CN111004542A - Degradable film water-based printing ink and preparation method thereof - Google Patents
Degradable film water-based printing ink and preparation method thereof Download PDFInfo
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- CN111004542A CN111004542A CN201911355223.9A CN201911355223A CN111004542A CN 111004542 A CN111004542 A CN 111004542A CN 201911355223 A CN201911355223 A CN 201911355223A CN 111004542 A CN111004542 A CN 111004542A
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- acrylic resin
- printing ink
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 238000007639 printing Methods 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 91
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 91
- 108010073771 Soybean Proteins Proteins 0.000 claims abstract description 49
- 235000019710 soybean protein Nutrition 0.000 claims abstract description 46
- 229920001285 xanthan gum Polymers 0.000 claims abstract description 46
- 235000010493 xanthan gum Nutrition 0.000 claims abstract description 43
- 239000000230 xanthan gum Substances 0.000 claims abstract description 43
- 229940082509 xanthan gum Drugs 0.000 claims abstract description 43
- 239000004368 Modified starch Substances 0.000 claims abstract description 38
- 229920000881 Modified starch Polymers 0.000 claims abstract description 38
- 235000019426 modified starch Nutrition 0.000 claims abstract description 38
- 239000010409 thin film Substances 0.000 claims abstract description 36
- 239000010408 film Substances 0.000 claims abstract description 32
- 239000004203 carnauba wax Substances 0.000 claims abstract description 16
- 239000000049 pigment Substances 0.000 claims abstract description 16
- 239000003755 preservative agent Substances 0.000 claims abstract description 16
- 230000002335 preservative effect Effects 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 235000013869 carnauba wax Nutrition 0.000 claims abstract description 15
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims description 74
- 239000000178 monomer Substances 0.000 claims description 48
- 239000003999 initiator Substances 0.000 claims description 45
- 239000003995 emulsifying agent Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 18
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000012875 nonionic emulsifier Substances 0.000 claims description 14
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 239000012874 anionic emulsifier Substances 0.000 claims description 5
- 229940001941 soy protein Drugs 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 12
- 229920006238 degradable plastic Polymers 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 230000036541 health Effects 0.000 abstract description 4
- 239000000976 ink Substances 0.000 description 69
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000463 material Substances 0.000 description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 9
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical group [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000004302 potassium sorbate Substances 0.000 description 2
- 229940069338 potassium sorbate Drugs 0.000 description 2
- 235000010241 potassium sorbate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- WSWCOQWTEOXDQX-MQQKCMAXSA-M (E,E)-sorbate Chemical compound C\C=C\C=C\C([O-])=O WSWCOQWTEOXDQX-MQQKCMAXSA-M 0.000 description 1
- 240000000972 Agathis dammara Species 0.000 description 1
- 235000004758 Bergkiefer Nutrition 0.000 description 1
- 229920002871 Dammar gum Polymers 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000010450 Pino mugo Nutrition 0.000 description 1
- 241001136577 Pinus mugo Species 0.000 description 1
- 235000002914 Pinus uncinata Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 210000001320 hippocampus Anatomy 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940075554 sorbate Drugs 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000008096 xylene Substances 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
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- 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
-
- 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
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention provides degradable film water-based printing ink and a preparation method thereof, wherein the degradable film water-based printing ink comprises the following components in parts by weight: 8-32 parts of soybean protein water-based acrylic resin, 10-25 parts of xanthan gum modified water-based acrylic resin, 6-22 parts of modified starch water-based acrylic resin, 15-40 parts of water-based environment-friendly pigment slurry, 1-5 parts of defoaming agent, 1-5 parts of preservative, 1-5 parts of carnauba wax agent and 4-20 parts of water. The degradable thin film water-based printing ink disclosed by the invention can be completely degraded, does not generate harmful substances, does not bring pollution to the environment, does not cause harm to human health, is a novel environment-friendly degradable thin film water-based printing ink, is applied to degradable plastic printing, solves the problems of non-degradable condition and secondary pollution caused by the fact that the conventional solvent is commonly adopted in the degradable thin film printing ink in the market at present, and has great market application significance.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, relates to a water-based ink preparation technology, and particularly relates to degradable thin-film water-based printing ink and a preparation method thereof.
Background
With the development of market economy, the packaging industry develops rapidly, various plastic films continuously appear, and meanwhile, the environmental problems caused by the application of the plastic films are not ignored. Under the large background of sustainable development, the degradable environment-friendly plastic packaging material is imperatively developed by adding an auxiliary agent to improve the components of the plastic. The concept is also suitable for printing ink of a printing film, and the plastic film ink is an important material widely applied to the printing industry and is mainly used for plastic printing of daily necessities, food, fruits, fresh foods and the like. Along with the increasing attention of people on environmental protection, the use amount of degradable films for printing and packaging is more and more in the market, but the printing ink for degradable film printing is mainly prepared from traditional resin components such as polypropylene and dammar resin serving as main binders at present, and the prepared printing ink can release toluene, xylene, chlorobenzene, acetone, propionaldehyde and other VOC (volatile organic compounds) harmful gases such as ethers, esters and alcohols in the printing process, can not be degraded when printed on the degradable films and can bring secondary environmental pollution. Therefore, the development of environment-friendly printing ink, the safety of the ink is ensured, and the reduction of the environmental pollution of the ink is an important direction for the development of the ink industry.
Disclosure of Invention
The invention aims to provide degradable thin film water-based printing ink and a preparation method thereof aiming at the defects of the prior art, the water-based printing ink can be completely degraded, does not generate harmful substances, does not bring pollution to the environment, does not cause harm to human health, is novel environment-friendly degradable thin film water-based printing ink, is applied to degradable plastic printing, solves the problems of non-degradability and secondary pollution caused by the fact that the conventional solvent is generally adopted in the degradable thin film printing ink in the market at present, and has great market application significance.
Based on the above purpose, the invention adopts the technical scheme that:
a degradable film water-based printing ink comprises the following components in parts by weight:
preferably, the degradable thin film water-based printing ink comprises the following components in parts by weight:
the degradable film water-based printing ink selects the soybean protein water-based acrylic resin, the xanthan gum modified water-based acrylic resin and the modified starch water-based acrylic resin as the main components of the ink, through the coupling crosslinking effect generated by the molecular chains of the three components, a reticular film forming material is formed, thereby improving the defects of water resistance and adhesion resistance of the ink, various technical performance indexes applied to the degradable film reach the standard of the traditional printing ink, no harmful substance is released in the printing process, no harm is caused to human health, the soybean protein water-based acrylic resin, the xanthan gum modified water-based acrylic resin and the modified starch water-based acrylic resin are successfully applied to the degradable plastic printing, and the problems of non-degradable condition and secondary pollution caused by the fact that the traditional solvent is commonly adopted in the degradable film printing ink in the market at present are solved.
Preferably, the soybean protein water-based acrylic resin is a self-made material; the soybean protein water-based acrylic resin has the density of 0.95-1.10g/mL, the viscosity of 1200-1800cPs, the pH value of 7.0-8.0, the glass transition temperature of 63-68 ℃ and good degradability.
The soybean protein water-based acrylic resin comprises the following raw materials in parts by weight:
40-60 parts of soybean protein powder, 2.5-5 parts of emulsifier, 150 parts of acrylate monomer, 5-10 parts of N-hydroxymethyl acrylamide, 10-20 parts of initiator and 400 parts of water 250.
Preferably, the emulsifier comprises one or more of a nonionic emulsifier and an anionic emulsifier. More preferably, the emulsifier is a non-ionic emulsifier OP-10 and/or sodium lauryl sulphate.
Preferably, the acrylate monomer is butyl acrylate and/or methyl methacrylate.
Preferably, the initiator is ammonium persulfate and/or potassium persulfate.
The invention also provides a preparation method of the soybean protein water-based acrylic resin, and the preparation method is used for preparing the soybean protein water-based acrylic resin in the components of the degradable film water-based printing ink.
A preparation method of a soybean protein water-based acrylic resin comprises the following steps:
adding soybean protein powder and an emulsifier into water, heating and stirring to obtain pre-emulsified soybean protein liquid;
mixing an acrylate monomer and N-hydroxymethyl acrylamide to obtain a mixed monomer;
and adding a certain amount of mixed monomer and a certain amount of initiator into the pre-emulsified soybean protein liquid, heating and stirring, adding the rest of mixed monomer and the rest of initiator, and preserving heat to obtain the soybean protein water-based acrylic resin.
Preferably, the pre-emulsified soybean protein liquid is obtained by adding soybean protein powder and an emulsifier into water, heating to 45-65 ℃, and stirring for 15-60min at a stirring speed of 80-100 rpm.
Preferably, the amount of the mixed monomers is 25-40% of the total amount of the mixed monomers; the certain amount of the initiator accounts for 25-40% of the total amount of the initiator.
Preferably, adding a certain amount of mixed monomers and a certain amount of initiator into the pre-emulsified soybean protein liquid, and heating to 75-95 ℃ under the stirring state; adding the rest mixed monomer and the rest initiator, and preserving the heat for 30-90min at 80-90 ℃ to obtain the soybean protein water-based acrylic resin.
More preferably, a certain amount of mixed monomers and a certain amount of initiator are added to the pre-emulsified soy protein liquid, and the pre-emulsified soy protein liquid is heated to 93 ℃ and then cooled to 75-85 ℃ under stirring.
More preferably, the remaining mixed monomers and the remaining initiator are slowly added dropwise over 1-2 h.
Preferably, the xanthan gum modified water-based acrylic resin is a self-made material; the molecular weight of the xanthan gum modified waterborne acrylic resin is 8000-10000, the viscosity is 3000-4000cPs, the softening point is 120-140 ℃, and the glass transition temperature is 83-88 ℃.
The xanthan gum modified water-based acrylic resin comprises the following raw materials in parts by weight:
10-20 parts of xanthan gum powder, 5-10 parts of emulsifier, 200 parts of acrylate monomer, 3-8 parts of acrylic acid, 5-10 parts of initiator and 300 parts of water 200-.
Preferably, the emulsifier comprises one or more of a nonionic emulsifier and an anionic emulsifier. More preferably, the emulsifier is a non-ionic emulsifier OP-10 and/or sodium lauryl sulphate.
Preferably, the acrylate monomer is butyl acrylate and/or methyl methacrylate.
Preferably, the initiator is ammonium persulfate and/or potassium persulfate.
The invention also provides a preparation method of the xanthan gum modified water-based acrylic resin, and the preparation method is used for preparing the xanthan gum modified water-based acrylic resin in the components of the degradable thin-film water-based printing ink.
A preparation method of xanthan gum modified water-based acrylic resin comprises the following steps:
adding xanthan gum powder and an emulsifier into water, heating and stirring to obtain a pre-emulsified xanthan gum solution;
mixing an acrylate monomer and acrylic acid to obtain a mixed monomer;
adding a mixed monomer into the obtained pre-emulsified xanthan gum solution, stirring, adding an initiator, and stirring to obtain a pre-emulsified liquid;
transferring a certain amount of the pre-emulsion to another container, heating and stirring, adding the rest pre-emulsion, heating and stirring, and keeping the temperature to obtain the xanthan gum modified water-based acrylic resin.
Preferably, the xanthan gum powder and the emulsifier are added into water, heated to 45-65 ℃ and stirred for 5-30min at the stirring speed of 300-800rpm to obtain the pre-emulsified xanthan gum liquid.
Preferably, the mixed monomer is added into the pre-emulsified xanthan gum liquid, and the mixture is stirred for 5 to 30 min; adding initiator, and stirring for 5-30min to obtain pre-emulsion.
Preferably, the amount of pre-emulsion is about 10-20% of the total amount of pre-emulsion.
Preferably, a certain amount of the pre-emulsion is transferred to another container, heated to 80-99 ℃, and stirred at 200-; adding the rest pre-emulsion, heating to 80-90 deg.C, stirring for 20-60min, and maintaining the temperature for 20-60min to obtain xanthan gum modified water-based acrylic resin.
More preferably, a quantity of the pre-emulsion is transferred to another vessel, heated to 98 ℃ and then lowered to 80-90 ℃ under stirring at 200-300 rpm.
More preferably, the remaining pre-emulsion is slowly added dropwise over 3-4 h.
Preferably, the modified starch water-based acrylic resin is a self-made material; the molecular weight of the modified starch water-based acrylic resin is 4000-5500, and the glass transition temperature is 22-30 ℃.
The modified starch water-based acrylic resin comprises the following raw material components in parts by weight:
15-30 parts of modified starch, 5-15 parts of emulsifier, 90-140 parts of methyl methacrylate, 60-80 parts of butyl acrylate, 3-9 parts of acrylic acid, 2-8 parts of N-hydroxymethyl acrylamide, 0.2-1 part of initiator and 400 parts of water 250.
Preferably, the emulsifier comprises one or more of a nonionic emulsifier and an anionic emulsifier. More preferably, the emulsifier is a non-ionic emulsifier OP-10 and/or sodium lauryl sulphate.
Preferably, the initiator is ammonium persulfate and/or potassium persulfate.
The invention also provides a preparation method of the modified starch water-based acrylic resin, and the preparation method is used for preparing the modified starch water-based acrylic resin in the components of the degradable film water-based printing ink.
A preparation method of modified starch water-based acrylic resin comprises the following steps:
mixing butyl acrylate, acrylic acid and N-hydroxymethyl acrylamide to obtain a mixed monomer;
adding modified starch and emulsifier into water, heating and stirring;
adding methyl methacrylate and a certain amount of initiator, heating and stirring;
adding the mixed monomer and the rest of the initiator, heating, stirring and preserving heat to obtain the modified starch water-based acrylic resin.
Preferably, the modified starch and the emulsifier are added to water and heated to 45-65 ℃ and stirred at 800rpm with a stirring speed of 300-.
Preferably, the amount of initiator is about 40 to 60% of the total amount of initiator.
Preferably, methyl methacrylate and a certain amount of initiator are added and heated to 75-95 ℃ with stirring.
More preferably, methyl methacrylate and an amount of initiator are added, heated to 93 ℃ and then reduced to 75-85 ℃ while stirring.
Preferably, the mixed monomer and the rest of the initiator are added, heated to 80-90 ℃ and stirred for 20-60 min; preserving the heat for 20-60min at 80-90 ℃ to obtain the modified starch water-based acrylic resin.
More preferably, the mixing of the monomers and the remainder of the initiator is carried out slowly over a period of from 1 to 2 hours.
Specifically, the water-based environment-friendly pigment slurry is preferably WB series water-based pigment slurry produced by Guangdong Kedi New Material science and technology Limited, has fine texture and bright color, can be directly diluted by water, and also can be directly added into water-based resin emulsion to be stirred and dispersed at a low speed, and has good chemical stability and acid and alkali resistance.
In particular, the defoamer is preferably of Germany winning, developing, solid and the like
Airex920W defoaming agent, which is white emulsion, can be diluted by water in any proportion, has excellent defoaming performance, and is used for inkThe defoaming of (2) improves the leveling property and wettability of the ink.
Preferably, the preservative is potassium sorbate. Specifically, the preservative is potassium osmanthalite sorbate of Nantong acetic acid chemical Co., Ltd, and the preservative has high-efficiency and safe corrosion resistance.
Specifically, the baxi palm wax agent is preferably T1 carnauba wax, guangzhou dynamite chemical company, ltd.
The invention also provides a preparation method of the degradable film water-based printing ink, which comprises the following steps:
mixing soybean protein water-based acrylic resin, xanthan gum modified water-based acrylic resin, modified starch water-based acrylic resin and water, and stirring;
adding aqueous environment-friendly pigment slurry, a defoaming agent and a preservative, stirring and grinding;
adding the carnauba wax agent, and stirring to obtain the degradable film water-based printing ink.
Preferably, the soybean protein water-based acrylic resin, the xanthan gum modified water-based acrylic resin, the modified starch water-based acrylic resin and water are added into a dosing cylinder for stirring, the stirring speed is 400-500rpm, and the stirring time is 25-30 min.
Preferably, the aqueous environment-friendly pigment slurry, the defoaming agent and the preservative are added under the stirring state, the stirring speed is 400-500rpm, and the stirring is continued for 10-20 min.
Preferably, the grinding is carried out with a sand mill at a constant temperature of 20-35 ℃.
Preferably, the carnauba wax agent is added under the stirring state, the stirring speed is 400-500rpm, and the stirring is continued for 5-20min, so as to obtain the degradable thin-film water-based printing ink.
Specifically, the preparation method of the degradable thin film water-based printing ink comprises the following steps:
adding the soybean protein water-based acrylic resin, the xanthan gum modified water-based acrylic resin, the modified starch water-based acrylic resin and water into a mixing cylinder, and stirring at the stirring speed of 400-500rpm for 25-30 min;
adding the aqueous environment-friendly pigment slurry, the defoaming agent and the preservative under stirring, continuing stirring for 10-20min, and grinding by using a sand mill at a constant temperature of 20-35 ℃;
adding the carnauba wax agent under stirring, and continuously stirring for 5-20min to obtain the degradable film water-based printing ink
More specifically, the preparation method of the degradable thin-film water-based printing ink comprises the following steps:
(1) adding the soybean protein water-based acrylic resin, the xanthan gum modified water-based acrylic resin, the modified starch water-based acrylic resin and water into a mixing cylinder according to the amount, and stirring at the stirring speed of 450rpm for 25 min;
(2) adding the aqueous environment-friendly pigment slurry, the defoaming agent and the preservative under the stirring state, and continuing stirring for 15 minutes;
(3) grinding the materials for one to three times by a sand mill under the condition of constant temperature of 30 ℃;
(4) adding the carnauba wax agent under the stirring state, and continuously stirring for 10min to obtain the degradable film water-based printing ink.
Compared with the prior art, the invention has the following advantages:
the invention provides degradable thin film water-based printing ink and a preparation method thereof, wherein the raw materials are nontoxic and pollution-free, no harmful gas is released in the printing process, the degradable thin film water-based printing ink is a novel environment-friendly degradable thin film water-based printing ink, is used for degradable plastic printing, solves the problems of non-degradability and secondary pollution caused by the fact that the conventional solvent is generally adopted in the degradable thin film printing ink in the market at present, and has great market application significance.
Detailed Description
Example 1
A degradable film water-based printing ink is composed of the following components in parts by weight:
the soybean protein water-based acrylic resin comprises the following raw materials in parts by weight:
50 parts of soybean protein powder, 3.5 parts of emulsifier, 144 parts of acrylate monomer, 6 parts of N-hydroxymethyl acrylamide, 16 parts of initiator and 300 parts of water.
The soybean protein powder is purchased from Linyi mountain pine biological products, Inc.; the emulsifier is nonionic emulsifier OP-10 and sodium dodecyl sulfate, and the mass ratio of the volume of the nonionic emulsifier OP-10 to the mass of the sodium dodecyl sulfate is 3: 4; the acrylate monomer is prepared by compounding butyl acrylate and methyl methacrylate according to the mass ratio of 5:4, wherein the butyl acrylate, the methyl methacrylate and the N-hydroxymethyl acrylamide are purchased from Sanwang chemical materials Co., Ltd, Guangzhou; the initiator is ammonium persulfate which is purchased from Sanwang chemical materials Co., Ltd.
A preparation method of a soybean protein water-based acrylic resin comprises the following steps:
adding soybean protein powder and emulsifier into a three-neck flask filled with water, heating to 55 ℃, and stirring at 80rpm for 20min to obtain pre-emulsified soybean protein liquid;
mixing an acrylate monomer and N-hydroxymethyl acrylamide to obtain a mixed monomer;
adding 30% of mixed monomer and 40% of initiator into the pre-emulsified soybean protein liquid, heating to 93 ℃ under stirring, then cooling to 78 ℃, slowly dripping the rest of mixed monomer and the rest of initiator within 1.5h, and keeping the temperature at 88 ℃ for 60min to obtain the soybean protein water-based acrylic resin.
The obtained soybean protein water-based acrylic resin is white liquid, the density is 1.02g/mL, the viscosity is 1500cPs, the pH value is 7.0, and the glass transition temperature is 65 ℃.
The xanthan gum modified water-based acrylic resin comprises the following raw materials in parts by weight:
14 parts of xanthan gum powder, 7 parts of emulsifier, 180 parts of acrylate monomer, 5 parts of acrylic acid, 7 parts of initiator and 250 parts of water.
The xanthan gum powder is purchased from Shandong Fufeng fermentation Co., Ltd; the emulsifier is nonionic emulsifier OP-10 and sodium dodecyl sulfate, and the mass ratio of the volume of the nonionic emulsifier OP-10 to the sodium dodecyl sulfate is 1: 2; the acrylate monomer is prepared by compounding butyl acrylate and methyl methacrylate according to the mass ratio of 3:2, wherein the butyl acrylate, the methyl methacrylate and the acrylic acid are purchased from Sanwang chemical materials Co., Ltd, Guangzhou; the initiator is potassium persulfate.
A preparation method of xanthan gum modified water-based acrylic resin comprises the following steps:
adding xanthan gum powder and emulsifier into a single-neck flask filled with water, heating to 55 ℃, and emulsifying for 15min at a stirring speed of 400rpm to obtain pre-emulsified xanthan gum liquid;
mixing an acrylate monomer and acrylic acid to obtain a mixed monomer;
adding the mixed monomer into the obtained pre-emulsified xanthan gum solution, stirring for 15min, adding an initiator, and stirring for 15min to obtain a pre-emulsified liquid;
adding 15% of pre-emulsion into a three-neck flask, heating to 98 ℃ under the stirring state of 250rpm, then cooling to 85 ℃, slowly dripping the rest pre-emulsion within 3.5h, stirring for 30 minutes at 85 ℃, heating to 90 ℃, keeping the temperature for 30 minutes to obtain xanthan gum modified waterborne acrylic resin, cooling to 35 ℃, and discharging.
The obtained xanthan gum modified water-based acrylic resin is transparent liquid, the molecular weight is 8600, the viscosity is 3500cPs, the softening point is 135 ℃, and the glass transition temperature is 85 ℃.
The modified starch water-based acrylic resin comprises the following raw material components in parts by weight:
22 parts of modified starch, 9 parts of emulsifier, 110 parts of methyl methacrylate, 74 parts of butyl acrylate, 6 parts of acrylic acid, 4 parts of N-hydroxymethyl acrylamide, 0.7 part of initiator and 276 parts of water.
The modified starch is purchased from Hippocampus starch chemistry, Inc. of Changshan city; the emulsifier is nonionic emulsifier OP-10 and sodium dodecyl sulfate, and the mass ratio of the volume of the nonionic emulsifier OP-10 to the mass of the sodium dodecyl sulfate is 4: 5; the initiator is ammonium persulfate; methyl methacrylate, butyl acrylate, acrylic acid, N-methylolacrylamide and ammonium persulfate were purchased from Sanwang chemical materials, Inc., Guangzhou.
A preparation method of modified starch water-based acrylic resin comprises the following steps:
mixing butyl acrylate, acrylic acid and N-hydroxymethyl acrylamide to obtain a mixed monomer;
adding modified starch and emulsifier into a three-neck flask filled with water, heating to 55 ℃, and emulsifying for 15min at a stirring speed of 400 rpm;
adding methyl methacrylate and 50% of initiator, heating to 93 ℃ under the stirring state, and then reducing to 80 ℃;
slowly dripping the mixed monomer and the rest of the initiator within 1.5h, stirring for 30 minutes at 85 ℃, heating to 88 ℃, keeping the temperature for 30 minutes to obtain the modified starch water-based acrylic resin, cooling to 35 ℃, and discharging.
The water-based environment-friendly pigment slurry is WB series water-based pigment slurry produced by Guangdong Kedi new material science and technology limited; the defoaming agent is prepared by the German winning, developing and solid match company
Airex920W defoamer; the preservative is potassium sorbate of Tiangui brand of Nantong acetic acid chemical Co.Ltd; the carnauba wax agent is T1 carnauba wax from Guangzhou toll peak chemical company Limited.
A preparation method of degradable thin-film water-based printing ink comprises the following steps:
(1) adding the soybean protein water-based acrylic resin, the xanthan gum modified water-based acrylic resin, the modified starch water-based acrylic resin and water into a mixing cylinder according to the amount, and stirring at the stirring speed of 450rpm for 25 min;
(2) adding the aqueous environment-friendly pigment slurry, the defoaming agent and the preservative under the stirring state, and continuing stirring for 15 minutes;
(3) grinding the materials for one to three times by a sand mill under the condition of constant temperature of 30 ℃;
(4) adding the carnauba wax agent under the stirring state, and continuously stirring for 10min to obtain the degradable film water-based printing ink.
Example 2
A degradable film water-based printing ink is composed of the following components in parts by weight:
the soybean protein aqueous acrylic resin, xanthan gum modified aqueous acrylic resin, modified starch aqueous acrylic resin, aqueous environmental protection pigment slurry, defoaming agent, preservative and carnauba wax agent of this example were the same as in example 1.
The method for preparing the degradable thin-film aqueous printing ink of the present example is the same as that of example 1.
Example 3
A degradable film water-based printing ink is composed of the following components in parts by weight:
the soybean protein aqueous acrylic resin, xanthan gum modified aqueous acrylic resin, modified starch aqueous acrylic resin, aqueous environmental protection pigment slurry, defoaming agent, preservative and carnauba wax agent of this example were the same as in example 1.
The method for preparing the degradable thin-film aqueous printing ink of the present example is the same as that of example 1.
Comparative example 1
A degradable film water-based printing ink is composed of the following components in parts by weight:
the comparative examples were the same as example 1 in terms of soybean protein aqueous acrylic resin, xanthan gum-modified aqueous acrylic resin, modified starch aqueous acrylic resin, aqueous environmental-friendly pigment slurry, antifoaming agent, preservative, and carnauba wax agent.
The preparation method of the degradable thin-film aqueous printing ink of this comparative example was the same as in example 1.
Comparative example 2
A degradable film water-based printing ink is composed of the following components in parts by weight:
the comparative examples were the same as example 1 in terms of soybean protein aqueous acrylic resin, xanthan gum-modified aqueous acrylic resin, modified starch aqueous acrylic resin, aqueous environmental-friendly pigment slurry, antifoaming agent, preservative, and carnauba wax agent.
The preparation method of the degradable thin-film aqueous printing ink of this comparative example was the same as in example 1.
Comparative example 3
This comparative example did not add modified starch waterborne acrylic resin.
A degradable film water-based printing ink is composed of the following components in parts by weight:
the comparative examples were the same as example 1 in terms of soybean protein aqueous acrylic resin, xanthan gum-modified aqueous acrylic resin, modified starch aqueous acrylic resin, aqueous environmental-friendly pigment slurry, antifoaming agent, preservative, and carnauba wax agent.
The preparation method of the degradable thin-film aqueous printing ink of this comparative example was the same as in example 1.
The components and parts by weight of the degradable thin film aqueous printing inks of examples 1 to 3 and comparative examples 1 to 3 are shown in table 1.
TABLE 1 degradable thin film aqueous printing inks components and parts by weight
The technical indexes of the degradable thin film water-based printing ink obtained in the examples 1 to 3 and the comparative examples 1 to 3 are detected, and the test results of the performance indexes are shown in table 2. Wherein the fineness is tested by a scraper fineness meter according to GB/T13217.3-2008 & lt & ltliquid ink fineness test method & gt; detecting the pH value by using a pH tester; the viscosity was measured by a viscometer according to the method of the Swan cup viscometer in GB/T13217.4-2008 "method for measuring viscosity of liquid ink" No. 3 Swan cup; the tinting strength is tested according to GB/T14624.2-2008 test for tinting strength of offset ink; the gloss is tested by a 60-degree standard gloss meter according to GB/T13217.2-2009 liquid ink gloss test method; water resistance was tested according to GB/T1733-1993 determination of Water resistance of paint films; the adhesion degree is tested according to GB T13217.8-2009 liquid ink anti-adhesion test method; printing the ink on a glass plate, according to GB/T19277.1-2011 method for determining the final aerobic biological decomposition capability of a material under controlled composting conditions by measuring the released carbon dioxide, part 1: the general method detects the biological decomposition rate.
TABLE 2 degradable film Water-based printing ink technical index
| Performance index | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Fineness/. mu.m | ≤10 | ≤10 | ≤10 | ≤10 | ≤10 | ≤10 |
| pH value | 8 | 8.3 | 8.2 | 8.5 | 8.6 | 8.2 |
| Viscosity/s | 18 | 19 | 19 | 18 | 17 | 19 |
| Coloring power% | 100 | 100 | 100 | 100 | 100 | 100 |
| Gloss of | 86° | 87° | 84° | 83° | 79° | 80° |
| Water resistance | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified |
| Degree of blocking | 0 | 0 | 0 | 4％ | 3％ | 2％ |
| Biological decomposition rate | ≥90％ | ≥90％ | ≥90％ | ≥90％ | ≥90％ | ≥90％ |
As can be seen from the technical index performance parameters of the degradable thin film water-based printing ink in Table 2, the degradable thin film water-based printing ink prepared in the embodiments 1-3 of the present invention has excellent technical index performance, and has bright and bright color, and the properties of fineness, viscosity, tinting strength, water resistance, blocking resistance, etc. reach higher standards. The degradable thin film water-based printing ink disclosed by the invention is completely degradable, and a degradation test is carried out under the condition of normal temperature and normal humidity, so that the degradable thin film water-based printing ink takes about 3 months for degradation to a stable stage (the biological decomposition rate is more than or equal to 90%), and the product function of the ink is met. Meanwhile, the degradable film water-based printing ink disclosed by the invention has no harmful substance release in the printing process, does not cause harm to human health, is a novel environment-friendly degradable film water-based printing ink, is used for printing degradable plastics, and solves the problems of non-degradable condition and secondary pollution caused by the fact that the conventional solvent is generally adopted in the degradable film printing ink in the market at present.
Comparing the components and parts by weight of the comparative examples 1-3 with those of the example 2, the soybean protein aqueous acrylic resin of the comparative example 1 is relatively less in parts by weight, the xanthan gum modified aqueous acrylic resin and the modified starch aqueous acrylic resin of the comparative examples 2 and 3 are relatively too less in parts by weight, and the degradable thin-film aqueous printing ink prepared in the comparative examples 1-3 achieves higher standards of tinting strength, gloss and water resistance under the condition that the fineness, the pH value and the viscosity are basically the same as those of the examples 1-3, but the images and texts of the comparative examples 1-3 are partially adhered, wherein the images and texts of the comparative example 1 are most seriously adhered.
The above-mentioned embodiments are only preferred embodiments of the present invention, and not intended to limit the scope of the present invention, so that equivalent changes or modifications made by the constructions, features and principles described in the claims of the present invention should be included in the scope of the present invention.
Claims (10)
1. The soybean protein water-based acrylic resin is characterized by comprising the following raw material components in parts by weight:
40-60 parts of soybean protein powder, 2.5-5 parts of emulsifier, 150 parts of acrylate monomer, 5-10 parts of N-hydroxymethyl acrylamide, 10-20 parts of initiator and 400 parts of water 250.
2. The soybean protein aqueous acrylic resin as claimed in claim 1, wherein the emulsifier is one or more of a nonionic emulsifier and an anionic emulsifier; the acrylate monomer is butyl acrylate and/or methyl methacrylate; the initiator is ammonium persulfate and/or potassium persulfate.
3. The method for preparing a soy protein water-based acrylic resin as claimed in claim 1 or 2, comprising the steps of:
adding soybean protein powder and an emulsifier into water, heating and stirring to obtain pre-emulsified soybean protein liquid;
mixing an acrylate monomer and N-hydroxymethyl acrylamide to obtain a mixed monomer;
adding 25-40% of mixed monomer and 25-40% of initiator into the pre-emulsified soybean protein liquid, heating and stirring, adding the rest of mixed monomer and the rest of initiator, and preserving heat to obtain the soybean protein water-based acrylic resin.
4. The degradable film water-based printing ink is characterized by comprising the following components in parts by weight:
5. the degradable thin-film aqueous printing ink according to claim 4, wherein the xanthan gum modified aqueous acrylic resin comprises the following raw material components in parts by weight:
10-20 parts of xanthan gum powder, 5-10 parts of emulsifier, 200 parts of acrylate monomer, 3-8 parts of acrylic acid, 5-10 parts of initiator and 300 parts of water 200-.
6. The degradable thin-film aqueous printing ink according to claim 5, wherein the emulsifier comprises one or more of a nonionic emulsifier and an anionic emulsifier; the acrylate monomer is butyl acrylate and/or methyl methacrylate; the initiator is ammonium persulfate and/or potassium persulfate.
7. The degradable thin-film aqueous printing ink according to claim 5 or 6, wherein the preparation method of the xanthan gum modified aqueous acrylic resin comprises the following steps:
adding xanthan gum powder and an emulsifier into water, heating and stirring to obtain a pre-emulsified xanthan gum solution;
mixing an acrylate monomer and acrylic acid to obtain a mixed monomer;
adding a mixed monomer into the obtained pre-emulsified xanthan gum solution, stirring, adding an initiator, and stirring to obtain a pre-emulsified liquid;
and transferring the 10-20% pre-emulsion to another container, heating and stirring, adding the rest pre-emulsion, heating and stirring, and keeping the temperature to obtain the xanthan gum modified water-based acrylic resin.
8. The degradable thin-film aqueous printing ink according to claim 4, wherein the modified starch aqueous acrylic resin comprises the following raw material components in parts by weight:
15-30 parts of modified starch, 5-15 parts of emulsifier, 90-140 parts of methyl methacrylate, 60-80 parts of butyl acrylate, 3-9 parts of acrylic acid, 2-8 parts of N-hydroxymethyl acrylamide, 0.2-1 part of initiator and 400 parts of water 250.
9. The degradable thin-film aqueous printing ink of claim 8, wherein the preparation method of the modified starch aqueous acrylic resin comprises the following steps:
mixing butyl acrylate, acrylic acid and N-hydroxymethyl acrylamide to obtain a mixed monomer;
adding modified starch and emulsifier into water, heating and stirring;
adding methyl methacrylate and 40-60% of initiator, heating and stirring;
adding the mixed monomer and the rest of the initiator, heating, stirring and preserving heat to obtain the modified starch water-based acrylic resin.
10. The method for preparing the degradable thin-film aqueous printing ink of any one of claims 4 to 9, comprising the steps of:
mixing soybean protein water-based acrylic resin, xanthan gum modified water-based acrylic resin, modified starch water-based acrylic resin and water, and stirring;
adding aqueous environment-friendly pigment slurry, a defoaming agent and a preservative, stirring and grinding;
adding the carnauba wax agent, and stirring to obtain the degradable film water-based printing ink.
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Denomination of invention: A degradable thin film water-based printing ink and its preparation method Effective date of registration: 20231213 Granted publication date: 20220527 Pledgee: Cuishanhu Technology Branch of Guangdong Kaiping Rural Commercial Bank Co.,Ltd. Pledgor: GUANGDONG DEKANG CHEMICAL INDUSTRY Co.,Ltd. Registration number: Y2023980071379 |