US20010009938A1 - Whitened polymers and the use thereof in coating slips for coating substrates - Google Patents
Whitened polymers and the use thereof in coating slips for coating substrates Download PDFInfo
- Publication number
- US20010009938A1 US20010009938A1 US09/463,208 US46320800A US2001009938A1 US 20010009938 A1 US20010009938 A1 US 20010009938A1 US 46320800 A US46320800 A US 46320800A US 2001009938 A1 US2001009938 A1 US 2001009938A1
- Authority
- US
- United States
- Prior art keywords
- whitened
- denotes
- polymer
- weight
- acid
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 66
- 239000000758 substrate Substances 0.000 title claims abstract description 20
- 238000000576 coating method Methods 0.000 title claims description 47
- 239000011248 coating agent Substances 0.000 title claims description 45
- 230000003287 optical effect Effects 0.000 claims abstract description 27
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000123 paper Substances 0.000 claims description 49
- 239000006185 dispersion Substances 0.000 claims description 38
- 239000003995 emulsifying agent Substances 0.000 claims description 29
- 229920001577 copolymer Polymers 0.000 claims description 21
- 150000001450 anions Chemical class 0.000 claims description 11
- -1 for example Chemical compound 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000013543 active substance Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000001023 inorganic pigment Substances 0.000 claims description 5
- 239000011087 paperboard Substances 0.000 claims description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 239000004753 textile Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 2
- HIWGDJVTAWTBNH-UHFFFAOYSA-N 2-methylidene-5-sulfopentanoic acid Chemical compound OC(=O)C(=C)CCCS(O)(=O)=O HIWGDJVTAWTBNH-UHFFFAOYSA-N 0.000 claims description 2
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 claims description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 150000003926 acrylamides Chemical class 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 claims description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 235000019641 whiteness Nutrition 0.000 description 32
- 239000007787 solid Substances 0.000 description 20
- 239000004815 dispersion polymer Substances 0.000 description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 13
- 239000000178 monomer Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000003999 initiator Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000000049 pigment Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 7
- 0 *OC(=O)C(CC(C)(C)C)C(C)C(=O)N*C.C*N1C(=O)C(C)C(CC(C)(C)C)C1=O.II.[Y].[Y] Chemical compound *OC(=O)C(CC(C)(C)C)C(C)C(=O)N*C.C*N1C(=O)C(C)C(CC(C)(C)C)C1=O.II.[Y].[Y] 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 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 6
- 238000007792 addition Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 5
- 239000004908 Emulsion polymer Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 238000005282 brightening Methods 0.000 description 3
- PLOYJEGLPVCRAJ-UHFFFAOYSA-N buta-1,3-diene;prop-2-enoic acid;styrene Chemical compound C=CC=C.OC(=O)C=C.C=CC1=CC=CC=C1 PLOYJEGLPVCRAJ-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 description 2
- 229920005789 ACRONAL® acrylic binder Polymers 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CXDOOEOXFHVEEG-UHFFFAOYSA-N CC1=CN(C2=CC3=C(C=C(N4N=C(C)C(C)=N4)C=C3)OC2=O)N=C1 Chemical compound CC1=CN(C2=CC3=C(C=C(N4N=C(C)C(C)=N4)C=C3)OC2=O)N=C1 CXDOOEOXFHVEEG-UHFFFAOYSA-N 0.000 description 2
- DCQMTQROWWTYEM-UHFFFAOYSA-N CN1C2=CC=CC=C2N=C1C1=CC=C(C2=NC3=C(C=CC=C3)N2C)O1 Chemical compound CN1C2=CC=CC=C2N=C1C1=CC=C(C2=NC3=C(C=CC=C3)N2C)O1 DCQMTQROWWTYEM-UHFFFAOYSA-N 0.000 description 2
- CNUWYNDMLFVRBU-UHFFFAOYSA-N COC1=CC=C2C(=O)N(C)C(=O)/C3=C/C=C\C1=C23 Chemical compound COC1=CC=C2C(=O)N(C)C(=O)/C3=C/C=C\C1=C23 CNUWYNDMLFVRBU-UHFFFAOYSA-N 0.000 description 2
- MCXYNQPAGNNUHE-UHFFFAOYSA-N COS(=O)C1=CC=C(N2CCC(C3=CC=C(Cl)C=C3)=N2)C=C1 Chemical compound COS(=O)C1=CC=C(N2CCC(C3=CC=C(Cl)C=C3)=N2)C=C1 MCXYNQPAGNNUHE-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005100 correlation spectroscopy Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- CRBTVNNAESVHSD-UHFFFAOYSA-N 4-(chloromethyl)-1,2-thiazolidin-3-one Chemical compound ClCC1CSNC1=O CRBTVNNAESVHSD-UHFFFAOYSA-N 0.000 description 1
- BPTAGWQRAZKHNV-IRTUOLCXSA-J C=C.C=C.O=S(=O)(O[Na])C1=CC=C(NC2=NC(N(CCO)CCO)=NC(NC3=CC(SOOO[Na])=C(/C=C/C4=CC=C(NC5=NC(NC6=CC=C(SOOO[Na])C=C6)=NC(N(O)O)=N5)C=C4S(=O)(=O)O[Na])C=C3)=N2)C=C1 Chemical compound C=C.C=C.O=S(=O)(O[Na])C1=CC=C(NC2=NC(N(CCO)CCO)=NC(NC3=CC(SOOO[Na])=C(/C=C/C4=CC=C(NC5=NC(NC6=CC=C(SOOO[Na])C=C6)=NC(N(O)O)=N5)C=C4S(=O)(=O)O[Na])C=C3)=N2)C=C1 BPTAGWQRAZKHNV-IRTUOLCXSA-J 0.000 description 1
- IQBFHKGECNYUMS-UHFFFAOYSA-N CC1=C(C)N(C)C(C)=C1C Chemical compound CC1=C(C)N(C)C(C)=C1C IQBFHKGECNYUMS-UHFFFAOYSA-N 0.000 description 1
- UODGTTOQFCCYAU-UHFFFAOYSA-N CC1=C(C)N(C)N(C)=C1C Chemical compound CC1=C(C)N(C)N(C)=C1C UODGTTOQFCCYAU-UHFFFAOYSA-N 0.000 description 1
- OLSQRYRKWXOFDG-UHFFFAOYSA-N CC1=C(C)NN(C2=CC=C3C=C(N4C=[N+](C)=CN4)C(=O)OC3=C2)=N1 Chemical compound CC1=C(C)NN(C2=CC=C3C=C(N4C=[N+](C)=CN4)C(=O)OC3=C2)=N1 OLSQRYRKWXOFDG-UHFFFAOYSA-N 0.000 description 1
- PNWJWSQAVUBDOX-UHFFFAOYSA-N CC1=CC=C(N2CCC(C3=CC=C(Cl)C=C3)=N2)C=C1 Chemical compound CC1=CC=C(N2CCC(C3=CC=C(Cl)C=C3)=N2)C=C1 PNWJWSQAVUBDOX-UHFFFAOYSA-N 0.000 description 1
- UGLRRFUKOGWZEU-UHFFFAOYSA-N COC1=CC=C2C=C(C3=C(C)C4=CC=C(C)C=C4N3C)OC2=C1 Chemical compound COC1=CC=C2C=C(C3=C(C)C4=CC=C(C)C=C4N3C)OC2=C1 UGLRRFUKOGWZEU-UHFFFAOYSA-N 0.000 description 1
- HHVFOQHDAWHOIO-UHFFFAOYSA-N COC1=CC=C2N=C(C3=C(C)C4=CC=CC=C4N3C)OC2=C1 Chemical compound COC1=CC=C2N=C(C3=C(C)C4=CC=CC=C4N3C)OC2=C1 HHVFOQHDAWHOIO-UHFFFAOYSA-N 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- RXRBXRIWFKOICY-UHFFFAOYSA-N N1=NN=C(C=C1)C(=C(C1=C(C(=C(C=C1)N)S(=O)(=O)O)S(=O)(=O)O)C1=NN=NC=C1)C1=CC=CC=C1 Chemical compound N1=NN=C(C=C1)C(=C(C1=C(C(=C(C=C1)N)S(=O)(=O)O)S(=O)(=O)O)C1=NN=NC=C1)C1=CC=CC=C1 RXRBXRIWFKOICY-UHFFFAOYSA-N 0.000 description 1
- 229910003202 NH4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- TUZBYYLVVXPEMA-UHFFFAOYSA-N butyl prop-2-enoate;styrene Chemical compound C=CC1=CC=CC=C1.CCCCOC(=O)C=C TUZBYYLVVXPEMA-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- 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 1
- 235000021240 caseins Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920005670 poly(ethylene-vinyl chloride) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 229940001941 soy protein Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
- Y10T428/31899—Addition polymer of hydrocarbon[s] only
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
- Y10T428/31899—Addition polymer of hydrocarbon[s] only
- Y10T428/31902—Monoethylenically unsaturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
- Y10T428/31906—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2582—Coating or impregnation contains an optical bleach or brightener or functions as an optical bleach or brightener [e.g., it masks fabric yellowing, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2762—Coated or impregnated natural fiber fabric [e.g., cotton, wool, silk, linen, etc.]
- Y10T442/277—Coated or impregnated cellulosic fiber fabric
- Y10T442/2779—Coating or impregnation contains an acrylic polymer or copolymer [e.g., polyacrylonitrile, polyacrylic acid, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2762—Coated or impregnated natural fiber fabric [e.g., cotton, wool, silk, linen, etc.]
- Y10T442/277—Coated or impregnated cellulosic fiber fabric
- Y10T442/2787—Coating or impregnation contains a vinyl polymer or copolymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
Definitions
- the invention relates to whitened polyacrylonitriles and acrylonitrile copolymers, especially as aqueous dispersions, to coating slips comprising them, and to their use for coating a wide variety of substrates.
- DE-A-195 00 195 describes how whitened, finely divided polymer materials affixed with brighteners suitable for the polymer material can be used as powders or as dispersions for whitening paper coating slips based on synthetic binders. This method is still in need of improvement, however, in terms of the rheological properties when the whitened polymer powder is used, or in terms of the solids contents of their dispersions.
- the invention therefore provides polyacrylonitriles or acrylonitrile copolymers, referred to below simply as polymers, which are whitened by means of optical brighteners and are obtainable by emulsion polymerization of acrylonitrile with or without comonomers, in the presence or absence of graftable substrates, with the addition of an optical brightener before, during or after the emulsion polymerization.
- the polymers of the invention are in the form of their aqueous dispersions.
- the aqueous polymer dispersion contains preferably:
- the aqueous polymer dispersion may additionally include customary additives such as preservatives, preferably from 0 to 15% by weight, based on the polymer of component a).
- Suitable surface-active substances are preferably anionic and/or nonionic surfactants.
- Preferred surface-active substances are the graftable substrates of types I to III below, preferably those of types I and II, and, in particular, those of type I.
- Suitable preservatives are methyl- and chloromethyl-isothiazolin-3-one, benzisothiazolin-3-one, or mixtures thereof.
- the polymers of the invention are preferably finely divided and in particular have an average particle size (measured by the method of laser correlation spectroscopy) of ⁇ 1 ⁇ m, preferably 50-800 nm, in particular 50-500 nm, and, with particular preference, 50-400 nm.
- the polymers preferably contain 50 or more mol-% of acrylonitrile units.
- suitable comonomers are nonionic and/or ionic-ethylenically unsaturated comonomers.
- Preferred nonionic comonomers are alkyl esters of acrylic and methacrylic acid, preferably C 1 -C 8 alkyl esters, and also ethoxylated and propoxylated esters of acrylic and methacrylic acid, styrene and ⁇ -methylstyrene and their derivatives, vinyl carboxylates, preferably vinyl acetate, conjugated dienes such as, for example, butadiene or isoprene, methacrylonitrile, vinyl chloride and vinylidene chloride, N-alkyl and N-aryl-substituted maleimides, and also hydrophilicizing comonomers such as acrylamides and methacrylamides, acrylic and methacrylic acid, N-vinylamides, such as, for example, 1-vinyl-2-pyrrolidone.
- Suitable ionic comonomers are vinylsulfonic acid and its salts, methallylsulfonic acid and also allylsulfonic acid and salts thereof, styrenesulfonic acid and its salts, (2-acrylamido-2-methyl)-propanesulfonic acid, its esters and its salts, (3-sulfopropyl)-acrylic acid and its salts, (3-sulfopropyl)-acrylic esters, and also the alkyl esters and oxyalkyl esters of said vinylic sulfonic acids.
- Particularly preferred comonomers are alkyl acrylates, styrene, and butadiene/styrene mixtures. Preferably, however, it is also possible to operate with acrylonitrile as sole monomer.
- the whitened polymers of the invention are obtainable by emulsion polymerization in the presence of graftable substrates.
- graftable substrates are preferably polymeric emulsifiers containing sulfonate groups.
- Particularly suitable are polymers of types I and II, which preferably have average molecular weights of M w >5000 g/mol.
- poly- and oligourethanes of type III which preferably have an average molecular weight of >1000 g/mol.
- the emulsifier of type I corresponds to the formula (I) and that of type II to the formula (II)
- M denotes a cation-forming radical, preferably H, Na, K, NH 4 or R 3 NH 3 ,
- n denotes 1 or 2
- R denotes a hydrocarbon chain having 1 to 10 carbon atoms or an aromatic radical having 6 to 10 carbon atoms, preferably —(CH 2 ) 2 NH(CH 2 ) 2 — or a radical derived from a C 1 -C 4 alkane or from benzene, methylbenzene or naphthalene,
- R 1 denotes H or —CH 3 ,
- R 2 denotes H, C 1 -C 16 alkyl, preferably —CH 3 , —C 2 H 5 , —C 4 H 9 , —CH 2 —C(CH 3 ) 3 , —C 14 H 29 , —C 16 H 33 or phenyl,
- R 3 denotes a hydrocarbon radical of an amine
- Particularly preferred emulsifiers are those of the formulae (I) and (II), in which
- R —CH 2 CH 2 —
- x: y from 1:1.0 to 1:1.1.
- Emulsifiers of the formulae I and II are known, for example, from EP-A 590 460.
- Emulsifiers of the type III are the oligourethanes known from EP-A 400 410 which are used in connection with the free-radically initiated emulsion polymerization for preparing surface sizing agents for paper.
- emulsifiers of the type III to the oligourethanes specified on p. 7 of EP-A 400 410, especially those obtainable by reacting a macrodiol and an oligoisocyanate having an NCO functionality of >2.
- HDI hexamethylene diisocyanate
- High molecular mass products exhibit heightened long-chain branching.
- Preferred polymers are those modified by strongly acidic groups.
- Preferred strongly acidic groups are sulfonate groups, the amount of strongly acidic groups being preferably 50-500, particularly 100-500, milliequivalents/kg of polymer.
- the amount of graftable substrates, especially of the abovementioned emulsifiers, which is preferably used for the emulsion polymerization is 2-20% by weight, preferably 2-10% by weight, based on the total amount of monomers to be polymerized.
- the polymers obtained in the presence of graftable substrates, especially their dispersions include not only homo- and/or copolymers of the acrylonitriles used for the polymerization and/or mixtures thereof with other monomers, preferably including fractions of graft polymer of the monomers used onto the polymeric emuslifiers, but also fractions of the ungrafted, graftable substrates, especially of the polymeric emulsifiers.
- the amount of emulsifier used preferably 50 or more mol-% is grafted.
- the grafting yield when using the polymeric emulsifiers specified as preferred is from 50 to 80 mol-%.
- optical brighteners are those commonly used in the textiles sector for whitening polyacrylonitrile. Particular preference is given to neutral brighteners, but especially cationic brighteners. Particularly suitable are optical brighteners which on the corresponding fiber material in the textiles sector have lightfastnesses of at least 4 as determined in accordance with the xenon test in accordance with the method by way of the guidelines determining colorfastness properties in accordance with DIN 54 004. Particularly advantageous for this application are all brighteners having lightfastnesses of 5-7.
- R 4 denotes ethyl or phenyl
- An ⁇ represents an anion
- X represents CH or N
- An ⁇ represents an anion
- R 5 represents CH 3 or CH 2 —C 6 H 5 .
- R 6 represents H or SO 2 —CH 3 ,
- R 7 represents NH 2 , CH 3 , C 2 H 4 —OH, NH—C 3 H 6 —N(CH 3 ) 2 , CH 2 —CH(CH 3 )—N(CH 3 ) 2 ,
- An ⁇ represents an anion, preferably the anion of a mineral acid or —O 3 SOCH 3 or
- R 8 denotes H or CH 3 ,
- R 9 represents CH 3 , CH 2 C(CH 3 ) 2 —CH 2 —N(CH 3 ) 3 + An ⁇ or
- An ⁇ denotes an anion, preferably the anion of a mineral acid or —O 3 SOCH 3 .
- Preferred polyacrylonitriles or acrylonitrile copolymers of the invention are whitened with optical brighteners of the formula (1), (2) or (3), especially (1) or (2).
- the emulsion polymerization generally takes place such that acrylonitrile and/or its mixtures with the comonomers and, if desired, graftable substrates in the presence of emulsifiers are polymerized in aqueous emulsion, using free-radical initiators, in a manner known per se.
- Suitable initiators are persulfates, hydrogen peroxide and various other organic peroxides which decompose below 100° C., and also the redox systems which respond in the temperature range from 20 to 100° C., such as, for example, H 2 O 2 /Rongalit, H 2 O 2 /thioglycol and t-butyl hydroperoxide/ascorbic acid.
- Particularly advantageous is the system persulfite/SO 2 , which is active at temperatures of 40-70° C. and which, by virtue of the incorporation of sulfonate and sulfate end groups, increases the level of acidic groups present.
- Particularly preferred emulsifiers are the above-described polymeric emulsifiers, containing sulfonic acid groups, of the formulae (I) to (III).
- emulsion polymerization it is preferred to include all or some of an aqueous solution of the emulsifier, preferably of the polymeric emulsifier described above, in the initial charge and then to add the monomers and the initiator gradually, for example over 2 to 6 hours, preferably separately.
- the remainder can then be metered in gradually, for example over 2 to 6 hours, together with the monomers and the initiator, preferably in separate streams.
- the emulsion polymerization is conducted at temperatures from 20 to 100° C., preferably in the range from 40 to 80° C.
- the product of the polymerization reaction comprises generally finely divided aqueous polymer emulsions which are free from precipitated coagulum.
- the whitened polymers of the invention as aqueous dispersions in the case of acrylonitrile homopolymers, preferably with solids contents of up to 45% by weight, and, in the case of acrylonitrile copolymers, preferably with solids contents of up to 65% by weight.
- the optical brightener can be applied to the polymer particles, for example, in accordance with the methods described in DE-A-195 00 195.
- the process of the invention has the particular feature that a suitable optical brightener is added before, during or after the emulsion polymerization.
- the brightener preferably a water-soluble cationic brightener, alone or in combination with further optically brightening compounds, is mixed into the aqueous dispersions of the polymers containing strongly acidic groups, and is then caused to attach to the polymer particles at elevated temperature. If desired, further auxiliaries are used.
- the attachment of the optical brightener preferably takes place above the hydrothermal softening temperature (TgH 2 O) of the polymer, preferably at 25-150° C., in particular at 50-100° C. This takes place largely with retention of the original particle size distribution of the emulsion polymers.
- TgH 2 O hydrothermal softening temperature
- optical brighteners it is advantageous to cause the optical brighteners to act on the dispersion comprising emulsion polymers, which still contains residual monomers. Subsequently, the monomers are separated off, preferably by distillation. It has been found that, in the case of this preferred attachment variant, the takeup capacity on the one hand and the attachment rate of the brightener on the other hand are increased.
- the amount of the optical brighteners used, based on the polymer, is guided by the desired brightener effect and is preferably 0.1-2% by weight of brightener, based on the polymer solids fraction in the dispersion.
- the invention additionally provides aqueous dispersions containing more than 30% by weight, especially 31-65% by weight and, with particular preference, 40-65% by weight, based on the dispersion, of a whitened polyacrylonitrile and/or acrylonitrile copolymer.
- This aqueous dispersion of the invention contains preferably 1-15% by weight, especially 2-10% by weight and, with particular preference, 5-10% by weight of at least one surface-active substance, based on whitened polymer.
- the preferred embodiments of these dispersions in terms of polymer, surface-active substances and possible further additives correspond to those for the abovementioned dispersions.
- the polymer is preferably obtained by the method of emulsion polymerization, in particular in accordance with the process described above.
- the aqueous polymer dispersions of the invention may include as further additives, like additives already described above to the whitened, finely divided polymer dispersions used in accordance with the invention, in the stated amounts, examples being surface-active substances, preservatives, etc.
- the invention additionally provides acrylonitrile homo- and/or copolymers whitened with optical brighteners, said polymers having been emulsion-polymerized in the presence of at least one polymeric emulsifier of the formulae I to III.
- the whitened polymers of the invention can be used without further treatment or purification or can be admixed with pigments and/or further auxiliaries.
- the invention additionally provides aqueous coating slips having a solids content of 25-80% by weight, especially 50-70% by weight, and containing:
- the polymer of the invention or the dispersion of the invention comprising a whitened polymer is preferably employed in the coating slips of the invention.
- the coating slips of the invention may also include wet strength agents, dispersants and, if desired, further additives.
- Suitable inorganic pigments are preferably clay, kaolin, barium sulfate, satin white, silica, alumina, aluminum silicate, titanium dioxide, talc, chalk and mixtures thereof.
- These pigments are preferably used in the form of an aqueous slurry.
- Suitable binders are those based on polymeric binding agents, such as, for example, butadiene-styrene, styrene-butyl acrylate, acrylonitrile-butadiene-styrene, styrene-butadiene-alkyl acrylate, alkyl acrylate, acrylonitrile-alkyl acrylate, acrylonitrile-styrene, ethylene-vinyl chloride, and ethylene-vinyl acetate copolymers and also the homopolymers polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, and polyaddition compounds such as polyurethanes.
- polymeric binding agents such as, for example, butadiene-styrene, styrene-butyl acrylate, acrylonitrile-butadiene-styrene, styrene-butadiene-alkyl
- binding agents such as, for example, starch, degraded starch, alginates and proteins, such as gelatin, casein and soy protein, for example.
- Sodium carboxymethylcellulose, polyvinyl alcohol, and synthetic, acrylate-based thickeners are also suitable.
- suitable dispersants are sodium polyacrylates, sodium polyphosphate and sodium citrate.
- the invention additionally provides for the use of such coating slips to coat substrates.
- substrates suitable for coating are:
- Paper such as coated paper, photographic paper, etc., paperboard, wood, polymer films, textiles and also nonwoven materials and building materials such as stone, plaster, etc.
- the abovementioned coating slips are preferably used to coat coated papers, photographic papers, and paperboard.
- the coating slip of the invention it is possible to coat paper and paperboard with the customary coating apparatus: for example, with an air knife, a coating knife, a brush, a roller, a knife coater, a rod or any other coating apparatus common in the paper industry.
- the coating slips of the invention can be used in particular for coating paper, especially for chromoprints, art prints/picture prints, offset prints, gravure prints, and paperboard.
- the aqueous coating slips used in accordance with the invention can comprise additional dispersants and/or emulsifiers and also customary anionic or cationic and/or nonionic surface-active substances, as are described, for example, in DE-A- 2 334 769, pp. 8-10 (corresponds to GB-A-1 417 071). Preference is given in this context to anionic and/or nonionic surfactants.
- aqueous coating slips of the invention can be used, for example, as topcoats.
- a particular advantage of this use in accordance with the invention lies in the very high gloss and extraordinary smoothness of the coated papers obtained in this case.
- the invention additionally provides the substrates, especially papers, coated with the coating slips of the invention.
- Rx, Ry and Rz are the readings from a three-filter photometer
- the coated papers were exposed at a distance of about 15 cm using the daylight fluorescent lamp Sylvania Daylight F 20 W/DRS for 72 h, and exhibited the following whitenesses before and after exposure: TABLE 2 Decrease in whiteness Brightener CIE whiteness due to Example in %, based on before after exposure 2) polymer exposure exposure (difference) none 80.6 80.3 0.3 a) 0.1 121.9 122.3 0 b) 0.2 129.1 129.0 0.1 c) 0.4 143.6 143.1 0.5 d) 0.8 148.2 147.4 0.8 e) 1 150 148.9 1.1
- the resulting stable, whitened polymer dispersion showed excellent white effects with high lightfastnesses, as a topcoat, and, moreover, was easy to incorporate into paper coating slips.
- a reactor equipped with stirrer and four metering devices was charged under a nitrogen blanket with 650 parts by weight of deionized water, 105 parts by weight of the polymeric emulsifier from Example 1 and 7.4 parts by weight of sodium styrene-sulfonate. After conditioning at 60° C., 4 parts by weight of iron(II) sulfate * 7H 2 O (0.1% strength) were added in order to activate free-radical polymerization, and the following solutions were metered in at a uniform rate over the course of 5 hours:
- Feed 1 610 parts by weight of acrylonitrile 499 parts by weight of methyl acrylate
- Feed 2 370 parts by weight of deionized water 1.85 parts by weight of butyl acrylate
- Feed 3 370 parts by weight of deionized water 1.40 parts by weight of Rongalit® C (NaSO 2 —CH 2 —OH * 2H 2 O)
- Feed 4 370 parts by weight of deionized water 14.80 parts by weight of sodium styrenesulfonate
- the solids content and the average particle size (determined by laser correlation spectroscopy) of the white pigment/polymer dispersions obtained in this way were as follows: TABLE 4 Example Brightener in %, Average particle size 4 based on polymer SC in % (nm) a) 0.2 43.8 542 b) 0.4 38.6 252/239 c) 0.8 37 256
- the coated slips 6a)-e) (not in accordance with the invention) and 6f)-i) (Inventive Examples) are applied to base paper with the aid of a manual knife coater or an experimental coating unit and are dried at 80° C.
- Table 6 shows the CIE whiteness of the papers following production and drying.
- Comparative optical brightener, based on solids content of the coating slip of Example 5 CIE Example (in % by weight) whiteness 5) — 69.0 6a) 0.025 78.0 6b) 0.05 82.4 6c) 0.1 88.2 6d) 0.2 91.2 6e) 0.3 91.3 6f) 0.016 78.7 6g) 0.032 83.9 6h) 0.064 90.2 6i) 0.128 97.2
- Base paper was precoated with a pigmented coating slip as in Example 5, without whitener, with an application of about 16 g/m 2 . Subsequently, the dispersion of Example 4b) was coated as topcoat with an application of 8 g/m 2 . The comparison used for a brightened coat was Example 6d). The lightfastnesses were determined in the xenon test in accordance with the guidelines for the determination of colorfastnesses in accordance with DIN 54 004.
- the coat furnished in this way exhibited not only high whiteness and excellent lightfastness but also high gloss and high smoothness.
- Base paper was precoated with an application of about 16 g/m 2 of the following pigment slip
- polyvinyl alcohol e.g., Mowiol® 28-99 or 2-88, from Hoechst
- cationic additive e.g., Additol® VXT 3529, from Hoechst
- the coated papers were exposed at a distance of about 15 cm for 72 h using the daylight fluorescent lamp Sylvania Daylight F 20 W/DRS and gave the following whitenesses before and after exposure: TABLE 10 Brightener in % by weight CIE whiteness Drop in Example based on Before After whiteness 10) polymer exposure due to exposure none 80.6 80.3 0.3 a) 0.1 115.8 114.3 1.5 b) 0.2 144.7 143.5 1.2 c) 0.4 148.6 145.1 3.5 d) 0.8 154.8 152.3 2.5
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Abstract
The present invention relates to polymers whitened with optical brighteners obtained by
(a) emulsion polymerization of acrylonitrile with or without a comonomer in the presence or absence of a graftable substrate, and
(b) addition of an optical brightener before, during, or after the emulsion polymerization.
Description
- The invention relates to whitened polyacrylonitriles and acrylonitrile copolymers, especially as aqueous dispersions, to coating slips comprising them, and to their use for coating a wide variety of substrates.
- In addition to the customary white pigments, especially china clay and calcium carbonate, the coating slips generally include anionic whiteners for the purpose of optical brightening, examples being those of the bis-triazinyl-aminostilbene-disulfonic acid type. These whiteners, however, lead only to highly unsatisfactory white effects and to very low grayness limits (=whitener concentration at which further addition of whitener produces no increase, or even a decrease, in whiteness). Furthermore, the whitener types referred to possess inadequate lightfastness in the coating slips.
- DE-A-195 00 195 describes how whitened, finely divided polymer materials affixed with brighteners suitable for the polymer material can be used as powders or as dispersions for whitening paper coating slips based on synthetic binders. This method is still in need of improvement, however, in terms of the rheological properties when the whitened polymer powder is used, or in terms of the solids contents of their dispersions.
- The preparation of whitened coatings on various substrates, especially on coated papers and cards with high whiteness, a high grayness limit and good lightfastness, is a difficult problem which has not been solved satisfactorily to date.
- It has now been found, surprisingly, that when specific whitened polymers are used in coating slips, they give the coatings produced therewith on a wide variety of substrates very high whitenesses, high grayness limits, high lightfastnesses, and high bleedfastnesses.
- The invention therefore provides polyacrylonitriles or acrylonitrile copolymers, referred to below simply as polymers, which are whitened by means of optical brighteners and are obtainable by emulsion polymerization of acrylonitrile with or without comonomers, in the presence or absence of graftable substrates, with the addition of an optical brightener before, during or after the emulsion polymerization.
- In one preferred embodiment the polymers of the invention are in the form of their aqueous dispersions.
- The aqueous polymer dispersion contains preferably:
- a) 1-65% by weight, in particular 10-55% by weight, of polymer of the invention, based on the dispersion, and
- b) 1-15% by weight, in particular 5-10% by weight, of surface-active substances, based on polymer of a).
- The aqueous polymer dispersion may additionally include customary additives such as preservatives, preferably from 0 to 15% by weight, based on the polymer of component a).
- Suitable surface-active substances are preferably anionic and/or nonionic surfactants.
- Preferred surface-active substances are the graftable substrates of types I to III below, preferably those of types I and II, and, in particular, those of type I.
- Examples of suitable preservatives are methyl- and chloromethyl-isothiazolin-3-one, benzisothiazolin-3-one, or mixtures thereof.
- The polymers of the invention are preferably finely divided and in particular have an average particle size (measured by the method of laser correlation spectroscopy) of <1 μm, preferably 50-800 nm, in particular 50-500 nm, and, with particular preference, 50-400 nm.
- The polymers preferably contain 50 or more mol-% of acrylonitrile units. Examples of suitable comonomers are nonionic and/or ionic-ethylenically unsaturated comonomers.
- Preferred nonionic comonomers are alkyl esters of acrylic and methacrylic acid, preferably C1-C8 alkyl esters, and also ethoxylated and propoxylated esters of acrylic and methacrylic acid, styrene and α-methylstyrene and their derivatives, vinyl carboxylates, preferably vinyl acetate, conjugated dienes such as, for example, butadiene or isoprene, methacrylonitrile, vinyl chloride and vinylidene chloride, N-alkyl and N-aryl-substituted maleimides, and also hydrophilicizing comonomers such as acrylamides and methacrylamides, acrylic and methacrylic acid, N-vinylamides, such as, for example, 1-vinyl-2-pyrrolidone.
- Examples of suitable ionic comonomers are vinylsulfonic acid and its salts, methallylsulfonic acid and also allylsulfonic acid and salts thereof, styrenesulfonic acid and its salts, (2-acrylamido-2-methyl)-propanesulfonic acid, its esters and its salts, (3-sulfopropyl)-acrylic acid and its salts, (3-sulfopropyl)-acrylic esters, and also the alkyl esters and oxyalkyl esters of said vinylic sulfonic acids.
- Particularly preferred comonomers are alkyl acrylates, styrene, and butadiene/styrene mixtures. Preferably, however, it is also possible to operate with acrylonitrile as sole monomer.
- In one preferred embodiment the whitened polymers of the invention are obtainable by emulsion polymerization in the presence of graftable substrates. These graftable substrates are preferably polymeric emulsifiers containing sulfonate groups. Particularly suitable are polymers of types I and II, which preferably have average molecular weights of Mw>5000 g/mol. Likewise preferred are poly- and oligourethanes of type III, which preferably have an average molecular weight of >1000 g/mol.
-
- in which
- M denotes a cation-forming radical, preferably H, Na, K, NH4 or R3NH3,
- n denotes 1 or 2,
- R denotes a hydrocarbon chain having 1 to 10 carbon atoms or an aromatic radical having 6 to 10 carbon atoms, preferably —(CH2)2NH(CH2)2— or a radical derived from a C1-C4 alkane or from benzene, methylbenzene or naphthalene,
- R1 denotes H or —CH3,
- R2 denotes H, C1-C16 alkyl, preferably —CH3, —C2H5, —C4H9, —CH2—C(CH3)3, —C14H29, —C16H33 or phenyl,
- R3 denotes a hydrocarbon radical of an amine, and
- x, y are chosen such that the average molecular weight Mw of the polymers (I) and (II) is from 2000 to 500,000, preferably from 5000 to 100,000, and the ratio x:y=from 1:4 to 1:1, preferably from 1:3 to 1:1.
- Particularly preferred emulsifiers are those of the formulae (I) and (II), in which
- 1A) R1=CH3 and R2=—CH2—C(CH3)3 or
- 2A) R1=CH3 and R2=CH3 or
- 3A) R1=H and R2=C6H5,
- where in each case
- R=—CH2CH2—,
- M=Na,
- n=1 and
- x: y=from 1:1.0 to 1:1.1.
- Very particular preference is given to the emulsifier of the type 1A).
- Emulsifiers of the formulae I and II are known, for example, from EP-A 590 460.
- Emulsifiers of the type III are the oligourethanes known from EP-A 400 410 which are used in connection with the free-radically initiated emulsion polymerization for preparing surface sizing agents for paper.
- Particular preference is given as emulsifiers of the type III to the oligourethanes specified on p. 7 of EP-A 400 410, especially those obtainable by reacting a macrodiol and an oligoisocyanate having an NCO functionality of >2.
- A macrodiol is, for example, a polyester of adipic acid, hexanediol, neopentyl glycol having an average molecular weight Mw=1700 g/mol. The oligoisocyanate is, for example, a hexamethylene diisocyanate (HDI) based trimer of the isocyanate type (f=3) and higher molecular mass oligomers (f=3) derived therefrom.
- At medium and high molecular weights, suitable linear and branched polyacrylonitriles and acrylonitrile copolymers exhibit intrinsic viscosities (measured in dimethylformamide at 20° C.) of [η]=from 0.5 to 10.0 dl/g, preferably of [η]= from 1.0 to 5.0 dl/g. High molecular mass products exhibit heightened long-chain branching.
- Preferred polymers are those modified by strongly acidic groups. Preferred strongly acidic groups are sulfonate groups, the amount of strongly acidic groups being preferably 50-500, particularly 100-500, milliequivalents/kg of polymer.
- The incorporation of strongly acidic groups into the copolymer can take place, for example:
- a) by using the above-described graftable emulsifiers containing sulfo groups,
- b) by using comonomers containing sulfonic acid groups and/or sulfonate groups, preferably the abovementioned ionic-ethylenic comonomers, and/or
- c) by the free-radical initiator components, preferably by using the initiator system: persulfate/sulfite.
- The amount of graftable substrates, especially of the abovementioned emulsifiers, which is preferably used for the emulsion polymerization is 2-20% by weight, preferably 2-10% by weight, based on the total amount of monomers to be polymerized.
- The polymers obtained in the presence of graftable substrates, especially their dispersions, include not only homo- and/or copolymers of the acrylonitriles used for the polymerization and/or mixtures thereof with other monomers, preferably including fractions of graft polymer of the monomers used onto the polymeric emuslifiers, but also fractions of the ungrafted, graftable substrates, especially of the polymeric emulsifiers.
- Based on the amount of emulsifier used, preferably 50 or more mol-% is grafted. Depending on the chosen polymerization conditions such as temperature, initiator system and nature of the comonomers, the grafting yield when using the polymeric emulsifiers specified as preferred is from 50 to 80 mol-%.
- Particularly suitable optical brighteners are those commonly used in the textiles sector for whitening polyacrylonitrile. Particular preference is given to neutral brighteners, but especially cationic brighteners. Particularly suitable are optical brighteners which on the corresponding fiber material in the textiles sector have lightfastnesses of at least 4 as determined in accordance with the xenon test in accordance with the method by way of the guidelines determining colorfastness properties in accordance with DIN 54 004. Particularly advantageous for this application are all brighteners having lightfastnesses of 5-7.
-
- in which
- R4 denotes ethyl or phenyl, and
- Anθ represents an anion,
-
- in which
- X represents CH or N,
- Anθ represents an anion,
- R5 represents CH3 or CH2—C6H5, and
- R6 represents H or SO2—CH3,
-
- in which
- R7 represents NH2, CH3, C2H4—OH, NH—C3H6—N(CH3)2, CH2—CH(CH3)—N(CH3)2,
- C2H4—CONH—C2H4—N(CH3)2, C2H4—O—CH(CH3)—CH2—N(CH3)2, NH—C3H6—N(CH3)3 +Anθ, C2H4—N(CH3)3 +Anθ,
- C2H4—CONH—C2H4—N(CH3)3 +Anθ, CH2—CH(CH3)—N(CH3)3 +Anθ, C2H4—O—CH(CH3)—CH2—N(CH3)3 +Anθ,
-
- in which
- R8 denotes H or CH3,
-
- in which
-
- where Anθ denotes an anion, preferably the anion of a mineral acid or —O3SOCH3.
- Preferred polyacrylonitriles or acrylonitrile copolymers of the invention are whitened with optical brighteners of the formula (1), (2) or (3), especially (1) or (2).
- The emulsion polymerization generally takes place such that acrylonitrile and/or its mixtures with the comonomers and, if desired, graftable substrates in the presence of emulsifiers are polymerized in aqueous emulsion, using free-radical initiators, in a manner known per se.
- Suitable initiators are persulfates, hydrogen peroxide and various other organic peroxides which decompose below 100° C., and also the redox systems which respond in the temperature range from 20 to 100° C., such as, for example, H2O2/Rongalit, H2O2/thioglycol and t-butyl hydroperoxide/ascorbic acid. Particularly advantageous is the system persulfite/SO2, which is active at temperatures of 40-70° C. and which, by virtue of the incorporation of sulfonate and sulfate end groups, increases the level of acidic groups present.
- Particularly preferred emulsifiers are the above-described polymeric emulsifiers, containing sulfonic acid groups, of the formulae (I) to (III).
- To conduct the emulsion polymerization it is preferred to include all or some of an aqueous solution of the emulsifier, preferably of the polymeric emulsifier described above, in the initial charge and then to add the monomers and the initiator gradually, for example over 2 to 6 hours, preferably separately. In the case where some of the emulsifier is included in the initial charge, the remainder can then be metered in gradually, for example over 2 to 6 hours, together with the monomers and the initiator, preferably in separate streams. Alternatively, it is possible to add the emulsifier, initiator and the monomers separately and continuously throughout the polymerization period and to include only water in the initial charge.
- It is also possible to operate batchwise, in which case, for example, emulsifier, monomer mixture and initiator are introduced together and this charge is then heated, for polymerization, to the desired polymerization temperature.
- Depending on the decomposition characteristics of the initiators used, the emulsion polymerization is conducted at temperatures from 20 to 100° C., preferably in the range from 40 to 80° C.
- The product of the polymerization reaction comprises generally finely divided aqueous polymer emulsions which are free from precipitated coagulum.
- Thus with the process of emulsion polymerization it is possible, for example, to produce the whitened polymers of the invention as aqueous dispersions in the case of acrylonitrile homopolymers, preferably with solids contents of up to 45% by weight, and, in the case of acrylonitrile copolymers, preferably with solids contents of up to 65% by weight.
- The resulting dispersions are extremely stable to additions of electrolyte, to temperature effects, and to the action of shear forces.
- The optical brightener can be applied to the polymer particles, for example, in accordance with the methods described in DE-A-195 00 195. The process of the invention has the particular feature that a suitable optical brightener is added before, during or after the emulsion polymerization.
- In one particularly preferred embodiment the brightener, preferably a water-soluble cationic brightener, alone or in combination with further optically brightening compounds, is mixed into the aqueous dispersions of the polymers containing strongly acidic groups, and is then caused to attach to the polymer particles at elevated temperature. If desired, further auxiliaries are used.
- The attachment of the optical brightener preferably takes place above the hydrothermal softening temperature (TgH2O) of the polymer, preferably at 25-150° C., in particular at 50-100° C. This takes place largely with retention of the original particle size distribution of the emulsion polymers.
- It is advantageous to cause the optical brighteners to act on the dispersion comprising emulsion polymers, which still contains residual monomers. Subsequently, the monomers are separated off, preferably by distillation. It has been found that, in the case of this preferred attachment variant, the takeup capacity on the one hand and the attachment rate of the brightener on the other hand are increased.
- The amount of the optical brighteners used, based on the polymer, is guided by the desired brightener effect and is preferably 0.1-2% by weight of brightener, based on the polymer solids fraction in the dispersion.
- The invention additionally provides aqueous dispersions containing more than 30% by weight, especially 31-65% by weight and, with particular preference, 40-65% by weight, based on the dispersion, of a whitened polyacrylonitrile and/or acrylonitrile copolymer. This aqueous dispersion of the invention contains preferably 1-15% by weight, especially 2-10% by weight and, with particular preference, 5-10% by weight of at least one surface-active substance, based on whitened polymer. The preferred embodiments of these dispersions in terms of polymer, surface-active substances and possible further additives correspond to those for the abovementioned dispersions. The polymer is preferably obtained by the method of emulsion polymerization, in particular in accordance with the process described above.
- The aqueous polymer dispersions of the invention may include as further additives, like additives already described above to the whitened, finely divided polymer dispersions used in accordance with the invention, in the stated amounts, examples being surface-active substances, preservatives, etc.
- The invention additionally provides acrylonitrile homo- and/or copolymers whitened with optical brighteners, said polymers having been emulsion-polymerized in the presence of at least one polymeric emulsifier of the formulae I to III.
- The preferred embodiments correspond to those indicated above.
- The whitened polymers of the invention, especially in the form of their aqueous dispersions, can be used without further treatment or purification or can be admixed with pigments and/or further auxiliaries.
- The invention additionally provides aqueous coating slips having a solids content of 25-80% by weight, especially 50-70% by weight, and containing:
- 30-70, preferably 40-60% by weight of at least one inorganic pigment, based on the solids content,
- 10-50% by weight of whitened polyacrylonitrile and/or acrylonitrile copolymer, based on the inorganic pigment, and
- 5-15% by weight of at least one binder, based on the inorganic pigment.
- The polymer of the invention or the dispersion of the invention comprising a whitened polymer is preferably employed in the coating slips of the invention.
- The coating slips of the invention may also include wet strength agents, dispersants and, if desired, further additives.
- Suitable inorganic pigments are preferably clay, kaolin, barium sulfate, satin white, silica, alumina, aluminum silicate, titanium dioxide, talc, chalk and mixtures thereof.
- These pigments are preferably used in the form of an aqueous slurry.
- Examples of suitable binders are those based on polymeric binding agents, such as, for example, butadiene-styrene, styrene-butyl acrylate, acrylonitrile-butadiene-styrene, styrene-butadiene-alkyl acrylate, alkyl acrylate, acrylonitrile-alkyl acrylate, acrylonitrile-styrene, ethylene-vinyl chloride, and ethylene-vinyl acetate copolymers and also the homopolymers polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, and polyaddition compounds such as polyurethanes.
- Also outstandingly suitable, however, are natural binding agents such as, for example, starch, degraded starch, alginates and proteins, such as gelatin, casein and soy protein, for example. Sodium carboxymethylcellulose, polyvinyl alcohol, and synthetic, acrylate-based thickeners are also suitable. Examples of suitable dispersants are sodium polyacrylates, sodium polyphosphate and sodium citrate.
- The coating slips per se into which the polymers of the invention, or the dispersions of the invention comprising whitened polymers, can be incorporated are known and are described, for example, in J. P.Casey “Pulp and Paper”, Chemistry and Chemical Technology, 2nd Ed. Vol. III, pp. 1648-1649 and McGraw-Hill “Pulp and Paper Manufacture”, 2nd and 5th Ed. Vol. II, p. 497.
- The invention additionally provides for the use of such coating slips to coat substrates.
- Examples that may be mentioned of substrates suitable for coating are:
- Paper, such as coated paper, photographic paper, etc., paperboard, wood, polymer films, textiles and also nonwoven materials and building materials such as stone, plaster, etc. The abovementioned coating slips are preferably used to coat coated papers, photographic papers, and paperboard.
- With the coating slip of the invention it is possible to coat paper and paperboard with the customary coating apparatus: for example, with an air knife, a coating knife, a brush, a roller, a knife coater, a rod or any other coating apparatus common in the paper industry.
- The coating slips of the invention can be used in particular for coating paper, especially for chromoprints, art prints/picture prints, offset prints, gravure prints, and paperboard.
- The aqueous coating slips used in accordance with the invention can comprise additional dispersants and/or emulsifiers and also customary anionic or cationic and/or nonionic surface-active substances, as are described, for example, in DE-A- 2 334 769, pp. 8-10 (corresponds to GB-A-1 417 071). Preference is given in this context to anionic and/or nonionic surfactants.
- The aqueous coating slips of the invention can be used, for example, as topcoats. A particular advantage of this use in accordance with the invention lies in the very high gloss and extraordinary smoothness of the coated papers obtained in this case.
- The invention additionally provides the substrates, especially papers, coated with the coating slips of the invention.
- The invention is illustrated using the following examples. The parts indicated in the examples are parts by weight; the percentages, unless stated otherwise, likewise relate to the weight of the substances employed.
-
- Sieving was carried out at 60° C. to remove a little sieve residue (8 mm). The whitened, fine polymer dispersion present was coated onto base paper using a manual knife coater (coat weight: about 15 g/m2). The coated papers exhibit the following whitenesses:
TABLE 1 Whitener based on Whiteness Example 1 polymer in % Berger CIE none 85.3 84.3 a) 0.1 112.6 112 b) 0.2 126.2 123.6 c) 0.4 131.3 126.4 - The Berger whiteness is calculated in accordance with the formula of Berger.
- W=Ry+3(Rz-Rx)
- Rx, Ry and Rz are the readings from a three-filter photometer
- A. Berger, Weiβgradformeln und ihre praktische Bedeutung [whiteness formulae and their practical significance]
- Die Farbe 8 (1956) 4/6, 187-202
- The CIE method was proposed in 1986 by the Commission intemationale de l'éclairage.
- The evaluation of whiteness, Colorimetry Second Edition, Publication CIE No. 15.2 (1986) pp. 36-38.
- 100 g of a fine acrylonitrile copolymer dispersion (SC: 40% of polymer, average particle size: about 480 nm; polymer-bound sulfonate group content: 340 meq/kg), containing 51% of an acrylonitrile-methyl acrylate-sodium styrene sulfonate copolymer (in the proportion of 53.5/44.5/2.0) and 9% of a polymeric emulsifier of type 1A which is grafted therewith (having an average molar weight Mw: 20,000 g/mol, [η]DMF=1.7 dl/g), were treated for 2 hours at room temperature and 1 h at 70° C. with a) 0.1, b) 0.2, c) 0.4 and d) 0.8% of the optical brightener, based on polymeric solid fraction, from Example 1. Sieving was carried out at room temperature to remove a little sieve residue (8 mm). The resulting whitened, fine dispersion was coated onto base paper using a manual knife coater (coat weight: about 15 g/m2). The coated papers were exposed at a distance of about 15 cm using the daylight fluorescent lamp Sylvania Daylight F 20 W/DRS for 72 h, and exhibited the following whitenesses before and after exposure:
TABLE 2 Decrease in whiteness Brightener CIE whiteness due to Example in %, based on before after exposure 2) polymer exposure exposure (difference) none 80.6 80.3 0.3 a) 0.1 121.9 122.3 0 b) 0.2 129.1 129.0 0.1 c) 0.4 143.6 143.1 0.5 d) 0.8 148.2 147.4 0.8 e) 1 150 148.9 1.1 - The resulting stable, whitened polymer dispersion showed excellent white effects with high lightfastnesses, as a topcoat, and, moreover, was easy to incorporate into paper coating slips.
- 100 g of a fine acrylonitrile copolymer dispersion (SC: 35% of polymer, average particle size: about 720 nm; polymer-bound sulfonate group content: 340 meq/kg), containing 51% of an acrylonitrile-methyl acrylate-sodium styrenesulfonate copolymer (in the proportion of 53.5/44.5/2.0) and 9% of a polymeric emulsifier of type 1A which is grafted therewith (having an average molar weight Mw: 20,000 g/mol, [η]DMF=1.8 dl/g), were treated for 2 hours at room temperature and 1 hour at 70° C. with a) 0.1, b) 0.2 and c) 0.4% of the optical brightener, based on polymeric solid fraction, of the formula
- The resulting whitened, fine dispersion was coated onto base paper using a manual knife coater (coat weight: about 30 g/m2). The subsequent daylight exposure took place as described in Example 2. The coated papers exhibited the following whitenesses before and after exposure.
TABLE 3 Decrease in Brightener CIE whiteness whiteness Example in %, based on before after due to 3) polymer exposure exposure exposure none 83.4 83.1 0.3 a) 0.1 118.1 115.6 2.5 b) 0.2 124.9 120.1 4.8 c) 0.4 132 122.8 9.2 - A reactor equipped with stirrer and four metering devices was charged under a nitrogen blanket with 650 parts by weight of deionized water, 105 parts by weight of the polymeric emulsifier from Example 1 and 7.4 parts by weight of sodium styrene-sulfonate. After conditioning at 60° C., 4 parts by weight of iron(II) sulfate * 7H2O (0.1% strength) were added in order to activate free-radical polymerization, and the following solutions were metered in at a uniform rate over the course of 5 hours:
- Feed 1: 610 parts by weight of acrylonitrile 499 parts by weight of methyl acrylate
- Feed 2: 370 parts by weight of deionized water 1.85 parts by weight of butyl acrylate
- Feed 3: 370 parts by weight of deionized water 1.40 parts by weight of Rongalit® C (NaSO2—CH2—OH * 2H2O)
- Feed 4: 370 parts by weight of deionized water 14.80 parts by weight of sodium styrenesulfonate
- Following the end of the metered additions reaction was continued for 1 hour. This gave an emulsion (SC: 39.5%) containing 51% of an acrylonitrile-methyl acrylate-sodium styrenesulfonate copolymer (in the proportion of 53.5/44.5/2.0) and 9% of a polymeric emulsifier of type 1A grafted therewith and having an average molar weight Mw: 20,000 g/mol; [η]DMF=1.75 dl/g. The polymer-bound sulfonate group content is about 340 meq/kg of polymer.
- For whitening, in each case 500 parts by weight of the emulsion polymer, which still contained residual monomers, were treated at 60° C. for 1.5 h with an aqueous solution (15% strength) of the optical brightener from Example 1 in an amount of a) 0.2%, b) 0.4% and c) 0.8%, based on the polymeric solids fraction. Thereafter, the residual monomer fractions were removed by vacuum distillation with the addition of 50 parts by weight of water. Subsequently, the final filtration through a filter cloth with a mesh size of 30 μm gave the whitened emulsion polymers. The solids content and the average particle size (determined by laser correlation spectroscopy) of the white pigment/polymer dispersions obtained in this way were as follows:
TABLE 4 Example Brightener in %, Average particle size 4 based on polymer SC in % (nm) a) 0.2 43.8 542 b) 0.4 38.6 252/239 c) 0.8 37 256 - The whitened, fine dispersions a)-c) obtained in this way were coated onto base paper using a manual knife coater (coat weight: about 20 g/m2). The whitenesses of the coated papers were as follows:
TABLE 5 Example Optical brightener in % Whiteness 4) based on polymer Berger CIE none 82 81.3 a) 0.2 131.4 130.2 b) 0.4 150.5 146.76 c) 0.8 162.4 153.9 - The resulting stable, whitened polymer dispersion was easy to incorporate into paper coating slips and exhibited excellent white effects with high lightfastnesses, even when added in large amounts.
- An unwhitened paper coating slip having a solids content of about 60% by weight, whose pH was adjusted to 9 using sodium hydroxide solution, was prepared by stirring together
- 60 parts of calcium carbonate pigment (chalk HC 90)
- 40 parts of kaolin pigment (china clay SPS)
- 0.25 parts of a dispersant based on Na salt of a polycarboxylic acid
- 10 parts of a commercial 50% polymer dispersion based on styrene-butadiene-acrylic acid copolymer (Baystal® P from Bayer) (corresponding amounts of an acrylate-containing copolymer (Acronal® 320 D from BASF) gave the same result)
- 0.75 parts of polyvinyl alcohol
- 66 parts of water.
-
- which is commonly used in paper coating slips, was added and incorporated.
- In a second series of tests, f) 10%, g) 20%, h) 40% and i) 80% (amount based on solids) of the pigment dispersion (SC: 38.6%) of Example 4b) were incorporated into this coating slip.
- To prepare the coated papers, the coated slips 6a)-e) (not in accordance with the invention) and 6f)-i) (Inventive Examples) are applied to base paper with the aid of a manual knife coater or an experimental coating unit and are dried at 80° C.
- Table 6 shows the CIE whiteness of the papers following production and drying.
TABLE 6 Comparative optical brightener, based on solids content of the coating slip of Example 5 CIE Example (in % by weight) whiteness 5) — 69.0 6a) 0.025 78.0 6b) 0.05 82.4 6c) 0.1 88.2 6d) 0.2 91.2 6e) 0.3 91.3 6f) 0.016 78.7 6g) 0.032 83.9 6h) 0.064 90.2 6i) 0.128 97.2 - The papers coated with the coating slips 6f)-i) (Inventive Examples) exhibited very high gloss and good smoothness in comparison to the papers coated with 6a)-e) (brighteners).
- Base paper was precoated with a pigmented coating slip as in Example 5, without whitener, with an application of about 16 g/m2. Subsequently, the dispersion of Example 4b) was coated as topcoat with an application of 8 g/m2. The comparison used for a brightened coat was Example 6d). The lightfastnesses were determined in the xenon test in accordance with the guidelines for the determination of colorfastnesses in accordance with DIN 54 004.
TABLE 7 Drop in whiteness CIE whiteness after after exposure 4 h of Example Pigmented slip before 1 h 2 h 4 h exposure 5) without 69 66 67.5 67.6 1.4 brighteners 6d) 0.2% by weight 91.2 83.7 82 75.2 16 comparative brightener 7) Precoat of 5) and 127.3 121.7 121.3 118.9 8.1 whitened polymer dispersion (coat weight 8 g/m2) - The coat furnished in this way exhibited not only high whiteness and excellent lightfastness but also high gloss and high smoothness.
- Base paper was precoated with an application of about 16 g/m2 of the following pigment slip
- 100 parts of calcium carbonate pigment (chalk HC 90)
- 7 parts of starch
- 0.25 parts of a dispersant based on Na salt of a polycarboxylic acid (Polysalz® S from BASF)
- 5 parts of a commercial 50% polymer dispersion based on styrene-butadiene-acrylic acid copolymer (Baystal® P from Bayer) and
- 72 parts of water (about 60% SC; pH: 8.8-9).
- a) without whitener, b) with 0.1% and c) with 0.2% of the comparative brightener from Example 6 (based in each case on the solids content of the coating slip).
- The precoated papers produced in accordance with Examples 8b) and c) with brightener were furnished with a topcoat of the following composition:
- 80 parts of calcium carbonate pigment (chalk HC 90)
- 20 parts of kaolin pigment (china clay SPS)
- 0.25 parts of a dispersant based on Na salt of a polycarboxylic acid (Polysalz® S from BASF)
- 10 parts of a commercial 50% polymer dispersion based on styrene-butadiene-acrylic acid copolymer (Baystal® P from Bayer ) (the same result was also obtained with an acrylate-containing copolymer (Acronal® 320 D from BASF)
- 0.75 parts of polyvinyl alcohol and
- 66 parts of water (SC: 60%, pH: 9)
- and also a) 0.25%, b) 0.5%, and c) 1% of the comparative brightener from Example 6 (based in each case on the solids content of the coating slip) (about 8-12g/m2 coat weight).
- In a second series of experiments, the paper precoated in accordance with Example 8a) without brightener was coated with a topcoat of the following composition
- a) 100 parts of a dispersion in accordance with Example 4b)
- 20 parts of precipitated calcium carbonate (PCC)
- 0.25 parts of Polysalz® S; BASF
- 0.2 parts of polyvinyl alcohol and
- 59 parts of water SC: about 50%
- or
- b) 100 parts of a dispersion in accordance with Example 4b)
- 40 parts of precipitated calcium carbonate (PCC)
- 0.25 parts of Polysalz® S
- 0.2 parts of polyvinyl alcohol and
- 18 parts of water SC: about 50%.
-
- The papers furnished in accordance with Examples 9 and 10 were subsequently exposed at a distance of about 15 cm for 5 days using the daylight fluorescent lamp Sylvania Daylight F 20 W/DRS. The whitenesses of the coated papers before and after exposure were as follows.
TABLE 8 CIE whiteness Drop in Precoat Topcoat Before After whiteness Example Example exposure exposure due to exposure 8b) 9a) 95.3 77.6 17.7 9b) 96.7 76.8 19.9 9c) 99.5 74.2 25.3 8c) 9a) 95.6 76.9 18.7 9b) 97.4 76.4 21 9c) 99.1 73.9 25.2 8a) 10a) 135 132.9 2.1 8a) 10b) 135.4 132.9 2.5 - Pigmented ink-jet coat:
- Using a manual knife coater or an experimental coating unit, the following paper coating slip (pigmented slip)
- 100 parts of a whitened polymer dispersion in accordance with Example 4b)
- 11.4 parts of precipitated silica or silica hydrogel
- 1 part of polyvinyl alcohol (e.g., Mowiol® 28-99 or 2-88, from Hoechst)
- 1 part of cationic additive (e.g., Additol® VXT 3529, from Hoechst)
- 50 parts of water
- having a solids content of 30% and a pH of about 6 was applied to base paper (coat weight: 10-12 g/m2). Drying gave color-printable papers of excellent quality with a high CIE whiteness of 136.7, which are outstandingly suitable for colored and black ink-jet printing.
-
- The coating of the whitened polymer dispersions prepared in this way on base paper was subsequently exposed at a distance of about 15 cm for 5 days using the daylight fluorescent lamp Sylvania Daylight F 20 W/DRS. The whitenesses of the coated papers before and after exposure were as follows.
TABLE 9 Brightener in % by weight CIE whiteness Drop in Example based on Before After whiteness 9) polymer exposure exposure due to exposure none 80.6 80.3 0.3 a) 0.2 141 143.3 0 b) 0.4 146 146.7 0 c) 0.8 145 144.9 0.1 d) 1 144.4 142.8 1.6 - The maximum white yield was achieved with a whitener concentration of just 0.4%. The drop in whiteness due to exposure was within the error margin of the measuring instinuent.
-
- followed by workup as described, likewise gave a polymer dispersion suitable for the brightening of the paper coating slips. The whitened, fine polymer dispersion thus obtained was coated onto base paper using a manual knife coater (coat weight: about 15 g/m2). The coated papers were exposed at a distance of about 15 cm for 72 h using the daylight fluorescent lamp Sylvania Daylight F 20 W/DRS and gave the following whitenesses before and after exposure:
TABLE 10 Brightener in % by weight CIE whiteness Drop in Example based on Before After whiteness 10) polymer exposure exposure due to exposure none 80.6 80.3 0.3 a) 0.1 115.8 114.3 1.5 b) 0.2 144.7 143.5 1.2 c) 0.4 148.6 145.1 3.5 d) 0.8 154.8 152.3 2.5 - As a topcoat, in a mixture with precipitated calcium carbonate, the resulting stable white pigment-polymer dispersion showed excellent white effects and was also easy to incorporate into paper coating slips. The high gloss and high smoothness of the coats are noteworthy.
Claims (13)
1. A polymer whitened by means of optical brighteners and obtainable by emulsion polymerization of acrylonitrile with or without comonomers, in the presence or absence of graftable substrates, with addition of an optical brightener before, during or after the emulsion polymerization.
2. The whitened polymer as claimed in , which is in the form of its aqueous dispersion.
claim 1
3. The whitened polymer as claimed in , which has an average particle size of <1 μm, in particular 50-800 nm, preferably 50-500 nm.
claim 1
4. The whitened polymer as claimed in , wherein comonomers used are nonionic comonomers from the group consisting of alkyl esters of acrylic and methacrylic acid, preferably C1-C8 alkyl esters, and also ethoxylated and propoxylated esters of acrylic and methacrylic acid, styrene and α-methylstyrene, and derivatives thereof, vinyl carboxylates, preferably vinyl acetate, conjugated dienes such as butadiene or isoprene, methacrylonitrile, vinyl chloride and vinylidene chloride, N-alkyl- and N-aryl-substituted maleimides, and also hydrophilicizing comonomers such as acrylamides and methacrylamides, acrylic and methacrylic acid, N-vinylamides such as, for example, 1-vinyl-2-pyrrolidone, and/or
claim 1
ionic comonomers from the group consisting of vinylsulfonic acid and its salts, methallylsulfonic acid and also allylsulfonic acid and salts thereof, styrenesulfonic acid and its salts, (2-acrylamido-2-methyl)-propanesulfonic acid, its esters and its salts, (3-sulfopropyl)-acrylic acid and its salts, (3- sulfopropyl)acrylic esters and also alkyl esters and oxyalkyl esters of said vinylic sulfonic acids.
5. The whitened polymer as claimed in , wherein polymerization is carried out in the presence of graftable substrates which are polymeric emulsifiers containing sulfonic acid groups and from the group consisting of compounds of the formulae I and II
claim 1
in which
M denotes a cation-forming radical, preferably H, Na, K, NH4, R3NH3,
n denotes 1 or 2,
R denotes a hydrocarbon chain having 1 to 10 carbon atoms or an aromatic radical having 6 to 10 carbon atoms, preferably —(CH2)2NH(CH2)2— or a radical derived from a C1-C4 alkane or from benzene, methylbenzene or naphthalene,
R1 denotes H or —CH3,
R2 denotes H, C1-C16 alkyl, preferably —CH3, —C2H5, —C4H9, —CH2—C(CH3)3, —C14H29, —C16H33 or phenyl,
R3 denotes a hydrocarbon radical of an amine, and
x, y are chosen such that the average molecular weight Mw of the polymers (I) and (II) is from 2000 to 500,000, preferably from 5000 to 100,000, and the ratio x:y=from 1:4 to 1:1, preferably from 1:3 to 1:1, and also
the oligourethanes disclosed in EP-A-400 410, p. 7, which are used for the free-radically initiated emulsion polymerization.
6. The whitened polymer as claimed in , wherein the optical brightener is selected from the group consisting of
claim 1
in which
R4 denotes ethyl or phenyl, and
Anθ represents an anion,
in which
X represents CH or N,
Anθ represents an anion,
R5 represents CH3 or CH2—C6H5, and
R6 represents H or SO2—CH3,
in which
R7 represents NH2, CH3, C2H4—OH, NH—C3H6—N(CH3)2, CH2—CH(CH3)—N(CH3)2,
C2H4—CONH—C2H4—N(CH3)2, C2H4—O—CH(CH3)—CH2—N(CH3)2, NH—C3H6—N(CH3)3 +Anθ, C2H4—N(CH3)3 +Anθ,
C2H4—CONH—C2H4—N(CH3)3 +Anθ, CH2—CH(CH3)—N(CH3)3 +Anθ, C2H4—O—CH(CH3)—CH2—N(CH3)3 +Anθ,
in which
R8 denotes H or CH3,
in which
where Anθ denotes the anion of a mineral acid or —O3SOCH3.
7. An aqueous dispersion containing more than 30% by weight, in particular from 31 to 65% by weight, based on the dispersion, of a polyacrylonitrile and/or acrylonitrile copolymer whitened by means of optical brighteners.
8. An aqueous dispersion containing
1-65 % by weight of whitened polymer as claimed in , and
claim 1
1-15 % by weight of surface-active substances, based on whitened polymer.
9. An acrylonitrile homo- or copolymer whitened by means of optical brighteners and emulsion-polymerized in the presence of at least one polymeric emulsifier from the group consisting of compounds of the formulae I and II
in which
M denotes a cation-forming radical, preferably H, Na, K, NH4 or R3NH3,
n denotes 1 or 2,
R denotes a hydrocarbon chain having 1 to 10 carbon atoms or an aromatic radical having 6 to 10 carbon atoms, preferably —(CH2)2NH(CH2)2— or a radical derived from a C1-C4 alkane or from benzene, methylbenzene or naphthalene,
R1 denotes H or —CH3,
R2 denotes H, C1-C16 alkyl, preferably —CH3, —C2H5, —C4H9, —CH2—C(CH3)3, —C14H29, —C16H33 or phenyl,
R3 denotes a hydrocarbon radical of an amine, and
x, y are chosen such that the average molecular weight Mw of the polymers (I) and (II) is from 2000 to 500,000, preferably from 5000 to 100,000, and the ratio x:y=from 1:4 to 1:1, preferably from 1:3 to 1:1
or in the presence of the oligourethanes disclosed in EP-A-400 410, p. 7.
10. An aqueous coating slip comprising
whitened polymer as claimed in at least one of claims 1, 7 and 9,
inorganic pigment, and
binder(s).
11. The use of an aqueous coating slip as claimed in to coat substrates.
claim 10
12. The use as claimed in to coat paper, photographic paper, paperboard, wood, polymer films, textiles or stone.
claim 11
13. A substrate coated with an aqueous coating slip as claimed in .
claim 10
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19732032A DE19732032A1 (en) | 1997-07-25 | 1997-07-25 | White-tinted polymers and their use in coating slips for coating substrates |
DE19732032.5 | 1997-07-25 | ||
DE19732032 | 1997-07-25 | ||
PCT/EP1998/004355 WO1999005188A1 (en) | 1997-07-25 | 1998-07-14 | Whitened polymers and the use thereof in coating slips for coating substrates |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1998/004355 Continuation WO1999005188A1 (en) | 1997-07-25 | 1998-07-14 | Whitened polymers and the use thereof in coating slips for coating substrates |
Publications (2)
Publication Number | Publication Date |
---|---|
US20010009938A1 true US20010009938A1 (en) | 2001-07-26 |
US6339117B2 US6339117B2 (en) | 2002-01-15 |
Family
ID=7836869
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/463,208 Expired - Fee Related US6339117B2 (en) | 1997-07-25 | 1998-07-14 | Whitened polymers and the use thereof in coating slips for coating substrates |
Country Status (3)
Country | Link |
---|---|
US (1) | US6339117B2 (en) |
DE (1) | DE19732032A1 (en) |
WO (1) | WO1999005188A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040154630A1 (en) * | 2001-08-07 | 2004-08-12 | Hiromi Tabuchi | Double wrapper cigarette, machine and method for manufacturing the same |
US7258815B2 (en) | 2002-04-19 | 2007-08-21 | Karl-Heinz Drenker | Use of brighteners for the preparation of coating slips |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080044633A1 (en) * | 2006-06-30 | 2008-02-21 | Yaqiang Frank Ming | Printing Quality Improvement of Pigmented Inks on Glossy Media |
EP2799618B1 (en) * | 2013-04-29 | 2016-04-27 | Blankophor GmbH & Co. KG | Use of micronized cellulose and fluorescent whitening agent for surface treatment of cellulosic materials |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3666680A (en) * | 1970-03-05 | 1972-05-30 | Purex Corp Ltd | Method of combining optical brighteners with polymers for stability in bleach and encapsulated product |
CH573400A5 (en) | 1972-07-11 | 1976-03-15 | Ciba Geigy Ag | |
JPS49133418A (en) * | 1973-04-24 | 1974-12-21 | ||
DE2823301A1 (en) * | 1978-05-29 | 1979-12-13 | Hoechst Ag | Aqueous PLASTIC DISPERSION BASED ON VINYLESTER POLYMER |
DE2905765A1 (en) * | 1979-02-15 | 1980-09-04 | Basf Ag | PAPER COATING |
DE3917647A1 (en) | 1989-05-31 | 1990-12-06 | Bayer Ag | paper size |
US5186993A (en) * | 1991-10-11 | 1993-02-16 | Rohm And Haas Company | Polymer blends |
DE4233026A1 (en) * | 1992-10-01 | 1994-04-07 | Bayer Ag | Highly concentrated aqueous poly (acrylonitrile) emulsion and process for its preparation |
DE19500195A1 (en) * | 1995-01-05 | 1996-07-11 | Bayer Ag | Use of white-tinted plastics for tinting paper coating slips and such white-tinted paper coating slips |
US5747585A (en) * | 1995-02-17 | 1998-05-05 | Eastman Kodak Company | Process for synthesizing latex polymers from solid monomer particles |
BR9712056A (en) * | 1996-09-18 | 1999-08-24 | Eastman Chem Co | Self-crosslinking polymer composition formulation for coating on the back processes for coating a woven substrate and for impregnating a non-woven substrate coated woven substrate and non-woven substrate impregnated with a formulation for back lining |
US5869589A (en) * | 1997-07-17 | 1999-02-09 | Raynolds; Peter Webb | Self-crosslinking aqueous dispersions |
DE19706238B4 (en) * | 1997-02-18 | 2005-09-01 | Bayer Chemicals Ag | Process for the preparation of substituted 4,4'-diaminostilbene-2,2'-disulfonic acids |
-
1997
- 1997-07-25 DE DE19732032A patent/DE19732032A1/en not_active Ceased
-
1998
- 1998-07-14 US US09/463,208 patent/US6339117B2/en not_active Expired - Fee Related
- 1998-07-14 WO PCT/EP1998/004355 patent/WO1999005188A1/en active Application Filing
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040154630A1 (en) * | 2001-08-07 | 2004-08-12 | Hiromi Tabuchi | Double wrapper cigarette, machine and method for manufacturing the same |
US8042551B2 (en) * | 2001-08-07 | 2011-10-25 | Japan Tobacco Inc. | Double wrapper cigarette, machine and method for manufacturing the same |
US7258815B2 (en) | 2002-04-19 | 2007-08-21 | Karl-Heinz Drenker | Use of brighteners for the preparation of coating slips |
Also Published As
Publication number | Publication date |
---|---|
WO1999005188A1 (en) | 1999-02-04 |
DE19732032A1 (en) | 1999-01-28 |
US6339117B2 (en) | 2002-01-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101200643B1 (en) | Use of a copolymer having at least one grafted alkoxy or hydroxy polyalkylene glycol function as an agent for improving optical brightening activation, and products obtained | |
AU2005298779B2 (en) | Compositions of fluorescent whitening agents | |
EP0040419B1 (en) | Heterogeneous polymer latex of relatively hard and relatively soft interpolymers of a monovinylidene aromatic monomer and an aliphatic conjugated diene monomer and paper coating compositions containing said latexes | |
US5563201A (en) | Aqueous papercoating compositions comprising a substantially H2 O-insoluble, alkali-soluble latex | |
EP2291420B1 (en) | Metal salt pigments containing paper coating agents containing aqueous dispersions of water-soluble copolymers | |
EP1975206A1 (en) | Aqueous dispersions and method for the production thereof | |
US4397984A (en) | Use of acrylate-based emulsion copolymer as the sole binder for a paper coating composition | |
JPS6235520B2 (en) | ||
US6736936B1 (en) | Coating color | |
US6339117B2 (en) | Whitened polymers and the use thereof in coating slips for coating substrates | |
JPH05310855A (en) | Water-insoluble novel cationic copolymer and novel dispersion | |
JP2000144037A (en) | Polymer composition for water retension and activation of fluorescent whitening agent, paper coating color, and sheet of coated paper thus obtained | |
AU679836B2 (en) | Binder mixtures for paper-coating materials | |
US6964993B2 (en) | Paper coating slip containing polyvinyl alcohol as a protective colloid | |
PL81385B1 (en) | Aqueous polymer dispersion method of producing same and their use as binders in paper coatings[us3746671a] | |
US4963604A (en) | Polymeric pigments used in paper coating compositions and a process for their preparation | |
JP2811420B2 (en) | Method for producing resin latex | |
US6447926B2 (en) | Paper coating slips based on low-crosslink binders | |
US3766151A (en) | Novel terpolymer containing styrene acrylonitrile and another acrylicmaterial | |
US20030020046A1 (en) | Polyvinyl alcohol stabilised polymerisate for improving the optimal brightening of coating materials | |
CA2260822A1 (en) | Process for preparing water-dispersible polymer blends | |
EP0109463B1 (en) | Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom | |
CA1058344A (en) | Casein replacement acidic/basic polymer dispersions | |
JPH04272297A (en) | Surface finishing agent of paper | |
CA1211244A (en) | Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: BAYER AKTIENGESELLSCHAFT PATENTE UND LIZENZEN, GER Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ECKSTEIN, UDO;KORTE, SIEGFRIED;FELDHUES, ULRICH;AND OTHERS;REEL/FRAME:012613/0784;SIGNING DATES FROM 20000107 TO 20000127 |
|
REMI | Maintenance fee reminder mailed | ||
LAPS | Lapse for failure to pay maintenance fees | ||
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20060115 |