CN112011218A - Novel environment-friendly odorless printing ink and preparation method thereof - Google Patents
Novel environment-friendly odorless printing ink and preparation method thereof Download PDFInfo
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- 238000007639 printing Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000009965 odorless effect Effects 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 63
- 239000001254 oxidized starch Substances 0.000 claims abstract description 36
- 235000013808 oxidized starch Nutrition 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 229920003055 poly(ester-imide) Polymers 0.000 claims abstract description 22
- 239000008187 granular material Substances 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000000049 pigment Substances 0.000 claims abstract description 12
- 229920000767 polyaniline Polymers 0.000 claims abstract description 9
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 8
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 5
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 229920002472 Starch Polymers 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000008107 starch Substances 0.000 claims description 23
- 235000019698 starch Nutrition 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 230000008961 swelling Effects 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 238000006068 polycondensation reaction Methods 0.000 claims description 13
- 150000002466 imines Chemical class 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 10
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims description 10
- 229920001225 polyester resin Polymers 0.000 claims description 10
- 239000004645 polyester resin Substances 0.000 claims description 10
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 150000002148 esters Chemical group 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 claims description 3
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 claims description 3
- 229960004419 dimethyl fumarate Drugs 0.000 claims description 3
- APWRLAZEMYLHKZ-UHFFFAOYSA-N 2-amino-5,6-dimethyl-1h-pyrimidin-4-one Chemical compound CC=1NC(N)=NC(=O)C=1C APWRLAZEMYLHKZ-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 2
- 230000021615 conjugation Effects 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 61
- 239000010410 layer Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 238000003848 UV Light-Curing Methods 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
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- 238000010992 reflux Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
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- 238000006467 substitution reaction Methods 0.000 description 2
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- 235000013311 vegetables Nutrition 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/16—Polyester-imides
-
- 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
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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 belongs to the technical field of printing coatings, and particularly relates to novel environment-friendly odorless printing ink and a preparation method thereof. The product developed by the invention comprises the following raw materials in parts by weight: 30-60 parts of pigment, 10-20 parts of polyester imide resin, 10-15 parts of nano graphene oxide, 3-5 parts of surfactant and 1-5 parts of defoaming agent; the polyester-imide resin takes n-butyl phthalate as a cross-linking agent, and the chain length between adjacent cross-linking points is greater than the length of a chain segment under the same condition; oxidized starch particles are embedded between the nano graphene oxide layers. In addition, sulfonated polyaniline is also adsorbed between the graphene oxide layers; at least part of the carboxyl groups in the oxidized starch granules are oxidized into aldehyde groups; the oxidized starch particles are connected with hydroxyl groups of a conjugation zone between the nano graphene oxide layers through aldehyde groups to form chemical bonding. The product obtained by the invention has excellent ink balance performance and good printing effect.
Description
Technical Field
The invention belongs to the technical field of printing coatings. And more particularly, to a novel environment-friendly odorless printing ink and a preparation method thereof.
Background
Ink is an essential raw material as one of five major printing elements. At present, the environmental protection ink mainly comprises water-based ink, UV curing ink and vegetable ink.
The water-based ink takes water as a carrier, has low viscosity and good fluidity, does not use volatile organic solvent, is beneficial to environmental protection, and is a green printing material which accords with environmental protection and no public nuisance. The solvent used by the ink is water or alcohol, so that the emission of VOCs is obviously reduced, the atmospheric pollution can be prevented, and the harm of toxic and harmful substances in the solvent type ink to human bodies and the pollution of packaged commodities are eliminated. Therefore, water-based inks are widely favored by the industry and have become a representative of environmentally friendly inks. At present, the packaging printing ink is mainly applied to packaging printing products with strict requirements on sanitary conditions, such as cigarettes, wines, medicines, toys for children and the like, but further wide application is yet to be popularized.
The UV curable ink is a curable ink in which a binder in the ink undergoes a photo-curing reaction under irradiation of ultraviolet rays having a certain wavelength, thereby completing curing without generating a contaminant. Therefore, the UV curing ink has the advantages of high environmental protection performance, wide adaptability of printing stocks, instant curing, good stability, high production efficiency and the like, so that the UV curing ink is determined by more and more enterprises in the printing and packaging industry and is mainly used in offset printing, flexo printing and ink jet printing. At present, domestic UV ink gradually replaces imported products, and most domestic ink production enterprises have UV ink of own brand. The UV ink with more price advantages is provided for printing enterprises, more technical services are provided, the popularization and application of the UV technology in China are actively promoted, and the field can be continuously developed at a high speed.
Vegetable ink is ink which contains vegetable oil components in the ink and replaces hydrocarbon substances in traditional ink by the components, and is generally environment-friendly soybean ink. The ink meets the requirement of environmental protection, has good printing performance, saves cost, has wide color range and rich colors, and has better color rendering capability. In addition, the appearance and research and development of the ink can not only reduce environmental pollution, but also promote the development of agriculture. The win-win development mode of enterprises and agriculture can be supported by places and countries, and is also a great trend in the future.
Through the analysis, the existing environment-friendly ink is based on the components of the ink, and the environment-friendly material is used for replacing harmful substances in the traditional ink, so that a new environment-friendly ink product is obtained. At present, both water-based ink and UV curing ink have certain problems. The defects and obstacles such as poor performance of the water-based ink, poor pigment wettability of the UV ink and poor balance performance of the water-based ink need further improvement, breakthrough and research.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings of poor printing effect of a product in the using process due to poor water-based ink and UV ink balance performance in the existing printing ink, and provides a novel environment-friendly odorless printing ink and a preparation method thereof.
The invention aims to provide novel environment-friendly odorless printing ink.
The invention also aims to provide a preparation method of the novel environment-friendly odorless printing ink.
The above purpose of the invention is realized by the following technical scheme:
a novel environment-friendly odorless printing ink comprises the following raw materials in parts by weight:
30-60 parts of pigment, 10-20 parts of polyester imide resin, 10-15 parts of nano graphene oxide, 3-5 parts of surfactant and 1-5 parts of defoaming agent;
the polyester-imide resin takes n-butyl phthalate as a cross-linking agent, and the chain length between adjacent cross-linking points is greater than the length of a chain segment under the same condition;
oxidized starch particles are embedded between the nano graphene oxide layers.
In the technical scheme, the polyester-imide resin is added, wherein the polyester-imide resin takes n-butyl phthalate as a cross-linking agent, and the chain length between adjacent cross-linking points is greater than the length of a chain segment under the same condition; therefore, the macromolecular chain segment in the resin is not easy to move, and the small molecular chain segment can still keep better movement capability, so that the rigidity and the flexibility of the macromolecular cross-linked network structure are unified, and when the ink supply amount to a printing plate exceeds balance in the actual use process of a product and ink is strongly extruded, the ink molecules are effectively bound, and the ink molecules are prevented from diffusing to a blank; on the contrary, when the water supply amount to the layout exceeds the balance value, the ink layer of the image-text part is protected, and the dark and dull print caused by emulsification is avoided;
in addition, according to the technical scheme, the nano graphene oxide is used as an auxiliary material, and the oxidized starch particles are embedded between the layers of the nano graphene oxide, so that the oxidized starch particles can swell under the action of moisture in the preparation process, the distance between the graphene oxide layers is widened, the widened distance between the layers can form an accommodating space to effectively accommodate pigment molecules, so that the pigment molecules can be adsorbed and fixed on the surface of the substrate by taking the graphene oxide as a medium in the use process of the product, and the nano graphene oxide with the oxidized starch particles embedded between the layers can be balanced by effectively coordinating ink and water, so that the surface tension of the substrate of the product is changed, and the pigment printing effect is improved.
Furthermore, sulfonated polyaniline is adsorbed between the graphene oxide layers.
By adsorbing sulfonated polyaniline between graphene oxide layers, certain electrostatic repulsion force exists between graphene oxide layer structures, the interlayer spacing is widened to a certain extent, and the embedding of starch particles in the subsequent preparation process is facilitated.
Further, at least a part of the carboxyl groups in the oxidized starch granules are oxidized to aldehyde groups.
Furthermore, the oxidized starch particles are connected with hydroxyl groups of a conjugation zone between the nano graphene oxide layers through aldehyde groups to form chemical bonding.
According to the technical scheme, the aldehyde group of the oxidized starch particle and the hydroxyl group of the conjugated region between the nano graphene oxide layers are subjected to an aldol condensation reaction to form chemical bonding, the embedded oxidized starch particle is effectively fixed between the layers of the oxidized graphene, the two are prevented from being separated in the product storage process, the storage stability of the product is improved, and the performance of the product can be effectively exerted in the using process.
A preparation method of novel environment-friendly odorless printing ink comprises the following specific preparation steps:
(1) synthesis of polyester-imide resin:
carrying out ester exchange reaction on dibasic ester, ethylene glycol and mosaic to obtain polyester resin with hydroxyl at two ends;
reacting trimellitic anhydride with diamine to obtain imine dibasic acid with carboxyl at two ends;
carrying out high-temperature polycondensation on the polyester resin with hydroxyl groups at two ends and the imine dibasic acid with carboxyl groups at two ends, uniformly mixing a polycondensation product and a solvent, adding n-butyl phthalate with the mass of 1-5% of that of the polycondensation product, and heating and stirring for reaction to obtain the polyester imine resin;
(2) modification of nano graphene oxide:
according to the weight parts, 80-120 parts of oxidized starch granules, 8-10 parts of glycerol and 3-5 parts of ethylene glycol are sequentially taken, stirred and mixed uniformly to obtain pretreated oxidized starch;
the pretreatment oxidized starch and the nano graphene oxide are mixed according to the mass ratio of 1: 10-1: 50, performing ball milling reaction for 48-72 hours to obtain a ball grinding material;
drying the ball milling material to constant weight to obtain modified nano graphene oxide;
(3) preparation of a printing ink product:
according to the weight parts, 30-60 parts of pigment, 10-20 parts of polyester imide resin, 10-15 parts of modified nano graphene oxide, 3-5 parts of surfactant and 1-5 parts of defoaming agent are sequentially taken and uniformly dispersed to obtain the printing ink.
Further, the dibasic ester is any one of dimethyl terephthalate, diethyl terephthalate, dimethyl fumarate, dimethyl carbonate, dimethyl sulfate and dipropyl adipate.
Further, the diamine is any one of 4 '4-diaminodiphenylmethane, 1' 6-hexamethylenediamine and ethylenediamine.
Further, the specific preparation steps further comprise:
oxidation of starch:
mixing starch and water according to a mass ratio of 1: 5-1: 10, mixing and swelling to obtain starch swelling liquid;
adding sodium periodate with the mass of 1-5% of the starch swelling liquid into the starch swelling liquid, heating and stirring for reaction, and then carrying out spray granulation to obtain oxidized starch granules.
Further, the nano graphene oxide in the step (2) is pre-treated nano graphene oxide;
the preparation process of the pretreated nano graphene oxide comprises the following steps:
mixing nano graphene oxide and water according to a mass ratio of 1: 10-1: 15, performing ultrasonic dispersion, adding sulfonated polyaniline accounting for 5-10% of the mass of the nano graphene oxide, heating, stirring, reacting, and performing spray drying to obtain the pretreated nano graphene oxide.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
Synthesis of polyester-imide resin:
taking 60 parts of dibasic ester, 80 parts of ethylene glycol and 3 parts of mosaic in sequence by weight, mixing, and carrying out ester exchange reaction to obtain polyester resin with hydroxyl at two ends;
trimellitic anhydride and diamine are mixed according to the mass ratio of 3: 1, heating and refluxing for 6 hours at the temperature of 75 ℃, and discharging to obtain imine dibasic acid containing carboxyl at two ends;
and (2) mixing the polyester resin containing hydroxyl groups at two ends and the imine dibasic acid containing carboxyl groups at two ends according to a molar ratio of 1: 1, carrying out high-temperature polycondensation reaction for 3 hours at the temperature of 85 ℃, and then mixing the polycondensation product and the solvent according to the mass ratio of 1: 5, uniformly mixing, adding n-butyl phthalate accounting for 1 percent of the mass of the polycondensation product, heating and stirring for reaction for 3 hours at the temperature of 75 ℃ and the rotating speed of 400r/min, and discharging to obtain the polyester-imide resin;
modification of nano graphene oxide:
mixing nano graphene oxide and water according to a mass ratio of 1: 10, performing ultrasonic dispersion for 30min under the ultrasonic frequency of 45kHz, adding sulfonated polyaniline accounting for 5 percent of the mass of the nano graphene oxide, heating and stirring for reaction for 1h under the conditions that the temperature is 50 ℃ and the rotating speed is 300r/min, and performing spray drying to obtain the pretreated nano graphene oxide;
mixing starch and water according to a mass ratio of 1: 5, mixing and swelling to obtain starch swelling liquid; adding sodium periodate with the mass of 1 percent of the starch swelling liquid into the starch swelling liquid, heating and stirring the mixture for reaction for 2 hours at the temperature of 75 ℃ and the rotating speed of 300r/min, and then carrying out spray granulation to obtain oxidized starch granules;
according to the weight parts, 80 parts of oxidized starch granules, 8 parts of glycerol and 3 parts of ethylene glycol are sequentially taken, stirred and mixed uniformly to obtain pretreated oxidized starch;
the pretreatment oxidized starch and the pretreatment nano graphene oxide are mixed according to the mass ratio of 1: 10, mixing and pouring into a ball milling tank, and mixing according to the ball material mass ratio of 10: 1, adding zirconia ball grinding beads, and performing ball-milling reaction for 48 hours to obtain a ball grinding material;
drying the ball milling material to constant weight to obtain modified nano graphene oxide;
preparation of a printing ink product:
according to the weight parts, 30 parts of pigment, 10 parts of polyester imide resin, 10 parts of modified nano graphene oxide, 3 parts of sodium dodecyl benzene sulfonate and 1 part of defoaming agent are sequentially taken and uniformly dispersed to obtain printing ink;
the dibasic ester is dimethyl terephthalate;
the diamine is 4' 4-diaminodiphenylmethane.
Example 2
Synthesis of polyester-imide resin:
taking 70 parts of dibasic ester, 85 parts of ethylene glycol and 5 parts of saxok in sequence by weight, mixing, and carrying out ester exchange reaction to obtain polyester resin with hydroxyl at two ends;
trimellitic anhydride and diamine are mixed according to a mass ratio of 4: 1, heating and refluxing for 7 hours at the temperature of 78 ℃, and discharging to obtain imine dibasic acid containing carboxyl at two ends;
and (2) mixing the polyester resin containing hydroxyl groups at two ends and the imine dibasic acid containing carboxyl groups at two ends according to a molar ratio of 1: 1, carrying out high-temperature polycondensation reaction for 4 hours at the temperature of 90 ℃, and then mixing the polycondensation product and the solvent according to the mass ratio of 1: 6, uniformly mixing, adding n-butyl phthalate accounting for 3% of the mass of the polycondensation product, heating and stirring for reaction for 4 hours at the temperature of 80 ℃ and the rotating speed of 500r/min, and discharging to obtain the polyester-imide resin;
modification of nano graphene oxide:
mixing nano graphene oxide and water according to a mass ratio of 1: 12, performing ultrasonic dispersion for 50min under the ultrasonic frequency of 55kHz, adding sulfonated polyaniline accounting for 8 percent of the mass of the nano graphene oxide, heating and stirring for reaction for 2h under the conditions that the temperature is 60 ℃ and the rotating speed is 400r/min, and performing spray drying to obtain the pretreated nano graphene oxide;
mixing starch and water according to a mass ratio of 1: 8, mixing and swelling to obtain starch swelling liquid; adding sodium periodate with the mass of 3 percent of that of the starch swelling solution into the starch swelling solution, heating and stirring the mixture for reaction for 3 hours at the temperature of 80 ℃ and the rotating speed of 400r/min, and then carrying out spray granulation to obtain oxidized starch granules;
according to the weight parts, 100 parts of oxidized starch granules, 9 parts of glycerol and 4 parts of ethylene glycol are sequentially taken, stirred and mixed uniformly to obtain pretreated oxidized starch;
the pretreatment oxidized starch and the pretreatment nano graphene oxide are mixed according to the mass ratio of 1: 30, mixing and pouring into a ball milling tank, and mixing according to the ball material mass ratio of 20: 1, adding zirconia ball grinding beads, and carrying out ball-milling reaction for 56 hours to obtain a ball grinding material;
drying the ball milling material to constant weight to obtain modified nano graphene oxide;
preparation of a printing ink product:
according to the weight parts, 50 parts of pigment, 15 parts of polyester imide resin, 12 parts of modified nano graphene oxide, 4 parts of emulsifier OP-10 and 3 parts of defoaming agent are sequentially taken, and the components are uniformly dispersed to obtain printing ink;
the dibasic ester is diethyl terephthalate;
the diamine is 1' 6-hexanediamine.
Example 3
Synthesis of polyester-imide resin:
mixing 80 parts by weight of dibasic ester, 90 parts by weight of ethylene glycol and 10 parts by weight of cecal in sequence, and then carrying out ester exchange reaction to obtain polyester resin with hydroxyl groups at two ends;
trimellitic anhydride and diamine are mixed according to the mass ratio of 5: 1, heating and refluxing for 8 hours at the temperature of 85 ℃, and discharging to obtain imine dibasic acid containing carboxyl at two ends;
and (2) mixing the polyester resin containing hydroxyl groups at two ends and the imine dibasic acid containing carboxyl groups at two ends according to a molar ratio of 2: 1, carrying out high-temperature polycondensation reaction for 5 hours at the temperature of 95 ℃, and then mixing the polycondensation product with a solvent according to the mass ratio of 1: 8, uniformly mixing, adding n-butyl phthalate accounting for 5 percent of the mass of the polycondensation product, heating and stirring for reaction for 5 hours at the temperature of 85 ℃ and the rotating speed of 600r/min, and discharging to obtain the polyester-imide resin;
modification of nano graphene oxide:
mixing nano graphene oxide and water according to a mass ratio of 1: 15, performing ultrasonic dispersion for 60min under the ultrasonic frequency of 65kHz, adding sulfonated polyaniline with the mass of 10% of that of the nano graphene oxide, heating and stirring for reaction for 3h under the conditions that the temperature is 70 ℃ and the rotating speed is 500r/min, and performing spray drying to obtain the pretreated nano graphene oxide;
mixing starch and water according to a mass ratio of 1: 10, mixing and swelling to obtain starch swelling liquid; adding sodium periodate with the mass of 5 percent of the starch swelling liquid into the starch swelling liquid, heating and stirring for reaction for 4 hours at the temperature of 85 ℃ and the rotating speed of 500r/min, and then carrying out spray granulation to obtain oxidized starch granules;
according to the weight parts, 120 parts of oxidized starch granules, 10 parts of glycerol and 5 parts of ethylene glycol are sequentially taken, stirred and mixed uniformly to obtain pretreated oxidized starch;
the pretreatment oxidized starch and the pretreatment nano graphene oxide are mixed according to the mass ratio of 1: 50, mixing and pouring into a ball milling tank, and mixing according to the ball material mass ratio of 30: 1, adding zirconia ball grinding beads, and carrying out ball-milling reaction for 72 hours to obtain a ball grinding material;
drying the ball milling material to constant weight to obtain modified nano graphene oxide;
preparation of a printing ink product:
according to the weight parts, 60 parts of pigment, 20 parts of polyester imide resin, 15 parts of modified nano graphene oxide, 5 parts of tween-60 and 5 parts of defoaming agent are sequentially taken, and the components are uniformly dispersed to obtain printing ink;
the dibasic ester is dimethyl fumarate;
the diamine is ethylenediamine.
Comparative example 1
This comparative example differs from example 1 in that: the polyester-imide resin is replaced by acrylic resin with equal mass, and the rest conditions are kept unchanged.
Comparative example 2
This comparative example differs from example 1 in that: no oxidized starch granules were added and the remaining conditions were kept unchanged.
Comparative example 3
Compared with example 1, the oxidized starch particles are directly added and are not embedded between the nano graphene oxide layers, and the rest conditions are kept unchanged.
The products obtained in examples 1 to 3 and comparative examples 1 to 3 were subjected to performance tests, and the specific test methods and test results were as follows:
tinting strength: the tinting strength of each product is tested by referring to GB/T13217.6-2009, and the specific test results are shown in Table 1;
and (3) color testing: testing the colors of the products by referring to GB/T13217.1-2009, wherein the specific test results are shown in Table 1;
gloss testing: testing the colors of the products by referring to GB/T13217.2-2009, wherein the specific test results are shown in Table 1;
table 1: product performance test results
As can be seen from the test results in Table 1, the product obtained by the invention has excellent color and luster, excellent ink balance performance in the using process and excellent tinting strength.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. The novel environment-friendly odorless printing ink is characterized by comprising the following raw materials in parts by weight:
30-60 parts of pigment, 10-20 parts of polyester imide resin, 10-15 parts of nano graphene oxide, 3-5 parts of surfactant and 1-5 parts of defoaming agent;
the polyester-imide resin takes n-butyl phthalate as a cross-linking agent, and the chain length between adjacent cross-linking points is greater than the length of a chain segment under the same condition;
oxidized starch particles are embedded between the nano graphene oxide layers.
2. The novel environment-friendly odorless printing ink according to claim 1, wherein sulfonated polyaniline is also adsorbed between graphene oxide layers.
3. The novel environmentally friendly odorless printing ink according to claim 1, wherein at least a part of the carboxyl groups in the oxidized starch granule are oxidized to aldehyde groups.
4. The novel environment-friendly odorless printing ink according to claim 3, wherein the oxidized starch particles are connected through aldehyde groups and hydroxyl groups in the conjugated region between the nano graphene oxide layers to form chemical bonds.
5. A preparation method of novel environment-friendly odorless printing ink is characterized by comprising the following specific preparation steps:
(1) synthesis of polyester-imide resin:
carrying out ester exchange reaction on dibasic ester, ethylene glycol and mosaic to obtain polyester resin with hydroxyl at two ends;
reacting trimellitic anhydride with diamine to obtain imine dibasic acid with carboxyl at two ends;
carrying out high-temperature polycondensation on the polyester resin with hydroxyl groups at two ends and the imine dibasic acid with carboxyl groups at two ends to obtain polyester-imine resin;
(2) modification of nano graphene oxide:
according to the weight parts, 80-120 parts of oxidized starch granules, 8-10 parts of glycerol and 3-5 parts of ethylene glycol are sequentially taken, stirred and mixed uniformly to obtain pretreated oxidized starch;
the pretreatment oxidized starch and the nano graphene oxide are mixed according to the mass ratio of 1: 10-1: 50, performing ball milling reaction for 48-72 hours to obtain a ball grinding material;
drying the ball milling material to constant weight to obtain modified nano graphene oxide;
(3) preparation of a printing ink product:
according to the weight parts, 30-60 parts of pigment, 10-20 parts of polyester imide resin, 10-15 parts of modified nano graphene oxide, 3-5 parts of surfactant and 1-5 parts of defoaming agent are sequentially taken and uniformly dispersed to obtain the printing ink.
6. The method for preparing novel environment-friendly odorless printing ink according to claim 5, wherein the dibasic ester is any one of dimethyl terephthalate, diethyl terephthalate, dimethyl fumarate, dimethyl carbonate, dimethyl sulfate and dipropyl adipate.
7. The method for preparing novel environment-friendly odorless printing ink according to claim 5, wherein the diamine is any one of 4 ', 4-diaminodiphenylmethane, 1', 6-hexamethylenediamine and ethylenediamine.
8. The preparation method of the novel environment-friendly odorless printing ink according to claim 5, wherein the specific preparation steps further comprise:
oxidation of starch:
mixing starch and water according to a mass ratio of 1: 5-1: 10, mixing and swelling to obtain starch swelling liquid;
adding sodium periodate with the mass of 1-5% of the starch swelling liquid into the starch swelling liquid, heating and stirring for reaction, and then carrying out spray granulation to obtain oxidized starch granules.
9. The preparation method of the novel environment-friendly odorless printing ink according to claim 5, wherein the nano graphene oxide in the step (2) is pre-treated nano graphene oxide;
the preparation process of the pretreated nano graphene oxide comprises the following steps:
mixing nano graphene oxide and water according to a mass ratio of 1: 10-1: 15, performing ultrasonic dispersion, adding sulfonated polyaniline accounting for 5-10% of the mass of the nano graphene oxide, heating, stirring, reacting, and performing spray drying to obtain the pretreated nano graphene oxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130699A (en) * | 2014-07-18 | 2014-11-05 | 上海晟然绝缘材料有限公司 | High adhesion and solvent resistant insulating paint for polyester imide enameled wire and preparation method thereof |
| CN104140757A (en) * | 2014-08-15 | 2014-11-12 | 无锡百川化工股份有限公司 | Method for producing polyester-imine wire coating enamel |
| CN107903774A (en) * | 2017-11-10 | 2018-04-13 | 陈建峰 | A kind of flame retardant type wire enamel |
-
2020
- 2020-10-07 CN CN202011067893.3A patent/CN112011218A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130699A (en) * | 2014-07-18 | 2014-11-05 | 上海晟然绝缘材料有限公司 | High adhesion and solvent resistant insulating paint for polyester imide enameled wire and preparation method thereof |
| CN104140757A (en) * | 2014-08-15 | 2014-11-12 | 无锡百川化工股份有限公司 | Method for producing polyester-imine wire coating enamel |
| CN107903774A (en) * | 2017-11-10 | 2018-04-13 | 陈建峰 | A kind of flame retardant type wire enamel |
Non-Patent Citations (1)
| Title |
|---|
| 李强军: "聚酯亚胺漆包线漆适度交联结构与性能研究", 《绝缘材料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898823A (en) * | 2021-01-25 | 2021-06-04 | 陈曦 | Novel environment-friendly odorless printing ink and preparation method thereof |
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