CN116970306A - High-temperature-resistant polyurethane ink and printing process thereof - Google Patents
High-temperature-resistant polyurethane ink and printing process thereof Download PDFInfo
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- CN116970306A CN116970306A CN202310828843.XA CN202310828843A CN116970306A CN 116970306 A CN116970306 A CN 116970306A CN 202310828843 A CN202310828843 A CN 202310828843A CN 116970306 A CN116970306 A CN 116970306A
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 86
- 239000004814 polyurethane Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 59
- 230000000996 additive effect Effects 0.000 claims abstract description 59
- -1 diphenyl sulphonyl imine Chemical class 0.000 claims abstract description 38
- 239000000839 emulsion Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 35
- 239000000945 filler Substances 0.000 claims abstract description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 19
- 229920000570 polyether Polymers 0.000 claims abstract description 19
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 18
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 18
- 239000004593 Epoxy Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 26
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- 235000011037 adipic acid Nutrition 0.000 claims description 12
- 239000001361 adipic acid Substances 0.000 claims description 12
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 12
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 239000000049 pigment Substances 0.000 claims description 11
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 claims description 11
- 125000005442 diisocyanate group Chemical group 0.000 claims description 10
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 125000006267 biphenyl group Chemical group 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 2
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract description 7
- 239000004926 polymethyl methacrylate Substances 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 238000006459 hydrosilylation reaction Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004576 sand Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 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 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- FQXGHZNSUOHCLO-UHFFFAOYSA-N 2,2,4,4-tetramethyl-1,3-cyclobutanediol Chemical compound CC1(C)C(O)C(C)(C)C1O FQXGHZNSUOHCLO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to the technical field of ink and discloses high-temperature-resistant polyurethane ink and a printing process thereof. According to the invention, allyl polyoxyalkyl epoxy ether is selected as a raw material, and is modified by using diphenyl sulphonyl imine and macromolecular polyether amine to obtain an allyl-terminated additive with good flexibility, good compatibility with polyurethane emulsion and good heat resistance, and the additive can form an interpenetrating network structure in the polyurethane emulsion, so that the chemical resistance and strength of the polyurethane emulsion are improved; the polymethyl methacrylate is coated by the hydrogen-terminated polydimethylsiloxane to prepare the modified filler with good heat resistance, weather resistance and water resistance, and after the filler is blended with the allyl-terminated additive, the hydrosilylation of the modified filler can be added and reacted with allyl and hydroxyl in the allyl-terminated additive, so that modified filler particles are coated in a network structure formed by the allyl-terminated additive and polyurethane emulsion, and the modified filler has stable performance.
Description
Technical Field
The invention relates to the technical field of ink and discloses high-temperature-resistant polyurethane ink and a printing process thereof.
Background
Polyurethane ink is a high-molecular synthetic material, has excellent performance, is widely applied to printing and coating of various materials, and becomes one of important materials in the printing and coating fields; however, the production of polyurethane inks is not environmentally friendly and sustainable.
The water-based polyurethane ink is novel environment-friendly ink, and the main components of the water-based polyurethane ink comprise water-based polyurethane resin, auxiliary agents, pigments and the like, water is used as a medium, the environment-friendly performance is good, the safety is high, but the water resistance, the heat resistance and the adhesive force of the water-based polyurethane ink are slightly insufficient compared with those of the traditional ink, the water-based polyurethane ink is modified by epoxy resin, acrylic acid, silicone oil, fillers and other substances commonly used in the prior art, and the water-based polyurethane ink with excellent comprehensive performance is difficult to obtain.
Therefore, the preparation of the polyurethane ink with good water resistance, good heat resistance, good adhesive force and stable performance has great significance.
Disclosure of Invention
The invention aims to provide high-temperature-resistant polyurethane ink and a printing process thereof. To solve the problems set forth in the background art.
In order to solve the technical problems, the invention provides the following technical scheme:
the high-temperature-resistant polyurethane ink comprises the following raw materials in parts by weight: 50 to 65 parts of polyurethane emulsion, 20 to 30 parts of water, 13 to 20 parts of composite additive, 8 to 12 parts of pigment, 0.5 to 1 part of flatting agent and 1 to 2 parts of dispersing agent.
More preferably, the preparation method of the composite additive comprises the following steps: s1: mixing methyl methacrylate, allyl acrylate, azodiisobutyronitrile and water, heating and stirring for 4-6 hours under the protection of nitrogen, adding sodium dodecyl benzene sulfonate and hydrogen-terminated polydimethylsiloxane, homogenizing, filtering, drying and crushing to obtain modified filler;
s2: taking allyl polyoxyalkyl epoxy ether, polyether amine, diphenyl sulphonyl imine and isopropanol, heating and stirring, and reacting for 4-5 hours to obtain an allyl-terminated additive;
s3: and (3) taking the modified filler, the terminal allyl additive, the isopropanol and the chloroplatinic acid, heating and stirring, and stirring for 3-6 hours at the temperature of 80-120 ℃ to obtain the composite additive.
More optimally, the composite additive comprises the following raw materials in parts by weight: 35-45 parts of modified filler, 15-20 parts of terminal allyl additive, 80-100 parts of isopropanol and 0.01-0.02 part of chloroplatinic acid.
More optimally, the allyl-terminated additive comprises the following raw materials in parts by weight: 15-20 parts of allyl polyoxyalkyl epoxy ether, 15-21 parts of polyether amine, 5-7 parts of diphenyl sulphonyl imine and 80-100 parts of isopropanol.
More preferably, the polyetheramine comprises a high molecular weight polyetheramine; the mass ratio of polyetheramine to diphenyl sulphonimide is 3:1.
more optimally, the modified filler comprises the following raw materials in parts by weight: 16 to 22 parts of methyl methacrylate, 1 to 4 parts of allyl acrylate, 0.1 to 0.2 part of azodiisobutyronitrile, 0.5 to 1.5 parts of sodium dodecyl benzene sulfonate, 8 to 15 parts of hydrogen end-capped polydimethylsiloxane and 40 to 50 parts of water.
More preferably, the preparation method of the polyurethane emulsion comprises the following steps: mixing adipic acid, 2, 4-tetramethyl-1, 3-cyclobutanediol and a catalyst, heating to 220-240 ℃ under the protection of nitrogen, reacting for 4-6 hours, adding terephthalyl diisocyanate, 2-dimethylolpropionic acid and polytetrahydrofuran, and reacting for 2-4 hours at normal temperature to obtain the polyurethane emulsion.
More optimally, the polyurethane emulsion comprises the following raw materials in parts by weight: 70 to 90 parts of adipic acid, 110 to 130 parts of 2, 4-tetramethyl-1, 3-cyclobutanediol, 0.1 to 0.3 part of catalyst, 40 to 60 parts of terephthal-isocyanate, 5 to 7 parts of 2, 2-dimethylolpropionic acid and 60 to 80 parts of polytetrahydrofuran.
More optimally, the printing process of the high-temperature-resistant polyurethane ink comprises the following steps of: printing high temperature resistant polyurethane ink at 70-80 deg.c, and drying at 50-60 deg.c for 0.5-1 hr.
Compared with the prior art, the invention has the following beneficial effects:
(1) The modified filler is prepared by coating polymethyl methacrylate with hydrogen-terminated polydimethylsiloxane, the heat resistance and the wear resistance can be enhanced by introducing polymethyl methacrylate, so that the modified filler is more durable, the heat resistance and the water resistance are improved by coating polymethyl methacrylate with hydrogen-terminated polydimethylsiloxane, the hydrosilyl of the hydrogen-terminated polydimethylsiloxane can be subjected to addition reaction with allyl and hydroxyl in an allyl-terminated additive in a subsequent step under the catalysis of chloroplatinic acid, a composite additive is obtained, and the problem of poor dispersibility of the modified filler in polyurethane emulsion is solved.
(2) The allyl polyoxyalkyl epoxy ether is selected as a raw material to prepare an allyl-terminated additive, the addition of the allyl polyoxyalkyl epoxy ether can improve the water resistance and the heat resistance of polyurethane emulsion, the polyurethane emulsion is modified by using diphenyl sulphonyl imine and polyether amine, the polyether amine is high molecular weight polyether amine, and the mass ratio of the diphenyl sulphonyl imine to the polyether amine is 1:3, the diphenyl sulphonyl imide can improve high temperature resistance, and brittleness is increased when the diphenyl sulphonyl imide is added too much; the polyether amine with large molecular weight can improve the weather resistance and flexibility of polyurethane ink, relieve the problem of brittleness increase caused by introduction of diphenyl sulphonyl imide, and can be used as a defoaming agent, and excessive addition can cause excessive polyurethane viscosity and overlong drying time; the end allyl additive with good flexibility, good compatibility with polyurethane emulsion and good heat resistance can be obtained by adding the diphenyl sulphonyl imine and the polyether amine in the proportion, amino in the additive can be added with isocyanate groups in the polyurethane emulsion to react, an interpenetrating network structure is formed in the polyurethane emulsion, the water resistance and the strength of the polyurethane emulsion are facilitated, and the adhesion of polyurethane ink is also facilitated to be improved.
(3) The allyl-terminated additive prepared by the invention contains allyl groups which can carry out addition reaction with hydrosilyl groups, chloroplatinic acid is added as a catalyst, so that the hydrosilyl groups of the modified filler can react with allyl groups in the allyl-terminated additive, the modified filler is connected with the allyl-terminated additive, and part of modified filler which is not connected with allyl groups can also be added with hydroxyl groups in a polyether structure, and finally, the composite additive with good compatibility with polyurethane is obtained, and the composite additive has a reticular structure which wraps the modified filler and has stable performance.
(4) The preparation method of the aqueous polyurethane emulsion is environment-friendly.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The following examples include the following materials: colorant (model: phthalocyanine blue B, shanghai source leaf); leveling agent (model: bi-167, dongguan Baolin New Material Co., ltd.); dispersing agent (model: 4035, dongguan chemical Co., ltd.); allyl polyoxyalkylene epoxy ether (model: CS, hubei scintillation Biotechnology Co., ltd.); polyetheramine (model: D-2000, shanghai Shake Co., ltd.); diphenyl sulphonimide (CAS: 2618-96-4); methyl methacrylate (CAS: 80-62-6); allyl acrylate (CAS: 999-55-3); azobisisobutyronitrile (CAS: 78-67-1); sodium dodecyl benzene sulfonate (CAS:25155-30-0); hydrogen-terminated polydimethylsiloxane (division of organosilicon, e.g., dongguan); adipic acid (CAS: 124-04-9); 2, 4-tetramethyl-1, 3-cyclobutanediol (CAS: 3010-96-6); catalyst (dibutyl tin dilaurate, CAS: 77-58-7); terephthalyl diisocyanate (CAS: 104-49-4); 2, 2-Dimethylolpropionic acid (CAS: 4767-03-7); polytetrahydrofuran (model: TH-3, hubei Jiang Mintai Huachen Co., ltd.); chloroplatinic acid (markanos technologies limited);
the following parts are mass parts;
example 1: s1: mixing 20 parts of methyl methacrylate, 3 parts of allyl acrylate, 0.1 part of azodiisobutyronitrile and 42 parts of water, heating and stirring for 5 hours under the protection of nitrogen, adding 1 part of sodium dodecyl benzene sulfonate and 10 parts of hydrogen-terminated polydimethylsiloxane, homogenizing for 8 minutes at room temperature at a rotating speed of 10000r/min, filtering, drying and crushing to obtain modified filler;
s2: taking 18 parts of allyl polyoxyalkyl epoxy ether, 18 parts of polyether amine D-2000, 6 parts of diphenyl sulphonyl imine and 90 parts of isopropanol, stirring, heating to 50 ℃, and reacting for 5 hours to obtain an allyl-terminated additive;
s3: adding 40 parts of modified filler, 18 parts of terminal allyl additive and 0.01 part of chloroplatinic acid into 85 parts of isopropanol, and stirring for 5 hours at 110 ℃ to obtain a composite additive;
s4: uniformly mixing 80 parts of adipic acid, 110 parts of 2, 4-tetramethyl-1, 3-cyclobutanediol and 0.2 part of catalyst, heating to 230 ℃ under the protection of nitrogen, reacting for 6 hours, adding 50 parts of terephthalyl diisocyanate, 6 parts of 2, 2-dimethylolpropionic acid and 70 parts of polytetrahydrofuran, and reacting for 3 hours at normal temperature to form polyurethane emulsion;
s5: 60 parts of polyurethane emulsion, 25 parts of water, 18 parts of composite additive, 10 parts of pigment, 0.5 part of flatting agent and 1 part of dispersing agent are taken, and are added into a sand mill to be ground for 0.5h at the speed of 1800r/min, so that the high-temperature-resistant polyurethane ink is obtained.
Example 2: s1: mixing 16 parts of methyl methacrylate, 2 parts of allyl acrylate, 0.1 part of azodiisobutyronitrile and 42 parts of water, heating and stirring for 5 hours under the protection of nitrogen, adding 0.5 part of sodium dodecyl benzene sulfonate and 8 parts of hydrogen-terminated polydimethylsiloxane, homogenizing for 8 minutes at room temperature at 10000r/min, filtering, drying and crushing to obtain modified filler;
s2: 15 parts of allyl polyoxyalkyl epoxy ether, 15 parts of polyether amine, 5 parts of diphenyl sulphonyl imine and 80 parts of isopropanol are taken, stirred and heated to 50 ℃ for 4 hours to obtain an allyl end additive;
s3: adding 35 parts of modified filler, 15 parts of terminal allyl additive and 0.01 part of chloroplatinic acid into 85 parts of isopropanol, and stirring for 5 hours at 110 ℃ to obtain a composite additive;
s4: uniformly mixing 70 parts of adipic acid, 110 parts of 2, 4-tetramethyl-1, 3-cyclobutanediol and 0.1-0.3 part of catalyst, heating to 230 ℃ under the protection of nitrogen, reacting for 6 hours, adding 40 parts of terephthalyl diisocyanate, 5 parts of 2, 2-dimethylolpropionic acid and 60 parts of polytetrahydrofuran, and reacting for 3 hours at normal temperature to form polyurethane emulsion;
s5: 50 parts of polyurethane emulsion, 20 parts of water, 13 parts of composite additive, 8 parts of pigment, 1 part of flatting agent and 2 parts of dispersing agent are taken and added into a sand mill, and the mixture is ground for 0.5h at the speed of 1800r/min, so that the high-temperature-resistant polyurethane ink is obtained.
Example 3: s1: mixing 22 parts of methyl methacrylate, 4 parts of allyl acrylate, 0.2 part of azodiisobutyronitrile and 50 parts of water, heating and stirring for 5 hours under the protection of nitrogen, adding 1.5 parts of sodium dodecyl benzene sulfonate and 15 parts of hydrogen-terminated polydimethylsiloxane, homogenizing for 8 minutes at room temperature at 10000r/min, filtering, drying and crushing to obtain modified filler;
s2: taking 20 parts of allyl polyoxyalkyl epoxy ether, 21 parts of polyether amine D-2000, 7 parts of diphenyl sulphonyl imine and 100 parts of isopropanol, stirring and heating to 50 ℃, and reacting for 5 hours to obtain an allyl-terminated additive;
s3: 45 parts of modified filler, 20 parts of terminal allyl additive and 0.01 part of chloroplatinic acid are added into 85 parts of isopropanol, and the mixture is stirred for 5 hours at 110 ℃ to obtain a composite additive;
s4: uniformly mixing 90 parts of adipic acid, 130 parts of 2, 4-tetramethyl-1, 3-cyclobutanediol and 0.1-0.3 part of catalyst, heating to 230 ℃ under the protection of nitrogen, reacting for 6 hours, adding 60 parts of terephthalyl diisocyanate, 7 parts of 2, 2-dimethylolpropionic acid and 80 parts of polytetrahydrofuran, and reacting for 3 hours at normal temperature to form polyurethane emulsion;
s5: 65 parts of polyurethane emulsion, 30 parts of water, 20 parts of composite additive, 12 parts of pigment, 1 part of flatting agent and 1 part of dispersing agent are taken and added into a sand mill, and the mixture is ground for 0.5h at 1800r/min to obtain the high-temperature-resistant polyurethane ink.
Example 4: the printing process comprises the following steps: printing the high-temperature-resistant polyurethane ink on the surface of the paperboard on a paperboard printer, wherein the temperature of a printing roller is 70 ℃, the drying treatment temperature is 50 ℃, and the treatment time is 1h.
Comparative example 1 (replacement of modified filler with hydrogen-terminated polydimethylsiloxane, the remaining process steps being identical to example 1): s1: taking 18 parts of allyl polyoxyalkyl epoxy ether, 18 parts of polyether amine D-2000, 6 parts of diphenyl sulphonyl imine and 90 parts of isopropanol, stirring, heating to 50 ℃, and reacting for 5 hours to obtain an allyl-terminated additive;
s2: adding 40 parts of hydrogen-terminated polydimethylsiloxane, 18 parts of an allyl-terminated additive and 0.01 part of chloroplatinic acid into 85 parts of isopropanol, and stirring at 110 ℃ for 5 hours to obtain a composite additive;
s3: uniformly mixing 80 parts of adipic acid, 110 parts of 2, 4-tetramethyl-1, 3-cyclobutanediol and 0.2 part of catalyst, heating to 230 ℃ under the protection of nitrogen, reacting for 6 hours, adding 50 parts of terephthalyl diisocyanate, 6 parts of 2, 2-dimethylolpropionic acid and 70 parts of polytetrahydrofuran, and reacting for 3 hours at normal temperature to form polyurethane emulsion;
s4: 60 parts of polyurethane emulsion, 25 parts of water, 18 parts of composite additive, 10 parts of pigment, 0.5 part of flatting agent and 1 part of dispersing agent are taken, and are added into a sand mill to be ground for 0.5h at the speed of 1800r/min, so that the high-temperature-resistant polyurethane ink is obtained.
Comparative example 2 (without making a composite additive, hydrogen-terminated polydimethylsiloxane, polymethyl methacrylate, polyetheramine, diphenyl sulphonimide, allyl polyoxyalkylene epoxy ether, and the remaining process steps were identical to example 1) was added directly to the polyurethane emulsion: s1: uniformly mixing 80 parts of adipic acid, 110 parts of 2, 4-tetramethyl-1, 3-cyclobutanediol and 0.2 part of catalyst, heating to 230 ℃ under the protection of nitrogen, reacting for 6 hours, adding 50 parts of terephthalyl diisocyanate, 6 parts of 2, 2-dimethylolpropionic acid and 70 parts of polytetrahydrofuran, and reacting for 3 hours at normal temperature to form polyurethane emulsion;
s2: 20 parts of polymethyl methacrylate, 18 parts of allyl polyoxyalkylene epoxy ether, 18 parts of polyether amine D-2000, 6 parts of diphenyl sulphonyl imine, 20 parts of hydrogen end-capped polydimethylsiloxane, 60 parts of polyurethane emulsion, 25 parts of water, 10 parts of pigment, 0.5 part of flatting agent and 1 part of dispersing agent are added into a sand mill, and the mixture is ground for 0.5h at 1800r/min to obtain the high-temperature-resistant polyurethane ink.
Comparative example 3 (varying the amount of polyetheramine and diphenylsulphonimide added to the terminal allyl additive, the remaining process steps being identical to example 1): s1: mixing 20 parts of methyl methacrylate, 3 parts of allyl acrylate, 0.1 part of azodiisobutyronitrile and 42 parts of water, heating and stirring for 5 hours under the protection of nitrogen, adding 1 part of sodium dodecyl benzene sulfonate and 10 parts of hydrogen-terminated polydimethylsiloxane, homogenizing for 8 minutes at room temperature at a rotating speed of 10000r/min, filtering, drying and crushing to obtain modified filler;
s2: taking 18 parts of allyl polyoxyalkyl epoxy ether, 22 parts of polyether amine D-2000, 2 parts of diphenyl sulphonyl imine and 90 parts of isopropanol, stirring, heating to 50 ℃, and reacting for 5 hours to obtain an allyl-terminated additive;
s3: adding 40 parts of modified filler, 18 parts of terminal allyl additive and 0.01 part of chloroplatinic acid into 85 parts of isopropanol, and stirring for 5 hours at 110 ℃ to obtain a composite additive;
s4: uniformly mixing 80 parts of adipic acid, 110 parts of 2, 4-tetramethyl-1, 3-cyclobutanediol and 0.2 part of catalyst, heating to 230 ℃ under the protection of nitrogen, reacting for 6 hours, adding 50 parts of terephthalyl diisocyanate, 6 parts of 2, 2-dimethylolpropionic acid and 70 parts of polytetrahydrofuran, and reacting for 3 hours at normal temperature to form polyurethane emulsion;
s5: 60 parts of polyurethane emulsion, 25 parts of water, 18 parts of composite additive, 10 parts of pigment, 0.5 part of flatting agent and 1 part of dispersing agent are taken, and are added into a sand mill to be ground for 0.5h at the speed of 1800r/min, so that the high-temperature-resistant polyurethane ink is obtained.
Comparative example 4 (silica coated polymethyl methacrylate with the remaining process steps being identical to example 1): s1: mixing 20 parts of methyl methacrylate, 3 parts of allyl acrylate, 0.1 part of azodiisobutyronitrile and 42 parts of water, heating and stirring for 5 hours under the protection of nitrogen, adding 1 part of sodium dodecyl benzene sulfonate and 10 parts of nano silicon dioxide, homogenizing for 8 minutes at room temperature at a rotating speed of 10000r/min, filtering, drying and crushing to obtain modified filler;
s2: taking 18 parts of allyl polyoxyalkyl epoxy ether, 18 parts of polyether amine D-2000, 6 parts of diphenyl sulphonyl imine and 90 parts of isopropanol, stirring, heating to 50 ℃, and reacting for 5 hours to obtain an allyl-terminated additive;
s3: adding 40 parts of modified filler, 18 parts of terminal allyl additive and 0.01 part of chloroplatinic acid into 85 parts of isopropanol, and stirring for 5 hours at 110 ℃ to obtain a composite additive;
s4: uniformly mixing 80 parts of adipic acid, 110 parts of 2, 4-tetramethyl-1, 3-cyclobutanediol and 0.2 part of catalyst, heating to 230 ℃ under the protection of nitrogen, reacting for 6 hours, adding 50 parts of terephthalyl diisocyanate, 6 parts of 2, 2-dimethylolpropionic acid and 70 parts of polytetrahydrofuran, and reacting for 3 hours at normal temperature to form polyurethane emulsion;
s5: 60 parts of polyurethane emulsion, 25 parts of water, 18 parts of composite additive, 10 parts of pigment, 0.5 part of flatting agent and 1 part of dispersing agent are taken, and are added into a sand mill to be ground for 0.5h at the speed of 1800r/min, so that the high-temperature-resistant polyurethane ink is obtained.
Experiment: (1) Referring to GB1037-88 standard, the high temperature resistant polyurethane inks prepared in examples 1-3 and comparative examples 1-4 were printed to obtain a film with a thickness of 50 μm, and subjected to a water resistance test to test the water vapor permeation amount after 24 hours; (2) The high temperature resistant polyurethane inks prepared in examples 1 to 3 and comparative examples 1 to 4 were tested for the decomposition temperature at 10%; specific data are shown in the following table;
conclusion: as can be seen from the table, the high-temperature-resistant polyurethane ink prepared in the example 1 has the best comprehensive performance; as is clear from comparative example 1, when the modified filler is replaced with hydrogen-terminated polydimethylsiloxane, the water resistance of the high-temperature-resistant polyurethane ink is not greatly affected, but the heat resistance is lowered; when the composite additive is not prepared, raw materials are directly added into polyurethane emulsion for modification, the water resistance and heat resistance of the obtained high-temperature-resistant polyurethane ink are obviously reduced due to the problems that part of raw materials are poor in compatibility with the polyurethane emulsion, complete cross-linked structures are not formed and the like; comparative example 3 changes the addition ratio of polyetheramine and diphenyl sulphonyl imine provided by the invention, and it can be seen that the high temperature resistance of the obtained high temperature resistant polyurethane ink is reduced due to the reduced addition amount of the diphenyl sulphonyl imine; the modified filler prepared in comparative example 4 contains no silicon hydride groups, cannot be added with allyl groups in allyl polyoxyalkylene epoxy ether, and the water resistance and heat resistance of the finally obtained high-temperature-resistant polyurethane ink are different from those of examples 1 to 3;
in conclusion, the scheme provided by the invention can prepare the polyurethane ink which has good water resistance, good heat resistance and meets the environmental protection requirement.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The high-temperature-resistant polyurethane ink is characterized by comprising the following raw materials in parts by weight: 50 to 65 parts of polyurethane emulsion, 20 to 30 parts of water, 13 to 20 parts of composite additive, 8 to 12 parts of pigment, 0.5 to 1 part of flatting agent and 1 to 2 parts of dispersing agent.
2. The high temperature resistant polyurethane ink of claim 1, wherein: the preparation method of the composite additive comprises the following steps: s1: mixing methyl methacrylate, allyl acrylate, azodiisobutyronitrile and water, heating and stirring for 4-6 hours under the protection of nitrogen, adding sodium dodecyl benzene sulfonate and hydrogen-terminated polydimethylsiloxane, homogenizing, filtering, drying and crushing to obtain modified filler;
s2: taking allyl polyoxyalkyl epoxy ether, diphenyl sulphonyl imide, polyether amine and isopropanol, heating and stirring, and reacting for 4-5 hours to obtain an allyl-terminated additive;
s3: and (3) taking the modified filler, the terminal allyl additive, the isopropanol and the chloroplatinic acid, heating and stirring the mixture at the temperature of 80-120 ℃ and stirring the mixture for 3-6 hours to obtain the composite additive.
3. The high temperature resistant polyurethane ink of claim 2, wherein: the composite additive comprises the following raw materials in parts by weight: 35-45 parts of modified filler, 15-20 parts of terminal allyl additive, 80-100 parts of isopropanol and 0.01-0.02 part of chloroplatinic acid.
4. The high temperature resistant polyurethane ink of claim 2, wherein: the allyl-terminated additive comprises the following raw materials in parts by weight: 15-20 parts of allyl polyoxyalkyl epoxy ether, 15-21 parts of polyether amine, 5-7 parts of diphenyl sulphonyl imine and 80-100 parts of isopropanol.
5. The high temperature resistant polyurethane ink of claim 2, wherein: the polyetheramine comprises a high molecular weight polyetheramine; the mass ratio of polyetheramine to diphenyl sulphonimide is 3:1.
6. the high temperature resistant polyurethane ink of claim 2, wherein: the modified filler comprises the following raw materials in parts by weight: 16 to 22 parts of methyl methacrylate, 1 to 4 parts of allyl acrylate, 0.1 to 0.2 part of azodiisobutyronitrile, 0.5 to 1.5 parts of sodium dodecyl benzene sulfonate, 8 to 15 parts of hydrogen end-capped polydimethylsiloxane and 40 to 50 parts of water.
7. The high temperature resistant polyurethane ink of claim 1, wherein: the preparation method of the polyurethane emulsion comprises the following steps: mixing adipic acid, 2, 4-tetramethyl-1, 3-cyclobutanediol and a catalyst, heating to 220-240 ℃ under the protection of nitrogen, reacting for 4-6 hours, adding terephthalyl diisocyanate, 2-dimethylolpropionic acid and polytetrahydrofuran, and reacting for 2-4 hours at normal temperature to obtain the polyurethane emulsion.
8. The high temperature resistant polyurethane ink of claim 7, wherein: the polyurethane emulsion comprises the following raw materials in parts by weight: 70 to 90 parts of adipic acid, 110 to 130 parts of 2, 4-tetramethyl-1, 3-cyclobutanediol, 0.1 to 0.3 part of catalyst, 40 to 60 parts of terephthal-isocyanate, 5 to 7 parts of 2, 2-dimethylolpropionic acid and 60 to 80 parts of polytetrahydrofuran.
9. A method for preparing the high temperature resistant polyurethane ink as claimed in any one of claims 1 to 8, characterized in that: the method comprises the following steps: and uniformly mixing polyurethane emulsion, water, a composite additive, pigment, a leveling agent and a dispersing agent, and grinding for 0.5-1 h to obtain the high-temperature-resistant polyurethane ink.
10. A printing process of high-temperature-resistant polyurethane ink is characterized in that: the method comprises the following steps: the high temperature resistant polyurethane ink as claimed in any one of claims 1 to 8 is printed at a temperature of 70 to 80 ℃ and after the printing is finished, the printing is dried at a temperature of 50 to 60 ℃ for 0.5 to 1 hour.
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