EP0274666B1 - Weisstönerhaltige Papierstreichmassen - Google Patents
Weisstönerhaltige Papierstreichmassen Download PDFInfo
- Publication number
- EP0274666B1 EP0274666B1 EP87118124A EP87118124A EP0274666B1 EP 0274666 B1 EP0274666 B1 EP 0274666B1 EP 87118124 A EP87118124 A EP 87118124A EP 87118124 A EP87118124 A EP 87118124A EP 0274666 B1 EP0274666 B1 EP 0274666B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- formula
- fluorescent brightener
- salt
- paper
- 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
- 239000007844 bleaching agent Substances 0.000 title 1
- 239000008199 coating composition Substances 0.000 title 1
- 239000011248 coating agent Substances 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 5
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 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 class 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 5
- 229920000642 polymer Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000123 paper Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000005282 brightening Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 3
- 125000002091 cationic group Chemical group 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
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000003165 hydrotropic effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Cc1ccccc1 Chemical compound Cc1ccccc1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960001716 benzalkonium Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier 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
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000012052 hydrophilic carrier Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000000080 wetting agent Substances 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
Definitions
- aqueous coating slips are used to a very large extent, which in addition to the usual white pigments - especially china clay and calcium carbonate - contain plastic dispersions as binders.
- whiteners of the alkali salt type of bistriazonylaminostilbene-disulfonic acids are generally used.
- these whiteners only have very unsatisfactory brightening effects and a very low graying limit (whitener concentration, at which further addition of the whitener does not result in an increase or even a decrease in the whiteness).
- the white toner types mentioned have a very low light fastness in those coating slips.
- this brightener salt for the stated purpose must be regarded as extremely surprising, since it is known that water-soluble brighteners based on bistriazonyl-aminostilbene-disulfonic acids, when used with conventional poly-cationic products according to GB-A-721 238 and GB-A -1 058 918 can be precipitated, in cobinder-free paper coating slips none or only very much unsatisfactory effect and the brightener salts mentioned in JP-A-57 123 262 have a significantly lower degree of whiteness (CIE).
- CIE degree of whiteness
- the brightener salt according to the invention shows a more or less pronounced fluorescence in finely divided or dissolved additive, even if the cationic component is used in excess.
- the reaction takes place in water and / or organic solvents, such as methanol, ethanol, propanol, isopropanol, butanol, glycol, glycol methyl ether, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide at temperatures from 20 ° C. to the reflux temperature of the corresponding solvent.
- organic solvents such as methanol, ethanol, propanol, isopropanol, butanol, glycol, glycol methyl ether, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide
- the poorly soluble whitening salt obtained in this way can be used as a whitening agent directly or after prior fine grinding or liquid formation.
- the dispersions according to the invention can be prepared as follows: The press cakes and / or powders are homogenized with vigorous stirring after the addition of a surface-active substance and optionally water. The amount of the surface-active substance can then be increased, if necessary to the total amount required for the stability of the dispersion.
- the suspension obtained is then comminuted and wet-ground.
- Pre-shredding can be carried out using stone or tooth colloid mills.
- the subsequent wet comminution can take place in colloid, vibratory, cone and vibromills as well as in dissolvers or in sub-micron dispersers.
- continuous agitator mills with grinding media preferably those made of SiO2 of 0.2 to 5 mm in diameter, are preferably used.
- surface-active substances or hydrotropic substances such as e.g. Ethylene glycol or glycerin, preservatives, wetting agents, defoamers and / or water are added, unless this has been done at an earlier point in time e.g. before grinding.
- a further possibility of producing the brightening agent according to the invention, which is sparingly or insoluble in water, and its dispersions, is the combination of the reaction and grinding process:
- the alkali salt of the brightener according to formula (II) is wet-comminuted together with the basic nitrogen compound of formula (III) and water and surface-active substances after homogenization and pre-comminution, the amounts used being able to be varied, as indicated above.
- the complete reaction of the whitening salt II with the basic nitrogen compound III takes place in the grinder, preferably in a continuous agitator mill with SiO 2 grinding media.
- Suitable surface-active substances are all customary, cationic and nonionic surface-active substances, as are described, for example, in DE-A 2 334 769, pages 8 to 10 (corresponds to GB-A 1 417 071).
- Nonionic surfactants are preferably used.
- the paper coating slips into which the brightener salts to be used according to the invention are incorporated are structured as follows: plastic dispersions based on styrene-butadiene, carboxylated styrene-butadiene or polyvinyl acetate copolymers or of acrylic acid esters in combination with white pigments, both with and without low levels of hydrophilic co-binders.
- the amount of compound I used depends on the desired lightening effect. In general, 0.01 to 0.5% by weight of pure active substance (based on the solids of the paper coating slip to be lightened) is sufficient.
- a particular advantage is that, depending on the composition of the coating slip, the graying limit that can be achieved (up to which a further brightener additive brings additional effects) is extremely high.
- 200 g of the water-insoluble brightener salt prepared according to Example 1 are homogenized together with 200 g of emulsifier W and 600 g of water and comminuted using a toothed colloid mill. The suspension is then wet crushed in a bead mill at room temperature with 4 passes. The resulting stable dispersion is easy to incorporate into paper coating slips and shows excellent white effects, even when large amounts are added (cf. Example 4).
- the suspension is wet-crushed at room temperature with 4 passes in a bead mill and shows excellent white effects after incorporation into paper coating slips.
- coated papers After spreading the lightened coating slip onto paper with the help of a hand-held squeegee or a test coater and after drying at 20-130 ° C, coated papers are obtained which, depending on the brightener additive, have a clear to excellent brightening effect. An increase in the degree of whiteness can usually still be achieved even with brightener additives higher than 50 g / kg of coating slip.
Landscapes
- Paper (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3643215 | 1986-12-18 | ||
DE19863643215 DE3643215A1 (de) | 1986-12-18 | 1986-12-18 | Weisstoenerhaltige papierstreichmassen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0274666A1 EP0274666A1 (de) | 1988-07-20 |
EP0274666B1 true EP0274666B1 (de) | 1992-03-25 |
Family
ID=6316456
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87118124A Expired - Lifetime EP0274666B1 (de) | 1986-12-18 | 1987-12-08 | Weisstönerhaltige Papierstreichmassen |
Country Status (5)
Country | Link |
---|---|
US (1) | US4888128A (fi) |
EP (1) | EP0274666B1 (fi) |
JP (1) | JPS63165596A (fi) |
DE (2) | DE3643215A1 (fi) |
FI (1) | FI87378C (fi) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR9000850A (pt) * | 1989-02-28 | 1991-02-05 | Ciba Geigy Ag | Formulacao aclaradora estavel a armazenagem,processo para sua preparacao e aplicacao |
NO903004L (no) * | 1989-07-21 | 1991-01-22 | Bayer Ag | Fremgangsmaate for hvittoning av papirbestrykningsmasser samt hvittoningspreparater for fremgangsmaaten. |
IT1246376B (it) * | 1990-04-11 | 1994-11-18 | Sigma Prodotti Chimici Srl | Patina per carta |
GB2277749B (en) * | 1993-05-08 | 1996-12-04 | Ciba Geigy Ag | Fluorescent whitening of paper |
DE19500195A1 (de) * | 1995-01-05 | 1996-07-11 | Bayer Ag | Verwendung weißgetönter Kunststoffe zum Weißtönen von Papierstreichmassen und derart weißgetönte Papierstreichmassen |
EP0905317B1 (en) * | 1997-09-16 | 2009-12-23 | Basf Se | A method for optically brightening paper |
NZ331438A (en) | 1997-09-16 | 2000-01-28 | Ciba Sc Holding Ag | A method of increasing the whiteness of paper by using a formulation containing a swellale layered silicate and an optical brightener 4,4-bis-(triazinylamino)-stilbene-2,2-disulphonic acid |
JPH11130975A (ja) * | 1997-10-29 | 1999-05-18 | Hakkooru Chemical Kk | 隠ぺい性の優れた蛍光性有機白色顔料組成物 |
US6046330A (en) * | 1998-04-24 | 2000-04-04 | Qinghong; Jessica Ann | Complexes of ultraviolet absorbers and quaternary ammonium compounds which are substantially free from unwanted salts |
US5948153A (en) * | 1998-04-24 | 1999-09-07 | Milliken & Company | Water-soluble complexes of optical brighteners and quaternary ammonium compounds which are substantially free from unwanted salts |
GB9813248D0 (en) | 1998-06-22 | 1998-08-19 | Clariant Int Ltd | Improvements in or relating to organic compounds |
GB9930177D0 (en) * | 1999-12-22 | 2000-02-09 | Clariant Int Ltd | Improvements in or relating to organic compounds |
GB9930247D0 (en) | 1999-12-22 | 2000-02-09 | Clariant Int Ltd | Improvements in or relating to organic compounds |
WO2002097193A1 (en) * | 2001-05-29 | 2002-12-05 | Ciba Specialty Chemicals Holding Inc. | A composition for the fluorescent whitening of paper |
EP1624034B1 (en) * | 2003-05-02 | 2011-06-15 | Canon Kabushiki Kaisha | Aqueous fluorescent ink, recorded image using same, and judging method |
US20080040865A1 (en) * | 2003-11-18 | 2008-02-21 | Ted Deisenroth | Fluorescent Whitening Pigments |
EP1712677A1 (en) * | 2005-04-08 | 2006-10-18 | Clariant International Ltd. | Aqueous solutions of optical brighteners |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1441109A (en) * | 1973-01-23 | 1976-06-30 | Ici Ltd | Coating compositions |
CH582275A5 (fi) * | 1973-02-02 | 1976-11-30 | Ciba Geigy Ag | |
JPS5725365A (en) * | 1980-07-22 | 1982-02-10 | Showa Kagaku Kogyo Kk | Dyestuff salt-containing fluorescent brightener composition |
JPS5725364A (en) * | 1980-07-22 | 1982-02-10 | Showa Kagaku Kogyo Kk | Dyestuff salt |
JPS57123262A (en) * | 1981-01-26 | 1982-07-31 | Showa Kagaku Kogyo Kk | Fluorescent brightener composition |
CH647021A5 (de) * | 1981-09-22 | 1984-12-28 | Ciba Geigy Ag | Verfahren zur herstellung lagerstabiler aufhellerformulierungen. |
DE3502038A1 (de) * | 1985-01-23 | 1986-07-24 | Sandoz-Patent-GmbH, 7850 Lörrach | Waessrige aufhellerpraeparate und deren verwendung im papierstrich |
-
1986
- 1986-12-18 DE DE19863643215 patent/DE3643215A1/de not_active Withdrawn
-
1987
- 1987-12-08 EP EP87118124A patent/EP0274666B1/de not_active Expired - Lifetime
- 1987-12-08 DE DE8787118124T patent/DE3777789D1/de not_active Expired - Lifetime
- 1987-12-10 JP JP62311145A patent/JPS63165596A/ja active Pending
- 1987-12-11 US US07/131,780 patent/US4888128A/en not_active Expired - Fee Related
- 1987-12-16 FI FI875517A patent/FI87378C/fi not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
DE3643215A1 (de) | 1988-06-30 |
DE3777789D1 (de) | 1992-04-30 |
FI87378B (fi) | 1992-09-15 |
JPS63165596A (ja) | 1988-07-08 |
FI87378C (fi) | 1992-12-28 |
EP0274666A1 (de) | 1988-07-20 |
US4888128A (en) | 1989-12-19 |
FI875517A (fi) | 1988-06-19 |
FI875517A0 (fi) | 1987-12-16 |
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