CN101755019A - 涂料组合物 - Google Patents
涂料组合物 Download PDFInfo
- Publication number
- CN101755019A CN101755019A CN200880024910A CN200880024910A CN101755019A CN 101755019 A CN101755019 A CN 101755019A CN 200880024910 A CN200880024910 A CN 200880024910A CN 200880024910 A CN200880024910 A CN 200880024910A CN 101755019 A CN101755019 A CN 101755019A
- Authority
- CN
- China
- Prior art keywords
- acid
- salt
- amine
- imines
- phosphorous
- 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
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- 239000008199 coating composition Substances 0.000 title claims abstract description 77
- 239000000203 mixture Substances 0.000 claims abstract description 117
- 239000002253 acid Substances 0.000 claims abstract description 72
- 150000003839 salts Chemical class 0.000 claims abstract description 56
- 150000001412 amines Chemical class 0.000 claims abstract description 50
- 150000002466 imines Chemical class 0.000 claims abstract description 40
- 239000000049 pigment Substances 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 99
- 239000000178 monomer Substances 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- -1 agroform Substances 0.000 claims description 50
- 229920000642 polymer Polymers 0.000 claims description 42
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 38
- 238000002360 preparation method Methods 0.000 claims description 36
- 238000004939 coking Methods 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 30
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 29
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 29
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 29
- 229930006000 Sucrose Natural products 0.000 claims description 28
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 28
- 239000005720 sucrose Substances 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- 229920000058 polyacrylate Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 229920001155 polypropylene Polymers 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000010425 asbestos Substances 0.000 claims description 8
- 239000003365 glass fiber Substances 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 8
- 229910052895 riebeckite Inorganic materials 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 7
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 7
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 229920005601 base polymer Polymers 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 6
- 108010010803 Gelatin Proteins 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000005538 encapsulation Methods 0.000 claims description 5
- 229920000159 gelatin Polymers 0.000 claims description 5
- 239000008273 gelatin Substances 0.000 claims description 5
- 235000019322 gelatine Nutrition 0.000 claims description 5
- 235000011852 gelatine desserts Nutrition 0.000 claims description 5
- 238000002372 labelling Methods 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 239000004376 Sucralose Substances 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000005026 oriented polypropylene Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- BAQAVOSOZGMPRM-QBMZZYIRSA-N sucralose Chemical compound O[C@@H]1[C@@H](O)[C@@H](Cl)[C@@H](CO)O[C@@H]1O[C@@]1(CCl)[C@@H](O)[C@H](O)[C@@H](CCl)O1 BAQAVOSOZGMPRM-QBMZZYIRSA-N 0.000 claims description 4
- 235000019408 sucralose Nutrition 0.000 claims description 4
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000002552 dosage form Substances 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 235000013305 food Nutrition 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229940047670 sodium acrylate Drugs 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims 1
- 239000004615 ingredient Substances 0.000 abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 41
- 239000000243 solution Substances 0.000 description 28
- 229960004793 sucrose Drugs 0.000 description 28
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 19
- 238000003384 imaging method Methods 0.000 description 19
- 239000007787 solid Substances 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- 239000000123 paper Substances 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000000976 ink Substances 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 11
- 239000011833 salt mixture Substances 0.000 description 11
- 229920002554 vinyl polymer Polymers 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000002174 Styrene-butadiene Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 7
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 239000011115 styrene butadiene Substances 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000600 sorbitol Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical group CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 5
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- 239000004593 Epoxy Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
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- GDCRSXZBSIRSFR-UHFFFAOYSA-N ethyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCOC(=O)C=C GDCRSXZBSIRSFR-UHFFFAOYSA-N 0.000 description 5
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- 125000006564 (C4-C8) cycloalkyl group Chemical group 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
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- 239000005864 Sulphur Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
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- 125000000081 (C5-C8) cycloalkenyl group Chemical group 0.000 description 3
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 3
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
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- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- PNLVGFSEHLOUTK-UHFFFAOYSA-N 2-(bromomethyl)pentanedinitrile Chemical compound BrCC(C#N)CCC#N PNLVGFSEHLOUTK-UHFFFAOYSA-N 0.000 description 2
- CGYGETOMCSJHJU-UHFFFAOYSA-N 2-chloronaphthalene Chemical compound C1=CC=CC2=CC(Cl)=CC=C21 CGYGETOMCSJHJU-UHFFFAOYSA-N 0.000 description 2
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
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- 239000011135 tin Substances 0.000 description 1
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- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
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- 229940082509 xanthan gum Drugs 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明描述的是用于标记基材的涂料组合物，其包含a)溶剂，b)含磷或含硼的酸与胺或亚胺的盐，c)不含磷和不含硼的酸与胺或亚胺的盐，d)基料，以及e)任选的附加组分，本发明还描述了它们的制造方法和用途，其中上述盐还可以以包封形式存在作为一种伪颜料。被上述组合物涂覆的基材可以通过激光辐射进行标记。
Description
本发明涉及一种用于标记基材的涂料组合物，尤其涉及以包封形式包含伪颜料(pseudo-pigment)的所述涂料组合物，涉及制备所述组合物或伪颜料的方法，涉及涂覆有这些组合物的未标记或标记基材，以及涉及它们的制备和标记方法。
包装通常需要标记上信息，例如标志、条形码、有效期限或批号。实现该标记的一种方式是以组合物涂覆包装，所述组合物在用能量如热进行处理后形成可见痕迹。假如所用涂料组合物允许高精度和高反差标记，那么当使用激光辐射作为能量时，该痕迹可以甚至小到人眼不可见或几乎不可见。
WO 2007/031454A2中描述了包含潜活化剂的涂料组合物，所述潜活化剂是酸与胺的盐，或者是酸衍生物。所提及的酸与胺的盐例如为硫酸铵或磷酸二氢铵。
在WO 2007/031454A2中公开的涂料组合物不能用于标记所有种类的基材，例如某些聚合物基材，如聚丙烯薄膜，因为某些基材例如所述膜在获得令人满意的痕迹之前被激光辐射破坏或甚至毁坏。
因此，亟需可以用于涂覆和激光标记基材的新涂料组合物，所述基材不能通过迄今为止已知的方法以高精度、高反差方式被涂覆和激光标记。
目前已经令人惊讶地发现：不止包含一种如WO 2007/031454A2中所公开的那些酸与胺的盐，而是包含至少两种这样的盐的混合物的新涂料组合物可以用于使用CO2IR激光成功地标记某些被如此涂覆的基材，该基材例如聚丙烯薄膜不能使用WO 2007/031454A2中公开的涂料组合物清楚地标记。使用盐混合物获得该有益效果，而盐的总量不增加。例如，6g磷酸二氢铵和6g硫酸铵的混合物优于单独的12g硫酸铵或单独的12g磷酸二氢铵。相对于单独的12g硫酸铵或单独的12g磷酸二氢铵，使用6g磷酸二氢铵和6g硫酸铵的混合物的其它优势在于：当使用混合物时痕迹的颜色为黑色或比单独使用硫酸铵或单独使用磷酸二氢铵时更深。
本发明涉及一种用于标记基材的涂料组合物，其包含
a)溶剂，
b)含磷或含硼的酸与胺或亚胺的盐，
c)不含磷和不含硼的酸与胺或亚胺的盐，以及
d)基料，
但不包含石棉和玻璃纤维。
本发明的涂料组合物并非主要预期用于耐火和阻燃，因此不包含典型耐火性物质，如苏联专利申请SU1712380A1中公开的石棉和玻璃纤维，即所述涂料组合物就所用基料而言不同于典型耐火和阻燃组合物。
虽然耐火和阻燃组合物中的基料优选水不溶性和不燃性，例如卤代物，如特别是氯代烃，如例如美国专利2,357,725中提及的卤代萘(例如Halowax[商品名])、多氯联苯(例如Arochlor[商品名])、氯化橡胶或neoprene(氯丁二烯橡胶，商品名)，但是本发明涂料组合物中的基料可以为可燃物。有时甚至可以期望基料的可燃性如下文对于术语“成焦剂”所解释的那样。
上述溶剂可以是水、有机溶剂(优选不同于多元醇，如特别是具有至少5个碳原子的多元醇，例如季戊四醇或山梨糖醇的有机溶剂)、液态单体、或其混合物。优选地，溶剂是水、有机溶剂或其混合物，该有机溶剂不同于多元醇，如特别是具有至少5个碳原子的多元醇，例如季戊四醇或山梨糖醇。
有机溶剂的实例是C1-4链烷醇、C2-4多元醇、C3-6酮、C4-6醚、C2-3腈、硝基甲烷、二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和环丁砜，其中C1-4链烷醇和C2-4多元醇可以被C1-4烷氧基取代。C1-4链烷醇的实例是甲醇、乙醇、丙醇、异丙醇或丁醇、异丁醇、仲丁醇和叔丁醇。其C1-4烷氧基衍生物的实例是2-乙氧基乙醇和1-甲氧基-2-丙醇。C2-4多元醇的实例是乙二醇和甘油。C3-6酮的实例是丙酮和甲基乙基酮。C4-6醚的实例是二甲氧基乙烷、二异丙基乙基和四氢呋喃。C2-3腈的实例是乙腈。
有机溶剂的优选实例是C1-4链烷醇、C3-6酮、C4-6醚、C2-3腈、硝基甲烷、二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和环丁砜，其中C1-4链烷醇可以被C1-4烷氧基取代。
更优选地，溶剂是水或水与有机溶剂的混合物，所述有机溶剂优选不同于多元醇，如特别是具有至少5个碳原子的多元醇，例如季戊四醇或山梨糖醇。
优选地，有机溶剂选自C1-4链烷醇、C2-4多元醇、C3-6酮、二甲基甲酰胺和二甲基乙酰胺，其中C1-4链烷醇和C2-4多元醇可以被C1-4烷氧基取代。
更优选地，有机溶剂选自C1-4-链烷醇、C3-6-酮、二甲基甲酰胺和二甲基乙酰胺，其中C1-4-链烷醇可以被C1-4烷氧基取代。
优选地，水与有机溶剂的混合物的水/有机溶剂的比为至少1/2，更优选至少1/1。
最优选地，溶剂是水。
含磷的成盐酸包括无机酸，如磷酸、硫代磷酸、氟磷酸、六氟磷酸、多磷酸和亚磷酸，以及基于磷的有机酸，例如苯基膦酸、甲烷膦酸、苯基次膦酸、2-氨乙基磷酸二氢盐、肌醇六磷酸、2-二氧磷基-L-抗坏血酸、甘油基磷酸二氢盐、二亚乙基三胺五(亚甲基膦酸)(DTPMP)、六亚甲基二胺四(亚甲基膦酸)(HDTMP)、次氮基三(亚甲基膦酸)和1-羟基亚乙基二膦酸。
在另一最优选的实施方案中，所述酸选自磷酸、多磷酸和有机磷酸及其混合物。
含硼的成盐酸优选硼酸(式H3BO3的原硼酸)，但还包括例如式HBO2的偏硼酸和式Hn-2BnO2n-1的多硼酸)。
不含磷和不含硼的成盐酸不包含磷原子也不包含硼原子，并可以为无机的或有机的。这样的无机酸的实例为硫酸、氟磺酸、氯磺酸、亚硝基硫酸、硫代硫酸、氨基磺酸、亚硫酸、甲脒亚磺酸、硝酸、盐酸、氯酸、高氯酸、氢溴酸、氢碘酸和氢氟酸。
这样的有机酸的实例是基于硫的有机酸，例如4-苯乙烯磺酸、对甲苯磺酸、苯磺酸、二甲苯磺酸、苯酚磺酸、甲烷磺酸、三氟甲烷磺酸、基于硫的有机多元酸如聚(4-苯乙烯磺酸)和包含4-苯乙烯磺酸单元的共聚物如聚(4-苯乙烯磺酸-共-马来酸)，以及羧酸，例如酒石酸、柠檬酸、二氯乙酸、三氯乙酸、草酸和马来酸。
优选地，不含磷和不含硼的酸选自硫酸、硫代硫酸、亚硫酸、盐酸、基于硫的有机酸、羧酸及其混合物。在一个最优选的实施方案中，所述酸选自硫酸、盐酸、基于硫的有机多元酸及其混合物。
成盐胺包括式NR1R2R3的胺，其中R1、R2和R3可以相同或不同，并为氢、C1-30烷基、C2-30链烯基、C4-8环烷基、C5-8环烯基、芳烷基、芳烯基或芳基，或者R1是氢、C1-30烷基、C2-30链烯基、C4-8环烷基、C5-8环烯基、芳烷基、芳烯基或芳基，并且R2和R3与式NR1R2R3的胺的氮一起形成5-至7-元环，由此C1-30烷基、C2-30链烯基、C4-8环烷基、C5-8环烯基、芳烷基和芳烯基可以不被取代或被NR4R5R6、亚氨基、氰基、氰氨基、羟基和/或C1-6烷氧基取代，以及芳基可以不被取代或被NR4R5R6、氰基、氰氨基、羟基、C1-6烷基和/或C1-4烷氧基取代，其中R4、R5和R6可以相同或不同，并为氢、C1-6烷基、C4-8环烷基或芳基。
C1-30烷基的实例是甲基、乙基、丙基、异丙基、丁基、仲丁基、异丁基、叔丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、肉豆蔻基、棕榈基、硬脂基和花生碱基(arachinyl)。C2-30链烯基的实例是乙烯基、烯丙基、亚麻基、二十二碳六烯基(docosahexaenoyl)、二十碳五烯基(eicosapentaenoyl)、亚油基、花生四烯基(arachidonyl)和油基。C4-8环烷基的实例是环戊基和环己基。C5-8环烯基的实例是环己烯基。芳烷基的实例是苄基和2-苯基乙基。芳基的实例是苯基、1，3，5-三嗪基或萘基。C1-6烷基的实例是甲基、乙基、丙基、异丙基、丁基、仲丁基、异丁基、叔丁基、戊基和己基。C1-4烷氧基的实例是甲氧基、乙氧基、丙氧基、异丙氧基和丁氧基。
优选的C1-30烷基是C1-10烷基，更优选的C1-30烷基是C1-6烷基。优选的C2-30链烯基是C2-10链烯基，更优选C2-6链烯基。C1-6烷基的实例如上文所给出的。C1-10烷基的实例是甲基、乙基、丙基、异丙基、丁基、仲丁基、异丁基、叔丁基、戊基、己基、庚基、辛基、壬基和癸基。C2-10链烯基和C2-6链烯基的实例是乙烯基和烯丙基。
式NR1R2R3的胺的实例是氨、三(羟基甲基)氨基甲烷、胍、甲胺、乙胺、丙胺、丁胺、二乙胺、乙二胺、1，2-二氨基丙烷、乙醇胺、三乙醇胺、环己胺、苯胺、三聚氰胺、羟甲基三聚氰胺、吡咯、吗啉、吡咯烷和哌啶。
优选地，胺为式NR1R2R3，其中R1是氢并且R2和R3如上文所定义。
更优选地，胺为式NR1R2R3，其中R1和R2是氢并且R3如上文所定义。
最优选地，胺为式NR1R2R3，其中R1、R2和R3是氢，即氨。
成盐亚胺包括式(R1R2)C＝NR3的亚胺，其中R1、R2和R3可以相同或不同，并且为氢或适当的有机基团。优选地，R3是氢。优选的亚胺是聚乙烯亚胺，其可以在市场上购买，商品名为“Lupasol P”。
本发明的涂料组合物中使用的盐混合物包含至少两种彼此不同的盐，其可由相同或不同的碱形成，例如两种盐均可以由氨形成，但需要由不同酸形成，例如磷酸和硫酸。优选地，混合物中的两种盐之一衍生自磷酸或另一含磷的酸。因此，优选的盐混合物例如包含磷酸二氢铵和硫酸铵；磷酸二氢铵和氯化铵；磷酸二氢铵和N-(2-羟基-乙基)-柠檬酸铵或N-(2-羟基-乙基)-酒石酸铵；硼酸的Lupasol P盐和硫酸铵；磷酸二氢铵和对甲苯磺酸的Lupasol P盐；以及硼酸铵(例如硼酸三铵、硼酸二铵、硼酸一铵或五硼酸铵)和硫酸铵。
盐彼此的重量比为1∶20-20∶1，优选1∶10-10∶1，更优选1∶5-5∶1，甚至更优选1∶2-2∶1，以及最优选约1∶1。
涂料组合物中的盐混合物含量基于组合物总重量为约1重量％-60重量％，优选2重量％-40重量％，更优选5重量％-30重量％，以及最优选10重量％-20重量％，例如15重量％。
本发明的组合物还包含基料，优选聚合物基料，特别是可燃性聚合物基料。基料是将本发明涂料组合物中的盐混合物与基材粘合或粘贴或者有助于本发明涂料组合物中的盐混合物与基材粘合或粘贴的任何物质，但优选不同于卤代物，如特别是氯代烃，如卤代萘(例如Halowax[商品名])、多氯联苯(例如Arochlor[商品名])、氯化橡胶或neoprene(氯丁二烯橡胶，商品名)。
根据基材和成焦剂的性质，在某些情况下成焦剂还可以同时用作基料。例如，当纸或包装用纸板作为基材时蔗糖可以用作成焦剂和用作基料。
聚合物基料的实例是丙烯酸类聚合物、苯乙烯聚合物及其氢化产物、乙烯基聚合物及其衍生物、聚烯烃及其氢化或环氧化产物、醛聚合物、环氧聚合物、聚酰胺、聚酯、聚氨基甲酸酯、基于砜的聚合物以及天然聚合物及其衍生物。聚合物基料还可以是聚合物基料的混合物。它还可以是液态单体与适当光引发剂的混合物，所述混合物在涂覆后在UV辐射下形成上文列出的聚合物基料之一。在该情况下，单体用作溶剂。
丙烯酸类聚合物是由至少一种丙烯酸类单体或由至少一种丙烯酸类单体和至少一种其它烯属不饱和聚合物形成的聚合物，所述其它烯属不饱和聚合物例如苯乙烯类单体、乙烯基单体、烯烃单体或马来酸类单体。
丙烯酸类单体的实例是(甲基)丙烯酸或其盐，(甲基)丙烯酰胺，(甲基)丙烯腈，(甲基)丙烯酸C1-6烷基酯例如(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯或(甲基)丙烯酸己酯，(甲基)丙烯酸2-乙基己酯，取代的(甲基)丙烯酸C1-6烷基酯例如甲基丙烯酸缩水甘油酯和甲基丙烯酸乙酰乙酰氧基乙酯，(甲基)丙烯酸二(C1-4烷基氨基)C1-6烷基酯例如丙烯酸二甲氨基乙酯或丙烯酸二乙氨基乙酯，由C1-6烷基胺、取代的C1-6烷基胺例如2-氨基-2-甲基-1-丙烷磺酸、铵盐，或者二(C1-4烷基氨基)C1-6烷基胺与(甲基)丙烯酸形成的酰胺，及其C1-4烷基卤化物加合物。
苯乙烯类单体的实例是苯乙烯、4-甲基苯乙烯和4-乙烯基联苯。乙烯基单体的实例是乙烯醇、氯乙烯、偏二氯乙烯、乙烯基异丁基醚和乙酸乙烯酯。烯烃单体的实例是乙烯、丙烯、丁二烯和异戊二烯及其氯化或氟化衍生物例如四氟乙烯。马来酸类单体的实例是马来酸、马来酸酐和马来酰亚胺。
丙烯酸类聚合物的实例是聚(甲基丙烯酸甲酯)和聚(甲基丙烯酸丁酯)，以及羧化的丙烯酸类共聚物，例如由Ciba以商品名
LE15、LS20和LS24销售的产品，苯乙烯丙烯酸类共聚物，例如由Ciba以商品名LS26和
C44销售的产品，以及聚丙烯酸聚合物，例如由Ciba以商品名
E11销售的产品。
苯乙烯聚合物是由至少一种苯乙烯类单体和至少一种乙烯基单体、烯烃单体和/或马来酸类单体形成的聚合物。苯乙烯聚合物的实例是苯乙烯丁二烯苯乙烯嵌段聚合物、苯乙烯乙烯丁二烯嵌段聚合物、苯乙烯乙烯丙烯苯乙烯嵌段聚合物和苯乙烯-马来酸酐共聚物。
乙烯基聚合物是由至少一种乙烯基单体形成的聚合物或者由至少一种乙烯基单体和至少一种烯烃单体或马来酸类单体形成的聚合物。乙烯基聚合物的实例是聚氯乙烯、聚乙烯醇、聚乙酸乙烯酯、部分水解的聚乙酸乙烯酯和甲基乙烯基醚-马来酸酐共聚物。它们的衍生物的实例是羧基改性的聚乙烯醇、乙酰乙酰基改性的聚乙烯醇、双丙酮改性的聚乙烯醇和硅改性的聚乙烯醇。
聚烯烃是由至少一种烯烃单体形成的聚合物或者由至少一种烯烃单体或马来酸类单体形成的聚合物。聚烯烃的实例是聚乙烯、聚丙烯、聚丁二烯和异丙烯-马来酸酐共聚物。
醛聚合物是由至少一种醛单体或聚合物和至少一种醇单体或聚合物、胺单体或聚合物和/或脲单体或聚合物形成的聚合物。醛单体的实例甲醛、糠醛和缩丁醛。醇单体的实例是苯酚、甲酚、间苯二酚和二甲苯酚。多元醇的一个实例是聚乙烯醇。胺单体的实例是苯胺和三聚氰胺。脲单体的实例是脲、硫脲和双氰胺。醛聚合物的实例是由缩丁醛和聚乙烯醇形成的聚乙烯醇缩丁醛。
环氧聚合物是由至少一种环氧单体和至少一种醇单体和/或胺单体形成的聚合物。环氧单体的实例是表氯醇和缩水甘油。醇单体的实例是苯酚、甲酚、间苯二酚、二甲苯酚、双酚A和二醇。环氧聚合物的实例是苯氧基树脂，其由表氯醇和双酚A形成。
聚酰胺是由至少一种具有酰胺基团或氨基以及羧基的单体形成的聚合物或者由至少一种具有两个氨基的单体与至少一种具有两个羧基的单体形成的聚合物。具有酰胺基团的单体的实例是己内酰胺。二胺的实例是1，6-二氨基己烷。二羧酸的实例是己二酸、对苯二甲酸、间苯二甲酸和1，4-萘二甲酸。聚酰胺的实例是聚六亚甲基己二酰二胺和聚己内酰胺。
聚酯聚合物由至少一种具有羟基以及羧基的单体形成或者由至少一种具有两个羟基的单体和至少一种具有两个羧基或内酯基团的单体形成。具有羟基以及羧基的单体的实例是己二酸。二醇的实例是乙二醇。具有内酯基团的单体的实例是己内酯(carprolactone)。二羧酸的实例是对苯二甲酸、间苯二甲酸和1，4-萘二甲酸。聚酯的实例是聚对苯二甲酸乙二醇酯。所谓的醇酸树脂也被认为属于聚酯聚合物。
聚氨基甲酸酯是由至少一种二异氰酸酯单体和至少一种多元醇单体和/或多胺单体形成的聚合物。二异氰酸酯单体的实例是六亚甲基二异氰酸酯、甲苯二异氰酸酯和二苯基甲烷二异氰酸酯。
基于砜的聚合物的实例是聚芳砜、聚醚砜、聚苯砜和聚砜。聚砜是由4，4-二氯二苯基砜和双酚A形成的聚合物。
天然聚合物的实例是淀粉、纤维素、明胶、酪蛋白(caesin)和天然橡胶。衍生物的实例是氧化淀粉、淀粉-乙酸乙烯酯接枝共聚物、羟乙基纤维素、羟丙基纤维素、甲基纤维素、乙基纤维素、羧甲基纤维素和乙酰纤维素。
聚合物基料是本领域公知的并可以通过已知方法例如由适当单体开始进行聚合来生产。
优选地，聚合物基料选自丙烯酸类聚合物、苯乙烯聚合物、乙烯基聚合物及其衍生物、聚烯烃、聚氨基甲酸酯和天然聚合物及其衍生物。
更优选地，聚合物基料选自丙烯酸类聚合物、苯乙烯丁二烯共聚物、苯乙烯-马来酸酐共聚物、聚乙烯醇、聚乙酸乙烯酯、部分水解的聚乙酸乙烯酯、甲基乙烯基醚-马来酸酐共聚物、羧基改性的聚乙烯醇、乙酰乙酰基改性的聚乙烯醇、双丙酮改性的聚乙烯醇和硅改性的聚乙烯醇、异丙烯-马来酸酐共聚物、聚氨基甲酸酯、纤维素、明胶、酪蛋白(caesin)、氧化淀粉、淀粉-乙酸乙烯酯接枝共聚物、羟乙基纤维素、甲基纤维素、乙基纤维素、羧甲基纤维素和乙酰纤维素。
更优选地，聚合物基料是聚乙烯醇或丙烯酸类聚合物，例如由Ciba以商品名
销售的产品，例如
LE15、LS26、E11或C44。
LS26是核壳聚合物，由70重量份用作核聚合物的55/45(w/w)苯乙烯/丙烯酸2-乙基己酯共聚物和30重量份用作壳聚合物的苯乙烯/丙烯酸共聚物组成。
最优选地，基料选自乙酸乙烯酯；(甲基)丙烯酸类和苯乙烯型均聚物和共聚物，例如甲基丙烯酸二甲氨基乙酯或甲基丙烯酸甲酯聚合物；羧甲基纤维素；以及淀粉型基料。基于乙酸乙烯酯、丁二烯、丙烯酸和苯乙烯均聚物和共聚物的适当基料由以商品名
销售。
优选地，本发明的组合物还包含成焦化合物(成焦剂)。当用例如由IR-激光产生的足够成焦能量(即足以形成焦的能量)例如热进行处理时，成焦化合物或成焦剂形成碳。通常，成焦化合物具有高碳和氧含量。
成焦化合物的实例是碳水化合物，例如单糖、二糖和多糖，及其衍生物，其中羰基已经被还原为羟基，所谓的糖醇。
单糖的实例是葡萄糖、甘露糖、半乳糖、阿拉伯糖、果糖、核糖、赤藓糖和木糖。二糖的实例是麦芽糖、纤维素二糖、乳糖和蔗糖。多糖的实例是纤维素、淀粉、阿拉伯树胶、糊精和环糊精。糖醇的实例是间赤藓醇、山梨糖醇、甘露糖醇和季戊四醇。
优选的成焦化合物是单糖和二糖。更优选的成焦化合物是蔗糖、半乳糖和三氯蔗糖(三氯-蔗糖；1，6-二氯-1，6-二脱氧-β-D-呋喃果糖基-4-氯-4-脱氧-α-D-吡喃葡萄糖苷)。最优选的成焦化合物是蔗糖(saccharose)(也被称为蔗糖(sucrose))。
优选地，本发明的组合物还可以包含附加组分。
可以包含在涂料组合物中的附加组分可以选自适于改善组合物性能的任何成分。附加组分可以是能够吸收入射能并将该能量以热或其它方式传递至系统的成分，例如UV吸收剂或IR吸收剂。其它类型的附加组分的实例是蜡、颜料、碱、稳定剂、抗氧化剂、流变改性剂、湿润剂、抗微生物剂、防烟剂和标记剂。标记剂是添加至产品以指示其制造来源的各种物质。
优选地，涂料组合物不包含染料或成色物质。
UV吸收剂的实例是2-羟基-4-甲氧基二苯甲酮。
IR吸收剂可以为有机的或无机的。有机IR吸收剂的实例是烷基化三苯基硫代磷酸酯，例如以商品名
211销售的产品，或者炭黑，例如以商品名
Black 2B或
BlackC-E2销售的产品。
无机IR吸收剂的实例是诸如铜、铋、铁、镍、锡、锌、锰、锆和锑的金属的氧化物、氢氧化物、硫化物、硫酸盐和磷酸盐，包括氧化锑(V)掺杂的云母和氧化锡(IV)掺杂的云母。
颜料可以作为用于增强未成像和成像区域之间对比度的无机IR吸收剂或者作为安全特征添加。
用作无机IR吸收剂的颜料的实例是高岭土、煅烧的高岭土、云母、氧化铝、氢氧化铝、硅酸铝、滑石、无定形二氧化硅和胶态二氧化硅。
可以被添加以增强未成像和成像区域之间对比度的颜料的实例是二氧化钛、碳酸钙、硫酸钡、聚苯乙烯树脂、脲-甲醛树脂、空心塑料颜料。
被添加作为安全特征的颜料的实例是荧光颜料或磁性颜料。
可以添加碱以调节组合物的pH。适当的碱是碱金属和碱土金属氢氧化物，或式NR1R2R3的胺，其中R1、R2和R3如上所定义。碱金属氢氧化物的实例是氢氧化钠和氢氧化钾。
流变改性剂的实例是黄原酸胶、甲基纤维素、羟丙基甲基纤维素或丙烯酸类聚合物，例如以商品名
112、
132和152销售的产品。
湿润剂的实例是
D、基于山梨糖醇的澄清剂。
抗微生物剂的实例是
MBS，其包含氯甲基异噻唑啉酮和甲基异噻唑啉酮的混合物，
410，其包含2-二溴-2，4-二氰基丁烷和1，2-苯并异噻唑啉-3-酮的组合，
721M，其包含1，2-二溴-2，4-二氰基丁烷和2-溴-2-硝基-1，3-丙二醇的混合物，以及
TK 100，其包含2-(4-噻唑基)-苯并咪唑。
防烟剂的实例是八钼酸铵。
在本发明的优选涂料组合物中，基料是聚合物基料，和/或它们包含另外的成焦化合物。
本发明的特别优选的涂料组合物包含：
a)溶剂，
b)含磷或含硼的酸与胺或亚胺的盐，
c)不含磷和不含硼的酸与胺或亚胺的盐，
d)基料，以及
e)成焦化合物。
本发明特别涉及用于标记基材的涂料组合物，其包含：
a)溶剂，其不同于多元醇，如特别是具有至少5个碳原子的多元醇，例如季戊四醇或山梨糖醇，
b)含磷或含硼的酸与胺或亚胺的盐，
c)不含磷和不含硼的酸与胺或亚胺的盐，以及
d)不同于卤代烃的基料，
但不包含石棉和玻璃纤维。
本发明具体涉及用于标记基材的涂料组合物，其包含：
a)溶剂，其选自：水、C1-4链烷醇、C3-6酮、C4-6醚、C2-3腈、硝基甲烷、二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和环丁砜，其中C1-4链烷醇可以被C1-4烷氧基取代，或其混合物，
b)含磷或含硼的酸与胺或亚胺的盐，
c)不含磷和不含硼的酸与胺或亚胺的盐，以及
d)不同于卤代烃的基料，
但不包含石棉和玻璃纤维。
本发明更具体地涉及用于标记基材的涂料组合物，其包含：
a)溶剂，其选自：水、C1-4链烷醇、C3-6酮、C4-6醚、C2-3腈、硝基甲烷、二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和环丁砜，其中C1-4链烷醇可以被C1-4烷氧基取代，或其混合物，
b)含磷或含硼的酸与胺或亚胺的盐，
c)不含磷和不含硼的酸与胺或亚胺的盐，以及
d)基料，其选自：乙酸乙烯酯、(甲基)丙烯酸类和苯乙烯型均聚物和共聚物；羧甲基纤维素；淀粉型基料；以及甲基丙烯酸二甲氨基乙酯/甲基丙烯酸甲酯聚合物，
但不包含石棉和玻璃纤维。
在本发明特别优选的组合物中，溶剂是水；和/或含磷或含硼的酸与胺或亚胺的盐是磷酸铵；和/或不含磷和不含硼的酸与胺或亚胺的盐是硫酸铵；和/或基料选自乙酸乙烯酯、(甲基)丙烯酸类和苯乙烯型均聚物和共聚物；羧甲基纤维素；淀粉型基料；以及甲基丙烯酸二甲氨基乙酯/甲基丙烯酸甲酯聚合物；和/或成焦化合物选自蔗糖、三氯蔗糖、2-乙醇胺和2-(2’-氨基乙氧基)-乙醇。
本发明的组合物可以包含基于组合物总重量为10重量％-95重量％，优选10重量％-90重量％，以及更优选20重量％-80重量％，最优选30重量％-70重量％，例如50重量％溶剂。
本发明的组合物可以包含基于组合物总重量为1干重％-80干重％，优选3干重％-70干重％，更优选5干重％-60干重％，以及最优选10干重％-50干重％基料。
本发明的组合物可以包含基于组合物总重量为0重量％-50重量％，优选5重量％-40重量％，更优选10重量％-30重量％，以及最优选15重量％-25重量％，例如约20重量％的成焦化合物。
本发明的组合物可以包含基于组合物总重量为0重量％-30重量％，优选0重量％-20重量％，更优选0重量％-10重量％的附加组分。
本发明的组合物可以由基于组合物总重量为1重量％-60重量％盐混合物、10重量％-95重量％溶剂、1重量％-80重量％基料、0重量％-50重量％成焦化合物和0重量％-30重量％附加组分组成，条件是所有组分之和不超过100重量％。
优选地，本发明的组合物可以由基于组合物总重量为2重量％-40重量％盐混合物、10重量％-90重量％溶剂、3重量％-70重量％基料、5重量％-40重量％成焦化合物和0重量％-20重量％附加组分组成，条件是所有组分之和不超过100％。
更优选地，本发明的组合物可以由基于组合物总重量为5重量％-30重量％盐混合物、20重量％-80重量％溶剂、5重量％-60重量％基料、10重量％-30重量％成焦化合物和0重量％-10重量％附加组分组成，条件是所有组分之和不超过100重量％。
最优选地，本发明的组合物可以由基于组合物总重量为10重量％-20重量％盐混合物、30重量％-70重量％溶剂、10重量％-50重量％基料、15重量％-25重量％成焦化合物和0重量％-10重量％附加组分组成，条件是所有组分之和不超过100重量％。
通过本发明的涂料组合物形成的涂层可以被例如层压层或罩印清漆再涂覆。如果选择另外的涂层材料例如层压层或罩印清漆使其在成像激光的波长处不吸收，则激光敏感性涂层可以穿过层压层成像，而不破坏或标记层压材料。而且理想地选择另外的涂料例如层压材料或罩印清漆，使得在能量处理之前不导致涂层着色。
不直接与涂料组合物成分相容的另一种使涂料组合物适于环境的可能性是例如通过一种包囊技术将其隐藏或伪装在聚合物壳中。与通过层压层或罩印清漆的上述另外的涂覆相反，本发明的涂料组合物不是在由此获得的涂层被第二涂层(顶涂层)保护或隐藏之前首先施用至基材，而是在将涂料组合物施用至基材前例如通过一种包囊技术将涂料组合物的活性物(即盐混合物)保护在例如聚合物壳中。被隐藏、伪装或包封的激光活性成分形成伪颜料。
本发明还涉及涂料组合物，其中以下组分以隐藏、伪装或包封形式存在，例如包封在聚合物中：
a)含磷或含硼的酸与胺或亚胺的盐，
b)不含磷和不含硼的酸与胺或亚胺的盐，以及
c)成焦化合物。
本发明还涉及组合物，其包含
a)含磷或含硼的酸与胺或亚胺的盐，
b)不含磷和不含硼的酸与胺或亚胺的盐，
c)成焦化合物，以及
d)聚合包封材料。
后一组合物是一种伪颜料组合物，其可以用于或用作本发明涂料组合物的形成部分并用于其制造。
用于形成聚合包封材料的适当聚合物是例如三聚氰胺甲醛聚合物、脲甲醛聚合物、聚丙烯酸、苯乙烯丙烯酸类聚合物、交联聚丙烯酰胺、交联丙烯酰胺-丙烯酸钠共聚物、交联聚丙烯酸羟基乙酯、明胶、纤维素衍生物、聚乙烯醇、苯乙烯-酸酐共聚物、聚乙烯基吡咯烷酮和淀粉。
本发明还涉及制造上述伪颜料组合物的方法，其包括通过例如高剪切均质机使水性组合物在两亲性稳定剂的存在下在水不混溶性液体中乳化以形成平均水滴尺寸直径低于30微米，优选低于20微米，例如1微米-20微米的乳液，所述水性组合物包含：
a)含磷或含硼的酸与胺或亚胺的盐，
b)不含磷和不含硼的酸与胺或亚胺的盐，
c)成焦化合物，以及
d)适当的单体混合物，或适当的活性树脂，或适当的水性聚合物制剂；如果从上述单体混合物开始则发生聚合反应以形成包囊；如果从上述活性树脂开始则通过例如添加酸而发生缩聚以形成包囊；除去水至低于伪颜料干含量的5％，并分离伪颜料。
适当的单体混合物例如为：
亚甲基双丙烯酰胺(MBA)/丙烯酰胺/丙烯酸及其碱性盐，例如丙烯酸钠；
MBA/丙烯酸及其碱性盐；
MBA/丙烯酸羟基乙酯，或者
MBA/乙烯基吡咯烷酮。
适当的活性树脂例如为水溶性氨基树脂预缩合物，例如脲-甲醛或三聚氰胺甲醛树脂，向所述树脂中添加酸(例如甲酸)例如至约pH 4进行缩聚反应以生成脲-甲醛和三聚氰胺甲醛聚合物。
适当的水性聚合物制剂可以为例如适当聚合物的水溶液、分散体、乳液或微乳液，如苯乙烯丙烯酸类聚合物、明胶、纤维素衍生物、聚乙烯醇、聚丙烯酸、苯乙烯-酸酐共聚物、聚乙烯基吡咯烷酮、或淀粉。优选的水性聚合物制剂例如为
LS270，其是可购自Ciba SpecialtyChemicals的46重量％的苯乙烯丙烯酸类聚合物在水中的微乳液。
水不混溶性液体例如为液态烃溶剂，如包含异链烷烃的溶剂，例如Isopar G，其是可购自ExxonMobil的馏程为155℃-179℃的异链烷烃。
两亲性稳定剂例如为聚合两亲性稳定剂，如适当的甲基丙烯酸硬脂基酯/甲基丙烯酸共聚物，例如20重量％的分子量为40,000g/mol的90/10(w/w)的甲基丙烯酸硬脂基酯/甲基丙烯酸共聚物的
D40溶液，所述
D40即为可购自ExxonMobil的沸点为154℃-187℃的脱芳构烃溶剂。
当由上述单体混合物开始时，可以通过例如添加适当的氢过氧化物如过氧化氢叔丁基来引发聚合反应以形成包囊。
当由上述活性树脂开始时，可以通过例如添加酸例如甲酸至pH为约4来引发缩聚以形成包囊。
例如通过优选在真空和在高温例如高达150℃，优选高达100℃下蒸馏可以除去水至低于伪颜料干含量的5％。
例如通过过滤和干燥例如在30℃下例如烘干来分离伪颜料。
本发明涉及被根据本发明的组合物涂覆的基材，例如被如此涂覆的聚丙烯薄膜，包括双轴取向聚丙烯(BOPP)膜，或者选自以下的基材：药物剂型、食品、纸、包装用纸板、胶粘标签、玻璃、纺织品、不同于BOPP膜(如上所述)的聚合物、和金属。
本发明还涉及用于制备被标记基材的方法，其包括以下步骤：
i)用本发明的组合物涂覆基材，以及
ii)使这些要标记的被涂覆基材部分暴露于由激光束产生的能量。
本发明具体涉及用于制备被标记基材的上述方法，其中所述基材是聚丙烯薄膜，包括双轴取向聚丙烯(BOPP)膜，或者其中所述基材选自药物剂型、食品、纸、包装用纸板、胶粘标签、玻璃、纺织品、不同于BOPP膜(如上所述)的聚合物、和金属。
本发明还涉及本发明的组合物，其为可激光标记的透明或白墨水例如基于二氧化钛的白墨水形式。
实施例
实施例1
丙烯酸类基料的制备
向配备有机械搅拌器、冷凝器、氮气入口、温度探针和进料口的1升树脂罐中放入98.9g水和483.9g8078，低分子量苯乙烯丙烯酸共聚物的铵盐溶液。将内容物加热至85℃并用氮脱气30分钟。通过将192.5g苯乙烯与157.5g丙烯酸2-乙基己酯混合来制备单体相。通过将1.97g过硫酸铵溶解在63.7g水中来制备引发剂进料。当反应器达到温度并脱气时，向反应器中添加0.66g过硫酸铵。2分钟后，使单体和引发剂开始进料，该进料分别适于3小时和4小时进料。在进料过程中将反应器内容物维持于85℃。在完成进料后，将反应器内容物在85℃下再保持1小时后冷却至低于40℃，此时添加0.9g Acticide LG(一种包含氯化和未氯化的甲基异噻唑啉酮的抗微生物剂)。这生成49.2％固体、pH 8.3且BrookfieldRVT粘度为1100cPs的乳液聚合物。
实施例2a
涂料组合物的制备
将6g磷酸二氢铵、6g硫酸铵和15g蔗糖溶解于33g水中。然后将所得溶液经15分钟滴加至40g实施例1中制备的丙烯酸类基料中。在滴加溶液的同时通过滴加氨水将pH维持大于7.5。
比较实施例1：
比较涂料组合物的制备
将12g硫酸铵和15g蔗糖溶解于33g水中。然后将所得溶液经15分钟滴加至40g实施例1中制备的丙烯酸类基料中。在滴加溶液的同时通过滴加氨水将pH维持大于7.5。将混合物搅拌10分钟。
比较实施例2：
比较涂料组合物的制备
将12g磷酸二氢铵和15g蔗糖溶解于33g水中。然后将所得溶液经15分钟滴加至40g实施例1中制备的丙烯酸类基料中。在滴加溶液的同时通过滴加氨水将pH维持大于7.5。将混合物搅拌10分钟。
实施例2b
涂料组合物的制备
制备类似于实施例2a的涂料组合物，不同的是使用40g
319，苯乙烯丁二烯格(styrene butadiene lattice)(固体含量为50％，粒度为0.12μm，玻璃化转变温度Tg为28℃)代替40g实施例1的丙烯酸类基料。
实施例2c
涂料组合物的制备
制备类似于实施例2a的涂料组合物，不同的是使用40g
318，苯乙烯丁二烯格(固体含量为50％，粒度为0.12μm，玻璃化转变温度Tg为22℃)代替40g实施例1的丙烯酸类基料。
实施例2d
涂料组合物的制备
制备类似于实施例2a的涂料组合物，不同的是使用40g
302，苯乙烯丁二烯格(固体含量为50％，粒度为0.15μm，玻璃化转变温度Tg为10℃)代替40g实施例1的丙烯酸类基料。
实施例2e
涂料组合物的制备
制备类似于实施例2a的涂料组合物，不同的是使用40g
304，苯乙烯丁二烯格(固体含量为50％，粒度为0.15μm，玻璃化转变温度Tg为20℃)代替40g实施例1的丙烯酸类基料。
实施例2f
涂料组合物的制备
通过将6g磷酸二氢铵、6g硫酸铵和15g蔗糖溶解于17g水中来制备涂料组合物。
实施例2g
涂料组合物的制备
将6g硫酸铵、6g磷酸二氢铵和15g蔗糖溶解于53g水中。然后在搅拌下将所得溶液缓慢添加至40g
74中，
74由BASF销售并为固体含量为48.5重量％的丙烯酸类聚合物乳液。
实施例2h
涂料组合物的制备
制备类似于实施例2g的涂料组合物，不同的是使用40g由BASF销售并为固体含量为46重量％的丙烯酸类聚合物乳液的
77代替40g
74。
实施例2i
涂料组合物制备
制备类似于实施例2g的涂料组合物，不同的是使用40g由BASF销售并为固体含量为47.4重量％的丙烯酸类聚合物溶液的
DFC3030代替40g
74。
实施例2j
涂料组合物制备
将6g硫酸铵、6g磷酸二氢铵和15g蔗糖溶解于33g水中。然后将所得溶液缓慢添加至40g
DFC 3040中，
DFC 3040由BASF销售并为固体含量为46重量％的丙烯酸类聚合物乳液，同时搅拌，并且搅拌最终混合物0.5小时。
实施例2k
涂料组合物制备
将14.6g由BASF销售并为固体含量为34.2重量％的丙烯酸类树脂溶液的
DFC 3025，以及22g也是由BASF销售并为固体含量为46重量％的丙烯酸类聚合物溶液的
DFC 3040组合。将6g硫酸铵、6g磷酸二氢铵和15g蔗糖溶解于36.4g水中。然后将所得溶液缓慢添加至正搅拌的基料混合物中，搅拌最终混合物0.5小时。
实施例2l
涂料组合物的制备
将6g硫酸铵、6g磷酸二氢铵和15g蔗糖溶解于35g水中。然后将所得溶液缓慢添加至40g
DFC 3050和3g丙二醇中，并搅拌最终混合物0.5小时，
DFC 3050由BASF销售并为固体含量为48.2重量％的丙烯酸类聚合物乳液。
实施例2m
涂料组合物的制备
将30g由BASF销售并为固体含量为46重量％的丙烯酸类聚合物溶液的
DFC 3040，以及10g为固体含量为48.2重量％的丙烯酸类聚合物乳液的
DFC 3050组合。将6g硫酸铵、6g磷酸二氢铵和15g蔗糖溶解于33g水中。将所得溶液缓慢添加至树脂中，并搅拌最终混合物0.5小时。
实施例2n
涂料组合物的制备
将6g硫酸铵、6g磷酸二氢铵和15g蔗糖溶解于33g水中。将所得溶液缓慢添加至40g Joncryl DFC 3040中同时搅拌，并搅拌最终混合物0.5小时，Joncryl DFC 3040由BASF销售并为固体含量为46重量％的丙烯酸类聚合物溶液。将3g Bacote
添加至混合物中，其中Bacote
是由MELChemicals销售的包含阴离子型羟基化锆聚合物的稳定了的碳酸铵锆的水溶液。
实施例2o
涂料组合物的制备
将6g硫酸铵、6g磷酸二氢铵和15g三氯蔗糖(1，6-二氯-1，6-二脱氧-β-D-呋喃果糖基-4-氯-4-脱氧-α-D-吡喃葡萄糖苷)溶解于33g水中。然后将所得溶液经15分钟滴加至40g实施例1中制备的丙烯酸类基料中，并搅拌混合物10分钟。
实施例2p
涂料组合物的制备
将6g磷酸二氢铵和6g硫酸铵与33.3g冰一起搅拌。滴加14.7g乙醇胺。然后在室温下将所得溶液经15分钟滴加至40g实施例1中制备的丙烯酸类基料中，并搅拌混合物10分钟。
实施例2q
涂料组合物的制备
将6g磷酸二氢铵和6g硫酸铵与22.8g冰一起搅拌。滴加25.2g 2-(2’-氨基乙氧基)乙醇。然后在室温下将所得溶液经15分钟滴加至40g实施例1中制备的丙烯酸类基料中，并搅拌混合物10分钟。
实施例2r
涂料组合物的制备
将6g磷酸二氢铵和6g硫酸铵添加至73g阳离子基料树脂，即甲基丙烯酸二甲氨基乙酯/甲基丙烯酸甲酯聚合物(15％固体)中，并搅拌混合物直到盐完全溶解。添加15g蔗糖并搅拌混合物直到蔗糖完全溶解。
涂料组合物在纸和聚合物膜上的施用
通过12μm涂覆杆(coating bar)将实施例2a以及比较实施例1和2的涂料组合物分别施用至复印纸(被涂覆的“Cento Copy”纸，购自M-Real，Biberist，Switzerland)聚酯膜并干燥以获得透明涂层。然后使用CO2IR激光(波长：10'600nm，功率：2W，激光束直径：0.35mm，线速度：1000mm/s)将涂层成像以获得如下表1所述的痕迹。
表1
表1显示出与分别包含12重量％硫酸铵和15重量％蔗糖(比较实施例1)、12重量％磷酸二氢铵和15重量％蔗糖(比较实施例2)的比较实施例1和2的比较涂料组合物相比，包含6重量％磷酸二氢铵、6重量％硫酸铵和15重量％蔗糖的实施例2a的涂料组合物在复印纸和聚酯(PES)膜上获得更深(更带黑色)棕色的痕迹。
通过12μm涂覆杆将实施例2a、2b、2c、2d、2e、2f、2g、2h、2i、2j、2k、2l、2m、2n、2o、2p、2q和2r的涂料组合物施用至普通纸、涂覆纸(例如复印纸，即适用于影印机或打印机的纸)和聚合物膜(例如聚酯膜)以获得透明涂层。通过12μm涂覆杆将实施例2g、2h、2i、2j、2k、2l、2m、2n和2r的涂料组合物再施用至牛皮纸。然后使用CO2IR激光(波长：10'600nm，功率：0.5W-4W，激光束直径：0.35mm，线速度：300mm/s-1000mm/s)将涂层成像以获得高反差深色痕迹。
用实施例2n的涂料组合物获得的涂层和痕迹还可防水，包括防酸性水。
涂料组合物在聚合物薄膜上的施用
通过12μm涂覆杆将实施例2a的涂料组合物施用至6μm BOPP(双轴取向聚丙烯)膜并干燥以获得透明涂层。然后使用CO2IR激光(波长：10'600nm，功率：0.5W-4W，激光束直径：0.35mm，线速度：300mm/s-1000mm/s)将涂层成像以获得高反差深色痕迹，而即使在以激光使未涂覆的背面侧成像时也不会破坏聚合物膜。
涂料组合物在已经预先印有白色背景区域的包装纸上的应用
通过12μm涂覆杆将实施例2a的涂料组合物施用至已经预先印有白色背景区域的包装纸并干燥以获得透明涂层。然后使用CO2IR激光(波长：10'600nm，功率：0.5W-4W，激光束直径：0.35mm，线速度：300mm/s-1000mm/s)将涂层成像以获得高反差深色痕迹，该痕迹也容易使用条形码阅读器读取。
涂料组合物与面漆一起在聚合物膜上的施用
通过12μm涂覆杆将实施例2a的涂料组合物施用至聚酯和聚丙烯膜。干燥后，施用多种面漆体系，包括基于丙烯酸酯的PVA和UV固化体系。然后使用CO2IR激光(波长：10'600nm，功率：0.5W-4W，激光束直径：0.35mm，线速度：300mm/s-1000mm/s)将涂层成像以获得高反差深色痕迹，甚至穿过面漆。该图像也容易使用条形码阅读器读取。
涂料组合物在可食用基材上的应用
通过刷子将实施例2a和2b的涂料组合物施用至可食用基材的表面并干燥以获得透明涂层，所述基材例如苹果、橙子、香蕉和鸡蛋。然后使用CO2IR激光(波长：10'600nm，功率：0.5W-4W，激光束直径：0.35mm，线速度：300mm/s-1000mm/s)将涂层成像以获得高反差深色痕迹。
涂料组合物在片剂(tablet)上的应用
将痕迹浸入实施例2a和2d的涂料组合物中持续几秒并干燥以获得透明涂层。然后使用CO2IR激光(波长：10'600nm，功率：0.5W-4W，激光束直径：0.35mm，线速度：300mm/s-1000mm/s)将涂层成像以获得高反差深色痕迹。
实施例3a
激光敏感性伪颜料的制备
本实施例例示了将激光活性组分包封、隐藏或伪装在苯乙烯丙烯酸类聚合物基质中。
水相的制备通过将9g正磷酸二氢铵、9g硫酸铵和22.5g蔗糖溶解于69.5g水中，然后添加60g
LS270，其为购自Ciba SpecialtyChemicals的46重量％的苯乙烯丙烯酸类聚合物在水中的微乳液。油相的制备通过将用作两亲性稳定剂的17g 20重量％的分子量为40,000g/mol的90/10(w/w)甲基丙烯酸硬脂基酯/甲基丙烯酸共聚物在
D40中的溶液和300g Isopar G混合，其中D40即购自ExxonMobil的沸点为154℃-187℃的脱芳构烃溶剂，Isopar G为购自ExxonMobil的馏程为155℃-179℃的异链烷烃。通过高剪切均质机将上述水相添加至油相中以形成平均水滴粒度为5μm的油包水乳液。将形成的乳液转移至用于蒸馏的1升烧瓶装置中。将乳液进行真空蒸馏以除去水连同Isopar G的低沸点馏分。继续真空蒸馏至90℃直到在馏出液中不再收集到水。接着将烧瓶内容物冷却至25℃并通过过滤和在30℃下烘干来分离伪颜料。最终产物是平均粒度直径为5μm的自由流动的灰白色伪颜料。
实施例3b
激光敏感性伪颜料
本实施例例示了将激光活性组分包封、隐藏或伪装在交联聚丙烯酰胺基质中。
单体溶液的制备通过将1g亚甲基双丙烯酰胺溶解于53.7g 49.5重量％丙烯酰胺水溶液中，然后添加由9g正磷酸二氢铵、9g硫酸铵和22.5g蔗糖和71.5g水组成的水溶液。通过添加0.5ml 99重量％乙酸将所得混合物的pH调节为5.0。制备组成如下的油相：用作两亲性稳定剂的17g 20重量％的分子量为40,000g/mol的90/10(w/w)甲基丙烯酸硬脂基酯/甲基丙烯酸共聚物的水溶液和300g为购自ExxonMobil的馏程为155℃-179℃的异链烷烃的Isopar G。向上述单体溶液中添加1.65ml1重量％亚硫酸钠溶液，然后通过高剪切均质机将所得水性混合物添加至上述油相中以形成平均水滴粒度为3μm的油包水乳液。将形成的乳液转移至1升烧瓶中，然后在整个乳化过程中通过氮气鼓泡除脱氧。接着添加0.5ml 7重量％的Isopar G中的过氧化氢叔丁基以引发丙烯酸类单体的聚合。烧瓶内容物发生放热反应从28℃到37℃。在聚合后，配置烧瓶用于真空蒸馏。将聚合的乳液进行真空蒸馏以除去水连同Isopar G的低沸点馏分。继续真空蒸馏至100℃直到馏出液中不再收集到水。接着将烧瓶内容物冷却至25℃并通过过滤和在50℃下烘干来分离伪颜料。最终干燥产物是平均粒度直径为3μm的自由流动的灰白色伪颜料。
实施例3c
激光敏感性伪颜料
该实施例例示了将激光活性组分包封、隐藏或伪装在三聚氰胺-甲醛聚合物壳中。
制备组成如下的水相：9g正磷酸二氢铵、9g硫酸铵和22.5g蔗糖、14.4g
P-604(其为可购自Ciba Specialty Chemicals的18重量％的阴离子聚丙烯酰胺水溶液)、35.7gPT-3336(其为购自BIPLimited的70重量％的三聚氰胺甲醛树脂溶液)、以及68.1g水。通过添加1.5ml 95重量％甲酸将该混合物的pH调节为4.0。制备组成如下的油相：用作两亲性稳定剂的17g 20重量％的分子量为40,000g/mol的90/10(w/w)甲基丙烯酸硬脂基酯/甲基丙烯酸共聚物在
D40中的溶液和300gIsopar G，
D40即购自ExxonMobil的沸点为154℃-187℃的脱芳构烃溶剂，Isopar G为购自ExxonMobil的馏程为155℃-179℃的异链烷烃。通过高剪切均质机将上述水相添加至油相中以形成平均水滴粒度为18μm的油包水乳液。将形成的乳液转移至1升烧瓶中，然后将内容物加温至60℃以固化三聚氰胺甲醛树脂。接着配置烧瓶用于真空蒸馏并将内容物进行蒸馏以除去水连同Isopar G的低沸点馏分。继续真空蒸馏至100℃直到在馏出液中不再收集到水。最后，将烧瓶内容物冷却至25℃并通过过滤和在50℃下烘干来分离伪颜料。最终产物是平均粒度直径为18μm的自由流动的浅黄色伪颜料。
伪颜料在纸和聚合物膜上的施用
将分别来自实施例3a、3b、3c(9.0g)的伪颜料缓慢添加至
319，苯乙烯丁二烯格(固体含量为50％，粒度为0.12μm，玻璃化转变温度Tg为28℃)(6.7g)和水(5.5g)的混合物中。搅拌混合物10分钟。
然后通过12μm涂覆杆将所获得的涂料组合物施用至复印纸和聚丙烯并干燥以获得透明涂层。然后使用CO2IR激光(波长：10'600nm，功率：0.5W-4W，激光束直径：0.35mm，线速度：300mm/s-1000mm/s)将涂层成像以获得高反差深色痕迹。该图像也容易使用条形码阅读器读取。
伪颜料在标签上的施用
聚丙烯标签
以50重量％浓度将来自实施例3a的伪颜料添加至压敏胶粘剂中，所述压敏胶粘剂分别为苯乙烯丁二烯、苯乙烯丙烯酸共聚物。然后将经此处理的胶粘剂用12μm涂覆杆涂覆至聚丙烯膜以形成激光敏感性标签。在施用至第二包装用纸板后，使用CO2IR激光(波长：10'600nm，功率：0.5W-4W，激光束直径：0.35mm，线速度：300mm/s-1000mm/s)将标签成像以获得高反差深色痕迹。
实施例4
透明凹印油墨(水基油墨，其在10600nm下对以CO2激光成像具有优异的敏感性；在以下糖&盐水平下聚合物含量增加：10％蔗糖，6％盐)配制剂：
油墨5，最终配制剂
1) 
104PA是表面活性剂，其包含50％异丙醇中的2，4，7，9-四甲基-5-癸炔-4，7-二醇，购自Air Products and Chemicals，Inc.，Allentown，Pa.，USA和Air Products Chemicals Europe(Utrecht)。
2) 
90是硬质非成膜de苯乙烯-丙烯酸类共聚合物乳液，由BASF Resins(Nijehaske，Netherlands)供应。
3) 
61E是在低固体下用于中等粘度的中分子量固态苯乙烯/丙烯酸类树脂，由BASF供应。
4)Echem DF 174是消泡剂，其包含植物油、脂肪、蜡和非离子乳化剂的掺混物；由eChem Ltd(England)供应。
5)S-395-N5PE Wax是聚乙烯(？)蜡，由Shamrock Technologies(Belgium)供应。
6)Fluoro HP PTFE Wax由Shamrock Technologies(Belgium)供应。
7)56Zahn#2和24Zahn#2定义粘度。Zahn#2是底部钻有非常精确尺寸的小孔的杯子。56和24分别定义杯内流体例如油墨从孔中排出直到漆料流中断(即不是直到全部流体已经从杯中排出)所需的时间[秒]。
对于激光设置可以改变速度、功率和频率，根据所需的设计和品质。
如果需要，上述油墨配制剂可以进一步优化加压稳定性和可印刷性。配制剂的添加物可以包括不同溶剂(solvent change)、增塑剂、蜡、助粘剂、二氧化硅、消泡剂、表面活性剂、表面改性剂、pH调节剂等等。
实施例5
基于二氧化钛的白油墨在10600nm下对以CO2激光成像具有优异光敏性。其对凹版印刷和胶版印刷有利并在应用于实际标签的白色背景上获得深色图像。
配制剂：
油墨9；在10600nm下对以CO2激光成像具有优异敏感性的水基油墨；平衡的糖&盐水平；15％TiO2
油墨9，最终配制剂
1)锐钛矿是天然发现的二氧化钛的矿物形式之一。锐钛矿A-HR TiO2由Huntsman(Basle，Switzerland)供应。
如果需要，上述油墨配制剂可以进一步优化加压稳定性和可印刷性。配制剂的附加物可以包括不同溶剂、增塑剂、蜡、助粘剂、二氧化硅、消泡剂、表面活性剂、表面改性剂、pH调节剂等等。
Claims (24)
1.一种用于标记基材的涂料组合物，其包含
a)溶剂，
b)含磷或含硼的酸与胺或亚胺的盐，
c)不含磷和不含硼的酸与胺或亚胺的盐，以及
d)基料，
但不包含石棉和玻璃纤维。
2.根据权利要求1所述的组合物，其中所述基料是聚合物基料。
3.根据权利要求1或2所述的组合物，其中所述基料不同于卤代烃。
4.根据权利要求1所述的组合物，其包含
a)溶剂，其不同于具有至少5个碳原子的多元醇，
b)含磷或含硼的酸与胺或亚胺的盐，
c)不含磷和不含硼的酸与胺或亚胺的盐，以及
d)不同于卤代烃的基料，
但不包含石棉和玻璃纤维。
5.根据权利要求1-4任一项所述的组合物，其还包含成焦化合物。
6.根据权利要求1所述的组合物，其包含
a)溶剂，
b)含磷或含硼的酸与胺或亚胺的盐，
c)不含磷和不合硼的酸与胺或亚胺的盐，
d)基料，以及
e)成焦化合物。
7.根据权利要求1-6任一项所述的组合物，其中所述溶剂选自水、C1-4链烷醇、C3-6酮、C4-6醚、C2-3腈、硝基甲烷、二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和环丁砜，其中C1-4链烷醇可以被C1-4烷氧基取代，或它们的混合物。
8.根据权利要求1所述的组合物，其包含
a)溶剂，其选自水、C1-4链烷醇、C3-6酮、C4-6醚、C2-3腈、硝基甲烷、二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和环丁砜，其中C1-4链烷醇可以被C1-4烷氧基取代，或它们的混合物，
b)含磷或含硼的酸与胺或亚胺的盐，
c)不含磷和不含硼的酸与胺或亚胺的盐，以及
d)基料，其选自乙酸乙烯酯、(甲基)丙烯酸类和苯乙烯型均聚物和共聚物；羧甲基纤维素；淀粉型基料；以及甲基丙烯酸二甲氨基乙酯/甲基丙烯酸甲酯聚合物，
但不包含石棉和玻璃纤维。
9.根据权利要求1-8任一项所述的组合物，其中所述溶剂是水。
10.根据权利要求1-9任一项所述的组合物，其中所述含磷或含硼的酸与胺或亚胺的盐是磷酸铵。
11.根据权利要求1-10任一项所述的组合物，其中所述不含磷和不含硼的酸与胺或亚胺的盐是硫酸铵。
12.根据权利要求1-11任一项所述的组合物，其中所述基料选自乙酸乙烯酯、(甲基)丙烯酸类和苯乙烯型均聚物和共聚物；羧甲基纤维素；淀粉型基料；以及甲基丙烯酸二甲氨基乙酯/甲基丙烯酸甲酯聚合物。
13.根据权利要求1-12任一项所述的组合物，其还包含成焦化合物，所述成焦化合物选自蔗糖、三氯蔗糖、2-乙醇胺和2-(2’-氨基乙氧基)乙醇。
14.根据权利要求1-13任一项所述的组合物，其为可激光标记的透明或白油墨形式。
15.根据权利要求5-13任一项所述的组合物，其中以下组分以隐藏、伪装或包封的形式存在：
a)含磷或含硼的酸与胺或亚胺的盐，
b)不含磷和不含硼的酸与胺或亚胺的盐，以及
c)成焦化合物。
16.根据权利要求15所述的组合物，其中以下组分被隐藏、伪装或包封在聚合物中：
a)含磷或含硼的酸与胺或亚胺的盐，
b)不含磷和不含硼的酸与胺或亚胺的盐，以及
c)成焦化合物。
17.用于权利要求15所述组合物的伪颜料组合物，其包含
a)含磷或含硼的酸与胺或亚胺的盐，
b)不含磷和不含硼的酸与胺或亚胺的盐，
c)成焦化合物，以及
d)聚合包封材料。
18.根据权利要求16或17所述的组合物，其中所述包封聚合物选自三聚氰胺甲醛聚合物、脲甲醛聚合物、聚丙烯酸、苯乙烯丙烯酸类聚合物、交联聚丙烯酰胺、交联丙烯酰胺-丙烯酸钠共聚物、交联聚丙烯酸羟基乙酯、明胶、纤维素衍生物、聚乙烯醇、苯乙烯-酸酐共聚物、聚乙烯基吡咯烷酮和淀粉。
19.权利要求1-18任一项所述的组合物用于涂覆和激光标记基材的用途。
20.用于制备权利要求17或18所述的伪颜料的方法，其包括使水性组合物在两亲性稳定剂的存在下在水不混溶性液体中乳化以形成平均水滴尺寸直径低于30微米的乳液，所述水性组合物包含：
a)含磷或含硼的酸与胺或亚胺的盐，
b)不含磷和不含硼的酸与胺或亚胺的盐，
c)成焦化合物，以及
d)适当的单体混合物或适当的活性树脂；或者适当的水性聚合物制剂；
如果从上述单体混合物开始则引发聚合反应以形成包囊；如果从上述活性树脂开始则引发缩聚以形成包囊；除去水至低于伪颜料干含量的5％，并分离所述伪颜料。
21.被权利要求1-18任一项所述的组合物涂覆的基材。
22.用于制备被标记基材的方法，其包括以下步骤：
i)以权利要求1-18任一项所述的组合物涂覆基材，以及
ii)使这些要标记的被涂覆基材部分暴露于由激光束产生的能量。
23.根据权利要求21所述的基材或权利要求22所述的方法，其中所述基材是聚丙烯薄膜，包括双轴取向聚丙烯(BOPP)膜。
24.根据权利要求21所述的基材或权利要求22所述的方法，其中所述基材选自药物剂型、食品、纸、包装用纸板、胶粘标签、玻璃、纺织品、聚合物和金属。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| EP07112662.7 | 2007-07-18 | ||
| EP07112662 | 2007-07-18 | ||
| PCT/EP2008/058547 WO2009010393A1 (en) | 2007-07-18 | 2008-07-03 | Coating compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101755019A true CN101755019A (zh) | 2010-06-23 |
Family
ID=38669328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880024910A Pending CN101755019A (zh) | 2007-07-18 | 2008-07-03 | 涂料组合物 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20100239642A1 (zh) |
| EP (1) | EP2167596B1 (zh) |
| JP (1) | JP2010533749A (zh) |
| KR (1) | KR20100063014A (zh) |
| CN (1) | CN101755019A (zh) |
| AT (1) | ATE527327T1 (zh) |
| CA (1) | CA2692724A1 (zh) |
| TW (1) | TW200916544A (zh) |
| WO (1) | WO2009010393A1 (zh) |
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| CN103561962B (zh) * | 2011-05-25 | 2016-08-24 | 利乐拉瓦尔集团及财务有限公司 | 改进的近红外吸收剂 |
| CN107043499A (zh) * | 2016-02-05 | 2017-08-15 | 奇美实业股份有限公司 | 可激光标记的树脂组成物 |
| CN107043499B (zh) * | 2016-02-05 | 2019-10-11 | 奇美实业股份有限公司 | 可激光标记的树脂组成物 |
| CN110591458A (zh) * | 2019-09-30 | 2019-12-20 | 常州大学 | 一种包含聚苯乙烯/纳米银复合物的激光标记涂料的制备方法及应用 |
| CN114602386A (zh) * | 2022-04-02 | 2022-06-10 | 山推建友机械股份有限公司 | 一种沥青混合料搅拌系统及方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2692724A1 (en) | 2009-01-22 |
| TW200916544A (en) | 2009-04-16 |
| WO2009010393A1 (en) | 2009-01-22 |
| EP2167596A1 (en) | 2010-03-31 |
| JP2010533749A (ja) | 2010-10-28 |
| KR20100063014A (ko) | 2010-06-10 |
| EP2167596B1 (en) | 2011-10-05 |
| ATE527327T1 (de) | 2011-10-15 |
| US20100239642A1 (en) | 2010-09-23 |
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