CN102492330B - Ultraviolet (UV) photocurable inkjet ink for glass substrate and preparation method for UV photocurable inkjet ink - Google Patents
Ultraviolet (UV) photocurable inkjet ink for glass substrate and preparation method for UV photocurable inkjet ink Download PDFInfo
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- CN102492330B CN102492330B CN201110396269.2A CN201110396269A CN102492330B CN 102492330 B CN102492330 B CN 102492330B CN 201110396269 A CN201110396269 A CN 201110396269A CN 102492330 B CN102492330 B CN 102492330B
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- 239000011521 glass Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000758 substrate Substances 0.000 title claims abstract description 7
- 150000003254 radicals Chemical class 0.000 claims abstract description 12
- 239000000049 pigment Substances 0.000 claims abstract description 10
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 6
- 239000012952 cationic photoinitiator Substances 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000005355 lead glass Substances 0.000 claims abstract 2
- 229910052710 silicon Inorganic materials 0.000 claims abstract 2
- 239000010703 silicon Substances 0.000 claims abstract 2
- 238000000016 photochemical curing Methods 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 24
- -1 methacryloxy Chemical group 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 238000005374 membrane filtration Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- 239000000080 wetting agent Substances 0.000 claims description 5
- 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 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 4
- 229920001427 mPEG Polymers 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 claims description 2
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical group C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 2
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical group C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- AXNCDCBLBGUMBO-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].C(=C)C1=CCCCC1 Chemical compound [O-2].[O-2].[Ti+4].C(=C)C1=CCCCC1 AXNCDCBLBGUMBO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004980 cyclopropylene group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 229940087305 limonene Drugs 0.000 claims description 2
- 235000001510 limonene Nutrition 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- XHIKSLHIZYVEQI-UHFFFAOYSA-N CC1=C(C(=O)[PH2]=O)C(=CC(=C1)C)C Chemical compound CC1=C(C(=O)[PH2]=O)C(=CC(=C1)C)C XHIKSLHIZYVEQI-UHFFFAOYSA-N 0.000 claims 1
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 239000000975 dye Substances 0.000 claims 1
- MWQBWSPPTQGZII-UHFFFAOYSA-N ethoxy(phenyl)phosphinic acid Chemical compound CCOP(O)(=O)C1=CC=CC=C1 MWQBWSPPTQGZII-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003085 diluting agent Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 239000010410 layer Substances 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NQBWNECTZUOWID-UHFFFAOYSA-N (E)-cinnamyl (E)-cinnamate Natural products C=1C=CC=CC=1C=CC(=O)OCC=CC1=CC=CC=C1 NQBWNECTZUOWID-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- NQBWNECTZUOWID-QSYVVUFSSA-N cinnamyl cinnamate Chemical compound C=1C=CC=CC=1\C=C/C(=O)OC\C=C\C1=CC=CC=C1 NQBWNECTZUOWID-QSYVVUFSSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- YMCOIFVFCYKISC-UHFFFAOYSA-N ethoxy-[2-(2,4,6-trimethylbenzoyl)phenyl]phosphinic acid Chemical compound CCOP(O)(=O)c1ccccc1C(=O)c1c(C)cc(C)cc1C YMCOIFVFCYKISC-UHFFFAOYSA-N 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- DMKSVUSAATWOCU-HROMYWEYSA-N loteprednol etabonate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)OCCl)(OC(=O)OCC)[C@@]1(C)C[C@@H]2O DMKSVUSAATWOCU-HROMYWEYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
The invention discloses ultraviolet (UV) nanometer inkjet ink for a glass substrate and a preparation method for the UV nanometer inkjet ink. The UV nanometer inkjet ink consists of the following components in percentage by weight: 2 to 15 percent of pigment, 60 to 90 percent of reactive diluent, 2 to 10 percent of active oligomer, 3 to 10 percent of free radical type photoinitiator, 2 to 10 percent of cationic photoinitiator, 0.2 to 2 percent of adhesion promoter and 0.5 to 5 percent of other aids. The UV nanometer inkjet ink does not yellow and crack after being roasted at high temperature of 250 DEG C for 1h; the inkjet ink can be firmly adhered to glass after being solidified, and does not fall off and whiten after being soaked in warm water (35 DEG C) for 1h; the ink can be directly sprayed on glass substrates, and the glass is not required to be pre-treated; and the ink can be simply and conveniently constructed, can be widely applied to ordinary glass in life, and can also be applied to substrates with higher performance requirements such as solar silicon crystal glass, color display glass and the like.
Description
Technical field
The present invention relates to a kind of UV curable ink, be specifically related to a kind of UV photo-curing ink-jet ink for glass baseplate and preparation method thereof.
Background technology
The curing ink-jet of UV combines the advantage of UV curing technology and inkjet technology, and existing UV is solidificated in economical and technical advantage, also has inkjet technology and is using and operational facility, has the feature of extensive versatility.But ink for ink-jet print not can be adsorbed on base material used easily, particularly glass.Because glass baseplate is the inorganic materials of atresia, and UV photo-curing ink-jet main component is organic compound, glass is difficult for being corroded, ink be difficult to infiltrate base material inside, therefore ink for ink-jet print be not easy to sprawl at glass surface, adhere firmly.
Printing (comprising ink jet printing) on glass baseplate is both at home and abroad first at pre-treatment (coating precoated layer to improve the sticking power of ink-jet to glass), then impressing pattern, the last spraying protective layer of carrying out on glass.This process complexity, and the solvent type not environmental protection coating material of great majority use, have a large amount of VOC volatilizations.
At present more for the research of the glass ink-jet of some common application scopes, as Chinese patent CN101624492A discloses at normal temperatures glass spray ink Printing on glass, there is cured film better to glass attachment power, the feature that viscosity is little.But when the curing glasswork of UV ink-jet contact water, especially contact after hot water, sticking power variation, cured film easily from glassly coming off, cracking etc.For the UV cured film water tolerance on solution glass baseplate and the problem of attachment fastness, prior art has been introduced following three kinds of methods: before ink-jet, first apply the resin that strengthens sticking power; Or after photocuring, carry out again curing process; Or glass is carried out to modification.Specifically in patent WO2010/115858, reported the method for the sticking power of a kind of UV of enhancing ink-jet on glass baseplate as people such as Lecolle F., between cured layer and glass baseplate, add a kind of sticking power layer and glass coating, sticking power layer includes epoxy resin, melamine resins etc., glass coating is the composition of some metal oxides.The people such as MATSUSAWA M. have introduced and have contained the oxide compound cured layers such as benzophenone, styracin and titanium oxide, zinc oxide in interpolation on glass in patent JP2009078531-A, and this cured layer is conducive to improve the sticking power of UV ink-jet.The people such as GRANT A. propose UV ink-jet spray printing after glass baseplate photocuring in patent WO 2009/118507, carry out again thermofixation, thermofixation refers to that at a certain temperature (100～400 ℃) bake, and ink-jet is solidified more complete, to reach the object that strengthens sticking power.But existing these method operating process complexity are also inconvenient in technique.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of UV photo-curing ink-jet ink that can be applicable to glass baseplate is provided, this ink has good sticking power and high fastness on glass baseplate.
Another object of the present invention is to provide the preparation method of the described UV photo-curing ink-jet ink for glass baseplate.
Above-mentioned purpose of the present invention is achieved by following technical solution:
For a UV photo-curing ink-jet ink for glass baseplate, formed by the component counting by weight percentage as follows:
Pigment 2～15%;
Reactive thinner 60～90%;
Living oligomer 2～10%;
Radical photoinitiator 3～10%
Cationic photoinitiator 2～10%;
Adhesion promoter 0.2～2%;
Auxiliary agent 0.5～5%;
Described reactive thinner is the mixture by single functionality monomer, difunctionality monomer and polyfunctionality monomer composition;
Described reactive thinner is the composition of cationic reactive thinner and free radical activity thinner simultaneously;
Described living oligomer is the composition of aliphatic urethane acrylate oligopolymer and origoester acrylate;
Described adhesion promoter is that general formula is R (CH
2)
nsiX
3silane coupling agent, wherein, R is vinyl, amido, epoxy group(ing), methacryloxy or sulfydryl; X is methoxy or ethoxy, and n is 0～3;
Described auxiliary agent is dispersion agent, wetting agent and defoamer.
Described reactive thinner, according to the number containing polymerizable functional group in molecule, can be categorized as single functionality monomer, difunctionality monomer, polyfunctionality monomer.
Here said functionality, refers to the number of epoxy group(ing) or carbon-carbon double bond Zhe Liangzhong functional group.
As a kind of preferred version, described single functionality monomer is preferably isooctyl acrylate, cyclopropylene acid TriMethylolPropane(TMP), 3,3,5-trimethylcyclohexyl acrylate, tetrahydrofurfuryl acrylate, methoxy poly (ethylene glycol) list (methyl) acrylate, any one or a few in 1,2-epoxy-4-vinyl cyclohexane or (R)-oxidation limonene;
Described difunctionality monomer is preferably 1,6-hexanediyl ester, propylene glycol diacrylate, the third oxidation neopentylglycol diacrylate, 3,4-epoxycyclohexyl methyl 3,4-epoxycyclohexyl manthanoate, titanium dioxide vinylcyclohexene or hexanaphthene-1, any one or a few in 2-dicarboxylic acid two (epoxy ethyl methyl) ester;
Described polyfunctionality monomer is preferably Viscoat 295, pentaerythritol triacrylate, any one or a few in double pentaerythritol C5 methacrylate or propoxylation multi-functional acrylate.
Reactive thinner can participate in photocuring reaction, thereby affects the laser curing velocity of ink-jet and the chemical property of cured film and physicals; Also play in addition dissolving, the effect of dilution oligopolymer.In general, functional group's number is more, and speed of response is faster, but the ink-jet viscosity of preparation is also larger, therefore the dilution capacity of the high reactive thinner of functionality weakens.General ink-jet systems requires below 15mpas viscosity; As more preferably scheme of one, in described reactive thinner, the weight of single functionality monomer is preferably and accounts for 65～95% of reactive thinner weight, it is 1～22% that the weight of difunctionality monomer is preferably what account for reactive thinner weight, and the weight of polyfunctionality monomer is preferably and accounts for 1～15% of reactive thinner weight.
It is over half that single functionality monomer accounts for reactive thinner formula, can guarantee that the viscosity of ink-jet is moderate, and single functionality monomer is because carbon-carbon double bond content is low, and while solidifying, volumetric shrinkage is few, contributes to improve sticking power; A small amount of high functionality monomer that adds can be accelerated curing speed and the physicals such as sticking power, water tolerance that improves cured film.
Described living oligomer is the composition of aliphatic urethane acrylate oligopolymer and origoester acrylate.Origoester acrylate has fabulous resistance to xanthochromia ability, and all kinds of different substrate materials are all had to good sticking power.In aliphatic urethane acrylate molecule, there is ammonia ester bond, can between macromolecular chain, form various hydrogen bonds, make cured film there is excellent wear resistance and snappiness, excellent combination property, the introducing of aliphatic chain is conducive to improve weather resistance, be used in conjunction with acrylate, can increase its sticking power to base material.But the physical strength of acrylate and hardness are all very low, consumption can affect the performance of cured film too much.As a kind of preferred version, in described living oligomer, the weight ratio of aliphatic urethane acrylate oligopolymer and origoester acrylate is preferably 2: 1～and 5: 1.
The present invention has adopted positively charged ion-free radical to mix photocuring, in same system, adopts two kinds of dissimilar polyreactions of positively charged ion and radical polymerization to make the curing method of system.The method combines the advantage of two kinds of polyreactions, utilizes free radical system inductive phase short and reach fast shaping, and the dark reaction of cationic system makes system thorough dry; And utilize the little feature expanding that even produces of cationic polymers volumetric shrinkage, and the volumetric shrinkage while making up radical polymerization, thus the sticking power of ink for ink-jet print to glass baseplate strengthened.
As a kind of preferred version; described radical photoinitiator is preferably 2-isopropyl thioxanthone; 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone; phenyl two (2; 4; 6-trimethylbenzoyl) any one or a few in phosphine oxide or 2,4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester.
As a kind of preferred version, described cationic photoinitiator is preferably macromole evocating agent.Compared with small molecules light trigger, macromolecular photoinitiator volatility is less, and can solve the toxicity problem that solidifies rear resin system residual light initiation fragment.
As a kind of preferred version, in described cationic photoinitiator, be preferably the salt compounded of iodine that contains polyurethanyl group, described in contain polyurethanyl group the structural formula of salt compounded of iodine suc as formula shown in (I):
Wherein, n is 8～18.
Because the introducing of polyurethanyl group has increased its stability to hydrolysis, the introducing of long aliphatic chain has increased again the solvability of salt greatly, and makes maximum absorption wavelength red shift.
The present invention is also by adding adhesion promoter, and concrete general formula is R (CH
2) n-Si-X
3silane coupling agent solve ink-jet in the poor problem of adsorptive power on glass, R group can react with organic constituent form covalent linkage; X group can be hydrolyzed generation silanol group, and silanol group and glass surface form siloxane bond, thereby organic constituent and inorganic materials are closely linked together by chemical bond, have strengthened ink-jet at sticking power on glass.
As a kind of preferred version, described silane coupling agent is preferably 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, vinyltriethoxysilane, 3-(methacryloxypropyl) propyl trimethoxy silicane, APTES or 3-sulfydryl propyl-triethoxysilicane.
Usually, existing UV photo-curing ink-jet ink is applicable to common unorganic glass, and glass baseplate of the present invention can be common unorganic glass, can also be the glass with special purpose; As a kind of preferred version, described glass baseplate is preferably sun power devitrified glass or colour display screen glass substrate.
The preparation method of the described UV nanometer ink for ink-jet print for glass baseplate, comprise the steps: first living oligomer, dispersion agent, part reactive thinner and pigment to be stirred after 0.5～1h under homogenizer, then sent in sand mill and ground, until be less than after 300nm containing its median size of compound of pigment, emit, mix with other component in formula with remaining reactive thinner again, be uniformly dispersed through clarifixator, finally, by the membrane filtration of 0.45 micron, make the UV photo-curing ink-jet ink for glass baseplate.
The present invention is by adopting positively charged ion-free radical hybrid UV curable paint, select suitable reactive thinner and living oligomer, interpolation can promote the silane coupling agent of sticking power to improve attachment fastness and the water tolerance of ink for ink-jet print to glass baseplate, reaches the object of completely straight spray.Be about to adopt UV photo-curing ink-jet machine directly UV nanometer ink for ink-jet print of the present invention to be beaten on glass baseplate; and be cured at once; need to before ink-jet, not apply in advance sticking power layer, need to be not armor coated on UV ink-jet cured layer yet, so just can simplify widely production process.
Compared with prior art, the present invention has following beneficial effect:
The present invention has adopted positively charged ion-free radical to mix photocuring, in same system, adopts two kinds of dissimilar polyreactions of positively charged ion and radical polymerization to make the curing method of system; The method combines the advantage of two kinds of polyreactions, utilizes free radical system inductive phase short and reach fast shaping, and the dark reaction of cationic system makes system thorough dry; And utilize the little feature expanding that even produces of cationic polymers volumetric shrinkage, and the volumetric shrinkage while making up radical polymerization, thus the sticking power of ink for ink-jet print to glass baseplate strengthened; Described UV photo-curing ink-jet ink can be realized straight spray, and without pre-treatment is carried out in glass baseplate surface, construction technology is simple, and has good attachment fastness and water tolerance.
Embodiment
Below in conjunction with specific embodiment, the present invention is further explained, but embodiments of the present invention is not limited in any way.
Embodiment 1
Raw material and the proportioning of the red UV nanometer of the present embodiment preparation used ink for ink-jet print are as shown in table 1:
Raw material and the proportioning of the red UV nanometer of table 1 preparation ink for ink-jet print
According to formula and consumption described in table 1, first by aliphatic urethane acrylate UA 9030 v oligopolymer, pure acrylate 6584N oligopolymer, methoxy poly (ethylene glycol) mono acrylic ester reactive thinner, pinkish red Meganta 176 pigment, Dispers 685 dispersion agents and Airex 900 defoamers stir after 0.5h under homogenizer, then gained compound is sent in sand mill and ground, be less than after 300nm when being ground to the median size of compound, emit, again with remaining reactive thinner, free radical photo-initiation, cation light initiator and Wet 270 wetting agents mix, disperse secondary through clarifixator, finally use the membrane filtration of 0.45 micron, make pinkish red UV photo-curing ink-jet ink.
Pinkish red UV photo-curing ink-jet ink prepared by embodiment 1, median size is 254nm, recording viscosity at 25 ℃ with the S61 rotor of Brookfield viscometer DV-II is 7.32mpas.The product that embodiment 1 is made is painted on devitrified glass, then complete photocuring under UV-irradiation, and the pencil hardness of its cured film is 3H; And according to the GB/T 13217.7-2009 liquid ink attachment fastness method of inspection, do not come off with 3M tape stripping film, attachment fastness 100%; 250 ℃ bake not xanthochromia of 1h film, do not chap; 35 ℃ of warm water soaking 1h cured film do not come off, do not whiten.
Embodiment 2
Raw material and the proportioning of the blue UV photo-curing ink-jet of the present embodiment preparation used ink are as shown in table 2:
Table 2 is prepared raw material and the proportioning of blue UV photo-curing ink-jet ink
According to formula and consumption described in table 2, first by aliphatic urethane acrylate oligopolymer UA 9033 v, pure acrylate 6533B-40 oligopolymer, 3, 3, 5-trimethylcyclohexyl acrylate reactive thinner, methoxy poly (ethylene glycol) mono acrylic ester reactive thinner, blue Cyan15:3 pigment, Dispers 680 dispersion agents and FoamexN defoamer stir after 0.5h under homogenizer, then gained compound is sent in sand mill and ground, be less than after 300nm when being ground to the median size of compound, emit, again with remaining reactive thinner, free radical photo-initiation, cation light initiator and BYK 3510 wetting agents mix, disperse secondary through clarifixator, finally use the membrane filtration of 0.45 micron, make blue UV photo-curing ink-jet ink.
Blue UV photo-curing ink-jet ink prepared by embodiment 2, median size is 269nm, recording viscosity at 25 ℃ with the S61 rotor of Brookfield viscometer DV-II is 8.84mpas.The product that embodiment 2 is made is painted on devitrified glass, then complete photocuring under UV-irradiation, and the pencil hardness of its cured film is 3H; And according to the GB/T 13217.7-2009 liquid ink attachment fastness method of inspection, do not come off with 3M tape stripping film, attachment fastness 100%; 250 ℃ bake not xanthochromia of 1h film, do not chap; 35 ℃ of warm water soaking 1h cured film do not come off, do not whiten.
Embodiment 3
The present embodiment is used, and to prepare raw material and the proportioning of black UV photo-curing ink-jet ink as shown in table 3:
Table 3 is prepared raw material and the proportioning of black UV photo-curing ink-jet ink
According to formula and consumption described in table 3, first by aliphatic urethane acrylate UA 19T oligopolymer, pure acrylate DR-A801 oligopolymer, 3, 3, 5-trimethylcyclohexyl acrylate, pentaerythritol triacrylate, black Black 7 pigment, BYK 168 dispersion agents and BYK 067A defoamer stir after 0.5h under homogenizer, then gained compound is sent in sand mill and ground, be less than after 300nm when being ground to the median size of compound, emit, again with remaining reactive thinner, free radical photo-initiation, cation light initiator and BYK 3500 wetting agents mix, disperse secondary through clarifixator, finally use the membrane filtration of 0.45 micron, make black UV photo-curing ink-jet ink.
Black UV photo-curing ink-jet ink prepared by embodiment 3, median size is 273nm, recording viscosity at 25 ℃ with the S61 rotor of Brookfield viscometer DV-II is 6.62mpas.The product that embodiment 3 is made is painted on devitrified glass, then complete photocuring under UV-irradiation, and the pencil hardness of its cured film is 3H; And according to the GB/T 13217.7-2009 liquid ink attachment fastness method of inspection, do not come off with 3M tape stripping film, attachment fastness 100%; 250 ℃ bake not xanthochromia of 1h film, do not chap; 35 ℃ of warm water soaking 1h cured film do not come off, do not whiten.
Claims (5)
1. for a UV photo-curing ink-jet ink for glass baseplate, it is characterized in that, formed by the component counting by weight percentage as follows:
Pigment 2 ~ 15%;
Reactive thinner 60 ~ 90%;
Living oligomer 2 ~ 10%;
Radical photoinitiator 3 ~ 10%
Cationic photoinitiator 2 ~ 10%;
Adhesion promoter 0.2 ~ 2%;
Auxiliary agent 0.5 ~ 5%;
Described reactive thinner is the mixture by single functionality monomer, difunctionality monomer and polyfunctionality monomer composition;
Described reactive thinner is the composition of cationic reactive thinner and free radical activity thinner simultaneously;
Described adhesion promoter is that general formula is R (CH
2)
nsiX
3silane coupling agent, wherein, R is vinyl, amido, epoxy group(ing), methacryloxy or sulfydryl; X is methoxy or ethoxy, and n is 0 ~ 3;
In described living oligomer, the weight ratio of aliphatic urethane acrylate oligopolymer and pure acrylic acid ester oligomer is 2:1 ~ 5:1;
Described auxiliary agent is dispersion agent, wetting agent and defoamer;
In described reactive thinner, the weight of single functionality monomer accounts for 65 ~ 95% of reactive thinner weight, and what the weight of difunctionality monomer accounted for reactive thinner weight is 1 ~ 22%, and the weight of polyfunctionality monomer accounts for 1 ~ 15% of reactive thinner weight;
Described radical photoinitiator is 2-isopropyl thioxanthone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone, phenyl two (2,4,6-trimethylbenzoyl) phosphine oxide or 2, any one or a few in 4,6-trimethylbenzoyl phenyl-phosphonic acid ethyl ester;
In described cationic photoinitiator, contain the salt compounded of iodine of polyurethanyl group, described in contain polyurethanyl group the structural formula of salt compounded of iodine as shown in formula I:
（Ⅰ）
Wherein, n is 8 ~ 18.
2. as claimed in claim 1 for the UV photo-curing ink-jet ink of glass baseplate, it is characterized in that, described single functionality monomer is isooctyl acrylate, cyclopropylene acid TriMethylolPropane(TMP), 3,3,5-trimethylcyclohexyl acrylate, tetrahydrofurfuryl acrylate, methoxy poly (ethylene glycol) list (methyl) acrylate, any one or a few in 1,2-epoxy-4-vinyl cyclohexane or (R)-oxidation limonene;
Described difunctionality monomer is 1,6-hexanediyl ester, propylene glycol diacrylate, the third oxidation neopentylglycol diacrylate, 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexyl manthanoate, titanium dioxide vinylcyclohexene or hexanaphthene-1, any one or a few in 2-dicarboxylic acid two (epoxy ethyl methyl) ester;
Described polyfunctionality monomer is Viscoat 295, pentaerythritol triacrylate, any one or a few in double pentaerythritol C5 methacrylate or propoxylation multi-functional acrylate.
3. as claimed in claim 1 for the UV photo-curing ink-jet ink of glass baseplate, it is characterized in that, described silane coupling agent is 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, vinyltriethoxysilane, 3-(methacryloxypropyl) propyl trimethoxy silicane, APTES or 3-sulfydryl propyl-triethoxysilicane.
4. as claimed in claim 1 for the UV photo-curing ink-jet ink of glass baseplate, it is characterized in that, described glass baseplate is solar power silicon crystal glass or colour display screen glass substrate.
Described in claim 1 for the preparation method of the UV photo-curing ink-jet ink of glass baseplate, it is characterized in that, comprise the steps: first by living oligomer, dispersion agent, part reactive thinner and pigment dyestuff stir after 0.5 ~ 1h under homogenizer, then sent in sand mill and ground, until be less than after 300nm containing its median size of compound of pigment, emit, mix with other component in formula with remaining reactive thinner again, be uniformly dispersed through clarifixator, finally by the membrane filtration of 0.45 micron, make the UV photo-curing ink-jet ink for glass baseplate.
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