CN109575681B - Water-based free radical-cation hybrid photocuring ink and application thereof - Google Patents
Water-based free radical-cation hybrid photocuring ink and application thereof Download PDFInfo
- Publication number
- CN109575681B CN109575681B CN201811332330.5A CN201811332330A CN109575681B CN 109575681 B CN109575681 B CN 109575681B CN 201811332330 A CN201811332330 A CN 201811332330A CN 109575681 B CN109575681 B CN 109575681B
- Authority
- CN
- China
- Prior art keywords
- water
- acid
- ink
- parts
- curing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 35
- 150000005839 radical cations Chemical class 0.000 title claims abstract description 20
- -1 polypropylene Polymers 0.000 claims abstract description 20
- 229920000728 polyester Polymers 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004033 plastic Substances 0.000 claims abstract description 13
- 229920003023 plastic Polymers 0.000 claims abstract description 13
- 238000007639 printing Methods 0.000 claims abstract description 13
- 239000012949 free radical photoinitiator Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012952 cationic photoinitiator Substances 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000009736 wetting Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 33
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- 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 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 2
- 229940018557 citraconic acid Drugs 0.000 claims description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 claims description 2
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 claims 1
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical group [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 24
- 239000004743 Polypropylene Substances 0.000 abstract description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 14
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 14
- 238000011417 postcuring Methods 0.000 abstract description 6
- 239000002085 irritant Substances 0.000 abstract description 4
- 231100000021 irritant Toxicity 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 229920001155 polypropylene Polymers 0.000 abstract description 3
- 238000007654 immersion Methods 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 62
- 150000003254 radicals Chemical class 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 125000002091 cationic group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000003848 UV Light-Curing Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KLQWZWNTTNRVOZ-UHFFFAOYSA-M [3-(3,4-dimethyl-9-oxothioxanthen-2-yl)oxy-2-hydroxypropyl]-trimethylazanium;chloride Chemical compound [Cl-].C1=CC=C2C(=O)C3=CC(OCC(O)C[N+](C)(C)C)=C(C)C(C)=C3SC2=C1 KLQWZWNTTNRVOZ-UHFFFAOYSA-M 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 3
- 125000003566 oxetanyl group Chemical group 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YCZWJBIXAUQULS-UHFFFAOYSA-M bis(4-methylphenyl)iodanium;bromide Chemical group [Br-].C1=CC(C)=CC=C1[I+]C1=CC=C(C)C=C1 YCZWJBIXAUQULS-UHFFFAOYSA-M 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 125000005520 diaryliodonium group Chemical group 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- FSLGCYNKXXIWGJ-UHFFFAOYSA-N silicon(1+) Chemical compound [Si+] FSLGCYNKXXIWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D11/104—Polyesters
-
- 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
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a water-based free radical-cation hybrid photo-curing ink and application thereof, wherein the photo-curing ink comprises the following components in percentage by weight: 55-75% of water-based organic silicon modified polyester oligomer containing oxygen heterocycle, 3-8% of water-soluble free radical photoinitiator, 1-3% of cationic photoinitiator, 5-22% of water-based color paste, 0.3-1.5% of defoaming agent, 0.5-3% of wetting dispersant, 0.1-1% of flatting agent, 8-15% of alcohol solvent and the balance of water. The ink disclosed by the invention is non-toxic, non-irritant, high in curing speed, good in water resistance, high in hardness of more than 2H, and high in adhesion to plastic substrates such as PP (polypropylene), PET (polyethylene terephthalate) and the like, has no change in ink film immersion in a post-curing process, and is completely suitable for printing the plastic substrates.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to aqueous free radical-cation hybrid photocuring ink and application thereof.
Background
Compared with the traditional UV ink, the water-based UV ink takes water as a solvent, and the viscosity of the water-based UV ink is not required to be adjusted by means of an active diluent, so that the irritation and toxicity of the active diluent to a human body are solved, and the problem that the traditional UV ink cannot give consideration to both hardness and flexibility is also solved. However, the aqueous UV ink mostly needs to be dried to remove water from the wet film before photocuring, which results in increased energy consumption and prolonged production time. The prepared water-based resin with high solid content and low viscosity is used as an ink binder, and the water content in the ink can be reduced, so that the drying speed is accelerated, and the energy consumption is reduced.
The UV light curing has two mechanisms of free radical curing and cationic curing, the former has wide application, but the use of the UV light curing is limited to a certain extent due to the problems of oxygen inhibition effect, large curing volume shrinkage, poor adhesive force and the like. The cationic photocuring has no oxygen inhibition, small curing volume shrinkage, strong base material adhesion and strong post-curing, can make up for the defect of free radical curing, is suitable for photocuring thick films and colored paints, and becomes one of the research hotspots in the field of photocuring. CN106188548A discloses an organic silicon cation photocuring resin with an oxetane structure, which is prepared by reacting oxetane with diisocyanate to prepare a polyurethane semi-adduct with one end of the urethane semi-adduct being the oxetane structure and the other end being an isocyanate structure, and then modifying polyurethane by organic siloxane. The resin can be used for preparing cationic light-cured ink, but the curing group can only be introduced into the terminal group of a molecular chain, the content of a UV curing group cannot be improved while the molecular weight is improved, the contradiction between hardness and flexibility cannot be solved, and the resin does not have a hydrophilic group and cannot be used for water-based UV ink; in addition, the simple cation curing speed is low, the variety of applicable initiators is few, and the price is high.
The free radical-cation hybrid photocuring system combines the advantages of both free radical curing and cation curing, and makes up for the deficiencies of the free radical curing and the cation curing. However, the oligomer used for radical photocuring is a resin with unsaturated double bonds, while the oligomer used for cationic photocuring is a resin with epoxy groups or vinyl ether groups, and the resins with two different curing mechanisms are mixed to prepare the ink, so that the appearance, hardness and adhesion of a cured film are poor easily due to the fact that the curing speeds of the radical photocuring and the cationic photocuring are asynchronous. While the hybrid photosensitive resin is an important research direction to overcome the above drawbacks, there are related patent reports, for example, the prior art discloses a hybrid photosensitive resin containing oxetane functional groups and (meth) acryloyloxy functional groups, which is terminated with double bonds and has oxetane in the side chain, and can realize radical-cation hybrid photocuring. However, the radical-cation hybrid photocuring systems currently under investigation are predominantly solvent-based or solvent-free systems.
Therefore, it is important to provide an aqueous radical-cation hybrid photo-curable ink.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the aqueous free radical-cation hybrid photo-curing ink. The photo-curing ink is non-toxic, non-irritant, fast in curing speed, strong in adhesive force to plastic substrates such as PP and PET in the post-curing process, good in water resistance of an ink film and good in hardness.
Another object of the present invention is to provide an application of the aqueous radical-cation hybrid photo-curing ink.
The above purpose of the invention is realized by the following technical scheme:
an aqueous free radical-cation hybrid photo-curing ink comprises the following components in percentage by weight: 55-75% of water-based organic silicon modified polyester oligomer containing oxygen heterocycle, 3-8% of water-soluble free radical photoinitiator, 1-3% of cationic photoinitiator, 5-22% of water-based color paste, 0.3-1.5% of defoaming agent, 0.5-3% of wetting dispersant, 0.1-1% of flatting agent, 8-15% of alcohol solvent and the balance of water;
the oxygen heterocyclic ring-containing water-based organic silicon modified polyester oligomer comprises the following components in parts by weight: 29-46 parts of saturated dibasic acid, 18-23 parts of polyhydric alcohol, 5-9 parts of carboxyl-terminated sulfonate, 6-12 parts of double-bond dibasic acid, 8-15 parts of 3, 3-hydroxymethyl-1-oxetane, 0.05-0.2 part of catalyst, 8-20 parts of hydroxyl-terminated polysiloxane and 65-100 parts of water.
The dibasic acid with double bonds and the 3, 3-bis-hydroxymethyl-1-oxetane can be respectively introduced into the molecular chain of the polyester oligomer through the condensation reaction of carboxyl and hydroxyl, so as to introduce double bonds capable of curing by free radicals and an oxetane capable of curing by cationic light. The double bonds and the oxygen hetero rings are randomly distributed in the molecular chain, and the molecular weight and the UV curing group content can be simultaneously increased without restriction as compared with those of the blocked type.
The invention realizes the aquosity of the oligomer by introducing the hydrophilic carboxyl-terminated sulfonate, and water replaces the active diluent of the traditional UV ink to adjust the viscosity of the ink, thereby being green, environment-friendly and nonirritating. Because the low polymer has smaller molecular weight, the water-based binder with high solid content and low viscosity can be prepared, the water content of the ink is reduced, and the early-stage drying speed can be accelerated.
Since the radical photocuring speed is high and the cationic photocuring speed is low, the curing reaction of the oxygen heterocycle is limited after the double bond reaction is cured. Through the condensation polymerization reaction with the hydroxyl-terminated polysiloxane, a flexible siloxane chain segment is introduced into a molecular chain of the oligomer, so that the chain segment is easy to rotate, and the subsequent cationic photocuring is facilitated. In addition, siloxanes are poorly hydrophilic and tend to concentrate toward the film surface during film formation, thereby improving ink film water resistance.
The catalyst is one or more of tetraisobutyl titanate, p-toluenesulfonic acid and antimony acetate.
The water-soluble free radical photoinitiator comprises ONE or more of Quantacure BTC, Quantacure BPQ, Quantacure ABP, Quantacure QTX, Darocur 2959, Irgacure 819DW, Esacure ONE and Esacure KTO 46.
The cationic photoinitiator comprises a mixture of one or more of diaryliodonium salts and triarylsulfonium salts.
The preparation method of the aqueous free radical-cation hybrid photocuring ink comprises the following steps: dissolving a cationic photoinitiator in an alcohol solvent, sequentially adding water, a water-soluble free radical photoinitiator, a defoaming agent, a wetting dispersant and a flatting agent, stirring uniformly, adding an oxygen-heterocycle-containing water-based organic silicon modified polyester oligomer and water-based color paste, and stirring and dispersing.
Preferably, the acid value of the water-based organic silicon modified polyester oligomer containing the oxygen heterocyclic ring is 16.0-48.5 mg KOH/g. The polyester oligomer is terminated by excessive carboxyl, when the carboxyl is excessive, the terminal groups of the oligomer are all carboxyl, and the carboxyl do not react, so the reaction is terminated. The average molecular weight of the oligomer (mass of oligomer/mole of oligomer) is higher than that of the oligomer, and since the terminal group of each oligomer molecule is a carboxyl group, the more the carboxyl group is excessive, the higher the acid value of the synthesized oligomer is, the smaller the molecular weight is, and vice versa. When the acid value is lower than 16.0mg KOH/g, the molecular weight of the oligomer is too large, the viscosity is increased, more water needs to be added to reduce the viscosity of the ink, so that the solid content of the ink is reduced, and the drying time is prolonged; when the acid value is higher than 48.5mgKOH/g, the molecular weight of the oligomer is too small, the ink film of the prepared water-based ink is still sticky after baking, and the prepared water-based ink is easy to be dusty before being sent to photocuring, so that the appearance of the ink film is influenced, and the adhesive force of the ink film is poor.
Preferably, the saturated dibasic acid is one or more of terephthalic acid, isophthalic acid, hexahydrophthalic acid and adipic acid.
Preferably, the carboxyl-terminated sulfonate is sodium m-phthalic acid-5-sulfonate or sodium methylsuccinate-5-sulfonate.
Preferably, the double-bond dibasic acid is a double-bond dibasic acid in which the double bond is conjugated with the carboxyl group.
Preferably, the double-bond dibasic acid is one or more of itaconic acid, mesaconic acid, citraconic acid and glutaconic acid.
Most preferably, the double-bonded dibasic acid is itaconic acid.
Preferably, the polyalcohol is one or more of ethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, trimethylolethane and trimethylolpropane.
Preferably, the preparation method of the oxygenated heterocyclic water-based organic silicon modified polyester oligomer comprises the following steps: mixing saturated dibasic acid, polyhydric alcohol, carboxyl-terminated sulfonate, dibasic acid with double bonds, 3-dihydroxymethyl-1-oxetane and a catalyst, reacting at 200-220 ℃, adding terminal hydroxyl polysiloxane, reacting until the acid value is not changed, cooling to below 100 ℃, adding water, and stirring to obtain the modified polyester oligomer.
The application of any one of the photo-curing printing ink in printing of plastic base materials is also within the protection scope of the invention, after the water-based free radical-cation hybrid photo-curing printing ink is used for printing a plastic base material sample, the plastic base material sample is dried by infrared, hot air or microwave, and then is irradiated by an ultraviolet lamp to be cured into a film, and the ink film has good water resistance and good hardness. The photo-curing ink disclosed by the method is non-toxic, non-irritant, high in curing speed, and capable of being completely applied to printing plastic substrates in a post-curing process.
Preferably, the plastic substrate is PP or PET. The photocuring ink disclosed by the invention has the adhesion force to PP (polypropylene) of more than 85% and the adhesion force to PET (polyethylene terephthalate) of more than 90%, is subjected to postcuring, is placed for 24 hours, has the adhesion force to PP and PET of up to 100%, is unchanged in soaking, has good water resistance, and has a good application effect on printing PP and PET plastic substrates.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a water-based free radical-cation hybrid photo-curing ink, which introduces double bonds capable of curing by free radicals and oxygen heterocycles capable of curing by cation light on a molecular chain through dibasic acid with double bonds and 3, 3-bis-hydroxymethyl-1-oxetane, realizes the water-based performance of an oligomer through hydrophilic carboxyl-terminated sulfonate, and further introduces hydroxyl-terminated polysiloxane to improve the water resistance of an ink film. The ink disclosed by the invention is non-toxic, non-irritant, high in curing speed, good in water resistance, high in hardness of more than 2H, and high in adhesion to plastic substrates such as PP (polypropylene), PET (polyethylene terephthalate) and the like, has no change in ink film immersion in a post-curing process, and is completely suitable for printing the plastic substrates.
Detailed Description
In order to more clearly and completely describe the technical scheme of the invention, the invention is further described in detail by the specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the invention, and are not used for limiting the invention, and various changes can be made within the scope defined by the claims of the invention.
Examples 1 to 4
An aqueous radical-cation hybrid photo-curable ink comprising the components in the weight percentages shown in table 1.
The preparation method comprises the following specific steps:
dissolving a cationic photoinitiator in an alcohol solvent, sequentially adding water, a water-soluble free radical photoinitiator, a defoaming agent, a wetting dispersant and a flatting agent, uniformly stirring, adding an oxygen-containing heterocyclic water-based organic silicon modified polyester oligomer and water-based color paste, and stirring and dispersing;
wherein the water-soluble free radical photoinitiator in example 1 is a mixture of Quantacure QTX and Irgacure 819DW, and the parts by weight of the water-soluble free radical photoinitiator are 1.8 parts and 1.2 parts respectively; the cationic photoinitiator is 4, 4' -dimethyl diphenyl iodonium hexafluorophosphate, and the aqueous slurry is Kedi R4254 aqueous red paste; the antifoaming agent is TEGO Foamex 830; the wetting dispersant is TEGO dispersant 745 w; the leveling agent is TEGO Glide 110; the alcohol solvent is methanol;
the water-soluble free radical photoinitiator in example 2 is a mixture of Irgacure 819DW and Esacure KTO 46, and the weight parts of the mixture are 1.5 parts and 6.5 parts respectively; the cationic photoinitiator is 4, 4' -diacetyl amide phenyl iodine hexafluorophosphate, and the aqueous slurry is Shanghai Caisheng 8401 aqueous white slurry; the defoaming agent is BYK-012; the wetting dispersant is BYK-156; the leveling agent is TEGO Glide 410; the alcohol solvent is ethanol;
the water-soluble free radical photoinitiator described in example 3 was Esacure ONE; the cationic photoinitiator is triphenyl sulfur hexafluorophosphate, and the aqueous slurry is TSE BH aqueous blue color paste of Jiangsu world name; the antifoaming agent is FoamStar ST 2438; the wetting dispersant is Dispex Ultra PX 4275; the leveling agent is TEGO Glide 410; the alcohol solvent is ethanol;
the water-soluble free radical photoinitiator in example 4 is a mixture of Esacure KTO 46 and Quantacure QTX, and the weight parts of the water-soluble free radical photoinitiator are 3 parts and 3 parts respectively; the cationic photoinitiator is triphenyl sulfur hexafluorophosphate, and the aqueous slurry is Kedi Y2003 aqueous yellow slurry; the antifoaming agent is TEGO Foamex 830; the wetting dispersant is TEGO Disperse 750 w; the leveling agent is BYK-333; the alcohol solvent is ethanol.
TABLE 1
The oxygen-heterocycle-containing water-based organic silicon modified polyester oligomer disclosed in the embodiment 1-4 is composed of the raw materials in parts by weight shown in Table 2.
The preparation method comprises the following specific steps:
mixing saturated dibasic acid, polyhydric alcohol, isophthalic acid-5-sodium sulfonate, itaconic acid, 3-bis (hydroxymethyl) -1-oxetane and a catalyst, reacting at 200-220 ℃ until the theoretical acid value is reached (41.6, 39.4, 29.7 and 72.2 in examples 1-4 and 92.8, 25.1 and 26.0 in comparative examples 1-3), adding terminal hydroxyl polysiloxane, reacting until the acid value is not changed, cooling to below 100 ℃, adding water, and stirring to obtain the compound.
TABLE 2
Comparative example 1
An aqueous radical-cation hybrid photo-curable ink which is substantially the same as in example 4 except that the acid value and the raw material composition in parts by weight of the oxygen-containing heterocyclic aqueous silicone-modified polyester oligomer are shown in table 2.
Comparative example 2
An aqueous radical-cation hybrid photo-curable ink which is substantially the same as in example 3 except that the acid value and the raw material composition in parts by weight of the oxygen-containing heterocyclic aqueous silicone-modified polyester oligomer are shown in table 2.
Comparative example 3
An aqueous radical-cation hybrid photo-curable ink, which is substantially the same as in example 1 except that the oxygen-containing heterocyclic aqueous silicone-modified polyester oligomer is composed of the raw materials in the parts by weight shown in table 2.
Results of Performance testing
The water-based inks described in the examples and comparative examples were respectively scraped and printed on PP and PET sheets, and after drying the printed samples by blowing at 80 ℃, the printed samples were cured for 5 seconds by ultraviolet irradiation. Respectively testing the ink film performance of the ink after photocuring and standing for 24 hours, wherein the ink viscosity: measured according to GB/T13217.4-2008;
ink film hardness: measuring according to GB/T6739-2006 after the ink is cured into a film;
water resistance of the ink film: inspecting according to a GB/T1733-93 soaking experimental method, and observing the change condition of the ink film after soaking for 24 hours;
ink film adhesion: and (4) observing the adhesion fastness of the ink on PP and PET printing materials according to the test of GB/T13217.7-2009.
The results of the performance tests are shown in table 3.
TABLE 3
As shown in Table 3, after the aqueous free radical-cation hybrid photo-curing ink prepared in examples 1 to 4 is subjected to UV curing, the hardness is over 2H, the adhesion to PP is greater than 85%, the adhesion to PET is greater than 90%, but the water resistance is poor, and the phenomena of light loss and wrinkling appear after soaking. But after the printing ink is cured after being present and is placed for 24 hours, the adhesion force of the printing ink to PP and PET reaches 100 percent, the printing ink is unchanged after being soaked in water, and the water resistance is good.
As can be seen from comparative example 1, when the acid value of the synthetic oligomer was high, the prepared ink was inferior in both adhesion and water resistance after curing. As can be seen from comparative example 2, when the acid value of the synthesized oligomer is low, the prepared ink has high viscosity, poor leveling of the scraping sample, relatively thick film formation, incomplete UV curing and slight edge cracking, so that the adhesive force and the water resistance of an ink film are poor, the performance is improved after the scraping sample is placed for 24 hours, the viscosity of the ink can be reduced by adding water, but the solid content of the ink is reduced, and the drying time is prolonged. As can be seen from comparative example 3, when no hydroxysiloxane was added, the water resistance of the film was poor, and the flexibility of the segment was lowered, which was not favorable for the reaction curing of the photo-curing group, resulting in a decrease in adhesion.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. It will be understood by those skilled in the art that various other changes and modifications may be made in the above-described embodiments, and it is not necessary, nor is it intended to be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (9)
1. The water-based free radical-cation hybrid photo-curing ink is characterized by comprising the following components in percentage by weight: 55-75% of water-based organic silicon modified polyester oligomer containing oxygen heterocycle, 3-8% of water-soluble free radical photoinitiator, 1-3% of cationic photoinitiator, 5-22% of water-based color paste, 0.3-1.5% of defoaming agent, 0.5-3% of wetting dispersant, 0.1-1% of flatting agent, 8-15% of alcohol solvent and the balance of water;
the oxygen heterocyclic ring-containing water-based organic silicon modified polyester oligomer comprises the following components in parts by weight: 29-46 parts of saturated dibasic acid, 18-23 parts of polyhydric alcohol, 5-9 parts of carboxyl-terminated sulfonate, 6-12 parts of double-bond dibasic acid, 8-15 parts of 3, 3-hydroxymethyl-1-oxetane, 0.05-0.2 part of catalyst, 8-20 parts of hydroxyl-terminated polysiloxane and 65-100 parts of water;
the dibasic acid with double bonds is the dibasic acid with double bonds, wherein the double bonds and the carboxyl are in a conjugated state.
2. The photocurable ink according to claim 1, wherein the oxygen-containing heterocyclic water-based silicone-modified polyester oligomer has an acid value of 16.0 to 48.5mg KOH/g.
3. The photo-curable ink according to claim 1, wherein the saturated dibasic acid is one or more of terephthalic acid, isophthalic acid, hexahydrophthalic acid and adipic acid.
4. The photocurable ink of claim 1 wherein the carboxyl-terminated sulfonate is sodium 5-sulfoisophthalate or sodium 5-sulfomethylsuccinate.
5. The photo-curable ink according to claim 1, wherein the double-bonded dibasic acid is one or more of itaconic acid, mesaconic acid, citraconic acid, and glutaconic acid.
6. The photo-curable ink according to claim 1, wherein the polyol is one or more selected from the group consisting of ethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol, trimethylolethane, and trimethylolpropane.
7. The photocurable ink according to claim 1, wherein the oxygen-containing heterocyclic water-based silicone-modified polyester oligomer is prepared by a method comprising the steps of:
mixing saturated dibasic acid, polyhydric alcohol, carboxyl-terminated sulfonate, dibasic acid with double bonds, 3-dihydroxymethyl-1-oxetane and a catalyst, reacting at 200-220 ℃, adding terminal hydroxyl polysiloxane, reacting until the acid value is not changed, cooling to below 100 ℃, adding water, and stirring to obtain the modified polyester oligomer.
8. Use of a photocurable ink according to any one of claims 1 to 7 for printing plastic substrates.
9. Use according to claim 8, wherein the plastic substrate is PP or PET.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811332330.5A CN109575681B (en) | 2018-11-09 | 2018-11-09 | Water-based free radical-cation hybrid photocuring ink and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811332330.5A CN109575681B (en) | 2018-11-09 | 2018-11-09 | Water-based free radical-cation hybrid photocuring ink and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109575681A CN109575681A (en) | 2019-04-05 |
| CN109575681B true CN109575681B (en) | 2022-04-19 |
Family
ID=65922080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811332330.5A Active CN109575681B (en) | 2018-11-09 | 2018-11-09 | Water-based free radical-cation hybrid photocuring ink and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109575681B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111205733A (en) * | 2020-02-28 | 2020-05-29 | 上海超彩油墨有限公司 | Cationic/free radical dual-curing UV gloss oil for tin printing ink and preparation method thereof |
| CN113999618A (en) * | 2021-11-22 | 2022-02-01 | 曹云来 | Low-odor and low-irritation dual-curing adhesive and preparation method thereof |
| CN115651589B (en) * | 2022-11-07 | 2024-03-19 | 深圳市优宝新材料科技有限公司 | Dual-curing adhesive and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1537149A (en) * | 2001-07-23 | 2004-10-13 | 3M | Ink jet ink compositions containing fluorochemical surfactants |
| CN1735638A (en) * | 2002-03-15 | 2006-02-15 | 太阳油墨制造株式会社 | Curable resins and curable resin compositions containing the same |
| CN102268138A (en) * | 2011-05-17 | 2011-12-07 | 中科院广州化学有限公司 | Aqueous organosilicon grafted (methyl) acrylic polymer and preparation method of emulsion thereof |
| CN103571310A (en) * | 2013-11-15 | 2014-02-12 | 东北大学 | Free radical-cationic hybrid light curing coating and preparation method and application method thereof |
| CN106188548A (en) * | 2016-07-16 | 2016-12-07 | 北京化工大学 | A kind of organosilicon cationic light-cured resin of oxygen heterocycle butane structure and preparation method thereof |
| CN107325237A (en) * | 2016-04-15 | 2017-11-07 | 常州强力电子新材料股份有限公司 | A kind of Free radical-Cationic Hybrid photocuring system and its application |
-
2018
- 2018-11-09 CN CN201811332330.5A patent/CN109575681B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1537149A (en) * | 2001-07-23 | 2004-10-13 | 3M | Ink jet ink compositions containing fluorochemical surfactants |
| CN1735638A (en) * | 2002-03-15 | 2006-02-15 | 太阳油墨制造株式会社 | Curable resins and curable resin compositions containing the same |
| CN102268138A (en) * | 2011-05-17 | 2011-12-07 | 中科院广州化学有限公司 | Aqueous organosilicon grafted (methyl) acrylic polymer and preparation method of emulsion thereof |
| CN103571310A (en) * | 2013-11-15 | 2014-02-12 | 东北大学 | Free radical-cationic hybrid light curing coating and preparation method and application method thereof |
| CN107325237A (en) * | 2016-04-15 | 2017-11-07 | 常州强力电子新材料股份有限公司 | A kind of Free radical-Cationic Hybrid photocuring system and its application |
| CN106188548A (en) * | 2016-07-16 | 2016-12-07 | 北京化工大学 | A kind of organosilicon cationic light-cured resin of oxygen heterocycle butane structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 光固化有机硅材料研究进展;刘长利等;《材料导报》;20060430;第20卷(第4期);第44-48页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109575681A (en) | 2019-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109575681B (en) | Water-based free radical-cation hybrid photocuring ink and application thereof | |
| CN102649895B (en) | Ultraviolet light-heat dual-curing gloss oil, and preparation method and application thereof | |
| CN102712820B (en) | Radiation-curable water-based paint compositions | |
| EP3336150A1 (en) | Ink composition and method of printing | |
| CN107987244A (en) | A kind of aqueous photosensitive supermolecule polyurethane resin and preparation method and application | |
| CN113072837A (en) | UV-LED two-piece can high-flexibility offset printing ink and preparation method thereof | |
| CN115093751A (en) | Water-based ink composition, preparation method and application thereof, plastic material and package | |
| CN111349366B (en) | UV-LED inkjet ink for PVC leather printing and preparation method thereof | |
| CN111647306B (en) | In situ generation of organized SiO 2 Environment-friendly enhanced waterborne polyurethane ink and preparation method thereof | |
| EP3736313A1 (en) | Conductive ink composition and article of manufacture made therefrom | |
| CN110498933B (en) | Self-emulsifying water-based epoxy emulsion and preparation method thereof | |
| CN112341863A (en) | UV ink-jet ink and preparation method thereof | |
| CN111234602A (en) | High-adhesion color water-based ink for plastics and preparation method thereof | |
| CN106590175A (en) | Bacteriostatic and antiseptic waterborne polyurethane gravure fluorescent ink and preparation method thereof | |
| US6605652B1 (en) | Energy curable inks and methods of preparing same | |
| CN106590174B (en) | Degradable gravure UV anti-counterfeiting ink and application thereof to gold and silver card paper | |
| CN115286957A (en) | Preparation method and application of photocuring self-emulsifying waterborne polyurethane composite pigment ink | |
| CN109354980B (en) | Water-based epoxy impregnating varnish and preparation method and application thereof | |
| CN106928824A (en) | A kind of refitted car aqueous enamel paint of dual cure and preparation method thereof | |
| CN117510786B (en) | Waterborne polyurethane containing two photochromic groups, preparation method thereof and application thereof in anti-counterfeiting ink | |
| CN116004107B (en) | 3C water-based paint and preparation method and application thereof | |
| CN117510785B (en) | Water-based polyurethane with visible light color change and ultraviolet light excited fluorescence, preparation method thereof and application thereof in anti-counterfeiting ink | |
| US20190144604A1 (en) | Alkoxylated polymers | |
| CN116904062A (en) | Low-shrinkage UV (ultraviolet) curing ink and marking adhesive tape applying same | |
| CN118222166B (en) | UV offset printing gloss oil and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220324 Address after: 528445 floor 2-3, building 3, No. 9, fuze Road, Sanjiao Town, Zhongshan City, Guangdong Province Applicant after: ZHONGSHAN BURUITE ENVIRONMENTAL PROTECTION PRINTING INK Co.,Ltd. Address before: 510275 No. 135 West Xingang Road, Guangzhou, Guangdong, Haizhuqu District Applicant before: He Guoxiong |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |