CN114773905A - White UV/thermal dual-curing FPC inkjet character ink and preparation method thereof - Google Patents
White UV/thermal dual-curing FPC inkjet character ink and preparation method thereof Download PDFInfo
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- CN114773905A CN114773905A CN202210395967.9A CN202210395967A CN114773905A CN 114773905 A CN114773905 A CN 114773905A CN 202210395967 A CN202210395967 A CN 202210395967A CN 114773905 A CN114773905 A CN 114773905A
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- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 54
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 39
- 238000001723 curing Methods 0.000 claims abstract description 39
- 239000003085 diluting agent Substances 0.000 claims abstract description 31
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 22
- 239000012463 white pigment Substances 0.000 claims abstract description 22
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- 238000001029 thermal curing Methods 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
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- 239000003822 epoxy resin Substances 0.000 claims abstract description 12
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- 239000002994 raw material Substances 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 58
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 58
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 50
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 18
- PLDLPVSQYMQDBL-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propoxy]methyl]oxirane Chemical compound C1OC1COCC(COCC1OC1)(COCC1OC1)COCC1CO1 PLDLPVSQYMQDBL-UHFFFAOYSA-N 0.000 claims description 15
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 15
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- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 11
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 10
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- 238000000034 method Methods 0.000 claims description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 9
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- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 7
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- 238000012986 modification Methods 0.000 claims description 7
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- 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 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 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
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound 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 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- LKFAPHHHWRMPGC-UHFFFAOYSA-N butan-1-ol prop-2-enoic acid Chemical compound CCCCO.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C LKFAPHHHWRMPGC-UHFFFAOYSA-N 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 229920002050 silicone resin Polymers 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 3
- FYYIUODUDSPAJQ-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 2-methylprop-2-enoate Chemical compound C1C(COC(=O)C(=C)C)CCC2OC21 FYYIUODUDSPAJQ-UHFFFAOYSA-N 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- NWWQVENFTIRUMF-UHFFFAOYSA-N diphenylphosphanyl 2,4,6-trimethylbenzoate Chemical compound CC1=CC(C)=CC(C)=C1C(=O)OP(C=1C=CC=CC=1)C1=CC=CC=C1 NWWQVENFTIRUMF-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 36
- 238000000576 coating method Methods 0.000 abstract description 36
- 238000007639 printing Methods 0.000 abstract description 7
- 238000000016 photochemical curing Methods 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
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- 235000006708 antioxidants Nutrition 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 61
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
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- 229910052786 argon Inorganic materials 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000007641 inkjet printing Methods 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
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- 229920002554 vinyl polymer Chemical group 0.000 description 2
- 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
- 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
- GDUZPNKSJOOIDA-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-methylprop-2-enoate Chemical compound C1C(OC(=O)C(=C)C)CCC2OC21 GDUZPNKSJOOIDA-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 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
- 239000006185 dispersion Substances 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
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
- C09D11/101—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
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a preparation method of white UV/heat dual-curing FPC inkjet character ink. The raw material components are as follows: 5-30 parts of epoxy resin; 5-30 parts of hyperbranched polyester acrylate; 20-70 parts of reactive diluent; 1-20 parts of modified oligomer; 1-10 parts of a photoinitiator; 1-10 parts of a thermal curing agent; 5-20 parts of a white pigment; 1-5 parts of an antioxidant; 1-5 parts of a stabilizer; 1-5 parts of a dispersant; 1-5 parts of adhesion promoter. According to the invention, the hyperbranched polyester acrylate and the modified oligomer are synthesized, and are mixed with different resins and reactive diluents, the coating can be rapidly surface-dried through photocuring, so that double-sided printing can be realized, the hardness and adhesive force performance of the coating can be improved through thermocuring, and the anti-oxidant can ensure that the coating is not yellowed, so that the printing ink has excellent comprehensive performance.
Description
Technical Field
The invention relates to the field of ink-jet ink, in particular to white UV/heat dual-curing FPC ink-jet character ink and a preparation method thereof.
Background
With the continuous development of science and technology, people realize the damage of Volatile Organic Compounds (VOCs) to people, the environmental awareness of people is continuously improved, and the requirements on solvents used by ink are also changed.
Inks can be divided into two main types, namely aqueous inks and oil-based inks, depending on the solvent. Among them, the aqueous ink has a disadvantage of extremely slow drying speed. Oil-based inks can also be classified into two types, one being volatile solvent-based inks and the other being reactive solvent-based inks. The former can cause a large amount of VOCs and seriously harm the health of production workers; the latter has the advantage of fast curing and no VOCS volatilization.
With the development of science and technology, electronic products used at high end are more and more, and the electronic products tend to be more and more refined and finer, so that the accuracy of characters on a Flexible Printed Circuit (FPC) is higher and higher, and an ink jet printing technology is required. Ink-jet character inks are required to have high hardness, excellent flexibility, yellowing resistance, heat resistance, low viscosity, and the like. However, this ink has two contradictory properties, namely, high hardness and low viscosity, and high hardness and good flexibility. Therefore, it is required to develop an FPC character ink having excellent properties.
Chinese invention patent 201380069172.8 discloses a method and apparatus for controlling shallowness in a color inkjet ink by a transparent white ink composition, wherein the UV curable inkjet ink composition includes a dendritic or hyperbranched polyester acrylate component present in the composition in an amount of 10% to 45% by weight of the UV curable inkjet ink composition; although the technology utilizes the hyperbranched polyester acrylate component to be beneficial to reducing the viscosity, the technology also has the contradiction between high hardness and low viscosity, and high hardness and good flexibility.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a white UV/thermal dual-curing FPC ink-jet character ink and a preparation method thereof, which can keep low viscosity and simultaneously have high hardness, good flexibility and extremely short tack-free time, and the specific requirements are as follows: 30-45cp at 25 ℃ and 9-11cp at 40-50 ℃; the hardness needs to reach 5H or above; the flexibility reaches 1 mm.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
a white UV/heat dual-curing FPC inkjet character ink comprises the following raw materials in parts by weight: 5-30 parts of epoxy resin; 5-30 parts of hyperbranched polyester acrylate; 20-70 parts of reactive diluent; 1-20 parts of modified oligomer; 1-10 parts of a photoinitiator; 1-10 parts of a thermal curing agent; 5-20 parts of white pigment; 1-5 parts of an antioxidant; 1-5 parts of a stabilizer; 1-5 parts of a dispersing agent; 1-5 parts of adhesion promoter;
the hyperbranched polyester acrylate is first-generation hyperbranched polyester acrylate, second-generation hyperbranched polyester acrylate, third-generation hyperbranched polyester acrylate or fourth-generation hyperbranched polyester acrylate;
the modified oligomer is obtained by partially modifying epoxy groups on a polyfunctional epoxy reactive diluent by acrylic acid, and the polyfunctional epoxy reactive diluent for modification is one or more of trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether.
To further achieve the object of the present invention, preferably, the modification and purification of the multifunctional epoxy reactive diluent for modification is achieved by the following method: mixing a polyfunctional epoxy active diluent, acrylic acid and a polymerization inhibitor hydroquinone, heating to 90-120 ℃, uniformly stirring, adding triphenylphosphine serving as a catalyst, and reacting for 2-6 hours under stirring to obtain a light yellow mixture; repeatedly washing, dissolving and washing the light yellow mixture to obtain yellow liquid; and vacuumizing to obtain the modified and purified polyfunctional epoxy reactive diluent.
Preferably, the mol ratio of the multifunctional epoxy reactive diluent to the acrylic acid is (1-4): 1; the addition amount of the polymerization inhibitor hydroquinone is 0.05 to 1 percent of the total mass of the polyfunctional group epoxy active diluent and the acrylic acid; the dosage of the triphenylphosphine is 0.5 to 2 percent of the total mass of the polyfunctional epoxy active diluent and the acrylic acid; the stirring speed for uniformly stirring and stirring reaction is 150-250 rpm; the washing is carried out by using petroleum ether, and the dissolution is carried out by using acetone.
Preferably, the synthesis process of the hyperbranched polyester acrylate comprises the following steps:
(1) mixing pentaerythritol and dimethylolpropionic acid in a molar ratio of 1:4-1:60, melting, stabilizing the system temperature at 130-; after the hyperbranched polyester is obtained, cooling the system to 90-110 ℃, adding 1-2 times of acrylic acid of the hydroxyl number at the tail end of the hyperbranched polyester, reacting for 4-6 hours, and cooling to obtain a yellow viscous liquid mixture;
(2) adding acetone into the yellow viscous liquid mixture for dilution, dropping the mixture into petroleum ether for precipitation to remove redundant acrylic acid, and filtering; repeating the operations for many times, and performing vacuum-pumping drying to obtain the hyperbranched polyester acrylate.
Preferably, the reactive diluent comprises one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, isobornyl methacrylate, 3, 4-epoxycyclohexyl methacrylate, vinyl acetate, hydroxymethyl propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate.
Preferably, the epoxy resin is one or more of bisphenol A epoxy resin E51, bisphenol A epoxy resin E44, hydrogenated bisphenol A epoxy resin EP-4080E, hydrogenated bisphenol A epoxy resin AL-3030 and epoxy modified silicone resin SH-023;
the photoinitiator comprises diphenyl- (2,4, 6-Trimethylbenzoyl) Phosphine Oxide (TPO), phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819), 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), 4-benzoyl-4' -methyl-diphenyl sulfide (BMS), 1-hydroxycyclohexyl phenyl ketone (184), one or more of mixed triaryl sulfonium hexafluorophosphate salt (cation GC-2291), diphenyl- (4-phenyl sulfur) phenyl sulfonium hexafluorophosphate (cation GC-2391), triaryl hexafluoroantimonate (cation GC-2671) and bis 2, 6-difluoro-3-pyrrol phenyl titanocene (784).
Preferably, the thermal curing agent is one or more of dicyandiamide, boron trifluoride-amine complex, oxaboron heterocyclic boron amine complex, organic hydrazide, thermal cation curing agent and acid anhydride;
the white pigment comprises one or more of titanium dioxide, zinc oxide, antimony oxide and barium sulfate;
the antioxidant is one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (1010), N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1076), tris [2, 4-di-tert-butylphenyl ] phosphite (168), N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine (1024) and trisnonylphenyl phosphite (TNPP).
Preferably, the dispersant is one or more of dispersant STA-1110A, dispersant BYK103, dispersant BYK110 and dispersant BYK 9076;
the adhesion promoter is one or more of an adhesion promoter ADP-S479, an adhesion promoter PN-701 and an adhesion promoter YF-1985-1.
The preparation method of the white UV/heat dual-curing FPC inkjet character ink comprises the following steps: firstly, uniformly stirring and mixing the epoxy resin, the hyperbranched polyester acrylate, the modified oligomer and the reactive diluent at normal temperature, then adding the white pigment and the dispersing agent to uniformly disperse the white pigment, cooling to normal temperature, then adding the photoinitiator, the thermal curing agent and the antioxidant to completely dissolve at normal temperature, and adding the stabilizer and the adhesion promoter to uniformly disperse to obtain the white UV/thermal dual-curing FPC inkjet character ink.
Preferably, the stirring and mixing at normal temperature is at a rotation speed of 200-500rpm and at normal temperature for 15-30 min; the white pigment is uniformly dispersed by firstly grinding and dispersing the ink for 1 to 3 hours by using a star-shaped ball mill and then ultrasonically treating the ink for 0.5 to 1 hour by using an ultrasonic cleaner; the stabilizer and the adhesion promoter are added and then uniformly dispersed, and the stabilizer and the adhesion promoter are added and stirred for 15-30min at the rotating speed of 300-800 rpm. The average particle diameter of the white pigment after grinding dispersion is less than 100 nm.
Compared with the prior art, the invention has the advantages that:
1) through epoxy resin prepolymer and Hyperbranched Polyester Acrylate (HPA)n) The ink-jet character ink can be stored for a long time at normal temperature, and quickly reaches surface drying under the photocuring effect, so that the generation of VOCs is reduced, the energy consumption of UVLED and the like is relatively low, and the coating has high hardness and good flexibility after being thermally cured, so that the printing quality of the ink in the market and the environment-friendly property are achieved.
2) In order to keep the low viscosity, high hardness and good flexibility of the ink, the invention is solved by selectively adding hyperbranched polyester acrylate and modified oligomer and matching with a proper reactive diluent. The invention synthesizes hyperbranched polyester acrylate containing terminal hydroxyl and vinyl and oligomer containing epoxy and vinyl. The hyperbranched polyester acrylate has lower viscosity than a linear polymer under the same molecular weight, can obviously reduce the overall viscosity of the ink, and simultaneously has a plurality of terminal vinyl groups, can greatly improve the crosslinking degree of a coating film, thereby improving the hardness of the coating film.
3) The epoxy resin added in the invention can enable the epoxy component and the acrylic component to mutually interpenetrate and generate entanglement in the physical aspect, and the epoxy resin has a rigid structure and can improve the hardness of a coating film in a limited way. Meanwhile, the modified oligomer has acrylic double bonds and epoxy groups, so that the epoxy component and the acrylic component can be effectively combined together in a chemical bond mode, the crosslinking degree is further improved, and the hardness of a coating film can be better improved.
4) In the aspects of high hardness and good flexibility, the hyperbranched polyester acrylate has the function of toughening a brittle material while improving the hardness by improving the crosslinking degree, so that the flexibility of a coating film can be improved. The active diluent has a certain flexible chain segment structure, so that the flexibility of the product can be improved while the viscosity is reduced.
Drawings
FIG. 1 is a nuclear magnetic spectrum of an acrylic acid partially modified pentaerythritol tetraglycidyl ether oligomer of example 3.
FIG. 2 is a nuclear magnetic spectrum of an acrylic acid partially modified trimethylolpropane triglycidyl ether oligomer of example 1.
Detailed Description
For better understanding of the present invention, the present invention is further described with reference to the following examples, which should be construed as being without limitation to the scope of the present invention.
The hyperbranched polyester acrylate synthesized in the embodiment of the invention comprises first-generation hyperbranched polyester acrylate, second-generation hyperbranched polyester acrylate, third-generation hyperbranched polyester acrylate and fourth-generation hyperbranched polyester acrylate, and is named as HPAn(n-1-4); the synthesis process is derived from the Shuichi paper of Shadong, the research on the synthesis and end group modification of hyperbranched polyester.
Example 1
1.36g (0.01mol) of pentaerythritol and 5.36g (0.04mol) of dimethylolpropionic acid are added into a three-neck flask for melting, then the system temperature is stabilized at 130 ℃, 0.0672g of paratoluenesulfonic acid is added as a catalyst, argon is introduced for protection, and the mixture is stirred at the rotating speed of 200rpm for reaction for 2 hours to obtain the first-generation hyperbranched polyester. After first-generation hyperbranched polyester is obtained, the temperature of the system is reduced to 90 ℃, 5.76g of acrylic acid is added for reaction for 5 hours, and a yellow viscous liquid mixture is obtained after cooling. 10ml of acetone is added to the yellow viscous liquid mixture for dilution, and the yellow viscous liquid mixture is slowly dropped into petroleum ether for precipitation to remove excessive acrylic acid, and then filtered. Repeating the operation for three times, vacuumizing and drying to obtain a first-generation hyperbranched polyester acrylate, namely HPA1。
Mixing 3.02g of trimethylolpropane triglycidyl ether, 1g of acrylic acid and 0.002g of polymerization inhibitor hydroquinone, adding the mixture into a three-neck flask, heating to 90 ℃, uniformly stirring at the rotating speed of 200rpm, adding 0.02g of triphenylphosphine which is based on the total mass of the trimethylolpropane triglycidyl ether and the acrylic acid and serves as a catalyst after the temperature is constant, and continuously stirring at the rotating speed of 200rpm for reacting for 2 hours to obtain a light yellow mixture. And dropping the mixture into petroleum ether, stirring to remove redundant acrylic acid, and separating liquid and pouring out the petroleum ether. Adding acetone to dissolve the product, dropping into petroleum ether for washing, and repeating the above operations for three times to obtain yellow liquid. And (3) vacuumizing by using a vacuum oven to remove a small amount of acetone and petroleum ether to obtain the acrylic acid partially modified trimethylolpropane triglycidyl ether oligomer, wherein the nuclear magnetic spectrum of the acrylic acid partially modified trimethylolpropane triglycidyl ether oligomer is shown in figure 2.
According to the parts by weight, firstly 20 parts of bisphenol A epoxy resin E51 and 5 parts of HPA110 parts of acrylic acid partially modified trimethylolpropane triglycidyl ether oligomer and 65 parts of reactive diluent hydroxyethyl methacrylate are stirred and uniformly mixed at the normal temperature and the rotating speed of 200 ℃ for 15min, then 12 parts of white pigment (the mass ratio of titanium dioxide to barium sulfate is 2:1) and 2 parts of dispersing agent BYK113 are added, firstly, a star-shaped ball mill is used for grinding and dispersing the ink for 1 hour, then, an ultrasonic cleaner is used for carrying out ultrasonic treatment for 0.5 hour to uniformly disperse the white pigment, the temperature of the ink rises after the ball milling and the ultrasonic treatment, cooling is needed to the normal temperature, 8 parts of photoinitiator (the mass ratio of TPO: 784 is 3:1), 7 parts of thermal curing agent TC3632 and 1 part of antioxidant (the mass ratio of 1076: 168 is 3:1) are added for complete dissolution at the normal temperature, finally, 1.5 parts of stabilizing agent TC3602H and 1.5 parts of adhesion promoter PN-701 are added, the mixture is stirred and uniformly dispersed at the rotating speed of 300 ℃ for 15min, obtaining the white UV/heat dual-curing FPC ink-jet character ink.
Coating the prepared white UV/thermal dual-curing FPC inkjet character ink on a PCB substrate by using a coating rod with the thickness of 10 microns, then carrying out ultraviolet curing on the coating film for 1s by using a 395nm UV-LED curing machine, and then carrying out thermal curing on the coating film for 150 ℃/1h to obtain a cured coating.
Example 2
0.68g (0.005mol) of pentaerythritol and 8.04g (0.06mol) of dimethylolpropionic acid are added into a three-neck flask for melting, then the system temperature is stabilized at 140 ℃, 0.0872g of p-toluenesulfonic acid is added as a catalyst, argon is introduced for protection, and the mixture is stirred at the rotating speed of 200rpm for reaction for 3 hours to obtain the second-generation hyperbranched polyester. After the second-generation hyperbranched polyester is obtained, the system is cooled to 100 ℃, 5.76g of acrylic acid is added for reaction for 4 hours, and yellow is obtained after coolingA viscous liquid mixture. The yellow viscous liquid mixture is diluted by adding 10ml of acetone, slowly dropped into petroleum ether to precipitate and remove the excessive acrylic acid, and filtered. Repeating the above operation for three times, and vacuum-pumping and drying to obtain the second-generation hyperbranched polyester acrylate, i.e. HPA2。
4.56g of trimethylolpropane triglycidyl ether, 1g of acrylic acid and 0.0056g of polymerization inhibitor hydroquinone are mixed and added into a three-neck flask, the temperature is raised to 100 ℃, the mixture is uniformly stirred at the rotating speed of 200rpm, after the temperature is constant, 0.0556g of triphenylphosphine in total mass of the trimethylolpropane triglycidyl ether and the acrylic acid is added as a catalyst, and the mixture is continuously stirred at the rotating speed of 200rpm for reaction for 3 hours to obtain a light yellow mixture. And (4) dripping the mixture into petroleum ether, stirring and washing off redundant acrylic acid, and separating and pouring out the petroleum ether. Adding acetone to dissolve the product, dropping into petroleum ether for washing, and repeating the above operations for three times to obtain yellow liquid. And (3) removing a small amount of acetone and petroleum ether by vacuumizing a vacuum oven to obtain the acrylic acid partially modified trimethylolpropane triglycidyl ether oligomer, wherein the nuclear magnetic spectrum is as shown in the figure 2.
According to the parts by weight, firstly 15 parts of bisphenol A epoxy resin E44 and 15 parts of HPA25 parts of acrylic acid partially modified trimethylolpropane triglycidyl ether oligomer and 65 parts of active diluent triethylene glycol dimethacrylate are stirred and mixed uniformly at the rotating speed of 300rpm and normal temperature for 15min, 5 parts of white pigment (titanium dioxide: zinc oxide: 1 by mass ratio) and 1 part of dispersing agent STA-1110A are added, a star-shaped ball mill is used for grinding and dispersing the ink for 2 hours, then an ultrasonic cleaner is used for carrying out ultrasonic treatment on the ink for 1 hour, so that the white pigment is uniformly dispersed, the temperature of the ink rises after the ball milling and the ultrasonic treatment, cooling is needed to the normal temperature, 10 parts of photoinitiator (TPO: 819: 2:1 by mass ratio), 9 parts of thermal curing agent dicyandiamide and 3 parts of antioxidant (1010: TNPP: 1) are added, and finally 3 parts of stabilizing agent TC3602H and 2.5 parts of adhesion promoter YF-1985-1 are added and stirred uniformly at the rotating speed of 800 for 30min, obtaining the white UV/heat dual-curing FPC ink-jet character ink.
Coating the prepared white UV/thermal dual-curing FPC inkjet character ink on a PCB substrate by using a coating rod with the thickness of 10 microns, then carrying out ultraviolet curing on the coating by using a 395nm UV-LED curing machine for 5s, and then carrying out thermal curing on the coating at the temperature of 150 ℃/1h to obtain a cured coating.
Example 3
0.34g (0.0025mol) of pentaerythritol and 9.38g (0.07mol) of dimethylolpropionic acid are added into a three-neck flask for melting, then the system temperature is stabilized at 150 ℃, 0.1744g of p-toluenesulfonic acid is added as a catalyst, argon is introduced for protection, and the mixture is stirred at the rotating speed of 200rpm for reaction for 5 hours to obtain the third-generation hyperbranched polyester. After the third-generation hyperbranched polyester is obtained, the system is cooled to 100 ℃, 5.93g of acrylic acid is added for reaction for 6 hours, and a yellow viscous liquid mixture is obtained after cooling. The yellow viscous liquid mixture is diluted by adding 10ml of acetone, slowly dropped into petroleum ether to precipitate and remove the excessive acrylic acid, and filtered. Repeating the operation for three times, and vacuumizing and drying to obtain the third-generation hyperbranched polyester acrylate, namely HPA3。
5.76g of pentaerythritol tetraglycidyl ether, 2g of acrylic acid and 0.0776g of polymerization inhibitor hydroquinone are mixed and added into a three-neck flask, the temperature is raised to 110 ℃, the mixture is uniformly stirred at the rotating speed of 200rpm, after the temperature is constant, trimethylolpropane triglycidyl ether and 0.1552g of triphenylphosphine in the total mass of acrylic acid are added as catalysts, and the mixture is continuously stirred at the rotating speed of 200rpm for reaction for 6 hours to obtain a light yellow mixture. And dropping the mixture into petroleum ether, stirring to remove redundant acrylic acid, and separating liquid and pouring out the petroleum ether. Adding acetone to dissolve the product, dropping into petroleum ether for washing, and repeating the above operations for three times to obtain yellow liquid. And vacuumizing by using a vacuum oven to remove a small amount of acetone and petroleum ether to obtain the acrylic acid partially modified pentaerythritol tetraglycidyl ether oligomer, wherein the nuclear magnetic spectrum of the acrylic acid partially modified pentaerythritol tetraglycidyl ether oligomer is shown in figure 1.
According to the parts by weight, 10 parts of epoxy modified organic silicon resin SH-023 and 20 parts of HPA are firstly added310 parts of acrylic acid partially modified pentaerythritol tetraglycidyl ether oligomer and 60 parts of active diluent hexanediol diacrylate (HDDA) are stirred and mixed uniformly at the rotating speed of 300rpm and normal temperature for 30min, and 20 parts of white pigment (the mass ratio of titanium dioxide to barium sulfate is 2:1)) And 5 parts of a dispersant BYK103, grinding and dispersing the ink for 2 hours by using a star ball mill, performing ultrasonic treatment on the ink for 1 hour by using an ultrasonic cleaner to uniformly disperse white pigment, raising the temperature of the ink after ball milling and ultrasonic treatment, cooling the ink to normal temperature, and adding 6 parts of a photoinitiator (mass ratio TPO: 819: 1), 6 parts of a thermal curing agent TC3632 and 2 parts of an antioxidant (mass ratio of 1024: 168-2: 1) completely dissolved at normal temperature, and finally adding 2 parts of a stabilizer TC3602H and 5 parts of an adhesion promoter ADP-S479, stirring at 500 rotating speed for 30min, and uniformly dispersing to obtain the white UV/thermal dual-curing FPC inkjet character ink.
Coating the prepared white UV/thermal dual-curing FPC inkjet character ink on a PCB substrate by using a coating rod with the thickness of 10 microns, then carrying out 3s ultraviolet curing on the coating by using a 395nm UV-LED curing machine, and then carrying out thermal curing on the coating at the temperature of 150 ℃/1h to obtain a cured coating.
Example 4
0.68g (0.005mol) of pentaerythritol and 8.04g (0.06mol) of dimethylolpropionic acid are added into a three-neck flask for melting, then the system temperature is stabilized at 150 ℃, 0.0872g of p-toluenesulfonic acid is added as a catalyst, argon is introduced for protection, and stirring reaction is carried out for 4 hours at the rotating speed of 200rpm, thus obtaining the fourth-generation hyperbranched polyester. After the fourth generation hyperbranched polyester is obtained, the temperature of the system is reduced to 100 ℃, then 6.78g of acrylic acid is added for reaction for 5 hours, and a yellow viscous liquid mixture is obtained after cooling. The yellow viscous liquid mixture is diluted by adding 10ml of acetone, slowly dropped into petroleum ether to precipitate and remove the excessive acrylic acid, and filtered. Repeating the operation for three times, vacuumizing and drying to obtain the fourth-generation hyperbranched polyester acrylate, namely HPA4。
5.76g of pentaerythritol tetraglycidyl ether, 1.5g of acrylic acid and 0.0642g of polymerization inhibitor hydroquinone are mixed and added into a three-neck flask, the temperature is raised to 100 ℃, the mixture is stirred uniformly at the rotation speed of 200rpm, after the temperature is constant, 0.0794g of triphenylphosphine which is based on the total mass of trimethylolpropane triglycidyl ether and acrylic acid is added as a catalyst, and the mixture is stirred and reacted for 5 hours at the rotation speed of 200rpm continuously to obtain a light yellow mixture. And (4) dripping the mixture into petroleum ether, stirring and washing off redundant acrylic acid, and separating and pouring out the petroleum ether. Adding acetone to dissolve the product, dropping into petroleum ether for washing, and repeating the above operations for three times to obtain yellow liquid. And vacuumizing by using a vacuum oven to remove a small amount of acetone and petroleum ether to obtain the acrylic acid partially modified pentaerythritol tetraglycidyl ether oligomer, wherein the nuclear magnetic spectrum of the acrylic acid partially modified pentaerythritol tetraglycidyl ether oligomer is the same as that in example 3.
According to the weight portion, 10 portions of hydrogenated bisphenol A epoxy resin EP-4080E and 10 portions of HPA are firstly mixed410 parts of acrylic acid partially modified pentaerythritol tetraglycidyl ether oligomer and 70 parts of active diluent tripropylene glycol diacrylate are stirred and uniformly mixed at the rotating speed of 300rpm and normal temperature for 20min, then 15 parts of white pigment (titanium dioxide: antimony oxide in mass ratio of 1:1) and 3 parts of dispersant BYK103 are added, firstly, a star-shaped ball mill is used for grinding and dispersing the ink for 1 hour, then, an ultrasonic cleaner is used for carrying out ultrasonic treatment on the ink for 0.5 hour, so that the white pigment is uniformly dispersed, the temperature of the ink rises after the ball milling and the ultrasonic treatment, cooling to the normal temperature is needed, 9 parts of photoinitiator (TPO: 1173: 2:1 in mass ratio), 8 parts of thermal curing agent TC3632 and 3 parts of antioxidant (TNPP: 1024: 1) are added, and finally, 3601.5 parts of stabilizer TC 2 3602H and 3 parts of adhesion promoter ADP-S479 are added and stirred at the rotating speed of 700 for 30min and uniformly dispersed, obtaining the white UV/heat dual-curing FPC ink-jet character ink.
Coating the prepared white UV/thermal dual-curing FPC inkjet character ink on a PCB substrate by using a coating rod with the thickness of 10 microns, then carrying out ultraviolet curing on the coating for 2s by using a 395nm UV-LED curing machine, and then carrying out thermal curing on the coating at the temperature of 150 ℃/1h to obtain a cured coating.
Example 5
0.34g (0.0025mol) of pentaerythritol and 9.38g (0.07mol) of dimethylolpropionic acid are added into a three-neck flask for melting, then the system temperature is stabilized at 140 ℃, 0.0982g of p-toluenesulfonic acid is added as a catalyst, argon is introduced for protection, and stirring reaction is carried out for 4 hours at the rotating speed of 200rpm, thus obtaining the third-generation hyperbranched polyester. After the third-generation hyperbranched polyester is obtained, the temperature of the system is reduced to 100 ℃, 7.83g of acrylic acid is added for reaction for 6 hours, and a yellow viscous liquid mixture is obtained after cooling. Viscous to yellowThe liquid mixture was diluted with 10ml of acetone, slowly dropped into petroleum ether to precipitate and remove excess acrylic acid, and filtered. Repeating the above operation for three times, and vacuum-pumping and drying to obtain three-generation hyperbranched polyester acrylate, i.e. HPA3。
5.76g of pentaerythritol tetraglycidyl ether, 2g of acrylic acid and 0.0817g of polymerization inhibitor hydroquinone are mixed and added into a three-neck flask, the temperature is raised to 100 ℃, the mixture is stirred uniformly at the rotation speed of 200rpm, after the temperature is constant, 0.0877g of triphenylphosphine serving as a catalyst based on the total mass of trimethylolpropane triglycidyl ether and acrylic acid is added, and the mixture is stirred and reacted for 5 hours at the rotation speed of 200rpm continuously to obtain a light yellow mixture. And (4) dripping the mixture into petroleum ether, stirring and washing off redundant acrylic acid, and separating and pouring out the petroleum ether. Adding acetone to dissolve the product, dropping into petroleum ether for washing, and repeating the above operations for three times to obtain yellow liquid. And (3) vacuumizing by using a vacuum oven to remove a small amount of acetone and petroleum ether, thus obtaining the acrylic acid partially modified pentaerythritol tetraglycidyl ether oligomer, wherein the nuclear magnetic spectrum of the acrylic acid partially modified pentaerythritol tetraglycidyl ether oligomer is the same as that of the example 3.
According to parts by weight, 10 parts of epoxy modified organic silicon resin SH-023 and 20 parts of HPA are firstly mixed310 parts of acrylic acid partially modified pentaerythritol tetraglycidyl ether oligomer and 60 parts of active diluent hexanediol diacrylate (HDDA) are stirred and uniformly mixed at the rotating speed of 300rpm and the normal temperature for 30min, 20 parts of white pigment (the mass ratio of titanium dioxide to barium sulfate is 2:1) and 5 parts of dispersant BYK103 are added, a star-type ball mill is used for grinding and dispersing the ink for 2 hours, an ultrasonic cleaner is used for carrying out ultrasonic treatment on the ink for 1 hour to uniformly disperse the white pigment, the temperature of the ink rises after the ball milling and the ultrasonic treatment, cooling is required to the normal temperature, 6 parts of photoinitiator (the mass ratio of TPO: 819 to 1:1), 6 parts of thermal curing agent 3632 and 2 parts of antioxidant (the mass ratio of 1024: 168 is 2:1) are added to be completely dissolved at the normal temperature, and finally 2 parts of stabilizer TC3602H and 5 parts of adhesion promoter ADP-S479 are added and uniformly stirred at the rotating speed of 500 min, obtaining the white UV/heat dual-curing FPC ink-jet character ink.
Coating the prepared white UV/thermal dual-curing FPC inkjet character ink on a PCB substrate by using a coating rod with the thickness of 10 microns, then carrying out 3s ultraviolet curing on the coating by using a 395nm UV-LED curing machine, and then carrying out 150 ℃/1h thermal curing on the coating to obtain a cured coating.
Comparative example 1
The comparative example 1 is an example 2 in the chinese patent CN201711382092.4, and the preparation method is as follows:
mixing 6.8 parts of hyperbranched polyester acrylate, 10-30% of monomer (comprising 10.6 parts of TMP (3EO) TA, 8 parts of PETA, 22 parts of DCPDA and 18.7 parts of EOEOEA), 1 part of dispersant Tyzor AA-105 and 13 parts of titanium dioxide, grinding the mixture by using a grinder until the pigment granularity D50 is less than 300nm, and filtering the mixture to obtain white nano color paste for later use; dissolving 7 parts of photoinitiator (TPO 819: 3:4) into the residual monomers, and uniformly mixing for later use; mixing 16 parts of organic silicon modified epoxy resin, 0.3 part of latent curing agent ECX412, a monomer dissolved with a photoinitiator, white nano color paste, 2 parts of TEGO Dispers 655, 0.3 part of TEGO Glide, 0.1 part of TEGO Airex900 and 0.2 part of TEGO WET 500, stirring uniformly, and filtering through a 1-micron filter membrane to obtain white character ink. The UV-LED ink-jet printing character ink of the embodiment is subjected to various tests, and then the character ink is sprayed and printed on a circuit board to test the mechanical property of the circuit board. The method for spraying and printing the UV-LED ink-jet printing character ink on the circuit board comprises the following steps: and (3) filling the UV-LED ink-jet character printing ink into a printer, carrying out jet printing on the circuit board substrate, irradiating for 0.5-10 seconds under a UV-LED lamp to primarily cure the ink, and then baking for 30-60 minutes at the temperature of 140-160 ℃ to carry out post-curing.
Comparative example 2
The comparative example 2 is an example 2 in chinese patent CN201910142486.5, and the preparation method is as follows:
mixing 10% of aliphatic urethane acrylate, 12% of cyclohexyl methacrylate, 15% of 1, 6-hexanediol diacrylate BYK180 and titanium dioxide, grinding until the granularity D50 is less than 300nm, and filtering to obtain white nano color paste; uniformly mixing 3% of photoinitiator 369, 3% of photoinitiator TPO, 3% of Irgacure261, the rest 10% of cyclohexyl methacrylate and the rest 13% of 1, 6-hexanediol diacrylate to obtain a mixed solution; uniformly mixing white nanometer color paste and mixed liquid, 12% of polyurethane modified epoxy resin, 2% of organic boron amine complex, 5% of C8-C10 alcohol glycidyl ether, 1% of BYK-361N and 1% of BYK088, and filtering through a 1-micrometer filter membrane to obtain the UV-LED ink-jet printing soft board character ink. Loading the UV-LED ink-jet printing soft board character ink into a printer, and carrying out jet printing on the soft board; the flexible board was irradiated under a UV-LED lamp for 5 seconds to perform photocuring, and then baked at 150 ℃ for 40 minutes to perform thermal curing.
The test results of the inventive examples and comparative examples are shown in table 1.
TABLE 1
As can be seen from Table 1, examples 1 to 5, except for example 4, are superior in hardness to comparative examples 1 and 2, and solve the problems of high hardness with low viscosity, high hardness and good flexibility. Compared with the comparative example, the hardness and flexibility of the coating film are not only solved by hyperbranched polyester acrylate, but also the epoxy component and the acrylic component are combined and interacted chemically and physically by adding the modified oligomer, so that the hardness of the coating film is further improved on the premise of not sacrificing the flexibility and improving the viscosity.
Claims (10)
1. A white UV/heat dual-curing FPC inkjet character ink is characterized by comprising the following raw materials in parts by weight: 5-30 parts of epoxy resin; 5-30 parts of hyperbranched polyester acrylate; 20-70 parts of a reactive diluent; 1-20 parts of modified oligomer; 1-10 parts of a photoinitiator; 1-10 parts of a thermal curing agent; 5-20 parts of white pigment; 1-5 parts of an antioxidant; 1-5 parts of a stabilizer; 1-5 parts of a dispersant; 1-5 parts of adhesion promoter;
the hyperbranched polyester acrylate is first-generation hyperbranched polyester acrylate, second-generation hyperbranched polyester acrylate, third-generation hyperbranched polyester acrylate or fourth-generation hyperbranched polyester acrylate;
the modified oligomer is obtained by partially modifying epoxy groups on a polyfunctional epoxy reactive diluent by acrylic acid, and the polyfunctional epoxy reactive diluent for modification is one or more of trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether.
2. The white UV/thermal dual-curing FPC inkjet character ink as claimed in claim 1, wherein the modification and purification of the multifunctional epoxy reactive diluent for modification is achieved by the following method: mixing a polyfunctional epoxy active diluent, acrylic acid and a polymerization inhibitor hydroquinone, heating to 90-120 ℃, uniformly stirring, adding triphenylphosphine serving as a catalyst, and reacting for 2-6 hours under stirring to obtain a light yellow mixture; repeatedly washing, dissolving and washing the light yellow mixture to obtain yellow liquid; and vacuumizing to obtain the modified and purified polyfunctional epoxy reactive diluent.
3. The white UV/thermal dual-cure FPC inkjet character ink according to claim 2, wherein a molar ratio of the multifunctional epoxy reactive diluent to acrylic acid is (1-4): 1; the addition amount of the polymerization inhibitor hydroquinone is 0.05 to 1 percent of the total mass of the polyfunctional group epoxy active diluent and the acrylic acid; the dosage of the triphenylphosphine is 0.5 to 2 percent of the total mass of the polyfunctional epoxy active diluent and the acrylic acid; the stirring speed for uniformly stirring and stirring reaction is 150-250 rpm; the washing is carried out by using petroleum ether, and the dissolution is carried out by using acetone.
4. The white UV/thermal dual-curing FPC inkjet character ink according to claim 1, wherein the synthesis process of the hyperbranched polyester acrylate is as follows:
(1) mixing pentaerythritol and dimethylolpropionic acid in a molar ratio of 1:4-1:60, melting, stabilizing the system temperature at 130-; after the hyperbranched polyester is obtained, cooling the system to 90-110 ℃, adding 1-2 times of acrylic acid of the hydroxyl number at the tail end of the hyperbranched polyester, reacting for 4-6 hours, and cooling to obtain a yellow viscous liquid mixture;
(2) adding acetone into the yellow viscous liquid mixture for dilution, dropping the mixture into petroleum ether for precipitation to remove redundant acrylic acid, and filtering; repeating the operations for many times, and performing vacuum-pumping drying to obtain the hyperbranched polyester acrylate.
5. A white UV/thermal dual cure FPC inkjet character ink according to claim 1, wherein said reactive diluent comprises one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, isobornyl methacrylate, 3, 4-epoxycyclohexylmethylmethacrylate, vinyl acetate, methylol propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate.
6. The white UV/thermal dual-curing FPC inkjet character ink according to claim 1, wherein the epoxy resin is one or more of bisphenol A epoxy resin E51, bisphenol A epoxy resin E44, hydrogenated bisphenol A epoxy resin EP-4080E, hydrogenated bisphenol A epoxy resin AL-3030, and epoxy-modified silicone resin SH-023;
the photoinitiator comprises one or more of diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 4-benzoyl-4' -methyl-diphenyl sulfide, 1-hydroxycyclohexyl phenyl ketone, mixed triaryl sulfonium hexafluorophosphate salt, diphenyl- (4-phenyl sulfur) phenyl sulfonium hexafluorophosphate, triaryl hexafluoroantimonate and bis 2, 6-difluoro-3-pyrrolyl phenyl titanocene.
7. The white UV/thermal dual-curing FPC inkjet character ink according to claim 1, wherein the thermal curing agent is one or more of dicyandiamide, boron trifluoride-amine complex, oxaborone heterocyclic boron amine complex, organic hydrazide, thermal cationic curing agent and acid anhydride;
the white pigment comprises one or more of titanium dioxide, zinc oxide, antimony oxide and barium sulfate;
the antioxidant is one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris [2, 4-di-tert-butylphenyl ] phosphite, N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine and trisnonylphenyl phosphite.
8. The white UV/thermal dual-curing FPC inkjet character ink as claimed in claim 1, wherein the dispersant is one or more of a dispersant STA-1110A, a dispersant BYK103, a dispersant BYK110 and a dispersant BYK 9076;
the adhesion promoter is one or more of an adhesion promoter ADP-S479, an adhesion promoter PN-701 and an adhesion promoter YF-1985-1.
9. The method for preparing white UV/thermal dual curing FPC inkjet character ink according to claim 1, wherein: firstly, uniformly stirring and mixing the epoxy resin, the hyperbranched polyester acrylate, the modified oligomer and the reactive diluent at normal temperature, then adding the white pigment and the dispersing agent to uniformly disperse the white pigment, cooling to normal temperature, then adding the photoinitiator, the thermal curing agent and the antioxidant to completely dissolve at normal temperature, and adding the stabilizer and the adhesion promoter to uniformly disperse to obtain the white UV/thermal dual-curing FPC inkjet character ink.
10. The method for preparing white UV/thermal dual cure FPC inkjet character ink according to claim 9, characterized in that: the stirring and mixing at normal temperature is carried out at the rotating speed of 200-500rpm and at normal temperature for 15-30 min; the white pigment is uniformly dispersed by firstly grinding and dispersing the ink for 1 to 3 hours by using a star-shaped ball mill and then ultrasonically treating the ink for 0.5 to 1 hour by using an ultrasonic cleaner; the stabilizer and the adhesion promoter are added and then uniformly dispersed, and the stabilizer and the adhesion promoter are added and stirred for 15-30min at the rotating speed of 300-800 rpm.
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