EP4103407A1 - Procédé de production d'au moins un matériau de substrat pourvu d'un motif imprimé - Google Patents
Procédé de production d'au moins un matériau de substrat pourvu d'un motif impriméInfo
- Publication number
- EP4103407A1 EP4103407A1 EP21706848.5A EP21706848A EP4103407A1 EP 4103407 A1 EP4103407 A1 EP 4103407A1 EP 21706848 A EP21706848 A EP 21706848A EP 4103407 A1 EP4103407 A1 EP 4103407A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pigment
- mixture
- weight
- color component
- red
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000000758 substrate Substances 0.000 title abstract description 4
- 239000000049 pigment Substances 0.000 claims abstract description 105
- 239000000203 mixture Substances 0.000 claims abstract description 88
- 238000007639 printing Methods 0.000 claims abstract description 75
- 239000001052 yellow pigment Substances 0.000 claims abstract description 50
- 239000003738 black carbon Substances 0.000 claims abstract description 6
- 239000001054 red pigment Substances 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 52
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 claims description 28
- 239000012876 carrier material Substances 0.000 claims description 24
- 238000005034 decoration Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical group [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004071 soot Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 184
- 229920005989 resin Polymers 0.000 description 155
- 239000011347 resin Substances 0.000 description 155
- 239000000123 paper Substances 0.000 description 62
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- 239000004640 Melamine resin Substances 0.000 description 30
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- 239000002023 wood Substances 0.000 description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 24
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 23
- 239000002245 particle Substances 0.000 description 23
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- 239000000835 fiber Substances 0.000 description 7
- -1 metal oxide hydrates Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
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- 239000011324 bead Substances 0.000 description 6
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- 239000004033 plastic Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- 239000000057 synthetic resin Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
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- 239000002347 wear-protection layer Substances 0.000 description 4
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229920002522 Wood fibre Polymers 0.000 description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000005018 casein Substances 0.000 description 3
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 3
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- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 description 3
- 238000007646 gravure printing Methods 0.000 description 3
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- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
- 239000002025 wood fiber Substances 0.000 description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 2
- BFEJTCHFLJECJN-UHFFFAOYSA-N 4,11-Dichloro-5,12-dihydroquino[2,3-b]acridine-7,14-dione Chemical compound N1C2=C(Cl)C=CC=C2C(=O)C2=C1C=C(C(C=1C=CC=C(C=1N1)Cl)=O)C1=C2 BFEJTCHFLJECJN-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 108010073771 Soybean Proteins Proteins 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 238000010017 direct printing Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000003906 humectant Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000012432 intermediate storage Methods 0.000 description 2
- 239000004849 latent hardener Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229940001941 soy protein Drugs 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000011155 wood-plastic composite Substances 0.000 description 2
- 229940015975 1,2-hexanediol Drugs 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- XPZQBGDNVOHQIS-UHFFFAOYSA-N 2,9-dichloro-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione Chemical compound N1C2=CC=C(Cl)C=C2C(=O)C2=C1C=C(C(=O)C=1C(=CC=C(C=1)Cl)N1)C1=C2 XPZQBGDNVOHQIS-UHFFFAOYSA-N 0.000 description 1
- TXWSZJSDZKWQAU-UHFFFAOYSA-N 2,9-dimethyl-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione Chemical compound N1C2=CC=C(C)C=C2C(=O)C2=C1C=C(C(=O)C=1C(=CC=C(C=1)C)N1)C1=C2 TXWSZJSDZKWQAU-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000019888 Vivapur Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
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- 239000004568 cement Substances 0.000 description 1
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- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- VPWFPZBFBFHIIL-UHFFFAOYSA-L disodium 4-[(4-methyl-2-sulfophenyl)diazenyl]-3-oxidonaphthalene-2-carboxylate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 VPWFPZBFBFHIIL-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
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- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000001053 orange pigment Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000000246 remedial effect Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/21—Ink jet for multi-colour printing
- B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0023—Digital printing methods characterised by the inks used
-
- 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
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment 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
- C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/06—Veined printings; Fluorescent printings; Stereoscopic images; Imitated patterns, e.g. tissues, textiles
Definitions
- the present invention relates to a method for producing a carrier material provided with a printed decoration, in particular a printed paper or a printed material plate, using a water-soluble digital printing ink.
- Carrier materials provided with a decoration are typically used as flooring elements or to cover walls and ceilings.
- the wood-based panels used as carrier materials were mostly coated with a decorative paper in the past, whereby there were or are no limits to the variety of decorative papers with different patterns.
- the printing techniques mainly used here are the gravure printing process and the digital printing process.
- Gravure printing is a printing technique in which the elements to be imaged are present as depressions in a printing form that is colored before printing.
- the printing ink is mainly located in the depressions and is transferred to the object to be printed, such as a carrier material, due to the pressure of the printing form and adhesive forces.
- digital printing on the other hand, the print image is transferred directly from a computer to a printing machine such as a laser printer or inkjet printer. There is no need to use a static printing form.
- CMYK color model
- CMYK subtractive color model
- CMYK the three color components cyan, magenta, yellow (yellow) and the black component key as color depth.
- CMYK the three color components cyan, magenta, yellow (yellow) and the black component key as color depth.
- CMYK color space is a compromise, which means that certain colors either cannot be generated at all or that additional colors must then be used. This problem arises particularly when reproducing wood decors in the furniture or laminate flooring industry, where different shades of brown have to be produced.
- the technical problem on which the invention is based was therefore to provide a method for producing decorative prints on different carrier materials with the same quality or comparable quality perception while avoiding metamerism, ensuring good reproduction of warm-looking wood decors on all carrier materials.
- a method for producing at least one carrier material provided with a printed decoration is provided, the printed decoration being applied to the at least one carrier material by means of digital printing, for example in an inkjet printing process.
- the ink used for digital printing is a water-soluble CRYK ink which has the following composition:
- Color component C at least one cyan pigment
- - Color component K at least one black carbon pigment
- Color component Y at least one yellow pigment; or a mixture of at least two different yellow pigments or a mixture of at least one yellow pigment and at least one red pigment
- Color component R at least one red pigment, or a mixture of at least two different red pigments or a mixture of at least one red pigment and at least one yellow pigment; whereby a CRYK ink with only one yellow pigment as color component Y and only one red pigment as color component R is excluded.
- the present method accordingly uses a digital printing ink in which, for example, only the color component Y, only the color component R or the two color components Y and R are modified.
- the magenta commonly used in inkjet inks has been replaced with a color component R in the form of a mixture of red color pigments and a yellow color pigment
- the color component Y has been replaced with a mixture of yellow color pigments and a red color pigment.
- the digital printing ink sets consist of only 4 colors, as this is due to the digital printer. Nevertheless, it became possible to adapt digital printing inks in a targeted manner by mixing different color pigments and processing them in a digital printing ink. It should be noted that the use of an orange pigment such as P071 is not intended and is therefore excluded.
- EP 2 865 528 B1 uses a CRYK ink for printing on a paper substrate.
- this CRYK ink contains the red pigment PR 254 as color component R and the yellow pigment PY151 as color component Y.
- the use of mixtures as color component R and / or color component Y is not emphasized separately.
- Disadvantages of the sole use of PR254 and PY151 in the provision of printed decorations for various carrier materials for use in the furniture and laminate flooring industry are, however, only an insufficient color shift in the direction of orange-red and the comparatively high cost of these pigments. So is with the EP 2 865 528 B1 described ink in digital printing only insufficient coverage of the orange-red color component is possible. However, this color space is important for the provision of warm tones for the furniture industry.
- the use according to the invention of a mixture or combination of red and yellow pigments for the color components R and Y in the printing ink enables the desired shift of the color space with an increase in the orange-red color component.
- This color space is adapted for warmer wood decors in analogue printing or gravure printing. It should be noted that at least 5 basic colors are usually used in the analog printing process, while digital printing is limited to 4 basic colors. With the present ink it is possible to use this larger color space both in analogue printing and in digital printing without changes occurring that would lead to undesirable metameric effects.
- white primed wood-based panels and, on the other hand, white primed papers can now be used as carrier materials. If the same decor with color sets with the pigments mentioned is printed on both carrier materials, metamerism is largely avoided. At the same time, costs are reduced.
- the color component Y is a mixture of two yellow pigments or a mixture of a yellow pigment and a red pigment or a mixture of two yellow pigments and a red pigment.
- PY150, 151, 154, 175, 180 or 194 can be used as yellow pigments, PY150 and PY181 being preferred.
- PY181 and PY151 are benzimidazolone azo pigments, but PY181 has different substituents than PY151.
- PY181 contains an amidobenzene side chain as the R4 substituent, while PY151 only has a hydrogen at the same position.
- PY181 has good acid and base stability as well as solvent stability and is easy to disperse.
- the color component Y is a mixture of a first yellow base pigment and up to 30% by weight, preferably up to 20% by weight, of a second yellow pigment, in particular a mixture of PY 150 and 20% by weight PY181 (% by weight are each based on the color component Y).
- the color component Y is a mixture of a first yellow base pigment and up to 10% by weight, preferably up to 5% by weight of a red pigment, in particular from the group of quinacridone pigments, in particular a mixture of PY150 and 5% by weight % PR 207 (% by weight are based on the color component Y) ..
- the red quinacridone pigment belongs to a group of organic pigments that are derived from the basic structure of the quinacridone. They have very good weather resistance, high color strength and high chemical resistance.
- the red pigment used is preferably selected from the group comprising 2,9-dimethylquinacridone (Pigment Red 122), 2,9-dichloroquinacridone (Pigment Red 202), mixed crystal of quinacridone and 4, 11 dichloroquinacridone (Pigment Red 207) and 3.10 -Dichlorquinacridone (Pigment red 209).
- the red pigment PR207 as a mixed crystal of quinacridone and 4, 11-dichloroquinacridone is particularly preferably used.
- a mixed crystal is to be understood as a solid solution that differs from a purely physical mixture of the individual components.
- the molecules of one component are built into the crystal lattice of the other component.
- PR207 is described with a yellowish-red color.
- the color component Y is a mixture of a first yellow base pigment, up to 20% by weight, preferably up to 15% by weight of a second yellow pigment and up to 10% by weight, preferably up to 5% by weight a red pigment, in particular from the group of quinacridone pigments, in particular a mixture of PY150, 15% by weight of PY181 and 5% by weight of PR207 (% by weight in each case are based on the color component Y).
- the color component R is a mixture of two red pigments or a mixture of a red pigment and a yellow pigment or a mixture of two red pigments and a yellow pigment.
- the color component R is a mixture of a first red base pigment and up to 60% by weight, preferably up to 50% by weight, of a second red pigment, in particular from the group of quinacridone pigments, in particular a mixture is composed of PR254 and 50% by weight of PR207 (% by weight are each based on the color component R).
- the red pigment PR254 belongs to the class of the diketopyrrolopyrrole pigments and is described with a yellowish-red color. PR254 is preferred for use in automotive coatings. However, other red pigments can also be used instead of PR254, such as PR266, 122, 202, 207.
- the color component R is a mixture of a mixture of a red pigment, in particular from the group of quinacridone pigments, and a yellow pigment, in particular a mixture of PR207 and PY181.
- the amount of PY181 is 5-15% by weight, preferably 6-10% by weight (% by weight are based in each case on the color component R).
- the color component R is a mixture of a first red base pigment, up to 60%, preferably up to 50%, of a second red pigment, in particular from the group of quinacridone pigments, and a yellow pigment, in particular a mixture of PR254, 50% by weight PR207 and PY181.
- the amount of PR207 is approx. 50% by weight and the amount of PY181 is 3-10% by weight, preferably 3-5% by weight (% by weight are each based on the color component R).
- the present CRYK digital printing ink can be used in the following combinations of the color components R and Y, at least one cyan pigment being present as color component C and at least one black carbon pigment being present as color component K: a) color component Y: mixture of two yellow pigments; Color component R: a red pigment; b) Color component Y: mixture of a yellow pigment and a red pigment, in particular from the group of the quinacridone pigments; Color component R: a red pigment; c) Color component Y: mixture of two yellow pigments and one red pigment, in particular from the group of quinacridone pigments; Color component R: a red pigment; d) Color component Y: a yellow pigment; Color component R: Mixture of two red pigments, one of the red pigments preferably being from the group of quinacridone pigments; e) Color component Y: mixture of two yellow pigments; Color component R: Mixture of two red pigments, one of the red pigments preferably being from the group of quinacridone pigments; f)
- the at least one cyan pigment is a copper phthalocyanine pigment, preferably Cl Pigment Blue (PB) 15: 3 or Cl Pigment Blue 15: 4, particularly preferably Cl Pigment Blue 15: 3.
- the black carbon pigment is a soot pigment, in particular selected from the group of Regal TM 400R, Mogul TM, L, Elftex TM 320 from Cabot Co., or Carbon Black FW18, Special Black TM 250, Special Black TM 350, Special Black TM 550, Printex TM 25, Printex TM 35, Printex TM 55, Printex TM 90, Printex TM 150T from DEGUSSA Co., MA8 from MITSUBISHI CHEMICAL Co., and Cl Pigment Black (PBL) 7 and Cl Pigment black 11.
- the total pigment concentration in the ink used in the present case is more than 8% by weight, preferably between 6 and 15% by weight, particularly preferably between 4 and 10% by weight, based on the total weight of the ink.
- the total pigment concentration changes insignificantly during mixing - only the proportion of the individual pigments is changed during mixing.
- the ink used in the present case is an aqueous ink.
- the water content in the ink is at least 50%, preferably more than 50%, particularly preferably at least 55%. e.g. at 51%, 52% or 53%.
- the ink used here also has a solvent content.
- the ink contains at least one organic solvent with a proportion of less than 45%, preferably less than 43%; e.g. 41%, 42%.
- the organic solvent keeps the ink, especially in combination with other additives such as dispersing agents, in a workable consistency.
- Glycol or other alcohols such as ethanol can be used as the organic solvent.
- the ink used in the present case can contain further additives such as biocides, humectants, acids / bases to adjust the pH value, surfactants as surface-active substances.
- humectants inter alia 2-pyrrolidone, glycerol and 1,2-hexanediol can be contained in an amount between 0.1 and 25% by weight, based on the total weight of the aqueous inkjet ink.
- the at least one carrier material to be printed is at least one raw paper.
- base papers are to be understood as those papers which were neither exposed to sizing in the mass nor to impregnation of the surface with a resin or glue.
- Base papers essentially consist of cellulose, pigments and fillers and the usual additives. Softwood pulp, hardwood pulp, or mixtures of both types of pulp can be used to produce raw papers such as decorative papers.
- Inorganic color pigments such as metal oxides, metal hydroxides and metal oxide hydrates, metal sulfides, metal sulfates, metal chromates and metal molybdates as well as organic color pigments and / or dyes such as carbonyl colorants, cyanine colorants and others can be used to color the base paper.
- the raw paper to be printed in the present case is at least one paper web without impregnation with at least one ink-receiving layer.
- the ink-receiving layer is preferably a hydrophilic coating which contains water-soluble or water-dispersible polymers or binders as well as inorganic pigments.
- polyvinyl alcohol polyvinylpyrrolidone
- polyvinyl acetate starch
- gelatin carboxymethyl cellulose
- ethylene / vinyl acetate polyvinyl acetate
- styrene / acrylic acid ester copolymers or mixtures thereof can be used as binders.
- Inorganic white pigments such as silicates, kaolin, calcium carbonate, aluminum hydroxide, talc, titanium dioxide or color pigments such as iron oxide, carbon black, or organic color pigments can be contained in the ink-absorbing layer.
- the ratio of pigment to binder in the ink-absorbing layer is between 1: 0.05-1: 1 based on the solids content.
- the ink-receiving layer contains silicates, aluminum oxides, aluminum hydroxides or aluminum silicates and, as a water-soluble polymeric binder, polyvinyl alcohol.
- the weight per unit area of the ink-receiving layer can be between 0.5-20 g / m 2 .
- the at least one carrier material to be printed is at least one pretreated, impregnated paper.
- a pre-treated paper or cellulose layer
- the paper can be impregnated with a wide variety of resin solutions, for example melamine resins and urea resins, plastic-acrylate compounds or starch glue. It is also possible to impregnate the paper using resin powder. The use of resin powder is described in detail below.
- an impregnated paper is used, which is provided with the following process steps (see also EP 2 980 313 A1): a) complete impregnation of the cellulose layer with a curable resin, eg melamine-formaldehyde resin), b) removal of the excess resin forming the surface (e.g. by peeling off or squeegeeing), c) drying the impregnated cellulose layer in such a way that after the water has evaporated from the resin, the cellulose fibers are at least partially exposed on the surface from which the resin was removed.
- a curable resin eg melamine-formaldehyde resin
- removal of the excess resin forming the surface e.g. by peeling off or squeegeeing
- drying the impregnated cellulose layer in such a way that after the water has evaporated from the resin, the cellulose fibers are at least partially exposed on the surface from which the resin was removed.
- the resin remaining on the surface of the cellulose layer is sealed with the fiber tips by peeling or doctoring. During the drying process, the resin is drawn back into the fibers, so that the fibers are soaked in the resin but not enclosed by the resin.
- Such a surface is suitable for printing with aqueous digital printing inks.
- the special device used for peeling off or doctoring works in a similar way to a spatula machine in which one or more rollers run backwards on the paper and absorb the excess resin.
- the amount can be precisely controlled and repeatability guaranteed by the different speeds of the rollers.
- the treated paper (base paper with or without an ink-absorbing layer, impregnated paper) can also be provided with a primer material.
- a water-based synthetic resin or acrylate resin dispersion which is completely miscible with water or partially soluble in water can be used as the primer material.
- the primer material should have a low solvent content of less than 3%.
- the printed decoration is applied to the carrier material in direct printing by means of a digital printing process using the CRYK ink described above.
- digital printing the print image is taken directly from a computer transferred to a printing machine such as an inkjet printer.
- the decor data is translated into machine data by software (e.g. RIP software from the manufacturer Colorgate).
- the printed papers can be provided with a resin layer as a protective layer after printing.
- This protective layer can consist of a resin that has not yet fully cured, preferably a formaldehyde-containing resin, particularly preferably melamine-formaldehyde resin, urea-formaldehyde resin and / or melamine-urea-formaldehyde resin, or a radiation-curable acrylate, preferably polyester acrylate, Polyether acrylates, urethane acrylate, hexanediol diacrylate or mixtures thereof exist.
- This protective layer serves to protect the printed decorations and enables temporary storage.
- the applied protective layer should not yet be fully cured, which is controlled in particular by the drying process.
- the resins used for the impregnation of paper layers go through various polymerization and crosslinking states in these processes.
- these melamine-formaldehyde monomers are subject to polycondensation, whereby the monomers are linked via ether and methylene groups and higher molecular weight precondensates and polycondensates are formed (see scheme II).
- Precondensates and polycondensates differ in terms of their molar mass and their solubility.
- the low molecular weight precondensates can still have limited water solubility, while the higher molecular weight polycondensates are insoluble.
- the limited water solubility of the precondensates is due, among other things, to methylol groups that are still free and the low degree of crosslinking of the mostly still linear oligomers.
- the precondensates are thus an intermediate polymerisation product. When the polycondensates harden completely, there is strong crosslinking with elimination of the methylol groups that are still present, with closely crosslinked plastics being formed via methylene groups (see scheme III).
- A-state easily soluble in solvent, meltable, curable
- impregnated paper layers to refine wood-based panels, e.g. to make high-quality floor panels
- the impregnating resin is not yet fully cured, but is preferably still in the partially crosslinked B-state. This enables flowing / filming in combination with further cross-linking of the synthetic resins during further processing in the press. Accordingly, the presently impregnated and printed papers are preferably dried to condition B.
- the printed and, if necessary, coated or impregnated paper can then be pressed with a material plate, at least one protective paper (overlay) and, if necessary, a backing paper.
- the at least one carrier material to be printed is at least one material board, in particular a wood-based board, such as MDF and HDF boards made of wood fibers, chipboard made of chips, OSB made of wood strands, the wood fibers, wood chips and wood strands each being mixed with suitable adhesives and hot-pressed), WPC panels, plastic panels, e.g. SPC (stone plastic composite) or a cement fiber panel.
- Carrier materials such as Wood-based materials, wood-based material-plastic mixtures, WPC, plastics or mixtures of different plastics, for example PE, PP, PVC, PU, all also with fillers such as chalk, talc or fibers.
- the surface of the material plate can be pretreated before printing to improve the adhesion of the subsequent layers. This can be cleaning with brushes, a bevel that also removes unevenness from the surface, and / or a plasma or corona treatment.
- an unsanded wood-based panel in particular MDF or HDF, can also be used, which is also provided with a pressed skin (rotting layer) on the upper side.
- Aqueous melamine resin is applied to the top to fill the pressed skin. The melamine resin is later melted in the short-cycle press and thus has a remedial effect in the area of this layer; i.e. it counteracts delamination.
- At least one primer is applied in a next step to increase the covering power.
- the primer preferably comprises casein, corn starch or soy protein and can contain inorganic color pigments and thus serve as a primer layer for the decorative layer to be subsequently printed on.
- White pigments such as titanium dioxide T1O2 can in turn be used as color pigments.
- Further color pigments can be calcium carbonate, barium sulfate or barium carbonate, but also iron oxide pigments (for a brownish primer).
- the primer can also contain water as a solvent.
- the amount of liquid primer applied can be between 10 and 50 g / m 2 , preferably between 15 and 30 g / m 2 , particularly preferably between 20 and 25 g / m 2 .
- the primer consists of at least one, preferably of at least two or more successively applied layers or orders (for example up to five orders), the amount applied between the layers or orders is the same or different, ie the application amount of each individual layer can vary.
- the primer can be applied to the material carrier plate using a roller with subsequent drying. It is also possible to apply the primer to the material plate using digital printing. In this case, water-based inks enriched with white color pigments are preferably used, which are suitable for the digital printing inks used below. An order using digital printing is advantageous because the printing system is significantly shorter than a roller device and thus saves space, energy and costs.
- a primer layer is applied to the primer, preferably as a single application with subsequent drying.
- the amount of the applied liquid primer is between 10 and 30 g / m 2 , preferably between 15 and 20 g / m 2 .
- Polyurethane-based compounds are preferably used as primers.
- the decorative layer can also be provided with a protective layer (as already described above for the papers).
- This protective layer can be a formaldehyde-containing resin (in the B-state, see above), in particular a melamine-formaldehyde resin, urea-formaldehyde resin or melamine-urea-formaldehyde resin and glass spheres (size 50-150 ⁇ m) as Spacers included for optional intermediate storage of the panels.
- This protective layer is used to temporarily protect the decorative layer for storage before further finishing.
- the protective layer on the decorative layer has not yet fully cured, but has a certain residual moisture content of approx. 10%, preferably approx. 6%, and can be further crosslinked. In the case of intermediate storage, the resin remains in state B (not yet fully cured and crosslinked), whereby the decoration is protected.
- the glass spheres can be added to the resin or sprinkled on it and act as spacers.
- Such protective layers are described, for example, in WO 2010/112125 A1 or EP 2 774 770 B1.
- At least one wear protection layer is applied to the printed material plate (with or without a protective layer).
- This wear protection layer can consist of one or more layers, e.g. three, four, five or six layers.
- a wear protection layer is applied using the following steps:
- the first resin layer having a solids content between 60 and 80% by weight, preferably 65 and 70% by weight, particularly preferably between 65 and 67% by weight;
- the first resin layer provided with the abrasion-resistant particles on the top of the material plate may not be dried after application,
- the second resin layer having a solids content between 60 and 80% by weight, preferably 65 and 70% by weight, particularly preferably between 65 and 67% by weight;
- the third resin layer having a solids content between 60 and 80% by weight, preferably 65 and 70% by weight, particularly preferably between 65 and 67% by weight, and containing glass spheres;
- the fourth resin layer having a solids content between 50 and 70% by weight, preferably 55 and 65% by weight, particularly preferably between 58 and 62% by weight, and containing glass spheres;
- the fifth resin layer having a solids content between 50 and 70% by weight, preferably 55 and 65% by weight, particularly preferably between 58 and 62% by weight, and containing glass spheres;
- the sixth resin layer having a solids content between 50 and 70% by weight, preferably 55 and 65% by weight, particularly preferably between 58 and 62% by weight, and not containing any glass spheres;
- the resin layers used for the wear protection layer are preferably based on aqueous formaldehyde-containing resins, in particular melamine-formaldehyde resin, urea-formaldehyde resin or melamine-urea-formaldehyde resin.
- the resins used preferably each contain additives, such as hardeners, wetting agents (surfactants or mixtures thereof), defoamers, release agents and / or other components.
- the wetting agent is used in the resin layers in an amount of 0.1-1% by weight.
- Release agents and smoothing agents are preferably added to the fifth and sixth resin layer in amounts between 0.5-1.5% by weight.
- a latent hardener is preferably used as the hardener, such as alkanolamine salts of acids, for example an alkanolamine salt of a sulfonic acid (see DeuroCure from the manufacturer Deurowood).
- the latent hardener is preferably added to the resin immediately before the application unit, in order to avoid premature hardening of the resin and thus losses. Accordingly, there is preferably no central admixing of the hardener, but rather an admixing of the variable amount of hardener only at the corresponding application units. This has the advantage that if the system fails, the resin can stay longer in the lines without the hardener. Only the application units with resin hardener have to be specifically adjusted to the pot life of the system. In this way, losses due to the need to pump out resin hardener in the event of a standstill / malfunction can be significantly reduced.
- the proportion of hardener in the individual resin layers varies and can be between 0.5 to 1.5% by weight, preferably 0.7 to 1.3% by weight. It is particularly preferred that the proportion of hardener per resin application decreases in the production direction; i.e. the proportion of hardener in the lower resin layers is greater than in the upper resin layers. By reducing the amount of hardener from the lower to the upper resin layers, the individual resin layers can be hardened evenly in the KT press.
- the first resin layer is applied in an amount between 10-100 g / m 2 , preferably 40-80 g / m 2 , particularly preferably 45-60 g / m 2 .
- the first resin layer is applied, for example, with a grooved application roller in a first application unit.
- the first resin layer can contain cellulose fibers or wood fibers, preferably cellulose fibers. By adding cellulose fibers, the viscosity of the resin to be applied can be adjusted and the application of the first cover layer to the wood-based panel can be increased.
- the amount of cellulose fibers that is applied with the first resin layer can be between 0.1 and 1% by weight, preferably between 0.5 and 0.8% by weight (based on the amount of resin to be applied) or between 0.1-0, 5 g / m 2 , preferably 0.2-0.4 g / m 2 , particularly preferably 0.25 g / m 2 .
- the cellulose fibers used with preference are white in color and are in the form of a fine or granular, slightly hygroscopic powder.
- the abrasion-resistant particles used are corundum particles (aluminum oxides), boron carbides, silicon dioxides, silicon carbides. Corundum particles are particularly preferred. This is preferably a high-grade corundum (white) with a high level of transparency, so that the visual effect of the underlying decoration is adversely affected as little as possible. Corundum has an uneven spatial shape.
- the amount of abrasion-resistant particles scattered on is 10 to 50 g / m 2 , preferably 10 to 30 g / m 2 , particularly preferably 15 to 25 g / m 2 . The amount of abrasion-resistant particles scattered on depends on the abrasion class to be achieved and the grain size.
- the amount of abrasion-resistant particles in the case of abrasion class AC3 is in the range between 10 to 15 g / m 2 , in abrasion class AC4 between 15 to 20 g / m 2 and in abrasion class AC5 between 20 to 25 g / m 2 when used the grit F200.
- the finished panels preferably have abrasion class AC4.
- Abrasion-resistant particles with grain sizes in classes F180 to F240, preferably F200, are used.
- the grain size of class F180 covers a range from 53 - 90 gm, F220 from 45-75 gm, F230 34-82 gm, F240 28-70 gm (FEPA standard).
- white aluminum oxide F180 to F240 preferably in a main grain range of 53-90 ⁇ m, are used as abrasion-resistant particles.
- corundum particles of class F200 are used, F200 being a mixture between F180 and F220 and having a diameter between 53 and 75 ⁇ m.
- the abrasion-resistant particles must not be too fine-grained (risk of dust formation), but also not too coarse-grained. The size of the abrasion-resistant particles is therefore a compromise.
- silanized corundum particles can be used.
- Typical silanizing agents are aminosilanes.
- the second resin layer to be applied to the top of the material plate is applied in an amount between 10-50 g / m 2 , preferably 20-30 g / m 2 , particularly preferably 20-25 g / m 2 . Overall, the amount of the second resin layer is less than the amount of the first resin layer. In a preferred embodiment, the second resin layer to be applied to the top of the material plate does not contain any glass spheres.
- the total amount of first and second resin layer is between 50-100 g / m 2 , preferably 60-80 g / m 2 , particularly preferably 70 g / m 2 . In one variant, the amount of the first resin layer is 50 g / m 2 and the amount of the second resin layer is 25 g / m 2 .
- the abrasion-resistant particles accumulate in the second resin layer due to the entrainment of loose particles by the second applicator. So it can turn out to be the second Resin layer to be applied resin set a content of abrasion-resistant particles of 5 to 15% by weight, preferably 10% by weight.
- the amount of the third resin layer applied to the top of the wood-based panel can be between 10-50 g / m 2 , preferably 20-30 g / m 2 , particularly preferably 25 g / m 2 .
- the third resin layer contains glass spheres that act as spacers.
- the glass spheres that are preferably used have a diameter of 90-150 ⁇ m.
- the glass spheres can be applied together with the third resin layer or separately sprinkled onto the third resin layer.
- the amount of glass spheres is 10 to 50 g / m 2 , preferably 10 to 30 g / m 2 , particularly preferably 15 to 25 g / m 2 .
- the approach preferably consists of approx. 40 kg of liquid resin plus glass beads and auxiliary materials.
- the glass beads can also be present in silanized form. By silanizing the glass beads, the embedding of the glass beads in the resin matrix is improved.
- the amount of the fourth resin layer applied to the top of the wood-based panel can be between 10-40 g / m 2 , preferably 15-30 g / m 2 , particularly preferably 20 g / m 2 .
- the solids content of the fourth resin layer (as well as the fifth and sixth resin layers) is lower compared to the first to third resin layers.
- the varying solids content of the resin layers to be applied enables, on the one hand, a higher total layer thickness due to the increased solids content in the first to third layers, and on the other hand, the reduced solids content in the fourth to sixth resin layers ensures that the drying and pressing time is sufficient for the overall structure.
- the amount of the fifth resin layer applied to the top of the wood-based panel can be between 10-40 g / m 2 , preferably 15-30 g / m 2 .
- the fifth resin layer also contains glass spheres.
- the glass spheres can be applied together with the third resin layer or separately sprinkled onto the third resin layer.
- the glass balls are applied in an amount of 8 to 10 kg per application unit.
- the sixth resin layer to be applied to the fifth resin layer after drying does not contain any glass spheres. The omission of glass spheres in the sixth resin layer ensures that the underlying resin layers, which have already dried, are not destroyed and the surface of the resin structure does not appear torn.
- the total thickness of the resin layers applied to the wood-based panel can be between 60 and 200 ⁇ m, preferably between 90 and 150 ⁇ m, particularly preferably between 100 and 120 ⁇ m.
- the total layer thickness is thus well above the previous methods, with which layer thicknesses of up to 50 ⁇ m are typically achieved.
- a resin layer is applied to the underside of the material plate together with the second, third, fourth, fifth and sixth resin layer to be applied to the upper side of the material plate.
- a resin layer is also applied to the underside of the material plate parallel to the second resin layer on the upper side of the material plate.
- the amount of the resin layer applied to the underside of the material plate can be between 50-100 g / m 2 , preferably 60-80 g / m 2 , particularly preferably 60 g / m 2 .
- the lower resin layer is preferably colored (eg brownish) in order to simulate a counter-pull.
- the second resin layer is preferably applied in parallel or simultaneously to the top and bottom of the material plate in at least one double application device (roller application unit). After the second resin layer has been applied, the structure of the first and second resin layers is dried (air-dried) in a first drying device.
- a third, fourth, fifth and sixth resin layer are applied to the underside parallel to the upper side in double applicators on the carrier plate and each dried after the application.
- the resin layer (s) applied to the underside act as a counterbalance. By applying the resin layers to the top and bottom of the material panels in approximately the same amounts, it is ensured that the tensile forces on the material panel that arise during the pressing process cancel each other out.
- the layer structure and the respective layer thickness of the backing applied to the underside approximately correspond to the layer sequence applied to the upper side, but without the addition of glass spheres.
- the resin layers are dried at dryer temperatures between 150 and 220 ° C., preferably between 180 and 210 ° C., in particular in a convection dryer.
- the temperature is adapted to the respective resin layers and can vary in the individual convection dryers;
- the temperature in the second, third and fourth convection dryers can be 205 ° C and in the fifth and sixth convection dryers can be 198 ° C in each case.
- convection dryers instead of convection dryers, however, other dryers can also be used.
- the layer structure is pressed under the influence of pressure and temperature in a short-cycle press at temperatures between 150 and 250 ° C, preferably between 180 and 230 ° C, particularly preferably at 200 ° C and a pressure between 30 and 60 kg / cm 2 , particularly preferably between 40 and 50 kg / cm 2 .
- the pressing time is between 5 and 15 seconds, preferably between 7 and 10 seconds.
- a pressure of 50-60 kg / cm 2 is applied for 16 seconds.
- the coated material panel in the short-cycle press is aligned with a structured press plate located in the short-cycle press using markings on the wood-based panel so that congruence between the decor on the wood-based panel and the structure of the press panel to be embossed is produced.
- a structured press plate located in the short-cycle press using markings on the wood-based panel so that congruence between the decor on the wood-based panel and the structure of the press panel to be embossed is produced.
- This enables the creation of a decor-synchronous structure.
- the melamine resin layers melt and a laminate is formed by a condensation reaction including the components corundum / glass / fibers.
- the material panel is processed with the following method steps: a) applying at least one first layer of at least one powdery resin to at least one side of a wood-based panel and melting the at least one applied layer made of a powdery resin; a1) optional application of at least one primer layer which can contain colored pigments, in particular white colored pigments; a2) optional application of at least one primer layer; b) applying at least one printed decoration or decorative layer by means of digital printing using the CRYK ink described above; and c) applying at least one further (second) layer of at least one powdered resin to the at least one printed decorative layer and melting the at least one layer of powdered resin scattered onto the decorative layer.
- the powdery resin is applied to the wood-based panel in an amount of 10 to 50 g / m 2 , preferably 15 to 30 g / m 2 , particularly preferably 20 to 25 g / m 2.
- This amount of resin powder applied essentially applies to all resin powder layers to be applied, whereby these can be adapted in each case.
- the scattering density is selected in such a way that covering layers are generated in each case.
- the particle size of the powdery resin is between 20 and 100 ⁇ m, preferably between 40 and 89 ⁇ m.
- the powdery resin to be applied is a formaldehyde resin, preferably a urea resin, a melamine resin or a phenolic resin, particularly preferably a melamine-formaldehyde resin. It is preferable if a melamine resin or a urea resin is used for the first resin layer. Only melamine resin is preferably used in the upper layers.
- “Melting” or “gelling” in the context of the present application means that the resin layer has not yet fully polymerized, but rather the polymerization is stopped at an intermediate stage in which further crosslinking or polymerization is still possible at a later processing time.
- the meaning of "gelling” is thus usually based on the fact that at a later point in time further functional layers are to be applied to the protective layer that has already been applied or the product would only be finished in further processing steps.
- salting, thickening, settling, curing-influencing effects, etc. substances that are poorly compatible with liquid melamine resin can be used. These can be salts to increase the Conductivity, organic or inorganic flame retardants, cellulose derivatives, radical scavengers, pigments, UV absorbers, etc.
- the powdery resin used can contain additives such as pigments, conductive substances and cellulose.
- the layer of the melted resin powder can simultaneously serve as a white primer layer for the decorative layer to be subsequently printed.
- White pigments such as titanium dioxide T1O2 can be used as color pigments.
- Further color pigments can be calcium carbonate, barium sulfate or barium carbonate. The proportion of color pigments can be up to 50% by weight of the total amount of powder.
- the addition of color pigments to the first layer of resin powder increases the covering power so that it can be used as the (sole) base or primer for the subsequent decorative layer.
- the resin powder is applied by means of electrostatic charging.
- the application can also be carried out by means of powder coating using the tribo process.
- the powder to be applied is charged by friction.
- the applied layer of powdery resin can be melted using an IR radiator, or microwave systems or the like.
- IR radiators is particularly preferred.
- the further powder resin layer applied and fused in step c) of the present method preferably comprises powder based on formaldehyde resin, particularly preferably melamine-formaldehyde resin.
- the amount of resin powder applied in this step is between 10 and 50 g / m 2 , preferably between 20 and 40 g / m 2 .
- abrasion-resistant particles are uniformly sprinkled onto the decorative layer or the resin powder layer applied in step c) (step d).
- At least one third layer of at least one powdery resin (step e), in particular on the layer of abrasion-resistant particles, is applied.
- This layer serves as a separating layer to block off the abrasion-resistant particles.
- the powder resin layer applied and fused in this step e) preferably comprises powder based on formaldehyde resin, particularly preferably melamine-formaldehyde resin.
- the amount of resin powder applied in this step is between 10 and 50 g / m 2 , preferably between 20 and 40 g / m 2 .
- glass spheres are sprinkled on, in particular on the at least one third melted resin powder layer (step f).
- the glass spheres act as spacers between abrasion-resistant particles and the subsequent press plate. In this way, the sheet metal wear can be at least partially reduced.
- At least one fourth layer of at least one powdery resin, in particular on the layer of glass spheres, is applied (step g). This layer serves to block off the glass spheres and as a finishing layer.
- the fourth powder resin layer applied and fused in this step g) preferably comprises powder based on formaldehyde resin, particularly preferably melamine-formaldehyde resin.
- the amount of resin powder applied in this step is between 10 and 50 g / m 2 , preferably between 20 and 40 g / m 2 .
- the layer structure is pressed in a short-cycle press (KT press) (step h).
- the pressing step takes place under the influence of pressure and temperature at temperatures between 180 and 250 ° C., preferably between 200 and 230 ° C., particularly preferably at 200 ° C. and a pressure between 30 and 60 kg / cm 2 , particularly preferably between 40 and 50 kg / cm 2 .
- the pressing time is between 8 and 30 seconds, preferably between 10 and 25 seconds.
- Embodiment 1a printing of raw paper
- a base paper (paper weight: 80 g / m 2 ) is unrolled by an unwinding device.
- a decorative layer is applied in the digital printing process using a CRYK ink with the following composition;
- Glycol is preferably used as the solvent.
- the printing inks are applied in an amount between 5 and 10 g / m 2 .
- the printed paper can be provided with a melamine-formaldehyde resin layer as a protective layer.
- This protective layer serves to protect the printed decorations and enables temporary storage.
- the paper is then dried in a convection dryer or by NIR (near infrared) to a moisture content of approx. 6% by weight, so that the resin layer is in the B-state.
- NIR near infrared
- Embodiment 1b Printing of base paper with an ink-receiving layer
- a base paper (paper weight: 80 g / m 2 ) is unrolled by an unwinding device. Then a pigmented (T1O2) ink-receiving layer (synthetic silicate with polyvinyl alcohol as a binder) (layer thickness 40 ⁇ m; after drying at 125 ° C dry basis weight 4 g / m 2 ) and a primer layer are applied and the layer structure is dried.
- T1O2 pigmented ink-receiving layer
- a decorative layer is applied to the paper obtained in this way (paper weight: 80 g / m 2 ) in a digital printing process using a CRYK ink with the above composition.
- the printing inks are applied in an amount between 5 and 10 g / m 2 .
- the printed paper can be provided with a melamine-formaldehyde resin layer as a protective layer. This protective layer serves to protect the printed decorations and enables temporary storage.
- the paper is then dried in a convection dryer or by NIR (near infrared) to a moisture content of approx. 6% by weight, so that the resin layer is in the B-state.
- NIR near infrared
- Embodiment 2a Printing a first impregnate with an ink-receiving layer
- the paper to be printed is impregnated on the front and back with a liquid melamine resin in an impregnation device. About 50 g melamine resin / m 2 with a solids content of about 50% are applied.
- a pigmented (T1O2) ink-receiving layer synthetic silicate with polyvinyl alcohol as a binder
- layer thickness 40 ⁇ m after drying at 125 ° C dry basis weight 4 g / m 2
- primer layer after drying at 125 ° C dry basis weight 4 g / m 2
- layer thickness 40 ⁇ m after drying at 125 ° C dry basis weight 4 g / m 2
- primer layer is applied and the layer structure is dried.
- a decorative layer is applied to the impregnate obtained in this way (paper weight: 80 g / m 2 ) in a digital printing process using a CRYK ink with the above composition.
- the printing inks are applied in an amount between 5 and 10 g / m 2 .
- the printed paper can be provided with a melamine-formaldehyde resin layer as a protective layer.
- the paper is then dried in a convection dryer or by NIR (near infrared) to a moisture content of approx. 6% by weight, so that the resin layer is in the B-state.
- NIR near infrared
- Embodiment 2b Printing a second impregnate with an ink-receiving layer
- the paper to be printed is coated in an application device with melamine resin powder in an amount of 25 g / m 2 with the aid of tribo guns.
- the melamine resin powder contained the usual auxiliaries such as hardeners, release agents, etc.
- the powder is then melted using infrared radiation.
- a pigmented (T1O2) ink-receiving layer synthetic silicate with polyvinyl alcohol as a binder
- layer thickness 40 ⁇ m after drying at 125 ° C dry basis weight 4 g / m 2
- a primer layer are applied and the layer structure is dried.
- a decorative layer is applied to the impregnate obtained in this way (paper weight: 80 g / m 2 ) in a digital printing process using a CRYK ink with the above composition.
- the printing inks are applied in an amount between 5 and 10 g / m 2 .
- the printed paper can be provided with a melamine-formaldehyde resin layer as a protective layer.
- the paper is then dried in a convection dryer or by NIR (near infrared) to a moisture content of approx. 6% by weight, so that the resin layer is in the B-state.
- NIR near infrared
- Embodiment 2c printing a third impregnate
- the paper to be printed is impregnated on the front and back with a melamine resin in an impregnation device. About 50 g melamine resin / m 2 with a solids content of about 50% are applied.
- the resin on the side of the impregnate to be printed is drawn off with a special device (e.g. a knife squeegee) so that fibers remain free to absorb the printer ink.
- a special device e.g. a knife squeegee
- a decorative layer is applied to the impregnate obtained in this way (paper weight: 80 g / m 2 ) in a digital printing process using a CRYK ink with the above composition.
- the printing inks are applied in an amount between 5 and 10 g / m 2 .
- the printed impregnate does not need to be dried any further, as the digital printing ink only brings in little moisture.
- Embodiment 3 Printing a plate with a liquid overlay
- An HDF board (fibreboard with increased bulk density) is first pre-coated with an aqueous synthetic resin (melamine-formaldehyde resin). The amount applied is 20-50 g Flarz liquid / m 2 (solids content: approx. 55%). The Flarz contains the usual auxiliaries such as wetting agents, hardeners, release agents and defoamers. The applied flarz is then dried in a convection dryer or a near-infrared oven to a moisture content of approx. 20%. Then several layers of a water-based, pigmented primer are applied (5 - 8 times). After each application, the primer is dried with the help of a convection dryer or a near-infrared dryer.
- the primed plate is printed with a motif using a digital printer. Approx. 6 - 8 g / m 2 of the water-based CRYK digital printing ink are used.
- melamine resin fluid solids content: 55% by weight
- auxiliaries hardeners, wetting agents, etc.
- a melamine resin is also applied to the underside of the plate with the first roller application unit (application quantity: 60 g Flarz fl. / M 2 , solids content: approx. 55% by weight).
- a melamine resin which also contains glass beads, is then applied to the surface of the board. These have a diameter of 60 - 80 pm.
- the amount of resin applied is approx. 20 g of melamine resin fluid / m 2 (solids content: 61.5% by weight).
- the recipe also contains a release agent.
- the amount of glass spheres applied is approx. 3 g / m 2 .
- a melamine resin is also applied to the underside of the plate using a roller application unit (application quantity: 40 g resin liquid area / m 2 , solids content: approx. 55% by weight). The plate is again dried in a circulating air dryer and then coated again with a melamine resin containing glass beads.
- Vivapur 302 Cellulose (Vivapur 302) is included as a further component.
- melamine resin fl. / m 2 solids content: 61.6% by weight
- the recipes also contain a release agent.
- a melamine resin is also applied to the underside of the plate using a roller application unit (application quantity: 30 g resin fluid / m 2 , solids content: approx. 55% by weight).
- the resin is again dried in a circulating air dryer and then the plate is pressed in a short-cycle press at 200 ° C. and a pressure of 400 N / cm 2.
- the pressing time was 10 seconds.
- a pressed sheet with a wooden structure was used as a structure generator.
- Embodiment 4 Printing a plate with a powder overlay
- melamine resin powder In an application device, they are then coated with melamine resin powder in an amount of 25 g / m 2 with the aid of tribo guns.
- the melamine resin powder contained the usual auxiliaries such as hardeners, release agents, etc. The powder is then melted using infrared radiation.
- the primed board is coated in multiple applications with a colored primer with subsequent intermediate drying (circulating air).
- the color primer is a mixture of casein and pigment (titanium dioxide).
- the application quantity per application is approx. 5 g b / m 2 .
- the job is repeated at least five times.
- a primer is then applied (application quantity: 10-20 g fl./m 2 ) with circulating air drying.
- the plate is then printed on with a digital printer using the aqueous CRYK ink.
- the application quantities of paint are 3 to 15 g fl. / M 2 .
- the paint is dried over IR radiation or circulating air.
- Corundum is sprinkled onto the print using a scattering device (application rate: 20 g corundum / m 2 , F 180).
- melamine resin powder is again applied with a tribo gun (application quantity: 80 g / m 2 ).
- This melamine resin powder is gelled again with the help of an IR radiator.
- the melamine resin powder contained the usual auxiliaries such as hardeners, release agents, etc.
- the plate is then pressed together with a counter-tension impregnate in a KT press.
- the pressed plate was then inspected visually, and no abnormalities were found.
- the surface tests subsequently carried out in accordance with DIN EN 15468 - August 2018 also showed no abnormalities. All requirements of exposure class 32 were met.
Landscapes
- 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)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Paper (AREA)
Abstract
La présente invention concerne un procédé de production d'au moins un matériau de substrat pourvu d'un motif imprimé, le motif imprimé étant appliqué sur ledit matériau de substrat par impression numérique, l'encre CMYK soluble dans l'eau utilisée pour l'impression numérique ayant la composition suivante : composant de couleur C : au moins un pigment cyan ; composant de couleur K : au moins un pigment noir de carbone ; composant de couleur Y : au moins un pigment jaune, ou un mélange d'au moins deux pigments jaunes différents ou un mélange d'au moins un pigment jaune et d'au moins un pigment magenta ; composant de couleur M : au moins un pigment magenta, ou un mélange d'au moins deux pigments magenta différents ou un mélange d'au moins un pigment magenta et d'au moins un pigment jaune.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20156613.0A EP3865309B1 (fr) | 2020-02-11 | 2020-02-11 | Procédé de fabrication d'au moins un matériau porteur pourvu d'un décor imprimé |
PCT/EP2021/052396 WO2021160469A1 (fr) | 2020-02-11 | 2021-02-02 | Procédé de production d'au moins un matériau de substrat pourvu d'un motif imprimé |
Publications (1)
Publication Number | Publication Date |
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EP4103407A1 true EP4103407A1 (fr) | 2022-12-21 |
Family
ID=69571813
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20156613.0A Active EP3865309B1 (fr) | 2020-02-11 | 2020-02-11 | Procédé de fabrication d'au moins un matériau porteur pourvu d'un décor imprimé |
EP21706848.5A Pending EP4103407A1 (fr) | 2020-02-11 | 2021-02-02 | Procédé de production d'au moins un matériau de substrat pourvu d'un motif imprimé |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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EP20156613.0A Active EP3865309B1 (fr) | 2020-02-11 | 2020-02-11 | Procédé de fabrication d'au moins un matériau porteur pourvu d'un décor imprimé |
Country Status (7)
Country | Link |
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US (1) | US20230124632A1 (fr) |
EP (2) | EP3865309B1 (fr) |
CN (1) | CN115066337A (fr) |
ES (1) | ES2925714T3 (fr) |
PL (1) | PL3865309T3 (fr) |
PT (1) | PT3865309T (fr) |
WO (1) | WO2021160469A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4417750A1 (fr) * | 2023-02-17 | 2024-08-21 | Flooring Technologies Ltd. | Procédé de préparation d'un matériau composite exempt de résine mélamine-formaldéhyde |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000186244A (ja) * | 1998-12-22 | 2000-07-04 | Dainippon Ink & Chem Inc | インク組成物およびカラー画像形成方法 |
ES2390944T3 (es) | 2009-03-31 | 2012-11-19 | Flooring Technologies Ltd. | Procedimiento para fabricar paneles y panel fabricado según el procedimiento |
EP2623567B1 (fr) * | 2012-02-03 | 2014-11-05 | Agfa Graphics N.V. | Impression par jet d'encre de couleurs de bois |
EP2774770B1 (fr) | 2013-03-08 | 2015-04-29 | Flooring Technologies Ltd. | Procédé d'impression d'une plaque en matériau dérivé du bois et plaque en matériau dérivé du bois dotée d'une couche décorative imprimée |
EP3293013B1 (fr) * | 2013-10-22 | 2024-05-15 | Agfa Nv | Fabrication de surfaces décoratives par impression à jet d'encre |
PT2980313T (pt) | 2014-07-29 | 2016-12-20 | Flooring Technologies Ltd | Método para a produção de um elemento impregnado, elemento impregnado e método para a produção de um laminado a partir do elemento impregnado |
EP4101651B1 (fr) * | 2014-10-31 | 2023-12-06 | Agfa Nv | Procédés de fabrication de stratifiés décoratifs par jet d'encre |
ES2879957T3 (es) * | 2017-08-22 | 2021-11-23 | Agfa Nv | Conjuntos de tintas de inyección acuosas y procedimientos de impresión por inyección de tinta |
EP3521048B1 (fr) * | 2018-01-31 | 2024-08-07 | Agfa Nv | Procédés d'impression par jet d'encre pour panneaux stratifiés décoratifs |
-
2020
- 2020-02-11 PL PL20156613.0T patent/PL3865309T3/pl unknown
- 2020-02-11 PT PT201566130T patent/PT3865309T/pt unknown
- 2020-02-11 EP EP20156613.0A patent/EP3865309B1/fr active Active
- 2020-02-11 ES ES20156613T patent/ES2925714T3/es active Active
-
2021
- 2021-02-02 WO PCT/EP2021/052396 patent/WO2021160469A1/fr unknown
- 2021-02-02 US US17/798,575 patent/US20230124632A1/en active Pending
- 2021-02-02 CN CN202180013582.5A patent/CN115066337A/zh active Pending
- 2021-02-02 EP EP21706848.5A patent/EP4103407A1/fr active Pending
Also Published As
Publication number | Publication date |
---|---|
US20230124632A1 (en) | 2023-04-20 |
PT3865309T (pt) | 2022-09-27 |
PL3865309T3 (pl) | 2022-11-14 |
WO2021160469A1 (fr) | 2021-08-19 |
ES2925714T3 (es) | 2022-10-19 |
EP3865309B1 (fr) | 2022-07-13 |
CN115066337A (zh) | 2022-09-16 |
EP3865309A1 (fr) | 2021-08-18 |
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