CN114350205A - UV ink-jet ink and preparation method thereof - Google Patents
UV ink-jet ink and preparation method thereof Download PDFInfo
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- CN114350205A CN114350205A CN202111668358.8A CN202111668358A CN114350205A CN 114350205 A CN114350205 A CN 114350205A CN 202111668358 A CN202111668358 A CN 202111668358A CN 114350205 A CN114350205 A CN 114350205A
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- monomer
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- acrylate
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- inkjet ink
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 100
- 229920001002 functional polymer Polymers 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000007822 coupling agent Substances 0.000 claims abstract description 20
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 238000000016 photochemical curing Methods 0.000 claims abstract description 11
- 229920000728 polyester Polymers 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000049 pigment Substances 0.000 claims abstract description 10
- -1 amine modified acrylate Chemical class 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical group C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 238000007142 ring opening reaction Methods 0.000 claims description 3
- 125000003341 7 membered heterocyclic group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 238000007639 printing Methods 0.000 abstract description 27
- 239000000758 substrate Substances 0.000 abstract description 13
- 239000000853 adhesive Substances 0.000 abstract description 10
- 230000001070 adhesive effect Effects 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
- 239000000976 ink Substances 0.000 description 70
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 238000010998 test method Methods 0.000 description 6
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 5
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 5
- 239000002585 base Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007779 soft material Substances 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- LAIJAUHBAWLPCO-UHFFFAOYSA-N (4-tert-butylcyclohexyl) prop-2-enoate Chemical compound CC(C)(C)C1CCC(OC(=O)C=C)CC1 LAIJAUHBAWLPCO-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- YMZIFDLWYUSZCC-UHFFFAOYSA-N 2,6-dibromo-4-nitroaniline Chemical compound NC1=C(Br)C=C([N+]([O-])=O)C=C1Br YMZIFDLWYUSZCC-UHFFFAOYSA-N 0.000 description 1
- QSLJCEYMKUNKJF-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C)OCCC(CO)(CO)CO Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C)OCCC(CO)(CO)CO QSLJCEYMKUNKJF-UHFFFAOYSA-N 0.000 description 1
- 101000720524 Gordonia sp. (strain TY-5) Acetone monooxygenase (methyl acetate-forming) Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- LFULEKSKNZEWOE-UHFFFAOYSA-N propanil Chemical compound CCC(=O)NC1=CC=C(Cl)C(Cl)=C1 LFULEKSKNZEWOE-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 239000012720 thermal barrier coating Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
The invention provides UV ink-jet ink and a preparation method and application thereof, wherein the ink comprises a monomer mixture, a functional polymer, a pigment color paste, a photoinitiator and an auxiliary agent, wherein the monomer mixture comprises an active monomer and a photocuring monomer, and the mass ratio of the active monomer to the photocuring monomer is 1: 2-1: 8; the functional polymer can be at least one of carboxyl functional polyester acrylate, epoxy acrylate and amine modified acrylate, and the preparation method comprises the steps of mixing a monomer mixture, the functional polymer, a coupling agent and a photoinitiator in proportion to obtain a first mixed material, and then mixing the first mixed material with an auxiliary agent and pigment color paste to obtain a second mixed material; the ink obtained after filtering has strong adhesive force, good stability and printing fluency, and can be used for printing process of information on the outer surfaces of various soft film substrates.
Description
Technical Field
The invention relates to the field of ink, in particular to UV (ultraviolet) ink-jet ink and a preparation method thereof.
Background
The UV ink has the advantage of diversification of printing substrates, is widely suitable for various substrates such as hard plates, soft materials, foam materials, PVC, resin glass, wood, metal sheets and the like, and has wide market space. However, as the variety of printing substrate materials increases, the difference of surface properties, especially surface polarity, smoothness and static electricity, of different plastic products in the printing substrate materials is large due to the difference of resin, additive and forming method, so that the adhesion degree of UV ink to the substrates of different materials is greatly different, for example, the adhesion degree of ink is poor for difficult-to-adhere substrates such as PP, PE, BOPP, TBC and aluminum-coated film, and the ink is easy to fall off from the surface of the printing substrate. In addition, the printing material is generally required to be deeply cleaned before packaging, so that the printing ink is free of pollutants, the printing ink is usually scrubbed by alcohol or cleaning solution containing alcohol, and the existing printing ink is not resistant to alcohol stimulation and corrosion after being printed and is easy to fade; particularly, in the printing of two-dimensional codes, bar codes and the like, the problems of blushing, even disappearance of surface patterns, reduction of adhesive force and the like of the surface of an ink coating layer after alcohol wiping are generally existed, and the problems of label failure caused by the conditions that the color becomes light, the function is influenced and the like after the ink coating layer is used for a certain time often occur.
Disclosure of Invention
The first purpose of the invention is to provide the UV ink-jet ink which has strong adhesion and good alcohol resistance, printing fluency and stability.
The second purpose of the invention is to provide a preparation method of the UV ink-jet ink.
In order to achieve the first purpose, the UV inkjet ink provided by the invention comprises pigment color paste, a photoinitiator, an auxiliary agent, a monomer mixture and a functional polymer, wherein the monomer mixture comprises an active monomer and a photo-curing monomer, the mass ratio of the active monomer to the photo-curing monomer is 1: 2-1: 8, and the functional polymer can be at least one of carboxyl functional polyester acrylate, epoxy acrylate and amine modified acrylate.
According to the scheme, the monomer mixture in the ink comprises the active monomer and the photo-curing monomer, the active monomer improves the rheological property of the polymer in the ink, the film forming toughness is good, the film forming weather resistance is outstanding, the stability of the ink is ensured, and the ink can be placed for a long time; the photo-curing monomer can improve the performances of the UV ink-jet ink in various aspects, such as the improvement of cohesiveness, the improvement of curing efficiency, the improvement of ink adhesion and the like, and the ratio of the active monomer to the photo-curing monomer is controlled, so that the ink has good hardness, rubber resistance and alcohol resistance after being cured, and the fading and ink dropping of a coating formed by the ink are reduced, and the appearance is influenced; the functional polymer can be at least one of carboxyl functional polyester acrylate, epoxy acrylate and amine modified acrylate, and the functional polymer can enhance the interaction between the ink and the surface chemical groups of the substrate, form hydrogen bonds or other intermolecular interactions and provide the adhesive force of the ink, so that the UV ink has strong adhesive force and good stability.
In a further embodiment, the reactive monomer contains a bridged ring structure and has more than 2 unsaturated bonds.
Therefore, the active monomer has a bridged ring structure and high glass transition temperature, has lower shrinkage rate than other difunctional monomers, even lower than most of monofunctional monomers, has good film forming toughness, strong impact resistance, outstanding weather resistance after film forming, good toughness and weather resistance, can resist various solvents such as acid, alkali and alcohol or chemical factors such as sunlight, ultraviolet light and the like in the using and storing processes, and can improve the chemical resistance of the ink.
The further scheme is that the photocuring monomer comprises a first monomer, a second monomer and a third monomer, wherein the first monomer is ether-containing modified acrylate with functionality of two or more than two, the second monomer is a 5-7-membered heterocyclic monofunctional acrylate monomer, and the third monomer is cyclohexyl acrylate.
Therefore, the reactive groups alpha-H are very easy to oxidize, can consume part of oxygen in the ink on one hand, and can quickly react with peroxy radicals on the other hand to regenerate the reactive radicals and transfer the initiating activity to chain segments with the initiating activity again, so that the polymerization inhibition of oxygen to the photocuring process is reduced, the curing degree of a curing system is improved, the curing shrinkage rate is reduced, and the chemical resistance of the ink is improved.
Further, the ether-containing modified acrylate with two or more functionalities can be at least one of bifunctional ethoxylated modified acrylate, trifunctional ethoxylated modified acrylate, bifunctional propoxylated modified acrylate and trifunctional propoxylated modified acrylate; and/or the 5-to 7-membered heterocyclic monofunctional acrylate monomer is oxygen heterocyclic monofunctional acrylate and/or nitrogen heterocyclic monofunctional acrylate.
The further proposal is that the acid value of the carboxyl functional polyester acrylate is 100mg KOH/g to 250mg KOH/g; and/or epoxy acrylate is at least one of aromatic epoxy acrylate resins obtained by the ring-opening reaction of monofunctional aromatic epoxy acrylate with acrylic acid; and/or the amine-modified acrylate is an acrylated polymeric amine resin.
Therefore, the quantity of carboxyl groups in the carboxyl functional polyester acrylate with the acid value is controlled within a certain range, and the influence of excessive carboxyl groups on the hardness and the adhesive force of the ink is avoided.
The further proposal is that the mass percentage ratio of the monomer mixture to the functional polymer is (55-80%): (2% to 15%).
It can be seen that the reactive monomer and the photo-curable monomer in the ratio range can provide better hardness, adhesion and weather resistance after the ink is cured.
Further, the UV inkjet ink includes a coupling agent, which may be a silane coupling agent and/or a titanate coupling agent.
Therefore, the coupling agent plays a role in chemical bridging between the ink coating and the base material, generates a crosslinking effect, and can improve the adhesive force and improve the chemical resistance.
The further proposal is that the UV ink-jet ink comprises 55 to 80 percent of monomer mixture, 2 to 15 percent of functional polymer, 0.1 to 3 percent of coupling agent, 10 to 25 percent of pigment color paste, 4 to 12 percent of photoinitiator and 0.05 to 1 percent of auxiliary agent according to the mass percentage.
The UV ink has the advantages that the monomer mixture and the functional polymer are used as basic components of the UC ink-jet ink, and other components are combined according to the proportion of the monomer mixture to the functional polymer, so that the viscosity of the finally obtained UV ink is 5-25 cp, the adhesion force of the ink after printing and curing to form a coating is 0-1 grade, the hardness is 1H-2H, and the ink cannot fade or fade after being rubbed for 50 times by an eraser and a non-woven fabric stained with alcohol.
In order to achieve the second object, the UV inkjet ink is prepared by the method for preparing the UV inkjet ink;
the preparation method comprises the following steps:
a) mixing the monomer mixture, the functional polymer, the coupling agent and the photoinitiator in proportion to obtain a first mixed material;
b) mixing the first mixed material with an auxiliary agent and pigment color paste to obtain a second mixed material;
c) and filtering the second mixed material to obtain the UV ink-jet ink.
The further proposal is that the mixing modes in the step a) and the step b) are respectively carried out in a stirring disperser, the stirring speed of the stirring disperser is 500r/min to 2000r/min, and the stirring time is 25min to 45 min.
Detailed Description
The UV ink-jet ink disclosed by the invention is applied to a printing process, particularly a digital printing process, and can realize real-time updating of printing information. The UV ink disclosed by the invention comprises a monomer mixture and a functional polymer, wherein the ratio of the monomer mixture to the functional polymer is adjusted to be 1: 2-1: 8, and the functional polymer can be at least one of carboxyl functional polyester acrylate, epoxy acrylate and amine modified acrylate, so that the obtained UV ink has good stability, adhesive force and printing fluency, and is suitable for printing processes of different material base materials, especially for printing processes of marking information (such as two-dimensional codes, bar codes and the like) of various film base materials.
According to the mass percentage, the UV ink-jet ink comprises 55 to 80 percent of monomer mixture, 2 to 15 percent of functional polymer, 0.1 to 3 percent of coupling agent, 10 to 25 percent of pigment color paste, 4 to 12 percent of photoinitiator, 0.1 to 3 percent of coupling agent and 0.05 to 1 percent of auxiliary agent; the monomer mixture comprises an active monomer and a light-cured monomer, and the mass ratio of the active monomer to the light-cured monomer is 1: 2-1: 8. The active monomer contains a bridged ring structure and has more than 2 unsaturated bonds; optimally, the reactive monomers are: at least one of monomer dicyclopentenyl acrylate DCPA (trade name: EM2051) of Changxing materials industries, Inc., monomer tricyclodecane dimethanol diacrylate DCPDA (trade name: EM2204) of Changxing materials industries, Inc., and monomer isobornyl acrylate IBOA (trade name: EM70) of Changxing materials industries, Inc.
The photo-curing monomer comprises a first monomer, a second monomer and a third monomer, wherein the first monomer is ether-containing modified acrylate with functionality of two or more than two, the second monomer is a 5-7-membered heterocyclic monofunctional acrylate monomer, and the third monomer is cyclohexyl acrylate. Optimally, the ether-containing modified acrylate with two or more functionalities can be at least one of difunctional ethoxylated modified acrylate, trifunctional ethoxylated modified acrylate, difunctional propoxylated modified acrylate and trifunctional propoxylated modified acrylate; the 5-7-membered heterocyclic monofunctional acrylate monomer is oxygen heterocyclic monofunctional acrylate and/or nitrogen heterocyclic monofunctional acrylate. Further preferably, the first monomer is Rahn's monomer 3- (ethoxy) trimethylolpropane triacrylate TMP (EO)3TA (trade name: MIRAMER M360), hexanediol diacrylate alkoxylated with a monomer of Saedoma (trade name: CD563), neopentyl glycol diacrylate propoxylated with a monomer of Changxing materials industries, Ltd. (trade name: EM2251), and trimethylolpropane triacrylate ethoxylated with a monomer of Changxing materials industries, Ltd. (trade name: EM 2380). The second monomer may be at least one of a monomer of KJ CHEMICAL, Acrylmorpholine ACMO, a monomer of N-vinylcaprolactam NVC, KJ CHEMICAL, N-vinylpyrrolidone NVP, KJ CHEMICAL, Inc., a monomer of tetrahydrofuran acrylate THFA (trade name: EM214), KJ CHEMICAL, Inc., a monomer of trimethylolpropane formal acrylate (trade name: EM 212). The third monomer may be 4-tert-butylcyclohexyl acrylate TBCHA (trade name: EM105) from Changxing materials industries, Inc. and/or 3,3, 5-trimethylcyclohexyl acrylate TMCHA (trade name: EM2104) from Changxing materials industries, Inc.
The functional polymer may be an oligomer, which generally refers to a polymer consisting of 10-20 repeating units, and may be at least one of a carboxyl functional polyester acrylate, an epoxy acrylate, and an amine modified acrylate. Optimally, the acid value of the carboxyl functional polyester acrylate is 100mg KOH/g to 250mg KOH/g; the epoxy acrylate is at least one of aromatic epoxy acrylate resins obtained by performing ring-opening reaction on monofunctional aromatic epoxy acrylate by using acrylic acid; the amine-modified acrylate is an acrylated polymeric amine resin. Further preferably, the functional polymer is at least one of a carboxyl functional polyester acrylate of Rahn (trade name: GENOMER 7151), a monofunctional epoxy acrylate oligomer of Rahn (trade name: Etercure 620-.
The coupling agent can be a silane coupling agent and/or a titanate coupling agent, preferably, the coupling agent is a titanate coupling agent, further preferably, the coupling agent is a chelate titanate, and further preferably, the coupling agent is a titanate coupling agent PN-311W of Nanjing pining.
Photoinitiator (2): TPO (2,4, 6-trimethylbenzoyl-diphenylphosphine oxide), or alternatively a commercially available product known to the person skilled in the art.
Auxiliary agent: a leveling agent BYK 333 from Bike, GENORAD series light stabilizer GENORAD 20 from Rahn, Switzerland.
The preparation method of the UV ink-jet ink comprises the following steps: the method comprises the following steps:
a) mixing and stirring the monomer mixture, the functional polymer, the coupling agent and the photoinitiator in a stirring and dispersing machine according to a certain proportion, wherein the stirring speed of the stirring and dispersing machine is 500-2000 r/min, and the stirring time is 25-45 min, so as to obtain a first mixed material;
b) mixing and stirring the first mixed material, the auxiliary agent and the pigment color paste in a stirring and dispersing machine, wherein the stirring speed of the stirring and dispersing machine is 500-2000 r/min, and the stirring time is 25-45 min, so as to obtain a second mixed material;
c) and filtering the second mixed material by a filter membrane with the aperture of 1.0 mu m to obtain the UV ink-jet ink.
The viscosity of the finally obtained UV ink is 5-25 cp, the adhesion force of the ink after printing and curing to form a coating is 0-1 grade, the hardness is 1H-2H, the ink cannot fade after being rubbed by an eraser and a non-woven fabric stained with alcohol for 50 times, and the ink is printed on the outer surface of a soft package lithium battery.
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In a specific embodiment, 6 examples and three comparative examples are provided, wherein the combinations of examples 1 to 6 and comparative examples 1 to 3 and the mass percentages thereof are shown in table 1.
Table 1: compositions and mass percentages thereof of examples 1 to 6 and comparative examples 1 to 3
As can be seen from table 1, in examples 1 to 6, the specific substances of the components and their ratios were adjusted in each example. In contrast to example 6, the mass fraction of the monomer mixture in comparative example 1 was 83% and exceeded the range of 55% to 80%, while the mass fraction of the functional polymer was 0.7% and was not in the range of 2% to 15%, i.e., the ratio between the monomer mixture and the functional polymer was too large. In comparative example 2, the mass fraction of the monomer mixture A was 52% and not in the range of 55% to 80%, while the mass fraction of the functional polymer was 22.7% and out of the range of 2% to 15%, i.e., the ratio of the monomer mixture to the functional polymer was too low. The functional polymer in comparative example 3 was changed to urethane acrylate (Happy DR-U161).
The UV inkjet inks provided in examples 1 to 6 and comparative examples 1 to 3 were applied to a BOPP film substrate (the BOPP film substrate is a soft substrate) by spraying two-dimensional code thereon, and cured by UV irradiation, and the properties of the coating were measured by the following test methods:
readability of image
And calling an equipment camera by using software on the smart phone or the tablet equipment, and reading the two-dimensional code image on the substrate. The A level is the occasion which can be well read, and only passes once scanning and only scans once; the B level is not similar to the A level in reading, and is suitable for the occasions of scanning along one line only but allowing repeated scanning; the C level represents that repeated scanning needs to be carried out for many times, and a device which can carry out repeated scanning and is provided with a plurality of scanning lines is generally used for obtaining a good reading effect; the grade D is that the bar code can not be read by some equipment, and if a good reading effect is obtained, equipment which can be repeatedly scanned and is provided with a plurality of scanning lines is used; and F level is unqualified, and the two-dimensional code cannot be used.
Second, adhesion test
The specific test method comprises the following steps: a 10 x 10 grid is scribed on the surface of the coating by a hundred grid knife, a standard test tape (3M Scotch600 tape) is attached to the grid, the tape is peeled off manually, and the grid shedding rate is calculated. The corresponding relation between the grid shedding rate and the adhesive force is as follows: level 0: the scribing edge is smooth, and no mark falls off at the scribing edge and the intersection point; level 1: 5% of falling rate; and 2, stage: 5 to 15 percent of falling rate; and 3, level: 15 to 35 percent of falling rate; 4, level: 35 to 65 percent of falling rate; and 5, stage: the degree of exfoliation is above grade 4.
Third, hardness test
The specific test method comprises the following steps: the hardness of the paint film was determined according to the test standard GB/T6739-2006 "determination of paint film hardness by the colored and varnished pencil method" using a pencil hardness meter. The test results are indicated by the pencil designations (6H, 5H, 4H, 3H, 2H, 1H, F, HB, B, 2B, 3B, 4B, 5B, 6B), with 6H being the hardest and softest, with hardness decreasing from 6H to 6B.
Fourth, test of Eraser resistance
The specific test method comprises the following steps: after the ink is printed on a BOPP film and solidified, the BOPP film is rubbed back and forth for 50 times by an eraser, and whether the ink fades or not is observed.
Fifth, testing alcoholic strength
The specific test method comprises the following steps: fixing the non-woven fabric stained with alcohol with the purity of more than or equal to 95 percent on a friction head of a testing machine, rubbing for 50 times at the testing speed of 42 times/minute, and observing whether the ink fades or not.
The performance data of the UV inkjet printing inks and the cured coatings thereof provided in the above examples 1 to 6 and comparative examples 1 to 3 are shown in table 2 below.
Sixthly, testing the storage stability of the ink
The specific test method comprises the following steps: particle size was measured with a PSS Nicomp Z3000 nm laser particle size analyzer. Then comparing the granularity of the ink under the conventional condition with the granularity after 2 weeks of accelerated aging at 60 ℃, wherein the relative change of the granularity is preferably less than 10%; a relative change of > 10% is not good.
Seventh, ink printing fluency test
The resulting ink was printed using a gloss G5 nozzle. 500mL of ink is continuously printed, the number of broken holes of a printing nozzle is less than or equal to 5, the printing smoothness is good, and the grade A is evaluated; 500mL of ink is continuously printed, the number of broken holes of a printing nozzle is more than 5, and the printing smoothness is evaluated as B level.
The test results are shown in table 2 below.
Table 2:
from the results in Table 2, it can be seen that when the ratio of the monomer mixture to the functional polymer is in the range of (55% to 80%): when the UV ink is 2-15%, the coating printed and cured by the UV ink-jet ink has good adhesive force, hardness, eraser resistance and alcohol resistance, the ink has good stability and printing process, and the printed pattern is clear and easy to identify. However, when the ratio of the monomer mixture to the functional polymer is too large or too small, the obtained UV inkjet printing ink has reduced hardness after curing, reduced resistance to erasure, poor alcohol resistance, difficulty in controlling stability and printing process, and blurred printed patterns, which are difficult to recognize. According to the invention, the monomer mixture is matched with the functional polymer in a proper range, and other components in the ink are combined, so that the coating formed by the obtained UV ink-jet printing ink has high adhesive force to a soft material, and has good hardness, eraser resistance and alcohol resistance.
Finally, it should be emphasized that the above-described preferred embodiments of the present invention are merely examples of implementations, rather than limitations, and that many variations and modifications of the invention are possible to those skilled in the art, without departing from the spirit and scope of the invention.
Claims (10)
- The UV ink-jet ink comprises pigment color paste, a photoinitiator and an auxiliary agent, and is characterized in that: the monomer mixture comprises an active monomer and a light-cured monomer, and the mass ratio of the active monomer to the light-cured monomer is 1: 2-1: 8; the functional polymer may be at least one of a carboxyl functional polyester acrylate, an epoxy acrylate, and an amine modified acrylate.
- 2. The UV inkjet ink of claim 1, wherein:the reactive monomer contains a bridged ring structure, and the reactive monomer has more than 2 unsaturated bonds.
- 3. The UV inkjet ink of claim 1, wherein:the photocuring monomer comprises a first monomer, a second monomer and a third monomer, wherein the first monomer is ether-containing modified acrylate with functionality of two or more than two, the second monomer is a 5-7-membered heterocyclic monofunctional acrylate monomer, and the third monomer is cyclohexyl acrylate.
- 4. The UV inkjet ink of claim 3, wherein:the ether-containing modified acrylate with two or more functionalities can be at least one of difunctional ethoxylated modified acrylate, trifunctional ethoxylated modified acrylate, difunctional propoxylated modified acrylate and trifunctional propoxylated modified acrylate;and/or the 5-to 7-membered heterocyclic monofunctional acrylate monomer is an oxygen-containing heterocyclic monofunctional acrylate and/or a nitrogen-containing heterocyclic monofunctional acrylate.
- 5. The UV inkjet ink of claim 1, wherein:the acid value of the carboxyl functional polyester acrylate is 100mg KOH/g to 250mg KOH/g;and/or the epoxy acrylate is at least one of aromatic epoxy acrylate resins obtained by performing ring-opening reaction on monofunctional aromatic epoxy acrylate with acrylic acid;and/or the amine-modified acrylate is an acrylated polymeric amine resin.
- 6. The UV inkjet ink of claim 1, wherein:the mass percentage ratio of the monomer mixture to the functional polymer is (55-80%): (2% to 15%).
- 7. The UV inkjet ink of claim 1, wherein:the UV inkjet ink includes a coupling agent, which may be a silane coupling agent and/or a titanate coupling agent.
- 8. The UV inkjet ink of claim 7, wherein:the UV ink-jet ink comprises, by mass, 55-80% of a monomer mixture, 2-15% of a functional polymer, 0.1-3% of a coupling agent, 10-25% of a pigment color paste, 4-12% of a photoinitiator and 0.05-1% of an auxiliary agent.
- The preparation method of the UV ink-jet ink is characterized by comprising the following steps: preparing a UV inkjet ink according to any one of claims 1 to 8;the preparation method comprises the following steps:a) mixing the monomer mixture, the functional polymer, a coupling agent and the photoinitiator in proportion to obtain a first mixed material;b) mixing the first mixed material with the auxiliary agent and the pigment color paste to obtain a second mixed material;c) and filtering the second mixed material to obtain the UV ink-jet ink.
- 10. The method of claim 9, wherein:the mixing modes in the step a) and the step b) are respectively carried out in a stirring disperser, the stirring speed of the stirring disperser is 500 r/min-2000 r/min, and the stirring time is 25 min-45 min.
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| WO2010029351A1 (en) * | 2008-09-09 | 2010-03-18 | Sericol Limited | A printing ink |
| CN111073391A (en) * | 2019-12-30 | 2020-04-28 | 珠海天威新材料股份有限公司 | Ultraviolet curing ink-jet neutral ink and preparation method and application thereof |
| CN111117347A (en) * | 2019-12-26 | 2020-05-08 | 上海维凯光电新材料有限公司 | Rapid printing etching-resistant ink |
| CN112625495A (en) * | 2020-12-31 | 2021-04-09 | 珠海天威新材料股份有限公司 | Printing UV ink and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010029351A1 (en) * | 2008-09-09 | 2010-03-18 | Sericol Limited | A printing ink |
| CN111117347A (en) * | 2019-12-26 | 2020-05-08 | 上海维凯光电新材料有限公司 | Rapid printing etching-resistant ink |
| CN111073391A (en) * | 2019-12-30 | 2020-04-28 | 珠海天威新材料股份有限公司 | Ultraviolet curing ink-jet neutral ink and preparation method and application thereof |
| CN112625495A (en) * | 2020-12-31 | 2021-04-09 | 珠海天威新材料股份有限公司 | Printing UV ink and preparation method and application thereof |
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