CN111849246B - UV ink-jet ink free of oligomer and resin and preparation method thereof - Google Patents
UV ink-jet ink free of oligomer and resin and preparation method thereof Download PDFInfo
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- CN111849246B CN111849246B CN202010730237.0A CN202010730237A CN111849246B CN 111849246 B CN111849246 B CN 111849246B CN 202010730237 A CN202010730237 A CN 202010730237A CN 111849246 B CN111849246 B CN 111849246B
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Links
- 229920005989 resin Polymers 0.000 title claims abstract description 19
- 239000011347 resin Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 107
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000000049 pigment Substances 0.000 claims abstract description 12
- 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 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 239000000080 wetting agent Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- XTLZRWNIJGNTCE-UHFFFAOYSA-N (2-ethoxyphenyl) prop-2-enoate Chemical compound CCOC1=CC=CC=C1OC(=O)C=C XTLZRWNIJGNTCE-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 3
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 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 3
- GUDMAODBWDKYMX-UHFFFAOYSA-N (2,3-diethoxyphenyl) prop-2-enoate Chemical compound CCOC1=CC=CC(OC(=O)C=C)=C1OCC GUDMAODBWDKYMX-UHFFFAOYSA-N 0.000 claims description 2
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
- DXAWXZCQCLLNNV-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C)OC(CC(CO)(CO)CO)(OCC)OCC Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C)OC(CC(CO)(CO)CO)(OCC)OCC DXAWXZCQCLLNNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- -1 trimethylol cyclohexyl Chemical group 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- 238000007639 printing Methods 0.000 abstract description 7
- 239000000976 ink Substances 0.000 description 33
- 238000012360 testing method Methods 0.000 description 15
- 239000007921 spray Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- WTOUYJXPUNLWSZ-UHFFFAOYSA-N 2,4-diethyl-1,3-thiazole 1-oxide Chemical compound C(C)C=1S(C=C(N1)CC)=O WTOUYJXPUNLWSZ-UHFFFAOYSA-N 0.000 description 2
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- VAZQKPWSBFZARZ-UHFFFAOYSA-N 2-(2-phenylphenoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1C1=CC=CC=C1 VAZQKPWSBFZARZ-UHFFFAOYSA-N 0.000 description 2
- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=C(C)C=C1 PUBNJSZGANKUGX-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000004901 spalling Methods 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- CHAGFXOGGUIYIM-UHFFFAOYSA-N (2-cyclohexyl-3-hydroxyphenyl)-phenylmethanone Chemical compound Oc1cccc(C(=O)c2ccccc2)c1C1CCCCC1 CHAGFXOGGUIYIM-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- NNAHKQUHXJHBIV-UHFFFAOYSA-N 2-methyl-1-(4-methylthiophen-2-yl)-2-morpholin-4-ylpropan-1-one Chemical compound CC1=CSC(C(=O)C(C)(C)N2CCOCC2)=C1 NNAHKQUHXJHBIV-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical group CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 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 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- RVRKDGLTBFWQHH-UHFFFAOYSA-N yttrium zirconium Chemical compound [Y][Zr][Y] RVRKDGLTBFWQHH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
Abstract
The invention belongs to the field of printing consumables and discloses UV (ultraviolet) ink-jet ink without oligomer and resin and a preparation method thereof. The UV ink-jet ink is mainly prepared from a monomer, a photoinitiator, a dispersant and a pigment; the monomers comprise a flexible folding-resistant monomer, a toughening monomer and a viscosity adjusting monomer; the flexible folding-resistant monomer is a monofunctional monomer; the toughening monomer is a monomer containing di-functionality or/and tri-functionality; the viscosity adjusting monomer comprises a low viscosity adjusting monomer and a high viscosity adjusting monomer. According to the invention, the functional monomer is adopted to replace the oligomer and the resin, and the UV ink-jet ink without the oligomer and the resin is prepared by selecting and matching the monomer and controlling the conditions, so that the printing smoothness is good, the nozzle cannot be blocked or broken, and meanwhile, a coating formed after the ink is sprayed has good flexibility and folding resistance.
Description
Technical Field
The invention belongs to the field of printing consumables, and particularly relates to UV (ultraviolet) ink-jet ink without oligomer and resin and a preparation method thereof.
Background
UV ink-jet printing has digital editing capability and good adaptability with various substrates, such as flexible film substrates due to good folding resistance and ductility; because of its good scratch resistance and adhesion, it can be used for hard substrates such as plastics, metals, ceramics, etc. Meanwhile, the UV ink-jet has the advantages of no solvent volatilization, rapid photocuring, energy saving, carbon reduction, green environment and the like.
For widely used flexible substrates, such as plastic films, wallpaper, soft pads, leather, plastic films, flexible metal sheets, etc., UV inks having high flexibility and folding resistance are urgently required. To meet the respective functional requirements, different oligomers or resins often have to be added to the inks. The oligomer or resin is a high molecular weight polymer formed by polymerizing a specific monomer or functional group, and the functional characteristics of the ink are highlighted in the photocuring process so as to make up for the defect that the functional properties of the monomer cannot be highlighted. Although the oligomer or resin can effectively improve the functionality of the ink, the oligomer or resin with high molecular weight has poor compatibility with the ink monomer, and is easy to be precipitated due to the polarization of ink concentration in the printing process, so that the problem of nozzle blockage or line breakage is caused due to overhigh local viscosity.
Accordingly, it is desirable to provide a UV inkjet ink that has good flexibility and folding resistance without causing head clogging or line breakage.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a UV ink-jet ink without oligomer and resin, which has good flexibility and folding resistance and can not cause the blockage or the disconnection of a spray head.
An oligomer and resin-free UV inkjet ink is mainly prepared from a monomer, a photoinitiator, a dispersant and a pigment; the monomers comprise a flexible folding-resistant monomer, a toughening monomer and a viscosity adjusting monomer;
the flexible folding-resistant monomer is a monofunctional monomer;
the toughening monomer is a monomer containing di-functionality or/and tri-functionality, the addition amount of each di-functionality monomer in the toughening monomer is less than or equal to 16%, the addition amount of each tri-functionality monomer is less than or equal to 8%, and the formula is required to be satisfied: [ (the total addition amount of difunctional monomers)/the total addition amount of 2+ trifunctional monomers ] < 8% (the total addition amount is the percentage of the total mass of the UV ink-jet ink);
the viscosity adjusting monomer comprises a low viscosity adjusting monomer and a high viscosity adjusting monomer, the viscosity value of the low viscosity adjusting monomer is less than or equal to 15cP at 25 ℃, and the viscosity value of the high viscosity adjusting monomer is more than or equal to 30cP at 25 ℃.
The invention adopts monomers to replace resin or polymer, and selects flexible folding-resistant monomers, toughening monomers and viscosity adjusting monomers. The flexible folding-resistant monomer is of a monofunctional structure, and forms straight-chain molecules during polymerization, so that the chains can be wound and slide, and the molecular chains have the capability of extending and bending. The toughening monomer is a monomer with a bifunctional or/and trifunctional structure, can improve the degree of cross-chain polymerization, increase the mechanical strength and flexibility of the coating, and avoid the disconnection of linear chain molecules due to bending or extension. The addition amount of the difunctional monomer in the toughening monomer is further controlled to be less than or equal to 16 percent, the trifunctional monomer is controlled to be less than or equal to 8 percent, and the following conditions are met: the additive amount of the [ (di-functionality monomer) and the additive amount of the 2+ tri-functionality monomer ] is less than or equal to 8 percent, so that the printing smoothness of the prepared UV ink-jet ink is realized, and a coating formed after spraying is folding-resistant and has good ductility; when the amount is more than 8%, the coating layer becomes hard and loses folding endurance and ductility.
Preferably, the mass ratio of the flexible folding-resistant monomer, the toughening monomer and the viscosity adjusting monomer is: (30-61):(3-16):(13-36).
Preferably, the total adding amount of the flexible folding-resistant monomer is in a range of 30% -60%, and the total adding amount is a percentage of the total mass of the UV inkjet ink. When the total adding amount of the flexible folding-resistant monomer is 30-60%, the function of flexible folding resistance is obtained.
Preferably, the UV ink-jet ink is mainly prepared from the following components in percentage by weight:
further preferably, the UV inkjet ink is mainly prepared from the following components in percentage by weight:
preferably, the flexible folding-resistant monomer is acrylate or/and pyrrolidone.
More preferably, the flexible folding-resistant monomer is at least one of tetrahydrofurfuryl acrylate (THFA), cyclo-trimethylolpropane formal acrylate (CTFA), trimethylol cyclohexyl acrylate (TMCHA), (ethoxy) phenol acrylate (PHEA), benzyl acrylate (BZA), 4-tert-butyl cyclohexyl acrylate (TBCHA), ethoxy ethyl acrylate (eoeoeoea), diethoxy phenol acrylate (PH (2EO) EA), or N-vinyl pyrrolidone (NVP).
Preferably, the toughening monomer is at least one of 1, 6-hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate (DPGDA), triethylene glycol diacrylate (TEGDA), dipropylene glycol diacrylate (NPG (2PO) DA), polyethylene glycol diacrylate, triethoxy trimethylolpropane triacrylate (TMP (3EO) TA), hexaethoxy trimethylolpropane triacrylate (TMP (6EO) TA), nonaethoxy trimethylolpropane triacrylate (TMP (9EO) TA), pentadecaethoxy trimethylolpropane triacrylate (TMP (15EO) TA), or tripropoxy trimethylolpropane triacrylate (TMP (3PO) TA). The toughening monomer has a bifunctional or trifunctional structure and a flexible alkoxy group, can further improve the degree of cross-chain polymerization, increases the mechanical strength and flexibility, and makes up the defect that linear chain molecules are broken due to bending or extension.
Preferably, the viscosity value of the low-viscosity adjusting monomer at 25 ℃ is less than or equal to 10 cP; further preferably, the viscosity value of the low-viscosity adjusting monomer at 25 ℃ is less than or equal to 5 cP.
Preferably, the viscosity value of the high-viscosity adjusting monomer at 25 ℃ is more than or equal to 50 cP; more preferably, the viscosity value of the high-viscosity adjusting monomer at 25 ℃ is more than or equal to 100 cP.
Preferably, the photoinitiator is bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide (photoinitiator 819), 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (photoinitiator TPO), hydroxycyclohexyl benzophenone (photoinitiator 184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator 1173), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (photoinitiator 369), 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (photoinitiator 379), 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone (photoinitiator 907), At least one of 2, 4-diethylthiazolone (photoinitiator DETX) or 2-isopropylthioxanthone (photoinitiator ITX). The photoinitiator has the function of decomposing to form initial free radicals to initiate monomer polymerization after absorbing Ultraviolet (UV), so that the photoinitiator with different absorption wave bands needs to be matched for carrying out photocuring reaction.
Preferably, the dispersant can be selected from Dispers 710/685/655 of degussa; BYK DisperbYK-168/9130/9131/9132/1950/1951/1952/2100/2200/2205; lubriu Solsperse 24000/32000/32500/36000/39000; EFKA 4310/4330/4030/4701 from ehf card, and the like. Dispersants are used to disperse pigments.
Preferably, the pigment can be selected from blue pigments PB15:1, PB15:2, PB15:3, PB15: 4; yellow pigments PY138, PY150, PY151, PY155, PY168, PY180, PY183, PY185, PY 194; red pigments PV19, PR122, PR146, PR254, PR 269; the black pigment is carbon black; the white pigment is titanium dioxide.
Preferably, the UV inkjet ink further comprises an auxiliary agent, the auxiliary agent comprising a wetting agent and/or a stabilizer.
Preferably, the addition amount of the wetting agent is 0-5% of the total mass of the UV ink-jet ink, and the addition amount of the stabilizer is 0-5% of the total mass of the UV ink-jet ink.
Preferably, the wetting agent is BYK-371/377/378/337/3500/3505/361. The wetting agent is used for wetting the substrate, so that the ink can be smoothly attached to the surface of the substrate and can be leveled to form a uniform coating.
Preferably, the stabilizer is 2, 6-di-tert-butyl-4-methylphenol BHT, 4-methoxyphenol MEHQ, GENORAD 16/18/20/22/23 from RAHN, or Cyanote S100/110/210/130. The stabilizer is used for stabilizing the ink so that the ink is not influenced by the photo-thermal effect of the environment to react and deteriorate in the storage process.
A method of making a UV inkjet ink free of oligomers and resins comprising the steps of:
and mixing the photoinitiator, the dispersant, the monomer and the pigment, grinding and filtering to obtain filtrate, namely the UV ink-jet ink.
Specifically, the preparation method of the UV ink-jet ink without oligomer and resin comprises the following steps:
adding a photoinitiator and a dispersant into a monomer, and stirring until the photoinitiator and the dispersant are completely dissolved; then adding the pigment into the mixture and stirring the mixture evenly, introducing the mixture into a sand mill and using grinding beads with the particle size of 0.1-0.5mm to grind the mixture to the particle size of 100-200 nm; filtering with 1.0 μm glass fiber and 0.45 μm PP filter membrane, and collecting the filtrate to obtain ink.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the functional monomer is adopted to replace the oligomer and the resin, and the UV ink-jet ink without the oligomer and the resin is prepared by selecting and matching the monomer and controlling the conditions, so that the printing smoothness is good, the nozzle cannot be blocked or broken, and meanwhile, a coating formed after the ink is sprayed has good flexibility and folding resistance.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
Folding endurance monomers include 27.2g of cyclotrimethylolpropane formal acrylate (CTFA), 10.0g of ethoxyphenol acrylate (PHEA), 10.0g of N-vinylpyrrolidone (NVP); the viscosity adjusting monomer comprises 10.0g of N-acryloyl morpholine (ACMO), 15.0g of 15.0g N, N-Dimethylacrylamide (DMAA) and 10.0g of o-phenylphenoxyethyl acrylate (OPPEA); toughening monomers included 3.0g nonaethoxylated trimethylolpropane triacrylate (TMP (9EO) TA); the photoinitiator included 7.0g2,4, 6-trimethylbenzoyldiphenylphosphine oxide (TPO), 3.0g 2, 4-Diethylthiazolone (DETX); the auxiliary agent comprises 1.0g of BYK-337 wetting agent and 0.3g of GENORAD 16 stabilizer; and 1.5g of dispersing agent Solsperse24000 is stirred until the dispersing agent is completely dissolved, the stirring speed is 1000rpm, and the stirring time is 4 hours, so as to obtain a pre-solution;
mixing and stirring the pre-solution and 2.0g of yellow pigment PY-150 until the pigment is completely wetted, wherein the stirring speed is 1000rpm, and the stirring time is 8 hours, so as to obtain a pre-dispersion solution; and then introducing the pre-dispersion solution into a sand mill, grinding at the rotating speed of 2000rpm, grinding with 0.4mm yttrium zirconium grinding beads at the temperature of 20-40 ℃, grinding to the particle size of 100-200nm, and filtering with 1.0 mu m glass fiber and 0.45 mu m PP filter membrane to obtain a filtrate, namely the UV ink-jet.
Examples 2 to 10
The formulations of examples 2-10 are shown in Table 1, and the preparation is as in example 1.
Comparative examples 1 to 6
The formulations of comparative examples 1-6 are shown in Table 2, and the preparation is the same as in example 1.
TABLE 1 formulations of examples 1-10
TABLE 2 formulations for comparative examples 1-6
Product effect test the UV inkjet inks prepared in examples 1 to 10 and comparative examples 1 to 6 were subjected to an effect test.
(1) A domestic wide-width printer is used, an LED-UV curing lamp with the wavelength of 395nm is carried, and a light-regulating five-generation industrial spray head MH5420 is adopted. And (4) testing the blockage of the spray head, setting the spray head to stand for 15min, printing after 30min and 45min under the non-flash state, and observing the blockage phenomenon of the ink spray head.
(2) The inks obtained in the examples and comparative examples were printed with pure color blocks on PVC flexible films, PVC and acrylic sheets. And (3) a flexibility and folding resistance test, namely adopting a first folding PVC flexible film and a second folding PVC flexible film, and observing whether the pure color block coating cracks or not after finger pressurization lasts for 1 min.
(3) And (3) performing adhesion test, namely performing a hundred-grid standard test on pure color blocks of the PVC and acrylic plates by adopting national standards GB9286 and ISO 2409. The grade 0 represents that the cut of the hundred-grid cutter is smooth and has no spalling or crevasse; grade 1 represents 5% spalling or crevasse; grade 2 represents 5-15% of the cracks or breaks; grade 3 represents 15-35% of the cracks or breaks; grade 4 represents 35-65% of the cracks or breaks; grade 5 represents more than 65% of the cracks or tears.
The results of the nozzle clogging test are shown in Table 3, the results of the flexibility and folding resistance test are shown in Table 4, and the results of the adhesion test are shown in Table 5
TABLE 3 spray head clogging test results
Note: o represents that the broken hole of the spray head is less than 5; delta represents that the broken hole of the spray head is 6-20; x represents that the broken hole of the spray head is more than 20.
TABLE 4 results of flexibility and folding endurance test
Note: o represents that the coating does not crack; x represents coating cracking.
Table 5 adhesion test results
Note: o represents the coating hundred lattice test above grade 1 (containing grade 1); delta represents coating hundred lattice test grade 2-3; x represents coating hundred grid test below grade 3.
Examples 1-10, in which 15% or more of a single flexible folding-resistant monomer was added, and the amount of difunctional monomer added to the toughening monomer was less than 16%, the amount of trifunctional monomer added was less than 8%, and the conditions of [ (amount of difunctional monomer added)/amount of 2+ trifunctional monomer added ] was not more than 8%, were not satisfied, and no resin or oligomer was added, and therefore, a folding-resistant and well-adhered ink coating could be obtained. In comparative examples 1-2, the monomer, the resin or the oligomer are added, and the nozzle is easy to block and break the hole when standing; comparative examples 2 to 3 had poor folding endurance and adhesion due to the addition of an excessive amount of toughening monomer. Comparative examples 4 to 6, in which no toughening monomer was added or the amount of the toughening monomer added was not satisfactory, also resulted in clogging of the head with ink or poor folding resistance.
Claims (7)
1. The UV ink-jet ink is characterized by mainly being prepared from a monomer, a photoinitiator, a dispersant and a pigment; the monomers comprise a flexible folding-resistant monomer, a toughening monomer and a viscosity adjusting monomer; the UV inkjet ink is free of oligomers and resins;
the flexible folding-resistant monomer is a monofunctional monomer;
the toughening monomer is a monomer containing di-functionality or/and tri-functionality, the addition amount of each di-functionality monomer in the toughening monomer is less than or equal to 16%, the addition amount of each tri-functionality monomer is less than or equal to 8%, and the formula is required to be satisfied: 5.5 percent or more (total addition amount of the difunctional monomer)/total addition amount of the 2+ trifunctional monomer) or less than 8 percent;
the viscosity adjusting monomer comprises a low viscosity adjusting monomer and a high viscosity adjusting monomer, the viscosity value of the low viscosity adjusting monomer is less than or equal to 15cP at 25 ℃, and the viscosity value of the high viscosity adjusting monomer is more than or equal to 30cP at 25 ℃;
the mass ratio of the flexible folding-resistant monomer to the toughening monomer to the viscosity adjusting monomer is as follows: (30-61) (3-16) (13-36);
the flexible folding-resistant monomer is at least one of tetrahydrofurfuryl acrylate, cyclotrimethylolpropane formal acrylate, trimethylol cyclohexyl acrylate, ethoxy phenol acrylate, benzyl acrylate, 4-tert-butyl cyclohexyl acrylate, ethoxy ethyl acrylate or diethoxy phenol acrylate.
2. The UV inkjet ink of claim 1, wherein the total amount of the flexible, fold-resistant monomer added is in a range of 30% to 60%.
3. The UV inkjet ink according to any one of claims 1-2, prepared from essentially the following components in weight percent:
65 to 90 percent of monomer
5 to 20 percent of photoinitiator
1 to 8 percent of dispersant
2 to 15 percent of pigment.
4. The UV inkjet ink of claim 3, wherein the UV inkjet ink is prepared from the following components in percentage by weight:
74-90% of monomer
5 to 20 percent of photoinitiator
1.5 to 6 percent of dispersant
2 to 12 percent of pigment.
5. The UV inkjet ink of any one of claims 1-2, wherein the toughening monomer is at least one of 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, polyethylene glycol diacrylate, triethoxy trimethylolpropane triacrylate, hexaethoxy trimethylolpropane triacrylate, nonaethoxy trimethylolpropane triacrylate, pentadecaethoxy trimethylolpropane triacrylate, or tripropoxy trimethylolpropane triacrylate.
6. The UV inkjet ink according to any one of claims 1 to 2, further comprising an auxiliary agent, wherein the auxiliary agent comprises a wetting agent and/or a stabilizer.
7. The method of making the UV inkjet ink of any one of claims 1-5, comprising the steps of:
and mixing the photoinitiator, the dispersant, the monomer and the pigment, grinding and filtering to obtain filtrate, namely the UV ink-jet ink.
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