temperature of the reaction system to 65 ℃, adding 5.6g of trimethylolpropane and 0.05g of triethylamine, uniformly stirring, then uniformly heating to 85 ℃, and continuing to react for 2 hours; second step carbamidation chain extension reaction: the reaction mass was cooled to 50-60 ℃. Simultaneously adding 4.2g of 2-methylpentamethylenediamine, 3.3g of monoethanolamine, 153.9g of ethyl acetate and 125.4g of isopropanol into another amine material kettle, stirring uniformly at 35 ℃, and transferring the material subjected to the second-step chain extension reaction into the amine material kettle at a constant speed;
(c) After the transfer, the material is heated to 50-60 ℃ and reacts for 1h, and then the material is discharged, thus obtaining the product.
Example 4:
the polyurethane binder for the high-solid low-viscosity ink is prepared from 30.5wt% of alcohol-soluble polyurethane, 26.5wt% of ethyl acetate, 23wt% of n-propyl acetate and 20wt% of isopropanol, and the viscosity of the polyurethane binder is 550mPa · s (25 ℃) through detection.
The preparation method of the polyurethane vehicle for the high-solid low-viscosity ink described in this embodiment includes:
(a) Prepolymerization reaction: weighing 30g of 600 molecular weight poly adipic acid-1,2 propylene glycol polyol and 70g of 600 molecular weight poly adipic acid-butanediol polyol according to the selected proportion, heating to 60 ℃, continuously adding 37g of isophorone diisocyanate and 29g of toluene diisocyanate, stirring uniformly, heating to 85 ℃ and reacting for 4 hours;
(b) Reacting by a two-step stepped branched chain extension method: the first step of branching and chain extension reaction: after the prepolymerization reaction is finished, closing heating, starting reflux water to cool the materials to 80 ℃, taking 125.4g of n-propyl acetate to add into the reaction material in the step a, controlling the temperature of the reaction system to 65 ℃, adding 5.7g of pentaerythritol and 0.05g of triethylamine, uniformly stirring, then uniformly heating to 85 ℃ and continuing the reaction for 2 hours; second step carbamidation chain extension reaction: the reaction mass was cooled to 50-60 ℃. Simultaneously adding 1.1 g of diethylenetriamine, 4.8g of isophorone diamine, 2.9g of monoethanolamine, 3.5g of tert-butylamine, 153.9g of ethyl acetate and 125.4g of isopropanol into another amine material kettle, uniformly stirring at 35 ℃, and then transferring the material after the second-step chain extension reaction into the amine material kettle at a constant speed;
(c) After the transfer, the material is heated to 50-60 ℃ and reacts for 1h, and then the material is discharged, thus obtaining the product.
Comparative example 1:
this comparative example was prepared from 30 wt.% alcohol ester-soluble polyurethane, 50 wt.% ethyl acetate, and 20 wt.% isopropyl alcohol as starting materials for a conventional ink polyurethane binder having a viscosity of 900 mPa-s (25 c).
The preparation method of the conventional polyurethane ink vehicle of the present comparative example includes:
(a) Prepolymerization reaction: weighing 100g of 1000-molecular-weight poly (adipic acid-1,2) propylene glycol polyol according to the selected ratio, heating to 60 ℃, continuously adding 34.8g of toluene diisocyanate, uniformly stirring, heating to 85 ℃ and reacting for 4 hours;
(b) Chain extension reaction: the reaction mass was cooled to 50-60 ℃. Meanwhile, 11.6g of cyclohexyldimethylamine, 244g of ethyl acetate and 97.6g of isopropanol are added into another amine material kettle, and the materials are uniformly stirred at 35 ℃ and then transferred into a prepolymerization kettle at a constant speed;
(c) After the transfer, the material is heated to 50-60 ℃ and reacts for 1h, and then the material is discharged, thus obtaining the product.
Examples
The polyurethane resins prepared in the above examples 1 to 4 and comparative example 1 were prepared into gravure composite inks according to the formulations shown in the following table 1, respectively, while the conventional ink formulations are shown in the following table 2.
Table 1 shows the formulation of gravure high solid low viscosity inks
Formulation of gravure conventional ink set forth in Table 2
| Raw materials | Mass portion of |
| Titanium dioxide pigment | 30 |
| 10% dispersing agent | 2.5 |
| |
12 |
| Polyurethane resin | 30 |
| N-propyl ester | 15.7 |
| Ethyl acetate | 5 |
| Isopropanol (I-propanol) | 4 |
| Filler material | 0.8 |
The usage amount of the solvent of the high-solid low-viscosity polyurethane ink obtained from the tables 1 and 2 is far less than that of the formula of the conventional ink, the solid content of the high-solid low-viscosity polyurethane ink is about 51 percent, the solid content of the conventional ink is 42.45 percent, the use amount of the solvent of the high-solid low-viscosity polyurethane ink is reduced, the hiding power after printing is far better than that of the conventional ink printing effect, and the depth of a gravure mesh is generally reduced in consideration of cost saving.
The inks prepared in the above examples 1 to 4 and comparative example 1 according to table 1 were tested for their application properties according to the following criteria:
GB/T2024-2012 gravure plastic film composite ink;
GBT 13217.4-2008 liquid ink viscosity test method;
GBT 13217.6-2008 liquid ink tinting strength test method;
GBT 13217.8-2009 liquid ink anti-blocking test method.
The results of the application properties test of the inks are shown in Table 3 below, against which a comparative example was compared.
Results of Performance testing of the inks set forth in Table 3
The initial viscosity of the ink for printing is generally 20-25 seconds, so that the ink with the viscosity has better storage stability, and as can be seen from the results in the table, the viscosity of the ink used for the high-solid low-viscosity system of the polyurethane ink binder is obviously lower than that of the comparative example, and the viscosity of the ink after the ink is placed for 7 days is more stable than that of the comparative example, so that the stability of the ink prepared in the example is better; the general ink needs to be diluted by adding a solvent to a certain viscosity for printing when being used on a printing machine, because the viscosity is high and the printing machine is not quick to start, the dilution is needed, the dilution can reach 13 to 14 seconds after the dilution of 5:3 in examples 1 to 4, the on-machine condition is met, the dilution of comparative example 1 still has 18.75 seconds, the solvent needs to be added for further dilution, the consumption of the solvent is increased, and the original purpose of the high-solid low-viscosity polyurethane ink is not met; the ink product of the present invention has superior performance to comparative example 1 in terms of anti-blocking performance. In conclusion, the polyurethane ink binder disclosed by the invention is more suitable for the performance requirements of high-solid low-viscosity polyurethane ink, and has more excellent comprehensive performance.
Example 5
In this embodiment, based on the above-mentioned preparation method, a preparation apparatus is provided to improve the stability of product quality during production and improve the continuity of the overall process, and the following detailed description refers to the drawings.
Comprises a heating cavity 12, a cooling cavity 11, a first amine material kettle 2 and a second amine material kettle 5 which are arranged in a shell 1, wherein the heating cavity 12 is positioned at the front end of the cooling cavity 11, and the heating cavity 12 is positioned at the left side of the cooling cavity 11 in the figure. The inner wall of the heating cavity 12 is provided with a heating pipe or is heated by adopting a heat conduction oil mode, and the inner wall of the cooling cavity 1 is used for guiding heat out by adopting a water cooling mode or other medium modes or maintaining the temperature. The two cavities are directly communicated with each other in nature, and only the inner walls of the two cavities are blocked by adopting heat insulation materials; in addition, the wall of the first amine material kettle 2 is made of good heat conduction material, but the left end and the right end are sealed and are heat insulation materials, so that when the first amine material kettle 2 is in the cooling cavity 11 or the heating cavity 12, the other cavity can be ensured to be relatively heat-insulated.
The first amine material kettle 2 is pushed to the cooling cavity 12 from the heating cavity 11, and the second amine material kettle 5 is fixedly arranged in the cooling cavity and positioned on one side of a pushing path of the first amine material kettle 2;
referring to fig. 2, the pushing mechanism includes a rotating shaft 4 driven by a motor, two sliding rods 41 are installed at the end of the rotating shaft 4 to form a sliding chute structure, an extending end 3 is arranged at one side of the first amine material kettle, the rotating shaft 4 extends into the extending end through a housing, a guide rod 31 is fixedly installed on the inner wall of the extending end 3, the guide rod 31 is slidably connected in the sliding chute structure, and when the rotating shaft rotates, the sliding chute and the guide rod form a crank sliding rod structure. Referring to the figure, the guide rod 31 protrudes from the side of the inner and outer walls of the extension end 3, and a track groove is formed in the wall of the housing 1, and the protruding portion slides in the track groove to perform a guiding function. The rotating shaft 4 rotates to drive the first amine material kettle 2 to rotate and horizontally displace at the same time, so that the heating cavity and the cooling cavity are switched; the angle of rotation and the horizontal length of the first amine material kettle 2 can be realized by the design length of the sliding rod 41 and the guide rod 31.
The first amine material kettle 2 is provided with a material guide pipe 21, the material guide pipe 21 is communicated with a feeding opening of the kettle body, extends into the kettle body from the opening, and the tail end of the material guide pipe is positioned at a deeper position. The outer wall of the heating cavity 12 is provided with a feeding port which is communicated with a feeding opening of the kettle body and can directly feed materials through a material guide pipe 21. The feeding of the material guide pipe 21 can directly feed boring materials with certain viscosity into the kettle body to be deeper, namely, the position where the whole materials are deeper, so that the materials are convenient to mix.
When the first amine material kettle 2 rotates to the cooling cavity, the first amine material kettle 2 is butted with a feeding opening of the second amine material kettle 5 (the positions of the first amine material kettle 2 and the second amine material kettle are butted and need to correspond to the rotating angle and the rotating length of the first amine material kettle and the second amine material kettle, and cooperation can be realized in specific implementation); in this state, because the first amine material kettle 2 is not in a full state, the tail end of the material guide pipe is not in contact with the materials, based on the specific design, the tail end of the material guide pipe 21 can be designed into an arc-shaped structure, the purpose is that the material guide pipe moves and rotates to a cooling cavity type in the first amine material kettle 2, the tail end is only communicated with the air in the kettle, the air in the first amine material kettle 2 can be discharged to the second amine material kettle 5, the heat is transferred to the second amine material kettle, the self cooling is met, and the heating of the second amine material kettle is also assisted;
referring to fig. 3, a valve is disposed at a gap B between the feeding pipe 21 and the feeding opening a of the first amine kettle, when the valve is opened, the first amine kettle 2 can directly convey the material to the second amine kettle 5, and a valve is also installed in the feeding pipe 21, and such a valve can be in the form of an electronic valve, which is convenient for control. The feed opening of the second amine pot 5 is also of this design. Two amine kettles may be provided with two feed openings, one for gas and one for feed, which are separate from the openings of the guide tubes 21.
In the specific work, in the prepolymerization reaction stage, the materials are put into a first amine material kettle 2 according to the preparation method, heated at 60 ℃ in a heating chamber 12, continuously added with the isocyanate raw materials with the selected proportion, stirred and uniformly mixed, and heated to 85-110 ℃ for reaction for 4 hours;
after the prepolymerization reaction is finished, the heating function of the heating cavity is closed, the internal materials are quickly reduced to 80 ℃, then n-propyl acetate with the selected proportion is added, the first amine material kettle is pushed into the cooling cavity 11, the temperature is quickly reduced to 65 ℃, the pushing mechanism pushes the first amine material kettle 2 back to the heating cavity 12, the branched chain extender and the catalyst are added, the heating is started, the temperature is uniformly increased to 85 ℃, and the reaction is maintained for 2 hours. When the cauldron body switches in two chambeies each time, all be accompanied with reinforced step, and switch the cauldron body every time and all rotate once, can let the material reaction more thoroughly, make things convenient for the mixture after reinforced.
Then, the first amine kettle 2 is continuously pushed into the cooling chamber 11, the temperature at this time is higher, a valve for butt-joint communication between the material guide pipe 21 and the second amine kettle 5 is opened, high-temperature gas in the first amine kettle 2 enters the second amine kettle 5 to accelerate heat dissipation of the first amine kettle 2 and supply heat to the second amine kettle 5, and the temperature of the second amine kettle can be quickly maintained to 35 ℃ while the temperature of the first amine kettle is maintained at 50-60 ℃. After the two temperatures are stable, the material guiding pipe 21 is closed. And adding a diamine chain extender, an amine end-capping agent, ethyl acetate and isopropanol in a proportional amount into the second diamine material kettle 5. The contents of the first amine pot 2 were then transferred to a second amine pot.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A polyurethane binder for a high-solid low-viscosity ink, the polyurethane binder having a viscosity of 500 to 600mPa · s at 25 ℃, characterized in that: the preparation raw materials comprise raw materials for preparing the alcohol ester soluble polyurethane resin and an organic solvent; wherein the content of the first and second substances,
the polyurethane binder comprises the following raw materials in percentage by total weight of the preparation raw materials of the polyurethane binder:
2. a polyurethane vehicle for a high solids, low viscosity ink as in claim 1, wherein: the raw materials for preparing the alcohol ester-soluble polyurethane resin comprise the following components in parts by weight:
3. a polyurethane vehicle for a high solids, low viscosity ink as claimed in claim 1 or claim 2 wherein: the polyester polyol is one or more of poly adipic acid-1,2 propanediol polyol, poly adipic acid-2 methyl 1,3 propanediol polyol, poly adipic acid-butanediol polyol, poly adipic acid-3 methyl 1,5 pentanediol polyol, and the average molecular weight of the polyol is 500-1000.
4. A polyurethane vehicle for a high solids, low viscosity ink as claimed in claim 1 or claim 2 wherein: the diisocyanate comprises one or more of isophorone diisocyanate, toluene diisocyanate, 4,4' -diphenylmethane diisocyanate and hexamethylene diisocyanate.
5. A polyurethane vehicle for high solids, low viscosity inks according to claim 1 or claim 2 wherein: the branched chain extender comprises one of pentaerythritol, glycerol and trimethylolpropane.
6. A polyurethane vehicle for a high solids, low viscosity ink as claimed in claim 1 or claim 2 wherein: the catalyst comprises one of dibutyltin dilaurate, tetraisobutyl titanate and triethylamine.
7. A polyurethane vehicle for a high solids, low viscosity ink as claimed in claim 1 or claim 2 wherein: the amine chain extender comprises one or a mixture of more of diethylenetriamine, 2-methylpentamethylenediamine, 1,3-cyclohexyldimethylamine and isophorone diamine.
8. Gravure printing high solid low viscosity ink, characterized in that it is prepared by using the polyurethane binder for high solid low viscosity ink according to any one of claims 1 to 7.
9. A preparation method of a polyurethane binder for high-solid low-viscosity ink is characterized by adopting a two-step stepped branched chain extension method:
(a) Prepolymerization reaction: weighing polyalcohol raw materials according to a selected proportion, heating to 60 ℃, continuously adding the isocyanate raw materials according to the selected proportion, uniformly stirring, and heating to 85-110 ℃ for reaction for 4 hours;
(b) Reacting by a two-step stepped branched chain extension method: the first step of branching chain extension reaction: after the prepolymerization reaction is finished, closing heating, starting reflux water to cool the materials to 80 ℃, adding n-propyl acetate with a selected proportion into the reaction material in the step a, controlling the temperature of a reaction system to 65 ℃, adding a branched chain extender and a catalyst, uniformly stirring, then uniformly heating to 85 ℃, and continuing to react for 2 hours; second step carbamidation chain extension reaction: the reaction mass was cooled to 50-60 ℃. Simultaneously adding a diamine chain extender, an amine end-capping agent, ethyl acetate and isopropanol in a certain proportion into the other amine material kettle, uniformly stirring at 35 ℃, and transferring the material subjected to the second-step chain extension reaction into the amine material kettle at a constant speed;
(c) After the transfer, the material is heated to 50-60 ℃ and reacts for 1h, and then the material is discharged, thus obtaining the product.
10. The preparation device of the polyurethane connecting material for the high-solid-content low-viscosity printing ink is characterized by comprising a heating cavity, a cooling cavity, a first amine material kettle and a second amine material kettle which are arranged in a shell, wherein the heating cavity is positioned at the front end of the cooling cavity;
the second amine material kettle is fixedly arranged in the cooling cavity and positioned on one side of a pushing path of the first amine material kettle;
the pushing mechanism comprises a rotating shaft driven by a motor, two sliding rods are mounted at the tail end of the rotating shaft to form a sliding groove structure, an extending end is arranged on one side of the first amine material kettle, the rotating shaft extends into the extending end through a shell, a guide rod is fixedly mounted on the inner wall of the extending end and is connected in the sliding groove structure in a sliding mode, when the rotating shaft rotates, the sliding groove and the guide rod form a crank sliding rod structure, the first amine material kettle is driven to rotate and perform horizontal displacement at the same time, and therefore switching between the heating cavity and the cooling cavity is achieved;
the first amine material kettle is provided with a material guide pipe, the material guide pipe is communicated with a feeding opening of the kettle body and extends into the kettle body from the opening, and when the first amine material kettle rotates to the cooling cavity, the feeding opening of the first amine material kettle is in butt joint with the feeding opening of the second amine material kettle; in this state, because the first amine material kettle is not full, the tail end of the material guide pipe is not contacted with the material, the air in the first amine material kettle can be discharged to the second amine material kettle, the heat is transferred to the second amine material kettle, the temperature reduction of the second amine material kettle is met, and the heating of the second amine material kettle is also assisted;
a valve is arranged at the gap between the material guide pipe and the feeding opening of the first amine material kettle, and when the valve is opened, the first amine material kettle can directly convey materials into the second amine material kettle.
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