EP0306447B1 - Preparations comprising brightening agents of the dispersion type - Google Patents
Preparations comprising brightening agents of the dispersion type Download PDFInfo
- Publication number
- EP0306447B1 EP0306447B1 EP88810563A EP88810563A EP0306447B1 EP 0306447 B1 EP0306447 B1 EP 0306447B1 EP 88810563 A EP88810563 A EP 88810563A EP 88810563 A EP88810563 A EP 88810563A EP 0306447 B1 EP0306447 B1 EP 0306447B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- auxiliary
- fluorescent brightener
- preparation
- dispersion
- preparation according
- 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.)
- Expired - Lifetime
Links
- 238000002360 preparation method Methods 0.000 title claims description 31
- 239000006185 dispersion Substances 0.000 title claims description 24
- 238000005282 brightening Methods 0.000 title claims description 4
- 238000000576 coating method Methods 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 26
- 239000002270 dispersing agent Substances 0.000 claims description 17
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000123 paper Substances 0.000 claims description 12
- 239000000049 pigment Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000008199 coating composition Substances 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000011111 cardboard Substances 0.000 claims description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 4
- 238000009837 dry grinding Methods 0.000 claims description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 4
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- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
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- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 claims description 2
- 150000000183 1,3-benzoxazoles Chemical class 0.000 claims description 2
- AGPLQTQFIZBOLI-UHFFFAOYSA-N 1-benzyl-4-phenylbenzene Chemical group C=1C=C(C=2C=CC=CC=2)C=CC=1CC1=CC=CC=C1 AGPLQTQFIZBOLI-UHFFFAOYSA-N 0.000 claims description 2
- ICVRZXVMQZSFLB-UHFFFAOYSA-N 1-hydroxy-2-phenyl-2H-naphthalene-1-carboxylic acid Chemical compound C1=CC2=CC=CC=C2C(C(=O)O)(O)C1C1=CC=CC=C1 ICVRZXVMQZSFLB-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
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- HPGJOUYGWKFYQW-UHFFFAOYSA-N diphenyl benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OC=2C=CC=CC=2)C=CC=1C(=O)OC1=CC=CC=C1 HPGJOUYGWKFYQW-UHFFFAOYSA-N 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- XAUGWFWQVYXATQ-UHFFFAOYSA-N n-phenylbenzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)NC1=CC=CC=C1 XAUGWFWQVYXATQ-UHFFFAOYSA-N 0.000 claims description 2
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- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 claims 9
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 claims 2
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- 239000000155 melt Substances 0.000 claims 1
- 229960000969 phenyl salicylate Drugs 0.000 claims 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 17
- -1 fatty alcohol sulphates Chemical class 0.000 description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
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- 229930195729 fatty acid Natural products 0.000 description 8
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 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 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 239000012463 white pigment Substances 0.000 description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Chemical class CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Chemical class CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Chemical class CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 239000005642 Oleic acid Chemical class 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Chemical class CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920000388 Polyphosphate Chemical class 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
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- 239000000654 additive Substances 0.000 description 2
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- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001408 amides Chemical class 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
- 239000011324 bead Substances 0.000 description 2
- PLOYJEGLPVCRAJ-UHFFFAOYSA-N buta-1,3-diene;prop-2-enoic acid;styrene Chemical class C=CC=C.OC(=O)C=C.C=CC1=CC=CC=C1 PLOYJEGLPVCRAJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- 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 2
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000002811 oleoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 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
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical class CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000008117 stearic acid Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- IRGCCOOWJSYZNL-UHFFFAOYSA-N tetradecyl 1H-benzimidazole-2-sulfonate Chemical class C1=CC=C2NC(S(=O)(=O)OCCCCCCCCCCCCCC)=NC2=C1 IRGCCOOWJSYZNL-UHFFFAOYSA-N 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000002087 whitening effect Effects 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
- 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
- D21H19/46—Non-macromolecular organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
- D06L4/664—Preparations of optical brighteners; Optical brighteners in aerosol form; Physical treatment of optical brighteners
Definitions
- the present invention relates to new solid and liquid dispersion brightener preparations, their preparation and their use for brightening coating slips, e.g. for the coating of paper, cardboard, wood, foils, textiles, non-woven materials and building materials.
- the predominantly synthetic latex binders based on e.g. Containing copolymers of styrene-butadiene-acrylic acid esters or styrene-butyl acrylate, it has therefore been proposed to use dispersion brighteners in the presence of dispersants and, if appropriate, nonionic emulsifiers (GB-1294173, GB-1349934).
- dispersion brighteners e.g. Containing copolymers of styrene-butadiene-acrylic acid esters or styrene-butyl acrylate.
- preparations which, in addition to at least one dispersion brightener and at least one dispersant and / or emulsifier, optionally further additives and water, also have at least one specific one Surprisingly, above 40 ° C to 200 ° C, preferably up to 120 ° C, water-insoluble aromatic or C14-C1 Hilfs fatty alcohol auxiliary or mixture of auxiliaries does not show these disadvantages.
- benzylphenyl ketone salicylic acid phenyl ester, benzophenone, dibenzyl, p-benzyl biphenyl, benzenesulfanilide, 1-hydroxy-2-phenylnaphthoate, terephthalic acid diphenyl ester, terephthalic acid dimethyl ester and / or phthalhexyl acid (PD) phthalate.
- benzylphenyl ketone salicylic acid phenyl ester
- benzophenone dibenzyl
- terephthalic acid diphenyl ester terephthalic acid dimethyl ester
- PD phthalhexyl acid
- auxiliaries are used in amounts of 0.1 to 150 parts, in particular in amounts of 1 to 100 parts and especially in amounts of 9 to 100 parts based on 1 part of dispersion brightener.
- Water-insoluble or water-insoluble brighteners as described, for example, in DE-A-2806195 are used as dispersion brighteners, but dispersion brighteners from the class of coumarins and / or benzoxazoles, in particular benzoxazolylthiophenes, are preferably used.
- the dispersion brighteners are known.
- the preparation according to the invention contains conventional anionic or cationic and / or nonionic emulsifiers and / or dispersants, preferably in amounts of 2-20%, in particular 5-10%, based on the sum of dispersion brighteners and auxiliaries.
- anionic emulsifiers are: Carboxylic acids and their salts, such as the sodium, potassium or ammonium salts of lauric, stearic or oleic acid, acylation products of aminocarboxylic acids and their salts, for example the sodium salt of oleoyl sarcoside.
- Sulphates such as fatty alcohol sulphates, eg lauryl sulphate and lorole sulphate, sulphates of hydroxy fatty acid esters, eg sulphated castor oil, of fatty acid hydroxyalkylamides, eg sulphated coconut fatty acid ethanol amide as well as sulphates of partially esterified or etherified polyhydroxy compounds such as sulphated oleic acid monoglycerate sulphate polyglycol ether sulfate, glycerol glycol sulfate, glycerol ether sulfate, and glycerol ether sulfate, as well Sulfonates such as primary and secondary alkyl sulfonates, for example C12-C16 paraffin sulfonic acids or their sodium salts, alkyl sulfonates with amide- or with ester-like acyl radicals such as oleyl methyl tauride and
- nonionic emulsifiers examples include: Esters and ethers of polyalcohols, such as alkyl polyglycol ethers, for example lauryl alcohol or oleyl alcohol, polyethylene glycol ethers, acyl polyglycol ethers such as oleic acid polyglycol ethers, alkylaryl polyglycol ethers such as the ethoxylation products of nonyl and dodecylphenol, acylated amino-alkanol polyglycol ethers, and also the known fatty acid amides, such as non-ionic amines, such as non-ionic amides, such as die amine acid amides, such as non-ionic amides, such as die amine ionides derived from sugars and their derivatives.
- polyalcohols such as alkyl polyglycol ethers, for example lauryl alcohol or oleyl alcohol, polyethylene glycol ethers, acyl polyglycol ether
- the anionic dispersants are the usual dispersants, for example condensation products of aromatic sulfonic acids with formaldehyde or lignin sulfonates, for example the compounds obtainable under the name sulfite waste liquor.
- naphthalene sulfonic acid / formaldehyde condensation products are particularly suitable. Mixtures of these dispersants can also be used.
- Individuals of the ethylene oxide units can be replaced by other epoxides, e.g. Styrene oxide or, in particular, propylene oxide.
- Mixtures of the ethylene oxide adducts according to a) to f) with one another can also be used. These mixtures are obtained by mixing individual reaction products or directly by ethoxylating a mixture of the compounds on which the adducts are based. An ethoxylated nonylphenol is preferably used.
- Quaternary fatty amine polyglycol ethers are suitable as cationic dispersants.
- the preparation can also contain 45-95% water, preservatives and defoamers. However, the solid preparations are preferred.
- the preparations according to the invention are prepared by simply mixing or dry grinding the components or by melting the dispersion brightener and the auxiliary, if appropriate in the presence of dispersants and / or emulsifiers, allowing them to solidify and then, if appropriate, dry-grinding or, if appropriate, wet-grinding in the presence of dispersants and / or emulsifiers will.
- the preparations according to the invention are suitable for lightening the coating slips usually used in the paper industry, specifically for lightening unpigmented, but in particular pigmented coating slips.
- These known coating slips contain, inter alia, binders.
- a preferred binder consists of styrene-butyl acrylate or styrene-butadiene-acrylic acid mixed polymers. Further polymer latices are described, for example, in US Pat. Nos. 3,265,654, 3,657,174, 3,547,899 and 3,240,740. The preparation according to the invention is incorporated into these binders, for example by means of melt emulsification.
- Aluminum silicates such as china clay and kaolin, barium sulfate, satin white, titanium dioxide or calcium carbonate (chalk) are usually used to pigment the coating slips.
- the coating slips according to the invention preferably contain 30 to 70% of a white pigment.
- the binder is preferably used in an amount sufficient that the dry content of polymeric compound is 1 to 30 percent by weight, preferably 5 to 25 percent by weight, of the white pigment.
- the amount of the brightener preparation according to the invention is calculated in such a way that the dispersion brightener is present in amounts of 0.001 to 1 percent by weight, in particular 0.01 to 0.55 percent by weight, based on the white pigment.
- the coating slip according to the invention can be produced by mixing the components in any order at temperatures from 10 to 100 ° C., preferably 20 to 80 ° C.
- the components here also include the usual auxiliaries that can be used to regulate the rheological properties such as viscosity or water retention of the coating slips.
- auxiliaries that can be used to regulate the rheological properties such as viscosity or water retention of the coating slips.
- Such tools are e.g.
- binders such as starch, casein, protein or gelatin, cellulose ethers such as carboxyalkyl cellulose or hydroxyalkyl cellulose, alginic acid, alginates, polyethylene oxide or polyethylene oxide alkyl ethers, copolymers of ethylene oxide and propylene oxide, polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble condensation products of formaldehyde with urea or melamine, polyphosphate salts or polyphosphates.
- cellulose ethers such as carboxyalkyl cellulose or hydroxyalkyl cellulose, alginic acid, alginates, polyethylene oxide or polyethylene oxide alkyl ethers, copolymers of ethylene oxide and propylene oxide, polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble condensation products of formaldehyde with urea or melamine, polyphosphate salts or polyphosphates.
- the coating slip according to the invention can be used to coat paper, wood, foils such as e.g. Polypropylene, polyethylene, polyester, cellulose, cellulose triacetate, textiles, non-woven materials and suitable building materials such as Wallpaper, room cladding, plastic covers can be used. Use on paper and cardboard and photo paper is particularly preferred.
- the coating slip can be applied to the substrate by any conventional method, for example using an air knife, a doctor knife, a brush, a roller, a squeegee or a stick, followed by coating with, for example, infrared dryers and / or hot air dryers at paper surface temperatures in the range of 70 up to 200 ° C, preferably 90 to 130 ° C, to a residual moisture content of 3-6%. Comparably high degrees of whiteness are thus achieved even at low drying temperatures.
- the coatings obtained are distinguished by an optimal distribution of the dispersion brighteners over the entire surface and a consequent increase in the white level as well as a high light fastness.
- the brightener of the formula is ground with the parts of the components listed in Table 1 at room temperature for 15 hours in a glass bead mixer (glass bead diameter 2 mm) in the presence of water.
- the brightener according to Example 1 is melted together with the components and parts shown in Table 2, dry-ground after cooling and then dispersed according to Example 1 in water.
- 700 g of a commercially available kaolin pigment and 300 g of a commercially available calcium carbonate pigment are dispersed with 385 g of water, 5 g of a dispersant based on sodium salt of a polycarboxylic acid at a pH of about 9 and under the action of strong shear forces.
- 240 g of a commercially available 50% polymer dispersion based on styrene-butyl acrylate copolymer Acronal S 320 D from BASF) and one of the brightener dispersion described in Examples 1 to 2 are added to the resulting pigment dispersion and stirred.
- the brightener is used at 0.3%, based on the amount of pigment used.
- the coating color is then adjusted to a solids content of 50% by dilution with water.
- the line is applied to wood-free coating paper which has been acid-glued according to the usual methods with the help of a hand knife, so that the line weight after drying with the help of an IR radiator is approx. 15 g per m2. The residual moisture still present after this drying is approx. 2%.
- the whiteness of the coating is determined according to "Ciba-Geigy whiteness", as described in "Status of the instrumental whiteness assessment with special consideration of the lighting", textile finishing 5/1983, p.
- the degree of whiteness of the preparations 1.1 to 2.7 is given in Table 3.
- a coating slip without additive, but with 0.3% of the brightener according to Example 1 and the dispersants mentioned in Table 4 is prepared and applied analogously to the procedure used in Example 3 (preparations 4.1 to 4.4). The results of the whiteness measurement are compared in Table 4 to those corresponding preparations from Example 2.
- the coating color thus obtained is adjusted to a solids content of 50% by dilution with water, applied in accordance with Example 3b) and the degree of whiteness is determined in accordance with Example 3c).
- the degrees of whiteness are shown in Table 5.
- Example 5a solid preparations with a brightener each of the formula and the components and parts specified in Table 6. These preparations are processed according to Example 5b). The degrees of whiteness are shown in Table 6.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Paper (AREA)
- Paints Or Removers (AREA)
- Detergent Compositions (AREA)
Description
Die vorliegende Erfindung betrifft neue feste und flüssige Dispersionsaufheller-Präparate, deren Herstellung sowie deren Verwendung zum Aufhellen von Streichmassen z.B. für die Beschichtung von Papier, Karton, Holz, Folien, Textilstoffen, nichtgewebten Materialien und Baustoffen.The present invention relates to new solid and liquid dispersion brightener preparations, their preparation and their use for brightening coating slips, e.g. for the coating of paper, cardboard, wood, foils, textiles, non-woven materials and building materials.
Es ist bekannt, Streichmassen für die Beschichtung von glatten Oberflächen mittels anionischer Verbindungen aus der Reihe der Triazinylflavonsäure optisch aufzuhellen. Gute Weissgrade liefert diese Stoffklasse jedoch nur in Streichmassen, die natürliche Bindemittel, wie Casein, Stärke, Protein oder Gelatine, enthalten.It is known to optically lighten coating compositions for coating smooth surfaces by means of anionic compounds from the series of triazinylflavonic acid. However, this class of material only delivers good degrees of whiteness in coating slips that contain natural binders such as casein, starch, protein or gelatin.
Für die heute gebräuchlichen Streichmassen, die überwiegend synthetische Latex-Binder auf Basis von z.B. Copolymeren aus Styrol-Butadien-Acrylsäureestern oder Styrol-Butylacrylat enthalten, wurde daher vorgeschlagen, Dispersionsaufheller in Gegenwart von Dispergatoren und gegebenenfalls nichtionogenen Emulgatoren zu verwenden (GB-1294173, GB-1349934). Nachteil dieser Verfahren ist der geringe maximal erreichbare Weissgrad und die starke Abhängigkeit des Weissgrades von der Trocknungstemperatur.For the coating slips in use today, the predominantly synthetic latex binders based on e.g. Containing copolymers of styrene-butadiene-acrylic acid esters or styrene-butyl acrylate, it has therefore been proposed to use dispersion brighteners in the presence of dispersants and, if appropriate, nonionic emulsifiers (GB-1294173, GB-1349934). The disadvantage of these processes is the low maximum whiteness that can be achieved and the strong dependence of the whiteness on the drying temperature.
Andere Lösungsvorschläge bestanden darin, durch Einarbeitung organischer Lösungsmittel (DE-A-2242597) und zusätzlicher Lösungsvermittler (DE-A-2806195) die Aufhelleffekte zu verbessern. Diese Formulierungen sind jedoch in der Praxis nur bedingt einsetzbar, da bei der Verdampfung der Lösungsmittel explosionsgefährliche Luftgemische entstehen können und die Lösungsmitteldämpfe zu gesundheitlichen Gefährdungen im Betrieb und zu Umweltbelästigungen führen können.Other proposed solutions were to improve the whitening effects by incorporating organic solvents (DE-A-2242597) and additional solubilizers (DE-A-2806195). In practice, however, these formulations can only be used to a limited extent, since explosive air mixtures can form during the evaporation of the solvents and the solvent vapors can lead to health hazards in operation and to environmental pollution.
Es wurde nun gefunden, dass Präparate, die neben mindestens einem Dispersionsaufheller und mindestens einem Dispergator und/oder Emulgator, gegebenenfalls weitern Zusätzen und Wasser noch mindestens ein spezifisches über 40°C bis 200°C, vorzugsweise bis 120°C schmelzendes, wasserunlösliches aromatisches oder C₁₄-C₁₈ fettalkoholisches Hilfsmittel oder Hilfsmittelgemisch enthalten überraschenderweise diese Nachteile nicht zeigen.It has now been found that preparations which, in addition to at least one dispersion brightener and at least one dispersant and / or emulsifier, optionally further additives and water, also have at least one specific one Surprisingly, above 40 ° C to 200 ° C, preferably up to 120 ° C, water-insoluble aromatic or C₁₄-C₁ Hilfs fatty alcohol auxiliary or mixture of auxiliaries does not show these disadvantages.
Als derartige Hilfsmittel werden Cetylalkohol und vor allem Verbindungen der Formel
worin R₁ = -COOR, -COR, SO₂NHR, R oder OH, und
R₂ = H, -COOR, -COR, SO₂NHR oder R,
R₃ = H oder Phenylen,
mit R = gegebenenfalls mit C₁-C₈-Alkyl, C₃-C₈-Cycloalkyl oder Phenyl substituiertes C₁-C₈-Alkyl, C₃-C₈-Cycloalkyl oder Phenyl bedeutet.Such auxiliaries are cetyl alcohol and especially compounds of the formula
wherein R₁ = -COOR, -COR, SO₂NHR, R or OH, and
R₂ = H, -COOR, -COR, SO₂NHR or R,
R₃ = H or phenylene,
with R = C₁-C₈-alkyl, C₃-C₈-cycloalkyl or phenyl optionally substituted C₁-C₈-alkyl, C₃-C₈-cycloalkyl or phenyl.
Es handelt sich dabei beispielsweise um folgende Verbindungen: Benzylphenylketon, Salicylsäurephenylester, Benzophenon, Dibenzyl, p-Benzylbiphenyl, Benzolsulfanilid, 1-Hydroxi-2-phenylnaphthoat, Terephthalsäurediphenylester, Terephthalsäuredimethylester und/oder Phthalsäuredicyclohexylester (PDCH).These are, for example, the following compounds: benzylphenyl ketone, salicylic acid phenyl ester, benzophenone, dibenzyl, p-benzyl biphenyl, benzenesulfanilide, 1-hydroxy-2-phenylnaphthoate, terephthalic acid diphenyl ester, terephthalic acid dimethyl ester and / or phthalhexyl acid (PD) phthalate.
Diese Hilfsmittel werden in Mengen von 0,1 bis 150 Teile, insbesondere in Mengen von 1 bis 100 Teile und vor allem in Mengen von 9 bis 100 Teile bezogen auf 1 Teil Dispersionsaufheller eingesetzt.These auxiliaries are used in amounts of 0.1 to 150 parts, in particular in amounts of 1 to 100 parts and especially in amounts of 9 to 100 parts based on 1 part of dispersion brightener.
Als Dispersionsaufheller werden wasserunlösliche bzw. in Wasser schwerlösliche Aufheller wie zum Beispiel in der DE-A-2806195 beschrieben, bevorzugt jedoch Dispersionsaufheller aus der Klasse der Cumarine und/oder Benzoxazole, insbesondere Benzoxazolyl-thiophene verwendet. Die Dispersionsaufheller sind bekannt. Von besonderem Interesse sind die Aufheller und Mischungen von Aufhellern der Formel
Als Dispergatoren und/oder Emulgatoren enthält das erfindungsgemässe Präparat übliche anionische oder kationische und/oder nichtionogene Emulgatoren und/oder Dispergatoren, vorzugsweise in Mengen von 2-20 % insbesondere 5-10 %, bezogen auf die Summe von Dispersionsaufheller und Hilfsmittel.As dispersants and / or emulsifiers, the preparation according to the invention contains conventional anionic or cationic and / or nonionic emulsifiers and / or dispersants, preferably in amounts of 2-20%, in particular 5-10%, based on the sum of dispersion brighteners and auxiliaries.
Als anionaktive Emulgatoren seien beispielsweise genannt:
Carbonsäuren und ihre Salze, wie die Natrium, Kalium- oder Ammoniumsalze der Laurin-, Stearin- oder Oelsäure, Acylierungsprodukte von Aminocarbonsäuren und ihre Salze, z.B. das Natriumsalz des Oleoylsarkosids. Sulfate wie Fettalkoholsulfate, z.B. Laurylsulfat und Lorolsulfat, Sulfate von Hydroxyfettsäureestern, z.B. sulfatiertes Ricinusöl, von Fettsäurehydroxyalkylamiden, z.B. sulfatiertes Kokosfettsäureethanolamid sowie Sulfate von partiell veresterten bzw. veretherten Polyhydroxyverbindungen, wie sulfatiertes Oelsäuremonoglycerid oder Glycerinethersulfate, ferner Sulfate substituierter Polyglykolether, z.B. Nonylphenolpolyglykolethersulfat. Sulfonate wie primäre und sekundäre Alkylsulfonate, z.B. C₁₂-C₁₆-Paraffinsulfonsäuren bzw. deren Natriumsalze, Alkylsulfonate mit amid- oder mit esterartig gebundenen Acylresten wie Oleyl-methyl-taurid und Sulfonate von Polycarbonsäureestern wie Di-iso-octylsulfatobernsteinsäureester; ferner solche mit aromatischen Gruppen wie Alkylbenzol, z.B. Dodecylbenzol-, Alkylnaphthalin-, wie Dibutylnaphthalin und Alkylbenzimidazol-, wie Tetradecylbenzimidazol-sulfonate.Examples of anionic emulsifiers are:
Carboxylic acids and their salts, such as the sodium, potassium or ammonium salts of lauric, stearic or oleic acid, acylation products of aminocarboxylic acids and their salts, for example the sodium salt of oleoyl sarcoside. Sulphates such as fatty alcohol sulphates, eg lauryl sulphate and lorole sulphate, sulphates of hydroxy fatty acid esters, eg sulphated castor oil, of fatty acid hydroxyalkylamides, eg sulphated coconut fatty acid ethanol amide as well as sulphates of partially esterified or etherified polyhydroxy compounds such as sulphated oleic acid monoglycerate sulphate polyglycol ether sulfate, glycerol glycol sulfate, glycerol ether sulfate, and glycerol ether sulfate, as well Sulfonates such as primary and secondary alkyl sulfonates, for example C₁₂-C₁₆ paraffin sulfonic acids or their sodium salts, alkyl sulfonates with amide- or with ester-like acyl radicals such as oleyl methyl tauride and sulfonates of polycarboxylic esters such as di-iso-octyl sulfate succinic acid ester; furthermore those with aromatic groups such as alkylbenzene, for example dodecylbenzene, alkylnaphthalene, such as dibutylnaphthalene and alkylbenzimidazole, such as tetradecylbenzimidazole sulfonates.
Als nichtionogene Emulgatoren seien beispielsweise genannt:
Ester und Ether von Polyalkoholen, wie Alkylpolyglykolether, z.B. Laurylalkohol oder Oleylalkohol, Polyethylenglykolether, Acylpolyglykolether wie Oelsäurepolyglykolether, Alkylarylpolyglykolether wie die Ethoxylierungsprodukte des Nonyl- und Dodecylphenols, acylierte Amino-alkanolpolyglykolether, ferner die bekannten nichtionogenen Tenside, die sich von Fettaminen wie Stearylamin, Fettsäureamiden oder von Zuckern und deren Derivaten ableiten.Examples of nonionic emulsifiers are:
Esters and ethers of polyalcohols, such as alkyl polyglycol ethers, for example lauryl alcohol or oleyl alcohol, polyethylene glycol ethers, acyl polyglycol ethers such as oleic acid polyglycol ethers, alkylaryl polyglycol ethers such as the ethoxylation products of nonyl and dodecylphenol, acylated amino-alkanol polyglycol ethers, and also the known fatty acid amides, such as non-ionic amines, such as non-ionic amides, such as die amine acid amides, such as non-ionic amides, such as die amine ionides derived from sugars and their derivatives.
Bei den anionischen Dispergiermitteln handelt es sich um die üblichen Dispergiermittel, z.B. um Kondensationsprodukte von aromatischen Sulfonsäuren mit Formaldehyd oder Ligninsulfonate, z.B. die unter der Bezeichnung Sulfitablauge erhältlichen Verbindungen. Besonders geeignet sind jedoch Naphthalinsulfonsäure/Formaldehyd-Kondensationsprodukte. Es können auch Gemische dieser Dispergiermittel verwendet werden.The anionic dispersants are the usual dispersants, for example condensation products of aromatic sulfonic acids with formaldehyde or lignin sulfonates, for example the compounds obtainable under the name sulfite waste liquor. However, naphthalene sulfonic acid / formaldehyde condensation products are particularly suitable. Mixtures of these dispersants can also be used.
Als nichtionogene Dispergiermittel seien Ethylenoxid-Addukte aus der Klasse der Anlagerungsprodukte von Ethylenoxid an höhere Fettsäuren, gesättigte oder ungesättigte Fettalkohole, Mercaptane, Fettsäureamide, Fettsäurealkylolamide oder Fettamine oder Alkylphenole oder Alkylthiophenole mit mindestens 7 Kohlenstoffatomen im Alkylrest, ferner Ricinolsäureester oder Hydroxyabietylalkohol genannt. Einzelne der Ethylenoxideinheiten können durch andere Epoxide, wie z.B. Styroloxid oder insbesondere Propylenoxid, ersetzt sein.Ethylene oxide adducts from the class of addition products of ethylene oxide with higher fatty acids, saturated or unsaturated fatty alcohols, mercaptans, fatty acid amides, fatty acid alkylolamides or fatty amines or alkylphenols or alkylthiophenols with at least 7 carbon atoms in the alkyl radical, and also ricinoleic acid esters or hydroxyabietyl alcohol may be mentioned as nonionic dispersants. Individuals of the ethylene oxide units can be replaced by other epoxides, e.g. Styrene oxide or, in particular, propylene oxide.
Als Ethylenoxid-Addukte sind im einzelnen genannt:
- a) Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettalkoholen mit 8 bis 20 C-Atomen, mit 20 bis 100 Mol Ethylenoxid pro Mol Alkohol;
- b) Umsetzungsprodukte von Alkylphenolen mit 7 bis 12 C-Atomen im Alkylrest mit 5 bis 20 Mol, vorzugsweise 8 bis 15 Mol, Ethylenoxid je Mol phenolische Hydroxylgruppe;
- c) Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettaminen mit 8 bis 20 C-Atomen mit 5 bis 20 Mol Ethylenoxid je Mol Amin;
- d) Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettsäuren mit 8 bis 20 C-Atomen mit 5 bis 20 Mol Ethylenoxid je Mol Fettsäure;
- e) ein Umsetzungsprodukt aus 1 Mol Ricinolsäureester und 15 Mol Ethylenoxid;
- f) ein Umsetzungsprodukt aus 1 Mol Hydroxyabietylalkohol und 25 Mol Ethylenoxid.
- a) reaction products of saturated and / or unsaturated fatty alcohols with 8 to 20 carbon atoms, with 20 to 100 moles of ethylene oxide per mole of alcohol;
- b) reaction products of alkylphenols with 7 to 12 carbon atoms in the alkyl radical with 5 to 20 moles, preferably 8 to 15 moles, of ethylene oxide per mole of phenolic hydroxyl group;
- c) reaction products of saturated and / or unsaturated fatty amines with 8 to 20 carbon atoms with 5 to 20 moles of ethylene oxide per mole of amine;
- d) reaction products of saturated and / or unsaturated fatty acids with 8 to 20 carbon atoms with 5 to 20 moles of ethylene oxide per mole of fatty acid;
- e) a reaction product of 1 mol of ricinoleic acid ester and 15 mol of ethylene oxide;
- f) a reaction product of 1 mol of hydroxyabietyl alcohol and 25 mol of ethylene oxide.
Auch Gemische der Ethylenoxid-Addukte nach a) bis f) untereinander sind verwendbar. Diese Gemische erhält man durch Mischen einzelner Umsetzungsprodukte oder direkt durch Ethoxylierung eines Gemisches der den Addukten zugrundeliegenden Verbindungen. Bevorzugt wird ein ethoxyliertes Nonylphenol eingesetzt.Mixtures of the ethylene oxide adducts according to a) to f) with one another can also be used. These mixtures are obtained by mixing individual reaction products or directly by ethoxylating a mixture of the compounds on which the adducts are based. An ethoxylated nonylphenol is preferably used.
Als kationische Dispergatoren kommen zum Beispiel quaternäre Fettaminpolyglykolether in Frage.Quaternary fatty amine polyglycol ethers, for example, are suitable as cationic dispersants.
Zudem kann das Präparat noch 45-95 % Wasser sowie Konservierungs und Entschäumungsmittel enthalten. Die festen Präparate werden jedoch bevorzugt.The preparation can also contain 45-95% water, preservatives and defoamers. However, the solid preparations are preferred.
Die Herstellung der erfindungsgemässen Präparate erfolgt durch einfaches Mischen oder Trockenmahlung der Komponenten oder dadurch, dass der Dispersionsaufheller und das Hilfsmittel gegebenenfalls in Gegenwart von Dispergatoren und/oder Emulgatoren zusammengeschmolzen, erstarren gelassen und anschliessend gegebenenfalls in Gegenwart von Dispergatoren und/oder Emulgatoren trockengemahlen oder gegebenenfalls nassgemahlen werden.The preparations according to the invention are prepared by simply mixing or dry grinding the components or by melting the dispersion brightener and the auxiliary, if appropriate in the presence of dispersants and / or emulsifiers, allowing them to solidify and then, if appropriate, dry-grinding or, if appropriate, wet-grinding in the presence of dispersants and / or emulsifiers will.
Die erfindungsgemässen Präparate eignen sich zum Aufhellen der in der Papierindustrie üblicherweise verwendeten Streichmassen und zwar zum Aufhellen von unpigmentierten, insbesondere aber von pigmentierten Streichmassen. Diese bekannten Streichmassen enthalten als Bindemittel u.a. Kunststoffdispersionen auf Basis von Copolymerisaten aus Butadien-Styrol, Acrylnitril-Butadien-Styrol, Acrylsäureestern, Ethylen-Vinylchlorid und Ethylen-Vinylacetat; Homopolymerisaten, wie Polyvinylchlorid, Polyvinylidenchlorid, Polyethylen und Polyvinylacetat oder Polyurethanen. Ein bevorzugtes Bindemittel besteht aus Styrol-Butylacrylat- oder Styrol-Butadien-Acrylsäure-Mischpolimerisaten. Weitere Polymerlatices sind beispielsweise in den US-PS-3265654, 3657174, 3547899 und 3240740 beschrieben. Das erfindungsgemässe Präparat wird zum Beispiel mittels Schmelzemulgierung in diese Bindemittel eingearbeitet.The preparations according to the invention are suitable for lightening the coating slips usually used in the paper industry, specifically for lightening unpigmented, but in particular pigmented coating slips. These known coating slips contain, inter alia, binders. Plastic dispersions based on copolymers of butadiene-styrene, acrylonitrile-butadiene-styrene, acrylic acid esters, ethylene-vinyl chloride and ethylene-vinyl acetate; Homopolymers, such as polyvinyl chloride, polyvinylidene chloride, polyethylene and polyvinyl acetate or polyurethanes. A preferred binder consists of styrene-butyl acrylate or styrene-butadiene-acrylic acid mixed polymers. Further polymer latices are described, for example, in US Pat. Nos. 3,265,654, 3,657,174, 3,547,899 and 3,240,740. The preparation according to the invention is incorporated into these binders, for example by means of melt emulsification.
Zum Pigmentieren der Streichmassen dienen üblicherweise Aluminiumsilikate wie China-Clay und Kaolin, ferner Bariumsulfat, Satinweiss, Titandioxid oder Calciumcarbonat (Kreide).Aluminum silicates such as china clay and kaolin, barium sulfate, satin white, titanium dioxide or calcium carbonate (chalk) are usually used to pigment the coating slips.
Rezepturen solcher bekannter Streichmassen für Papier sind beispielswiese in J.P. Casey "Pulp and Paper"; Chemistry and Chemical Technology, 2. Ed. Vol. III, S. 1648-1649 und in Mc Graw-Hill "Pulp and Paper Manufacture", 2. und 5. Ed. Vol. II, S. 497, beschrieben.Recipes of such known coating slips for paper are, for example, in JP Casey "Pulp and Paper"; Chemistry and Chemical Technology, 2nd Ed. Vol. III, pp. 1648-1649 and in Mc Graw-Hill "Pulp and Paper Manufacture", 2nd and 5th Ed. Vol. II, p. 497.
Die erfindungsgemässen Streichmassen enthalten vorzugsweise 30 bis 70 % eines Weisspigmentes. Das Bindemittel wird vorzugsweise in einer Menge verwendet, die ausreicht, dass der Trockengehalt an polymerer Verbindung 1 bis 30 Gewichtsprozent, vorzugsweise 5 bis 25 Gewichtsprozent des Weisspigmentes ausmacht. Die Menge des erfindungsgemässen Aufhellerpräparats berechnet sind derart, dass der Dispersions-Aufheller in Mengen von 0,001 bis 1 Gewichtsprozent, insbesondere 0,01 bis 0,55 Gewichtsprozent, bezogen auf Weisspigment, vorliegt.The coating slips according to the invention preferably contain 30 to 70% of a white pigment. The binder is preferably used in an amount sufficient that the dry content of polymeric compound is 1 to 30 percent by weight, preferably 5 to 25 percent by weight, of the white pigment. The amount of the brightener preparation according to the invention is calculated in such a way that the dispersion brightener is present in amounts of 0.001 to 1 percent by weight, in particular 0.01 to 0.55 percent by weight, based on the white pigment.
Die erfindungsgemässe Streichmasse kann dadurch hergestellt werden, dass man die Komponenten in beliebiger Reihenfolge bei Temperaturen von 10 bis 100°C, vorzugsweise 20 bis 80°C, mischt. Zu den Komponenten zählen hier auch die üblichen Hilfsmittel, die zur Regulierung der rheologischen Eigenschaften wie Viskosität oder Wasserrückhaltevermögen der Streichmassen eingesetzt werden können. Solche Hilfsmittel sind z.B. natürliche Bindemittel wie Stärke, Casein, Protein oder Gelatine, Celluloseether wie Carboxyalkylcellulose oder Hydroxyalkylcellulose, Alginsäure, Alginate, Polyethylenoxid oder Polyethylenoxidalkylether, Mischpolymerisate von Ethylenoxid und Propylenoxid, Polyvinylalkohol, Polyvinylpyrrolidon, wasserlösliche Kondensationsprodukte von Formaldehyd mit Harnstoff oder Melamin, Polyphosphate oder polyacrylsaure Salze.The coating slip according to the invention can be produced by mixing the components in any order at temperatures from 10 to 100 ° C., preferably 20 to 80 ° C. The components here also include the usual auxiliaries that can be used to regulate the rheological properties such as viscosity or water retention of the coating slips. Such tools are e.g. natural binders such as starch, casein, protein or gelatin, cellulose ethers such as carboxyalkyl cellulose or hydroxyalkyl cellulose, alginic acid, alginates, polyethylene oxide or polyethylene oxide alkyl ethers, copolymers of ethylene oxide and propylene oxide, polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble condensation products of formaldehyde with urea or melamine, polyphosphate salts or polyphosphates.
Die erfindungsgemässe Streichmasse kann zum Beschichten von Papier, Holz, Folien wie z.B. Polypropylen, Polyethylen, Polyester, Cellulose, Cellulosetriacetat, Textilstoffen, nicht gewebten Materialien und geeigneten Baustoffen wie z.B. Tapeten, Raumverkleidungen, Kunststoffüberzügen verwendet werden. Besonders bevorzugt ist die Anwendung auf Papier und Karton sowie Photopapieren.The coating slip according to the invention can be used to coat paper, wood, foils such as e.g. Polypropylene, polyethylene, polyester, cellulose, cellulose triacetate, textiles, non-woven materials and suitable building materials such as Wallpaper, room cladding, plastic covers can be used. Use on paper and cardboard and photo paper is particularly preferred.
Die Streichmasse kann auf das Substrat durch jedes herkömmliche Verfahren aufgebracht werden, beispielsweise mit einem Luftmesser, einem Streichmesser, einer Bürste, einer Rolle, einer Rakel oder einem Stab, worauf dann die Beschichtung z.B. mit Infrarottrocknern und/oder Heisslufttrocknern bei Papieroberflächentemperaturen im Bereich von 70 bis 200°C, vorzugsweise 90 bis 130°C, bis auf eine Restfeuchte von 3-6 % getrocknet werden. Vergleichbar hohe Weissgrade werden somit schon beiniedrigen Trocknungstemperaturen erreicht.The coating slip can be applied to the substrate by any conventional method, for example using an air knife, a doctor knife, a brush, a roller, a squeegee or a stick, followed by coating with, for example, infrared dryers and / or hot air dryers at paper surface temperatures in the range of 70 up to 200 ° C, preferably 90 to 130 ° C, to a residual moisture content of 3-6%. Comparably high degrees of whiteness are thus achieved even at low drying temperatures.
Durch die Verwendung der erfindungsgemässen Präparate bzw. Hilfsmittel zeichnen sich die erhaltenen Beschichtungen durch eine optimale Verteilung der Dispersions-Aufheller über die gesamte Oberfläche und eine dadurch bedingte Steigerung des Weissniveaus sowie eine hohe Lichtechtheit aus.As a result of the use of the preparations or auxiliaries according to the invention, the coatings obtained are distinguished by an optimal distribution of the dispersion brighteners over the entire surface and a consequent increase in the white level as well as a high light fastness.
Die Erfindung wird durch die folgenden Beispiele näher erläutert, worin alle Teile und Prozentangaben in Gewicht ausgedrückt sind, sofern nichts anderes angegeben ist.The invention is illustrated in more detail by the following examples, in which all parts and percentages are expressed in weight, unless stated otherwise.
Der Aufheller der Formel
Der Aufheller gemäss Beispiel 1 wird mit den in Tabelle 2 angegebenen Komponenten und Teilen zusammengeschmolzen, nach Abkühlung trockengemahlen und anschliessend gemäss Beispiel 1 in Wasser dispergiert.
700 g eines handelsüblichen Kaolinpigments und 300 g eines handelsüblichen Calciumcarbonatpigments werden mit 385 g Wasser, 5 g eines Dispergators auf Basis Na-salz einer Polycarbonsäure bei einem pH von ca. 9 und unter Einwirkung starker Scherkräfte dispergiert. Zu der entstehenden Pigmentdispersion werden 240 g einer handelsüblichen 50 %igen Polymerdispersion auf Basis von Styrol-Butylacrylat-Copolymer Acronal S 320 D der BASF) und eine der in den Beispielen 1 bis 2 beschriebenen Aufhellerdispersion zugesetzt und verrührt. Der Einsatz des Aufhellers beträgt 0,3 %, bezogen auf die eingesetzte Menge Pigment. Anschliessend wird die Streichfarbe durch Verdünnung mit Wasser auf einen Feststoffgehalt von 50 % eingestellt.700 g of a commercially available kaolin pigment and 300 g of a commercially available calcium carbonate pigment are dispersed with 385 g of water, 5 g of a dispersant based on sodium salt of a polycarboxylic acid at a pH of about 9 and under the action of strong shear forces. 240 g of a commercially available 50% polymer dispersion based on styrene-butyl acrylate copolymer Acronal S 320 D from BASF) and one of the brightener dispersion described in Examples 1 to 2 are added to the resulting pigment dispersion and stirred. The brightener is used at 0.3%, based on the amount of pigment used. The coating color is then adjusted to a solids content of 50% by dilution with water.
Der Strich wird auf holzfreies und nach den üblichen Methoden sauer geleimtes Streichrohpapier mit Hilfe einer Handrakel aufgebracht, so dass das Strichgewicht nach der Trocknung mit Hilfe eines IR-Strahlers ca. 15 g pro m² beträgt. Die nach dieser Trocknung noch vorhandene Restfeuchte beträgt ca. 2 %.The line is applied to wood-free coating paper which has been acid-glued according to the usual methods with the help of a hand knife, so that the line weight after drying with the help of an IR radiator is approx. 15 g per m². The residual moisture still present after this drying is approx. 2%.
Die Weisse der Beschichtung wird nach "Ciba-Geigy-Weissgrad" ermittelt, wie in "Stand der instrumentellen Weissbewertung unter besonderer Berücksichtigung der Beleuchtung", Textilveredlung 5/1983, S. 157-162 beschrieben. Der Weissgrad der Präparate 1.1 bis 2.7 ist in Tabelle 3 angegeben.
Es wird eine Streichmasse ohne Hilfsmittelzusatz, jedoch mit 0,3 % des Aufhellers gemäss Beispiel 1 und den in Tabelle 4 genannten Dispergatoren analog dem im Beispiel 3 angewendeten Vorgehen hergestellt und appliziert (Präparate 4.1 bis 4.4). Die Resultate der Weissgradmessung sind in Tabelle 4 denjenigen entsprechenden Präparaten des Beispiels 2 gegenüber gestellt.
- a) Der Aufheller der Formel (1) wird mit den in Tabelle 5 angegebenen Komponenten und Teilen zusammengeschmolzen und nach Abkühlung trockengemahlen.a) The brightener of the formula (1) is melted together with the components and parts shown in Table 5 and, after cooling, dry-milled.
- b) Das so erhaltene feste pulverförmige Präparat wird in eine 90°C heisse Lösung aus 9 %igem wässrigem Polyvinylalkohol (Mowiol 4-98 der Firma Hoechst) eingetragen und durch Anwendung von Scherkräften schmelzemulgiert. Anschliessend wird soviel dieser wässrigen Formulierung mit der Pigmentdispersion gemäss Beispiel 3a) verrührt, dass die entstehende Streichfarbe 0,4 % Polyvinylalkohol bezogen auf die Menge an Pigment enthält. Der Einsatz von Aufheller beträgt 0,3 % oder 0,1 % bezogen auf die eingesetzte Menge Pigment.b) The solid powdery preparation obtained in this way is introduced into a 90 ° C. solution of 9% aqueous polyvinyl alcohol (Mowiol 4-98 from Hoechst) and melt-emulsified by application of shear forces. Then so much of this aqueous formulation is stirred with the pigment dispersion according to Example 3a) that the coating color formed contains 0.4% polyvinyl alcohol based on the amount of pigment. The use of brighteners is 0.3% or 0.1% based on the amount of pigment used.
Die so erhaltene Streichfarbe wird durch Verdünnung mit Wasser auf einen Feststoffgehalt von 50 % eingestellt, gemäss Beispiel 3b) aufgetragen und der Weissgrad gemäss Beispiel 3c) bestimmt. Die Weissgrade sind Tabelle 5 zu entnehmen.
Gemäss Beispiel 5a werden feste Präparate mit je einem Aufheller der Formel
Claims (13)
R₁ is -COOR, -COR, -SO₂NHR, -R or -OH,
R₂ is -H, -COOR, -COR, -SO₂NHR or -R, and
R₃ is -H or phenylene, where
R is C₁-C₈alkyl, C₃-C₈cycloalkyl or phenyl, each of which is unsubstituted or substituted by C₁-C₈alkyl, C₃-C₈cycloalkyl or phenyl,
or a mixture of the above auxiliaries.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH3263/87 | 1987-08-26 | ||
| CH326387 | 1987-08-26 |
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| Publication Number | Publication Date |
|---|---|
| EP0306447A1 EP0306447A1 (en) | 1989-03-08 |
| EP0306447B1 true EP0306447B1 (en) | 1992-02-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88810563A Expired - Lifetime EP0306447B1 (en) | 1987-08-26 | 1988-08-17 | Preparations comprising brightening agents of the dispersion type |
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| Country | Link |
|---|---|
| US (1) | US5064570A (en) |
| EP (1) | EP0306447B1 (en) |
| CA (1) | CA1327429C (en) |
| DE (1) | DE3868462D1 (en) |
| ES (1) | ES2029345T3 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX9207050A (en) * | 1991-12-19 | 1993-06-01 | Ciba Geigy Ag | STABLE BLEACH DISPERSION DURING STORAGE |
| GB2274661B (en) * | 1993-02-02 | 1996-07-17 | Ciba Geigy Ag | Fluorescent whitening of paper |
| EP0686691B1 (en) * | 1994-06-10 | 2001-08-08 | The Procter & Gamble Company | Aqueous emulsions with brighteners |
| GB2310215A (en) * | 1995-10-13 | 1997-08-20 | Ecc Int Ltd | Coating composition |
| US5879512A (en) * | 1995-10-13 | 1999-03-09 | Ecc Internatinal Ltd. | Paper coating |
| GB2310216A (en) * | 1995-10-13 | 1997-08-20 | Ecc Int Ltd | Coating composition |
| US5785766A (en) * | 1996-03-01 | 1998-07-28 | Davis; Ronald O. | Process for the color recovery of vinyl plastics |
| US6048908A (en) | 1997-06-27 | 2000-04-11 | Biopore Corporation | Hydrophilic polymeric material |
| US6121221A (en) * | 1999-07-26 | 2000-09-19 | Ronald O. Davis | Kit for cleaning vinyl plastics |
| DE19945580C5 (en) | 1999-09-23 | 2007-03-15 | Stora Enso Publication Paper Gmbh & Co. Kg | Coated, optically brightened printing paper and process for its production |
| GB0021404D0 (en) * | 2000-09-01 | 2000-10-18 | Clariant Int Ltd | Improvement in or to organic compounds |
| KR20080095862A (en) * | 2006-01-26 | 2008-10-29 | 클라리언트 파이넌스 (비브이아이)리미티드 | Process for producing optically brightened paper |
| TW201000716A (en) * | 2008-01-28 | 2010-01-01 | Akzo Nobel Nv | A method for production of paper |
| CN117430985B (en) * | 2023-11-27 | 2024-06-25 | 双润新材料科技(南京)有限公司 | Colloidal fluorescent material, preparation method thereof, coating and thickness detection coating for injury detection |
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|---|---|---|---|---|
| US2797198A (en) * | 1954-04-29 | 1957-06-25 | Hercules Powder Co Ltd | Solid foam-combating composition |
| DE1150274B (en) * | 1959-03-21 | 1963-06-12 | Leonar Werke Ag | Process for the production of a photographic material with optical brighteners embedded in a diffusion-proof manner |
| GB911104A (en) * | 1959-11-19 | 1962-11-21 | Warwick Chemical Yorkshire Ltd | Optical whitening compositions and their application |
| US3434837A (en) * | 1964-06-05 | 1969-03-25 | Eastman Kodak Co | Photographic element |
| GB1122643A (en) * | 1965-07-01 | 1968-08-07 | Kodak Ltd | Photographic print materials |
| GB1151590A (en) * | 1966-11-25 | 1969-05-07 | Ilford Ltd | Photographic Silver Halide Colour Emulsions |
| GB1349934A (en) * | 1970-08-13 | 1974-04-10 | Ici Ltd | Coating process |
| US3789012A (en) * | 1972-01-31 | 1974-01-29 | Eastman Kodak Co | Brightening composition containing a hydrophilic colloid and an oil-soluble vinylene brightening agent |
| CH597335A5 (en) * | 1973-09-14 | 1978-03-31 | Ciba Geigy Ag | |
| US4042320A (en) * | 1974-05-09 | 1977-08-16 | Ciba-Geigy Ag | Anionic and nonionic emulsified dye suspension with formalin, hydrotropic agent |
| DE2500915C3 (en) * | 1975-01-11 | 1980-09-18 | Bayer Ag, 5090 Leverkusen | Process for tinting textile fibers made of polyesters or mixed fibers of polyesters and cellulose or wool white |
| DE2733950A1 (en) * | 1976-07-29 | 1978-02-02 | Ciba Geigy Ag | METHOD OF MANUFACTURING PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL |
| CH622921B (en) * | 1978-07-27 | Ciba Geigy Ag | PROCESS FOR FINISHING, IN PARTICULAR COLORING, PRINTING OR LIGHTENING. | |
| DE3001387A1 (en) * | 1980-01-16 | 1981-07-23 | Chemische Fabrik Stockhausen & Cie, 4150 Krefeld | Suspension of higher alkanol contg. emulsifier - and liq. hydrocarbon, as anti-foam in aq. system |
| US4341565A (en) * | 1980-08-26 | 1982-07-27 | American Organics Corporation | Liquid colorant composition |
| US4460374A (en) * | 1981-02-12 | 1984-07-17 | Ciba-Geigy Corporation | Stable composition for treating textile substrates |
| ATE7898T1 (en) * | 1981-02-26 | 1984-06-15 | Ciba-Geigy Ag | AMPHOTERE STYRENE DERIVATIVES. |
| US4559150A (en) * | 1982-08-11 | 1985-12-17 | Ciba Geigy Corporation | Stable composition for treating textile substrates |
-
1988
- 1988-08-17 DE DE8888810563T patent/DE3868462D1/en not_active Expired - Lifetime
- 1988-08-17 ES ES198888810563T patent/ES2029345T3/en not_active Expired - Lifetime
- 1988-08-17 EP EP88810563A patent/EP0306447B1/en not_active Expired - Lifetime
- 1988-08-24 CA CA000575535A patent/CA1327429C/en not_active Expired - Fee Related
-
1990
- 1990-01-24 US US07/469,704 patent/US5064570A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
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| DE3868462D1 (en) | 1992-03-26 |
| US5064570A (en) | 1991-11-12 |
| EP0306447A1 (en) | 1989-03-08 |
| ES2029345T3 (en) | 1992-08-01 |
| CA1327429C (en) | 1994-03-08 |
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