CN114836077B - PET (polyethylene terephthalate) film printing ink - Google Patents
PET (polyethylene terephthalate) film printing ink Download PDFInfo
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- CN114836077B CN114836077B CN202210622976.7A CN202210622976A CN114836077B CN 114836077 B CN114836077 B CN 114836077B CN 202210622976 A CN202210622976 A CN 202210622976A CN 114836077 B CN114836077 B CN 114836077B
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- 238000007639 printing Methods 0.000 title claims abstract description 31
- 229920000139 polyethylene terephthalate Polymers 0.000 title claims description 16
- 239000005020 polyethylene terephthalate Substances 0.000 title description 15
- -1 polyethylene terephthalate Polymers 0.000 title description 4
- 239000000049 pigment Substances 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 239000000839 emulsion Substances 0.000 claims abstract description 29
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000012528 membrane Substances 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229920002799 BoPET Polymers 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 8
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 7
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 7
- CNQHZBFQVYOFGD-UHFFFAOYSA-N 5-hydroxy-5-methylimidazolidine-2,4-dione Chemical compound CC1(O)NC(=O)NC1=O CNQHZBFQVYOFGD-UHFFFAOYSA-N 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 239000012024 dehydrating agents Substances 0.000 claims description 7
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 6
- 229920000053 polysorbate 80 Polymers 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- 229920001577 copolymer Polymers 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 abstract description 25
- 239000004814 polyurethane Substances 0.000 abstract description 25
- 239000002245 particle Substances 0.000 abstract description 20
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 238000007641 inkjet printing Methods 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000000976 ink Substances 0.000 description 56
- 230000000694 effects Effects 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000010023 transfer printing Methods 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material 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
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
- C08F220/603—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing oxygen in addition to the carbonamido oxygen and nitrogen
-
- 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
- C09D11/30—Inkjet printing inks
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a PET membrane printing ink, which belongs to the technical field of ink-jet printing and comprises the following raw materials: 33-45 parts of water, 26-32 parts of pigment color paste, 9-12 parts of polyurethane emulsion, 15-19 parts of dihydric alcohol and 0.8-1.2 parts of auxiliary agent; adding pigment color paste and an auxiliary agent in water in sequence according to a certain proportion, grinding for 2-3h, adding polyurethane emulsion and dihydric alcohol, stirring uniformly, and filtering to obtain the product. The auxiliary agent prepared by the invention contains-COOH and-SO on the side chain of the molecule 3 The high molecular polymer of H can be effectively adsorbed on the surface of the pigment particles, so that the pigment particles are uniformly dispersed in the ink, and the high molecular polymer can help research, improve the uniformity, the dispersibility and the stability of pigment color paste from multiple aspects and improve the quality of the ink; in addition, a plurality of-NCl groups are introduced on the side chain of the auxiliary agent through the polymerizable monomer, so that the auxiliary agent is endowed with excellent antibacterial activity, and the effective period of the ink is prolonged.
Description
Technical Field
The invention belongs to the technical field of ink-jet printing, and particularly relates to a PET (polyethylene terephthalate) membrane printing ink.
Background
The 'pyrography' refers to that patterns are printed on a PET film, the film with the patterns is used for pyrography on the surface of the garment material through high temperature and high pressure after being dried, the waste film is torn off, and the patterns can be transferred to the surface of the garment material. The existing pyrograph transfer printing process on the market is a traditional silk-screen transfer process with an additional engraving technology, has complex working procedures and cannot meet the requirements of small-batch and personalized production. In order to simplify the process, the pyrograph transfer printing process is completed by using the water-based pigment ink for ink-jet printing, and the water-based pigment ink used at present has good color expressive property and the advantage of environmental protection. However, the printing effect of the water-based pigment ink on a common PET film coated with a release agent is not ideal, and when the ink amount is small, ink drops are in a water droplet shape on the film, so that the ink gathering phenomenon is generated; when the amount of ink is large, ink droplets easily bleed on the film, and the fineness of the printed pattern is low. In addition, pigment color paste in the ink can cause partial pigment particles to settle after being stored in a water dispersion medium for a long time, so that the ink with uniform and plump chromaticity is difficult to form, bacteria are easy to breed when the ink is not properly stored, and the expiration date of the ink is reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a PET film printing ink.
The invention synthesizes the polymer monomer and the assistant through the polymer monomer, SO that the prepared assistant is a polymer with the molecular side chain containing-COOH and-SO simultaneously 3 The high molecular polymer of the H group can be effectively adsorbed on the surface of the pigment particles to form a steric hindrance effect and a larger electrokinetic potential, so that the pigment particles are uniformly dispersed in the ink, and can be further ground and refined, the uniformity, the dispersibility and the stability of the pigment color paste are improved from multiple aspects, the ink has good and uniform chromaticity and stability, and the quality of the ink is improved; in addition, a plurality of-NCl groups are introduced on the side chain of the assistant through the polymerizable monomer, so that the assistant has excellent antibacterial activity, the effective period of the ink is prolonged, the dispersion effect of the assistant can be further improved, and the stability of the ink is improved.
The purpose of the invention can be realized by the following technical scheme:
the PET film printing ink comprises the following raw materials in parts by weight: 33-45 parts of water, 26-32 parts of pigment color paste, 9-12 parts of polyurethane emulsion, 15-19 parts of dihydric alcohol and 0.8-1.2 parts of auxiliary agent;
the preparation method comprises the following steps: and sequentially adding pigment color paste and an auxiliary agent into water according to a certain proportion, grinding for 2-3h, adding polyurethane emulsion and dihydric alcohol, uniformly stirring, and filtering to obtain the PET membrane printing ink.
Further, the dihydric alcohol is a mixture of propylene glycol and diethylene glycol in a mass ratio of 1:2.
Further, the solid content of the polyurethane emulsion is 40%, and the polyurethane emulsion is acrylate (soft monomer) copolymerization polyurethane emulsion; this polyurethane emulsion can form the powerful rete of good adhesive force and tensile on the PET diaphragm, improve the infiltration phenomenon of ink on the PET diaphragm, and because copolymerization has the acrylic ester monomer in the polyurethane emulsion, glass transition temperature is lower, present the soft state when carrying out the heat-transfer seal, make the ink transfer seal to the fabric from the PET membrane more easily, when making the rendition effect of ink on the surface fabric better, the adhesive force reinforcing of stamp pattern, effectively improve the antifriction and the fastness to washing of the pattern on the surface fabric after printing.
Further, the auxiliary agent is prepared by the following method:
s1, adding 5-hydroxy-5-methylhydantoin into a reaction kettle, adding a dehydrating agent at the temperature of 15-18 ℃, cooling the mixed solution to below 12 ℃, adding acrylonitrile, uniformly stirring, introducing vaporized isobutene, reacting for 90-100min at the temperature of 5-10 ℃ after introducing, standing, crystallizing, filtering, washing and refining to obtain a polymerizable monomer; the dosage ratio of the 5-hydroxy-5-methylhydantoin, the dehydrating agent, the acrylonitrile and the isobutene is 143-149g;
in the presence of a dehydrating agent, 5-hydroxy-5-methylhydantoin reacts with acrylonitrile and isobutene to obtain a polymerizable monomer, and double bonds are introduced into the molecule of the polymerizable monomer to provide a reaction site for subsequent polymerization reaction; in addition, a single molecule of the polymerizable monomer contains three-NH groups, and in the subsequent chlorination process, a-NCl group is formed, so that the product has extremely high antibacterial property; the specific reaction equation is as follows:
s2, under magnetic stirring, adding a polymerizable monomer, methyl methacrylate, itaconic acid, 2-acrylamide-2-methylpropanesulfonic acid, sodium hypophosphite and deionized water into a round-bottom flask with a reflux condenser, adding a small amount of Tween 80, introducing nitrogen, heating to 70 ℃, slowly dropwise adding an ammonium persulfate aqueous solution into a reaction flask under the protection of the nitrogen, after dropwise adding, heating the reaction temperature to 80 ℃, and reacting for 8-10 hours to obtain a polymer; the use ratio of the polymerizable monomer, methyl methacrylate, itaconic acid, 2-acrylamide-2-methylpropanesulfonic acid, sodium hypophosphite, deionized water and an ammonium persulfate aqueous solution is (10g); the concentration of the ammonium persulfate aqueous solution is 0.78mol/L; the adding amount of the Tween 80 is 3 percent of the mass of the deionized water;
the method comprises the following steps of carrying out emulsion polymerization on a polymerizable monomer, methyl methacrylate, itaconic acid and 2-acrylamide-2-methylpropanesulfonic acid under the action of an initiator to obtain a polymer, wherein a side chain of the polymer contains a carboxylic acid group, a sulfonic acid group and a polymerizable monomer molecular chain, and the specific reaction equation is as follows:
s3, after the temperature of the polymer is reduced to room temperature, adding a sodium hypochlorite solution, adjusting the pH value of the mixed solution to 6.8-7.0, raising the temperature to 40-45 ℃, and stirring for reacting for 50-60min to obtain an auxiliary agent; the mass fraction of the sodium hypochlorite solution is 0.5 percent, and the addition amount of the sodium hypochlorite solution is 0.06-0.07 time of the volume of the polymer; under the action of sodium hypochlorite, the-NH on the side chain of the polymer molecule is subjected to chlorination reaction to form-NCl group, and the assistant with antibacterial effect is obtained.
Further, the specific steps of refining in step S1 are: and mixing the washed product with an ethanol water solution (the mass fraction of 30 percent), adding the mixture into a recrystallization kettle, carrying out recrystallization operation, and then carrying out centrifugal drying.
The auxiliary agent prepared by the process contains-COOH and-SO on the side chain of the molecule 3 The high molecular polymer of the H group, -COOH can generate hydrogen bond action with the surface of pigment particles (effective substances in pigment color paste), so as to generate adsorption effect, so that polymer molecules are adsorbed on the surface of the pigment particles, and polymer high molecular chains are formed on the surface of the pigment, so that larger steric hindrance effect is generated between the pigment particles, van der Waals attractive force between the particles is resisted, and excellent dispersion effect is achieved; in addition, in addition to the steric effect brought by adsorption generated by the action of hydrogen bonds, carboxylic acid and sulfonic acid groups generate high charge density, so that the surfaces of the particles have larger electrokinetic potential, stronger inter-particle electrostatic repulsion effect is generated, the dispersion of pigment particles is facilitated to a certain extent, and the grinding effect is improved; moreover, polymer molecular chains adsorbed on the surface of the pigment particles can effectively wet the particlesThe particle surface can also permeate into the micro cracks of the particles, so that the particles are softened and can be easily ground and crushed, and more uniform, fine and good-dispersion color paste is formed; therefore, the auxiliary agent prepared by the invention can improve the uniformity, the dispersibility and the stability of the pigment color paste from multiple aspects, so that the ink has good and uniform chromaticity and stability, and the quality of the ink is improved;
in addition, a-NH group is introduced into a molecular side chain of the auxiliary agent, a-NCl group is formed after chlorination reaction, and when oxidizing Cl contained in an N-Cl bond is contacted with a bacterial body, the oxidizing Cl can quickly react with a receptor on a cell membrane to inactivate cell biological enzyme, so that the bacterial body is dead to achieve an antibacterial effect; the invention has the advantages that through the synthesis of polymerizable monomers, three-NH groups are introduced on one monomer molecule to greatly improve the content of antibacterial active ingredients, so that the high-efficiency antibacterial effect can be realized by adding a small amount of the antibacterial active ingredients; in addition, in the subsequent chlorination operation process, part of non-chlorinated-NH groups, namely amide groups (-CO-NH-) can also generate hydrogen bond action with the surfaces of the pigment particles, so that the adsorption effect of the pigment particles on the auxiliary agent is enhanced, and the dispersion effect of the auxiliary agent on the pigment is further assisted to be improved.
The invention has the beneficial effects that:
according to the invention, the polyurethane emulsion is added into the ink as a film forming substance and is acrylate (soft monomer) copolymerization polyurethane emulsion, the polyurethane emulsion can form a film layer with good adhesive force and tensile strength on a PET film, the bleeding phenomenon of the ink on the PET film is improved, and the polyurethane emulsion is copolymerized with the acrylate monomer, so that the glass transition temperature is lower, the ink is in a soft state during heat transfer printing, the ink is more easily transferred to a fabric from the PET film, the transfer effect of the ink on the fabric is better, the adhesive force of a printed pattern is enhanced, and the friction resistance and the washing fastness of the printed pattern on the fabric are effectively improved;
the invention synthesizes the polymer monomer and the assistant through the polymer monomer, SO that the prepared assistant is a polymer with the molecular side chain containing-COOH and-SO simultaneously 3 Macromolecules with H groupsThe polymer can be effectively adsorbed on the surface of pigment particles to form a steric hindrance effect and a larger electrokinetic potential so as to enable the pigment particles to be uniformly dispersed in the ink, and can be further ground and refined, so that the uniformity, the dispersibility and the stability of pigment color paste are improved from multiple aspects, the ink has good and uniform chromaticity and stability, and the quality of the ink is improved; in addition, a plurality of-NCl groups are introduced on the side chain of the auxiliary agent through the polymerizable monomer, so that the auxiliary agent has excellent antibacterial activity, the effective period of the ink is prolonged, the dispersion effect of the auxiliary agent can be further improved, and the stability of the ink is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing an auxiliary agent:
s1, adding 143g of 5-hydroxy-5-methylhydantoin into a reaction kettle, adding 0.2mol of dehydrating agent at the temperature of 15 ℃, cooling the mixed solution to below 12 ℃, adding 102g of acrylonitrile, uniformly stirring, introducing 56g of vaporized isobutene, reacting for 100min at the temperature of 5 ℃, standing, crystallizing, filtering and washing, mixing the washed product with an ethanol water solution (the mass fraction is 30%), adding the mixture into a recrystallization kettle, performing recrystallization, and then performing centrifugal drying to obtain a polymerizable monomer;
s2, under magnetic stirring, adding 10g of polymerizable monomer, 1.4g of methyl methacrylate, 9g of itaconic acid, 7.1g of 2-acrylamide-2-methylpropanesulfonic acid, 9.6g of sodium hypophosphite and 35mL of deionized water into a round-bottom flask with a reflux condenser, adding 1.05g of Tween 80, introducing nitrogen, heating to 70 ℃, slowly dropwise adding 6.2mL of ammonium persulfate aqueous solution (the concentration is 0.78 mol/L) into a reaction flask under the protection of the nitrogen, raising the reaction temperature to 80 ℃ after dropwise adding, and reacting for 8 hours to obtain a polymer;
and S3, after the temperature of the polymer is reduced to room temperature, adding 0.06 time of sodium hypochlorite solution (the mass fraction is 0.5%), adjusting the pH value of the mixed solution to 6.8-7.0, raising the temperature to 40 ℃, and stirring for reacting for 50min to obtain the auxiliary agent.
Example 2
Preparing an auxiliary agent:
s1, firstly, 149g of 5-hydroxy-5-methylhydantoin is added into a reaction kettle, 0.2mol of dehydrating agent is added at the temperature of 18 ℃, then the temperature of the mixed solution is reduced to below 12 ℃, 139g of acrylonitrile is added, 56g of vaporized isobutene is introduced after uniform stirring, after introduction, the reaction is carried out for 90min at the temperature of 10 ℃, standing, crystallization, filtration and washing are carried out, the washed product and an ethanol water solution (the mass fraction is 30%) are mixed and then added into a recrystallization kettle for recrystallization, and then centrifugal drying is carried out, so as to prepare polymerizable monomer;
s2, under magnetic stirring, adding 10g of polymerizable monomer, 1.4g of methyl methacrylate, 9g of itaconic acid, 7.1g of 2-acrylamide-2-methylpropanesulfonic acid, 9.6g of sodium hypophosphite and 35mL of deionized water into a round bottom flask with a reflux condenser, adding 1.05g of Tween 80, introducing nitrogen, heating to 70 ℃, slowly dropwise adding 6.2mL of ammonium persulfate aqueous solution (with the concentration of 0.78 mol/L) into the reaction flask under the protection of the nitrogen, after dropwise adding, raising the reaction temperature to 80 ℃, and reacting for 10 hours to obtain a polymer;
and S3, after the temperature of the polymer is reduced to room temperature, adding 0.07 time of sodium hypochlorite solution (the mass fraction is 0.5%), adjusting the pH value of the mixed solution to 6.8-7.0, raising the temperature to 45 ℃, and stirring and reacting for 60min to obtain the auxiliary agent.
Example 3
Preparing PET film printing ink:
and (2) sequentially adding 260g of pigment color paste and 8g of the auxiliary agent prepared in the example 1 into 330g of water, grinding for 2 hours, adding 90g of polyurethane emulsion and 150g of dihydric alcohol, uniformly stirring, and filtering to obtain the PET membrane printing ink.
The dihydric alcohol is a mixture of propylene glycol and diethylene glycol according to a mass ratio of 1:2.
The solid content of the polyurethane emulsion is 40 percent, and the polyurethane emulsion is acrylate (soft monomer) copolymerization polyurethane emulsion.
Example 4
Preparing PET film printing ink:
290g of pigment paste and 10g of the auxiliary agent prepared in the embodiment 1 are sequentially added into 390g of water, ground for 2.5 hours, then 105g of polyurethane emulsion and 175g of dihydric alcohol are added, stirred uniformly and filtered, and the PET membrane printing ink is obtained.
The dihydric alcohol is a mixture of propylene glycol and diethylene glycol according to a mass ratio of 1:2.
The solid content of the polyurethane emulsion is 40 percent, and the polyurethane emulsion is acrylate (soft monomer) copolymerization polyurethane emulsion.
Example 6
Preparing PET film printing ink:
and (3) sequentially adding 320g of pigment color paste and 12g of the auxiliary agent prepared in the embodiment 2 into 450g of water, grinding for 3 hours, adding 120g of polyurethane emulsion and 190g of dihydric alcohol, uniformly stirring, and filtering to obtain the PET membrane printing ink.
The dihydric alcohol is a mixture of propylene glycol and diethylene glycol according to a mass ratio of 1:2.
The solid content of the polyurethane emulsion is 40 percent, and the polyurethane emulsion is acrylate (soft monomer) copolymerization polyurethane emulsion.
Comparative example 1
The adjuvant in example 3 was changed to a conventional surfactant (OP-10), and the remaining raw materials and preparation process were unchanged.
Comparative example 2
The auxiliary raw materials in example 3 were removed, and the rest of the raw materials and the preparation process were unchanged.
The inks obtained in examples 3 to 5 and the inks obtained in comparative examples 1 to 2 were subjected to the following performance tests:
basic properties: testing the viscosity and the surface tension by using an SNB-2 digital viscometer; adhesion strength was tested according to ASTM D3359 addition Test with 1A min and 5A max; standing for 5 weeks to determine the stability rate of the ink;
printing performance: taking 500mL of ink, printing on an EPSON-T3280 ink-jet printer, wherein the printing medium is a PET membrane, performing ink-jet printing according to a single color block and 100% ink-jet setting, and observing and recording while printing;
antibacterial property: qualitatively detecting the antibacterial effect of the ink by adopting an antibacterial ring method, adopting staphylococcus aureus and escherichia coli as strains, and testing the sterilization rate for 48 hours;
the results of the above tests are shown in the following table:
as can be seen from the data in the table above, the surface tension and viscosity of the ink prepared in examples 3-5 both meet the use requirements, the printing effect is good, the printing is smooth, and the adhesion with the PET substrate is strong; after the inks prepared in examples 3 to 5 are settled for 5 weeks, the stability rate is 97.4 to 97.9 percent, which shows that the inks prepared by the invention have extremely high dispersion performance and stability; the inks prepared in the embodiments 3 to 5 have extremely high bactericidal rate to staphylococcus aureus and escherichia coli, which indicates that the ink prepared by the invention has antibacterial property and can effectively prolong the effective period of the ink; the data of comparative example 1 and comparative example 2 show that the assistant of the present invention not only can improve the dispersion and stability of the ink, but also can endow the ink with certain antibacterial property.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (9)
1. The PET film printing ink is characterized by comprising the following raw materials in parts by weight: 33-45 parts of water, 26-32 parts of pigment color paste, 9-12 parts of styrene-acrylic emulsion, 15-19 parts of dihydric alcohol and 0.8-1.2 parts of auxiliary agent;
the preparation method comprises the following steps: sequentially adding pigment color paste and an auxiliary agent into water according to a certain proportion, grinding for 2-3h, adding styrene-acrylic emulsion and dihydric alcohol, stirring uniformly, and filtering to obtain PET membrane printing ink;
wherein the auxiliary agent is prepared by the following method:
s1, adding 5-hydroxy-5-methylhydantoin into a reaction kettle, adding a dehydrating agent at the temperature of 15-18 ℃, cooling the mixed solution to below 12 ℃, adding acrylonitrile, uniformly stirring, introducing vaporized isobutene, reacting for 90-100min at the temperature of 5-10 ℃ after introduction, standing, crystallizing, filtering, washing and refining to obtain a polymerizable monomer;
s2, under magnetic stirring, adding a polymerizable monomer, methyl methacrylate, itaconic acid, 2-acrylamide-2-methylpropanesulfonic acid, sodium hypophosphite and deionized water into a round-bottom flask with a reflux condenser, adding a small amount of Tween 80, introducing nitrogen, heating to 70 ℃, slowly dropwise adding an ammonium persulfate aqueous solution into a reaction flask under the protection of the nitrogen, after dropwise adding, heating the reaction temperature to 80 ℃, and reacting for 8-10 hours to obtain a polymer;
and S3, after the temperature of the polymer is reduced to room temperature, adding a sodium hypochlorite solution, adjusting the pH value of the mixed solution to 6.8-7.0, raising the temperature to 40-45 ℃, and stirring for reacting for 50-60min to obtain the auxiliary agent.
2. The PET film printing ink as claimed in claim 1, wherein the glycol is a mixture of propylene glycol and diethylene glycol in a mass ratio of 1:2.
3. The PET film printing ink as claimed in claim 1, wherein the styrene-acrylic emulsion has a solid content of 40% and is an acrylate copolymer styrene-acrylic emulsion.
4. The PET film printing ink according to claim 1, wherein the usage ratio of 5-hydroxy-5-methylhydantoin, dehydrating agent, acrylonitrile and isobutylene in step S1 is 143-149g.
5. The PET film printing ink as claimed in claim 1, wherein the refining in step S1 comprises the following steps: and mixing the washed product with an ethanol water solution, adding the mixture into a recrystallization kettle, performing recrystallization operation, and then performing centrifugal drying.
6. The PET film printing ink as claimed in claim 5, wherein the ethanol aqueous solution is 30% by mass.
7. The PET film printing ink according to claim 1, wherein the polymerizable monomer, methyl methacrylate, itaconic acid, 2-acrylamide-2-methylpropanesulfonic acid, sodium hypophosphite, deionized water and the ammonium persulfate aqueous solution in the step S2 are used in a ratio of 10g.
8. The PET film printing ink according to claim 1, wherein the concentration of the ammonium persulfate aqueous solution in the step S2 is 0.78mol/L; the adding amount of the Tween 80 is 3 percent of the mass of the deionized water.
9. The PET film printing ink as claimed in claim 1, wherein the mass fraction of the sodium hypochlorite solution in step S3 is 0.5%, and the amount of the sodium hypochlorite solution added is 0.06-0.07 times of the volume of the polymer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE848812A (en) * | 1975-11-28 | 1977-03-16 | COMPOSITIONS OF BIOCIDAL RESINS AND THEIR PREPARATION, | |
| CN1181182A (en) * | 1996-10-11 | 1998-05-13 | 罗姆和哈斯公司 | Phenylamides as marine antifouling agents |
| CN105229077A (en) * | 2013-05-21 | 2016-01-06 | 信越聚合物株式会社 | Electroconductive polymer dispersion liquid and conductive coating |
| CN111607286A (en) * | 2020-05-28 | 2020-09-01 | 珠海天威新材料股份有限公司 | Environment-friendly pyrograph ink, PET film heat transfer printing method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE848812A (en) * | 1975-11-28 | 1977-03-16 | COMPOSITIONS OF BIOCIDAL RESINS AND THEIR PREPARATION, | |
| CN1181182A (en) * | 1996-10-11 | 1998-05-13 | 罗姆和哈斯公司 | Phenylamides as marine antifouling agents |
| CN105229077A (en) * | 2013-05-21 | 2016-01-06 | 信越聚合物株式会社 | Electroconductive polymer dispersion liquid and conductive coating |
| CN111607286A (en) * | 2020-05-28 | 2020-09-01 | 珠海天威新材料股份有限公司 | Environment-friendly pyrograph ink, PET film heat transfer printing method and application thereof |
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