EP1419298B1 - Procede de fabrication de papier couche extremement blanc - Google Patents

Procede de fabrication de papier couche extremement blanc Download PDF

Info

Publication number
EP1419298B1
EP1419298B1 EP02767338A EP02767338A EP1419298B1 EP 1419298 B1 EP1419298 B1 EP 1419298B1 EP 02767338 A EP02767338 A EP 02767338A EP 02767338 A EP02767338 A EP 02767338A EP 1419298 B1 EP1419298 B1 EP 1419298B1
Authority
EP
European Patent Office
Prior art keywords
paper
coating
acid
activator
coated
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
Application number
EP02767338A
Other languages
German (de)
English (en)
Other versions
EP1419298A1 (fr
EP1419298B8 (fr
Inventor
Thierry Blum
Friedrich Linhart
Stephan Frenzel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7694600&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1419298(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by BASF SE filed Critical BASF SE
Publication of EP1419298A1 publication Critical patent/EP1419298A1/fr
Application granted granted Critical
Publication of EP1419298B1 publication Critical patent/EP1419298B1/fr
Publication of EP1419298B8 publication Critical patent/EP1419298B8/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/30—Pretreatment of the paper
    • 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
    • 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
    • D21H19/10—Coatings without pigments
    • D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
    • 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
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • D21H19/828—Paper comprising more than one coating superposed two superposed coatings, the first applied being non-pigmented and the second applied being pigmented
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Definitions

  • the invention relates to a novel process for the production of coated paper, which is characterized by a particularly high degree of whiteness. Furthermore, the invention relates to papers, which are produced by this method and the printing of papers, which are produced by this method.
  • Paper coatings consist essentially of a mostly white pigment, a polymeric binder and additives which influence, for example, the rheological properties of the coating color and the properties of the surface of the coated paper in the desired sense.
  • additives are often referred to as "cobinders".
  • binder By the binder, the pigments are fixed on the paper and ensures the cohesion in the resulting coating.
  • Coating with paper coating slips gives base papers a smooth, uniform white surface.
  • the paper coatings also improve the printability of the paper.
  • papers are also often coated twice or three times, that is, a second or a third time a coating is applied to an already precoated or "pre-painted" paper.
  • pre-coated paper paper with improved properties, especially with higher whiteness To make available.
  • the coating in particular those who want to form the top layer, so-called “whitener” (fluorescent or phosphorescent) or “optical brightener” to.
  • whitener fluorescent or phosphorescent
  • optical brightener dye-like fluorescent Compounds that absorb the short-wave, ultraviolet light invisible to the human eye and re-emit it as longer-wavelength blue light, thereby giving the human eye a higher whiteness, thus increasing the whiteness.
  • optical brighteners used in the paper industry are usually 1,3,5-triazinyl derivatives of 4,4'-diaminostilbene-2,2'-disulfonic acid, which may carry additional sulfonic acid groups.
  • An overview of such brighteners can be found, for example, in: Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2000 Electronic Release, OPTICAL BRIGHTENERS - Chemistry of Technical Products. But there are also newer Aufhellertypen in question, z. B. Derivatives of 4,4'-distyrylbiphenyls, as also described in the aforementioned literature Ullmann's Encyclopedia of Industrial Chemistry.
  • the use of the optical brighteners in the coating material only leads to optimum success if they are present in the finished coating of the paper in an optimal structure, conformation and distribution, since e.g. in stilbenes only the trans-form is optically active and only fluoresces maximally when it is monomolecularly distributed and held in one plane (KP Kreutzer, Basic processes of paper production 2: Interfacial processes in the use of chemical aids, H.-G. Völkel and R Border (Ed.), PTS Kunststoff, 2000, PTS manuscript: PTS-GPE - SE 2031-2).
  • activator polymeric compounds which enhance the effect of the optical brightener in the coating slip and are referred to as "activator”, "carrier” or “carrier” are added to the paper coating slip. So far, these activators have basically been mixed into the paper coating slip.
  • suitable cobinder can be water-soluble polymers, for. Polyvinyl alcohol, carboxymethyl cellulose, anionic or nonionic degraded starches, casein, soy protein, water-soluble styrene-acrylate copolymers and acrylic ester-containing copolymers (see, e.g., K. P. Kreutzer, supra).
  • activators are polymeric compounds whose problem is that they increase the viscosity of the coatings. As a result, an increase in their application rate to get a higher whiteness, narrow limits.
  • Particularly effective with respect to the activation of optical brighteners are paper coating slips with polymers and copolymers which copolymerizes N-vinylformamide as described in the German application with the file number 100 55 592.6.
  • This invention has for its object to develop a method by which the whiteness of coated paper can be increased.
  • a process has now been found for the production of paper coated with at least one optical brightener by treating raw paper or prepainted paper with at least one substance which enhances the effectiveness of optical brighteners prior to applying the optical brightener.
  • polymers and copolymers which comprise at least one N-vinylcarboxamide, for example of the formula (I), in copolymerized form, bring about a particularly marked improvement in the properties of the coated paper when used in accordance with the invention Apply the raw paper or prepainted paper before coating the paper with a coating containing at least one optical brightener. In particular, brightness and / or whiteness are increased.
  • R 1 and R 2 independently of one another are hydrogen or C 1 to C 20 -alkyl, where the alkyl radical may be straight-chain or branched.
  • R 1 and R 2 are independently hydrogen or C 1 to C 10 alkyl, more preferably hydrogen or C 1 to C 4 alkyl, most preferably hydrogen or methyl and especially hydrogen.
  • R 1 and R 2 may also together form a straight chain or branched chain containing 2 to 8 carbon atoms, preferably containing 3 to 6 and more preferably containing 3 to 5 carbon atoms.
  • one or more carbon atoms may be used be replaced by heteroatoms, such as oxygen, nitrogen or sulfur.
  • radicals R 1 and R 2 are methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl or n-eicosyl.
  • radicals R 1 and R 2 which together form a chain are 1,2-ethylene, 1,2-propylene, 1,3-propylene, 2-methyl-1,3-propylene, 2-ethyl-1, 3-propylene, 1,4-butylene, 1,5-pentylene, 2-methyl-1,5-pentylene, 1,6-hexylene or 3-oxa-1,5-pentylene.
  • N-vinylcarboxamides of the formula (I) are N-vinylformamide, N-vinylacetamide, N-vinylpropionamide, N-vinylbutyramide, N-vinylisobutyric acid amide, N-vinyl-2-ethylhexanoic acid amide, N-vinyldecanoic acid amide, N-vinyldodecanoic acid amide, N- Vinyl stearic acid amide, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide, N-methyl-N-vinylpropionamide, N-methyl-N-vinylbutyramide, N-methyl-N-vinylisobutyric acid amide, N-methyl-N-vinyl 2-ethylhexanoic acid amide, N-methyl-N-vinyldecanoic acid amide, N-methyl-N-vinyldodecanoic acid amide,
  • N-vinylformamide Preference is given to N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone or N-vinylcaprolactam; N-vinylformamide is particularly preferred.
  • the at least contains an optical brightener treated according to the invention is obtained according to an increase in the brightness and whiteness of the coated paper.
  • activators are polyvinyl alcohol, carboxymethyl cellulose, anionic or nonionic degraded starches, casein, soy protein, water-soluble styrene-acrylate copolymers and acrylic ester-containing copolymers.
  • such polyvinyl alcohols can be used as activators having degrees of polymerization in the range of about 500 to 2500, corresponding to molar masses of about 20,000 to 100,000 g / mol.
  • the degrees of hydrolysis of the polyvinyl alcohols which can be used according to the invention are generally at least 70 mol%; preferred polyvinyl alcohols have a degree of hydrolysis of either 98-99 or 87-89 mol% and, as mostly partially hydrolyzed polyvinyl acetates, have a residual content of acetyl groups of approx. 1 - 2 or 11 - 13 mol%.
  • the polyvinyl alcohols which can be used according to the invention predominantly have 1,3-diol units, the content of 1,2-diol units is generally below 2%, preferably below 1%.
  • Polyvinyl alcohol is here understood to mean a polymer which comprises at least 10% by weight, preferably at least 20% by weight and more preferably at least 50% by weight and in particular at least 90% by weight, based on the polymer, of vinyl acetate in copolymerized and optionally cleaved form contains.
  • Unitika Poval® Unitika
  • Elvanol® Du Pont
  • Gelvatol® Greenigan Resins
  • Lemol ® Boundedoviol®
  • carboxymethylcellulose such products can be used according to the invention as activators which have a molecular weight of 50,000 to 500,000 g / mol.
  • the carboxymethylcellulose can be used as the sodium salt or as the free acid or as a mixture thereof, preferably as the sodium salt.
  • the degree of substitution of carboxymethyl groups per anhydroglucose unit may be between 0.5 and 1.5.
  • anionic or nonionic degraded starches for example, hydroxyethyl, hydroxypropyl, methyl, ethyl or carboxymethyl starches can be used according to the invention which have a molecular weight of between 50,000 and 2,000,000 g / mol.
  • Acrylic-containing copolymers are understood as meaning copolymers which contain at least 10% by weight, preferably at least 20% by weight and more preferably at least 50% by weight and in particular at least 70% by weight, based on the copolymer, of at least one acrylic acid ester polymerized form contain, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate.
  • Acrylic acid, methacrylic acid, acrylonitrile, vinyl acetate, vinyl propionate, N-vinylformamide, allylacetic acid, vinylacetic acid, maleic acid, fumaric acid, N-vinylpyrrolidone or hydroxybutyl vinyl ether in copolymerized form can be contained as further monomers, for example.
  • These acrylic ester-containing copolymers can be used, for example, in the form of their aqueous solutions or dispersions having a copolymer content of from 10 to 75% by weight, preferably from 20 to 60% by weight.
  • Acrosol® grades from BASF AG are preferably used here, for example Acrosol® A30D, A40D, B37D, C50L or E20D, preferably Acrosol® C50L.
  • Polyvinyl alcohols and / or (co) polymers which contain N-vinylcarboxamides in copolymerized form are preferably used in accordance with the invention, particularly preferably (co) polymers which contain monomers of the formula (I) in copolymerized form.
  • N-alkyl-N-vinylcarboxamides and their polymers and copolymers is known or carried out by known methods, see, for example Kirk-Othmer, Encyclopedia of Chemical Technology, 4th Edition, Volume 24, J. Wiley & Sons, NY, 1995 , N-vinyl amide polymers, page 1070; Uchino, N., Machida, S., Japan. Kokai JP 51100188 (CA 86: 73393) or DE-A 42 41 117 ,
  • Polyvinyl alcohol has been produced on an industrial scale since 1939 and has been used in papermaking for many decades ( Handbook of Water-Soluble Gums and Resins, Robert L. Davidson ed., McGraw-Hill, New York, 1980 ).
  • Suitable monomers of group a) are, for example, the abovementioned N-vinylcarboxamides of the formula (I).
  • the monomers mentioned can be used either alone or in a mixture with one another.
  • N-vinylacetamide, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone or N-vinylcaprolactam and particularly preferably N-vinylformamide are preferably used from this group of monomers.
  • the copolymers contain the monomers of group a) in amounts of 5 to 100, preferably 30 to 100 mol% in copolymerized form.
  • Suitable monomers of group b) are monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and the water-soluble salts of these monomers.
  • This group of monomers includes, for example, acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylenemalonic acid, allylacetic acid, vinylacetic acid, crotonic acid, fumaric acid, mesaconic acid and itaconic acid. From this group of monomers are preferably used acrylic acid, methacrylic acid, maleic acid or mixtures of said carboxylic acids, in particular mixtures of acrylic acid and maleic acid or mixtures of acrylic acid and methacrylic acid.
  • the monomers of group b) can be used either in the form of the free carboxylic acids or in partially or completely neutralized form in the copolymerization.
  • To neutralize the monoethylenically unsaturated carboxylic acids for example, use is made of alkali metal, alkaline earth metal bases, ammonia or amines, e.g. Caustic soda, potassium hydroxide, soda, potash, sodium bicarbonate, magnesium oxide, calcium hydroxide, calcium oxide, ammonia, triethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine.
  • the copolymers contain at least one monomer from group b) in an amount of 95 to 0, preferably 70 to 0 mol% in copolymerized form.
  • copolymers of the monomers a) and b) may optionally be modified by using in the copolymerization at least one other monoethylenically unsaturated compound which is copolymerizable with the monomers a) and b).
  • Suitable monomers of group c) are, for example, the esters, amides and nitriles of the carboxylic acids indicated under a), for example methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, 2- or 3-hydroxypropyl acrylate, 2- or 4-hydroxybutyl acrylate, hydroxyethyl methacrylate, 2- or 3-hydroxypropyl methacrylate, hydroxyisobutyl acrylate, hydroxyisobutyl methacrylate, monomethyl maleate, dimethyl maleate, monoethyl maleate, diethyl maleate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylamide, methacrylamide, N-dimethylacrylamide, N-tertiary butylacrylamide, acrylonitrile, methacrylonitrile, dimethylaminoethyl
  • Suitable monomers of group c) are acrylamidoglycolic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate and acrylamidomethylpropanesulfonic acid and phosphonic acid group-containing monomers such as vinyl phosphate, allyl phosphate and acrylamidomethanepropanephosphonic acid.
  • Further suitable compounds of this group are N-vinyl-2-methylimidazoline, diallylammonium chloride, vinyl acetate and vinyl propionate.
  • mixtures of said monomers of group c for example mixtures of acrylic esters and vinyl acetate, mixtures of various acrylic esters, mixtures of acrylic esters and acrylamide or mixtures of acrylamide and hydroxyethyl acrylate.
  • monomers of group c) are preferably used acrylamide, acrylonitrile, vinyl acetate, N-vinylimidazole or mixtures of these monomers, for example mixtures of acrylamide and vinyl acetate or mixtures of acrylamide and acrylonitrile. If the monomers of group c) are used to modify the copolymers, they are present in amounts of up to 30 mol% in copolymerized form in the copolymers, preferably in amounts of 1 to 20 mol%.
  • copolymers of the monomers a) and b) and, if appropriate, c) can furthermore be modified by carrying out the copolymerization in the presence of at least one monomer of group d), which are compounds which have at least two ethylenically unsaturated nonconjugated Have double bonds in the molecule.
  • the concomitant use of the monomers of group d) in the copolymerization causes an increase in the K values (see above) of the copolymers.
  • Suitable compounds of group d) are, for example, methylenebisacrylamide, esters of acrylic acid and methacrylic acid with polyhydric alcohols, such as glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate and at least two times with acrylic acid or methacrylic acid esterified polyethylene glycols or polyols, such as pentaerythritol and glucose.
  • Suitable crosslinkers are also divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose.
  • water-soluble monomers such as glycol diacrylate or glycol diacrylates, of polyethylene glycols having a molecular weight of up to 3,000. If the monomers of group d) are used to modify the copolymers, the amounts used are up to 2 mol%. In the case of their use, they are preferably contained in 0.01 to 1 mol% in copolymerized form in the copolymers.
  • Examples include homopolymers of N-vinylformamide, copolymers of N-vinylformamide, acrylic acid and acrylamide, copolymers of N-vinylformamide, acrylic acid and acrylonitrile, copolymers of N-vinylformamide, acrylic acid and vinyl acetate, copolymers of N-vinylformamide, acrylic acid and N-vinylpyrrolidone , Copolymers of N-vinylformamide, acrylic acid, acrylonitrile and vinyl acetate, copolymers of N-vinylformamide, acrylic acid, acrylamide and arynitrile.
  • the acrylic acid may be wholly or partly replaced by methacrylic acid.
  • Acrylic acid or methacrylic acid may be partially or completely neutralized with caustic soda, potassium hydroxide, calcium hydroxide or ammonia.
  • the preparation of the copolymers is carried out by known free-radical processes, e.g. solution, precipitation, suspension or emulsion polymerization using compounds which form radicals under the polymerization conditions.
  • the polymerization temperatures are usually in the range of 30 to 200, preferably 40 to 110, more preferably 40 to 100 ° C, optionally at reduced or elevated pressure.
  • Suitable initiators include, for example, azo and peroxy compounds as well as the usual redox initiator systems, such as combinations of hydrogen peroxide and reducing compounds, e.g. Sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxilate and hydrazine. These systems may optionally additionally contain small amounts of a heavy metal salt.
  • the copolymers are preferably prepared by solution polymerization in water, wherein the monomers of group b) are preferably used in the salt form and the pH during the Polymerization between 4 and 10, preferably between 6 and 8 holds.
  • a buffer such as disodium hydrogen phosphate.
  • the polymerization initiator used is preferably water-soluble azo compounds, such as 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2) methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-amidinopropane) hydrochloride or 4,4'-azobis (4'-cyano) pentanoic acid).
  • 2,2'-azobis (2-methylpropionamidine) dihydrochloride 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile)
  • 2,2'-azobis (2) methyl-N-phenylpropionamidine dihydrochloride 2,2'-azobis (isobutyronitrile)
  • 2,2'-azobis (2-amidinopropane) hydrochloride or 4,4'
  • the compounds mentioned are usually used in the form of aqueous solutions or dispersions, the lower concentration being determined by the amount of water acceptable in the (co) polymerization and the upper concentration by the solubility of the compound in question in water.
  • the concentration is 0.1 to 30 wt .-%, preferably 0.5 to 20 wt .-%, particularly preferably 1.0 to 10 wt .-%, based on the solution.
  • the amount of initiators is generally from 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, based on the (co) polymerizing monomers. It is also possible to use a plurality of different initiators in (co) polymerization.
  • solvent or diluent e.g. Water, alcohols, such as methanol, ethanol, n- or iso-propanol, n- or iso-butanol, or ketones, such as acetone, ethyl methyl ketone, diethyl ketone or isobutyl methyl ketone.
  • alcohols such as methanol, ethanol, n- or iso-propanol, n- or iso-butanol
  • ketones such as acetone, ethyl methyl ketone, diethyl ketone or isobutyl methyl ketone.
  • the copolymerization is carried out in the presence of a regulator.
  • Suitable regulators are, for example, secondary alcohols such as isopropanol and sec-butanol, hydroxylamine, formic acid and mercapto compounds such as mercaptoethanol, mercaptopropanol, mercaptobutanol, thioglycolic acid, thiolactic acid, tert-butylmercaptan, octylmercaptan and dodecylmercaptan.
  • the regulators are usually used in amounts of 0.01 to 5 wt .-%, based on the monomers used. If secondary alcohols are used as regulators, the polymerization can also be carried out in the presence of substantially larger amounts, for example in amounts of up to 80% by weight, based on the monomers. In these cases, the secondary alcohols are also solvents for the monomers.
  • the (co) polymers thus obtainable have K values of 30 to 300, preferably 50 to 250.
  • the K values are determined according to H.Fikentscher in 5% strength aqueous sodium chloride solution at pH 7, 25 ° C. and a polymer concentration of 0, 1% by weight.
  • the (co) polymerization can also be carried out in another manner known to the person skilled in the art, e.g. as solution, precipitation, water-in-oil emulsion or reverse suspension polymerization.
  • the solution polymerization is preferred.
  • ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers are used as surface-active compounds.
  • the (co) polymerization gives (co) polymers of a different molecular weight, which is characterized in this document by means of the K values according to Fikentscher.
  • (Co) polymers with a high K value e.g. above 80, are preferably prepared by (co) polymerizing the N-alkyl-N-vinylcarboxylic acid amide (I) in water.
  • (Co) polymers having a high K value are also obtained, for example, by (co) polymerizing the monomers in the form of reverse suspension polymerization or by (co) polymerizing the monomers by the water-in-oil polymerization method.
  • the oil phase used is saturated hydrocarbons, for example hexane, heptane, cyclohexane, decalin or aromatic hydrocarbons, such as benzene, toluene, xylene and cumene.
  • the ratio of oil phase to aqueous phase in the reverse suspension polymerization is, for example, 10: 1 to 1:10.
  • (Co) polymer with a low K value, e.g. below 80 is obtained by carrying out the (co) polymerization in the presence of polymerization regulators or in a solvent which controls the (co) polymerization, e.g. Alcohols such as methanol, ethanol, n- or iso-propanol, or ketones such as acetone, ethyl methyl ketone, diethyl ketone or isobutyl methyl ketone.
  • Alcohols such as methanol, ethanol, n- or iso-propanol
  • ketones such as acetone, ethyl methyl ketone, diethyl ketone or isobutyl methyl ketone.
  • (Co) polymers having low molecular weights and correspondingly low K values are furthermore obtained by means of the customary methods, ie use of relatively large amounts of polymerization initiator or use of polymerization regulators or combinations of the measures mentioned.
  • the molecular weight of the (co) polymers which can be used according to the invention is not limited. Preference is given to (co) polymers having K values between 30 and 110, with K values between 40 and 90 being particularly preferred.
  • N-alkyl-N-vinylcarboxamides for example of the formula (I) and especially N-vinylformamide, in copolymerized form containing (co) polymers can be used according to the invention both partially or fully cleaved as well as in un-cleaved form.
  • a degree of hydrolysis is preferably between 0 and 30%, particularly preferably between 0 and 20% and very particularly preferably between 0 and 10%.
  • the nature of the cleavage of the carboxylic acid or formyl group is not limited, it can be carried out for example in the presence of acid or base, preferably cleavage in the presence of bases, such as sodium hydroxide, potassium hydroxide, alkaline earth metal: l hydroxides, ammonia or amines.
  • amphoteric (co) polymers are formed.
  • a cleavage of the carboxylic acid group is desired, this can be carried out, for example, in water.
  • the cleavage of the formyl group in the hydrolysis takes place at temperatures in the range from 20 to 200, preferably 40 to 180 ° C, in the presence of acids or bases.
  • the hydrolysis in the presence of acids or bases is preferably carried out in the temperature range of 70 to 90 ° C.
  • each carboxylic acid group equivalent in the poly-N-alkyl-N-vinylcarboxamide about 0.05 to 1.5 equivalents of an acid, such as hydrochloric, hydrobromic, phosphoric, sulfuric, are required for acid hydrolysis.
  • the pH of the acidic hydrolysis is in the range of 2 to 0, preferably 1 to 0.
  • the hydrolysis of N-vinylformamide proceeds much faster than that of (co) polymers of other N-alkyl-N-vinylcarboxamides, such , As the N-methyl-N-vinylformamide, and therefore can under gentler conditions, ie at lower temperatures and without a high excess of acids.
  • the hydrolysis of the formyl groups of the poly-N-alkyl-N-vinylcarboxamide can also be carried out in alkaline medium, e.g. in the pH range of 11 to 14. This pH is preferably adjusted by the addition of sodium hydroxide solution or potassium hydroxide solution. However, it is also possible to use ammonia, amines and / or alkaline earth metal bases. For the alkaline hydrolysis use 0.05 to 1.5, preferably 0.4 to 1.0 equivalents of a base.
  • the cleavage can also be carried out at high temperatures, for example above 100 ° C., preferably 120 to 180 ° C., particularly preferably 140 to 160 ° C. in the presence of a solvent, e.g. Water, be carried out without acid or base. This is preferably carried out at conditions above the critical point, for example with supercritical water.
  • a solvent e.g. Water
  • the carboxylic acid group is split off in water in the presence of acids or bases from the poly-N-vinylcarboxamide, the by-product carboxylic acid, for example formic acid, or salts thereof is obtained.
  • the solutions obtained are treated, for example, with ion exchangers.
  • the residue separated from the hydrolysis products can then be incorporated into the coating compositions or used as an activator for the pretreatment.
  • the molecular weight of the present invention (co) polymers is, as stated above, not limited, but it should be adapted to the respective application method.
  • the molecular weight should be relatively high, while it should be relatively low for the order with a sprayer.
  • the application of the activators by the process according to the invention to the surface of the coating base paper or prepainted paper can be carried out according to the methods customary for the surface treatment of paper in the paper industry.
  • the application of the activators can also be done in the calendering of the paper on the humidification.
  • the activator is applied to the raw or prepainted paper in one operation before applying the coating composition containing optical brighteners.
  • the usable for the pretreatment according to the invention, optionally already vorgeleimte, uncoated base paper usually has a water content of not more than 10% by weight, preferably not more than 8% by weight, more preferably between 3 and 8% by weight and especially between 5 and 8 wt %.
  • the prepainted paper which can be used for the pretreatment according to the invention has generally already undergone one or two brushing operations.
  • the activators can be applied to the paper from aqueous solution or as a solution in methanol, ethanol, isopropanol , n-propanol, n-butanol, ethyl acetate, acetone or N-methylpyrrolidone, preferably from aqueous solution, the concentration being chosen in this way should be that the respective application method can be optimally performed due, for example, the viscosity of the substance or solution to be applied.
  • Usual concentrations are between 10 and 60% by weight.
  • the activators can be applied to the paper as individual substances, but also in mixtures with each other. But you can also apply the activators on the paper surface in admixture with other paper chemicals that affect other paper properties.
  • paper chemicals that can be applied to the paper together with the brightener activators according to the method of the invention are, for.
  • starch cationic starch, other starch derivatives such. Hydroxyethyl, hydroxymethyl, methyl or ethyl starch ethers, others Polysaccharides such. Guar or guar derivatives, carboxymethyl, hydroxyethyl, hydroxymethyl, methyl or ethyl cellulose ethers or surface sizing agents.
  • the activator-containing composition in addition to at least one activator and optionally solvent at least one pigment, at least one known per se binder and optionally other paper-typical auxiliaries (s.u.).
  • optical brighteners are preferably applied first with a coating compound in a following step (see below).
  • the amount in which the activator is applied to the paper according to the method of the invention can vary within wide limits. In general, one should apply an amount of 0.05 g to 5 g per m 2 of paper, but an amount of 0.1 g to 3 g is preferable.
  • a suitable activator for the optical brightener is added to the coating composition.
  • This may be the same activator as used to pretreat the coating base paper or one of the previous lines, but also another activator.
  • Suitable activators are, for example, those already mentioned above.
  • Preferred are those (co) polymers containing N-vinylcarboxamides, e.g. the o.g. N-vinyl-N-alkylcarboxamides of the formula (I), in copolymerized form.
  • the (co) polymers containing N-vinylcarboxamides can be used both partially or completely cleaved as well as in un-cleaved form.
  • a degree of hydrolysis is preferably between 0 and 30%, particularly preferably between 0 and 20% and very particularly preferably between 0 and 10%.
  • the amount of activator in the coating will be chosen so that the viscosity of the coating composition is in processing areas favorable. Usually, it is between 0.2 and 10% based on the pigment in the coating.
  • the amount of (co) polymers containing N-alkyl-N-vinylcarboxamides, e.g. of the formula (I) which can be added to the paper coating slip depends on the amount of the brightener in the coating slip.
  • optical brightener per 100 parts by weight of pigment is added to the coating.
  • the (co) polymer is usually added the same to five times the amount of optical brightener to the coating composition, that is 0.2 to 10 parts by weight, preferably 0.5 to 8 and particularly preferably 1 to parts by weight.
  • the paper coating slip applied after the pretreatment according to the invention with an activator preferably contains at least one optical brightener.
  • the paper coating slips contain at least one white pigment and at least one binder.
  • the paper coating slips may contain further components known to the person skilled in the art. Consider, for example, Flow control agents, thickeners, wetting aids for the pigments, etc.
  • optical brighteners that can be used in conjunction with the method of the invention are not limited.
  • such brighteners can be used as described in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2000 Electronic Release, OPTICAL BRIGHTENERS - Chemistry of Technical Products.
  • Suitable optical brighteners include, for example, the group of distyrylbenzenes, for example cyano-substituted 1,4-distyrylbenzenes with cyano groups in positions 2 'and 3 "[CAS RegNo. 79026-03-2], or in positions 2' and 2" [ 13001-38-2], 3 'and 3 "[36755-00-7], 3' and 4" [79026-02-1] and 4 'and 4 "[13001-40-6], or amphoteric compounds, such as [84196-71-4], in the 2 'and 2 "position each one group -O- (CH 2 ) 2 -N + (C 2 H 5 ) 2 -CH 2 COO - 4,4'-di (2-sulfostyryl) biphenyl disodium salt [27344-41-8], 4,4'-di (3-sulfostyryl) biphenyl disodium salt [51119-63-2], 4,4'-di (4-chloro-3-sulf
  • Stilbenyl 2H-triazoles eg stilbenyl 2H-naphtho [1,2-d] triazoles such as the sodium salt of 4- (2H-naphtho [1,2-d] triazol-2-yl) stilbene-2-sulfonic acid [6416 -68-8] or those in position 6 at the naphtholri and at position 2 of the stilbene skeleton carry a sulfonic acid [2583-80-4], or at the stilbene backbone in position 2 a cyano group and in position 4 'carry a chloro group [5516-20-1] or eg Bis (1,2,3 -triazol-2-yl) stilbenes such as 4,4'-bis (4-phenyl-1,2,3-triazol-2-yl) stilbene-2,2'-disulfonic acid dipotassium salt [52237-03-3] or 4,4'-bis (4- (4'-bis (4- (4'-)
  • Furans, benzo [b] furans and benzimidazoles e.g. Bis (benzo [b] furan-2-yl) biphenyls, for example, sulfonated 4,4'-bis (benzo [b] furan-2-yl) biphenyls or cationic benzimidazoles, for example, 2,5-di (1-methylbenzimidazole-2 -yl) furan [4751-43-3], [72829-17-5], [74878-56-1], [74878-48-1] or [66371-25-3], or 1,3-diphenyl -2-pyrazolines, eg 1- (4-amidosulfonylphenyl) -3- (4-chlorophenyl) -2-pyrazoline [2744-49-2]; [60650-43-3], [3656-22-2], [27441-70-9], [32020-25-0], [61931-42-8] or [81209-71-4], and tertiary and
  • 4,4'-distyrylbiphenyl derivatives or stilbene derivatives which are substituted by up to 6, particularly preferably having 2, 4 or 6 sulphonic acid groups may be used, preferably the Blankophor® grades from Bayer AG, particularly preferred are Blankophor P ® and Blankophor.RTM ® PSG, preference is further given the Tinopal® grades from Ciba Specialty Chemicals, particularly preferably Tinopal ® MC liquid, Tinopal ® ABP-Z liquid, Tinopal ® SPP-Z liquid and Tinopal ® SK-B liquid and further preferred are the Leukophor® brands from Clariant AG, particularly preferably Leukophor® APN, UO, NS or SHR.
  • the pigments which can be used in the coating compositions are likewise not limited.
  • satin white calcium carbonate in ground or precipitated (precipitated) form
  • barium sulfate in ground or precipitated form kaolin (clay)
  • calcined clay talc
  • silicates or organic pigments e.g. As plastics in particulate form, can be used.
  • binders ((co) polymeric binders) which can be used in the coating slips according to the invention are likewise not limited.
  • casein, starch, soy protein, carboxymethyl cellulose, alginate and / or polyvinyl alcohol or dispersions containing acrylic acid, acrylic esters, vinyl acetate and / or styrene in copolymerized form e.g. (Co) polymers of acrylic ester / styrene, styrene / butadiene or vinyl acetate may be used.
  • the paper coating slips may continue to be e.g. Contain dispersant.
  • Suitable dispersants are polyanions, for example of polyphosphoric acids or of polyacrylic acids (polysalts), which are usually present in amounts of from 0.1 to 3% by weight, based on the amount of pigment.
  • the paper pond compounds are usually aqueous paper coating slips.
  • the water content can be adjusted depending on the desired viscosity or flow properties.
  • the content of water in the paper coating slip is usually adjusted to 25 to 75% by weight, based on the total paper coating slip (including water).
  • the coating compositions are processed completely analogously to the processing of coating colors according to the prior art, eg according to "The Essential Guide to Aqueous Coating of Paper and Board", TWR Dean (ed.), Published by the Paper Industry Technical Association (PITA), 1997, the "Guide to the use of BASF products in paper and board coking", BASF Aktiengesellschaft, D-6700 Ludwigshafen, Federal Republic of Germany, B 376 d, 09.77 or Ullmann's Encyclopadie der Technischen Chemie, 4th Edition, Vol. 17, p. 603 ff ,
  • a thickener may be added.
  • Suitable thickeners besides free-radically (co) polymerized (co) polymers, customary organic and inorganic thickeners such as hydroxymethylcellulose or bentonite.
  • the ingredients can be mixed in a known manner.
  • the paper coating slips are suitable for coating eg paper or cardboard.
  • the paper coating slip can then be applied by conventional methods to the papers or cardboard to be coated.
  • the papers or paperboards coated with the paper coating compositions of the invention can be prepared by conventional methods, e.g. Offset, gravure or gravure printing processes or digital printing processes, e.g. Laser printing or ink-jet printing process can be printed.
  • the process according to the invention makes it easier for a person skilled in the art to work out a formulation for a coating composition which conventionally also contains the brightener-enhancing activator in addition to the many other components influencing the rheology and the coating quality.
  • activators in addition to their brightener-enhancing effect also change the properties of the coating composition and even influence the rheological properties of the coating composition by their interaction with the optical brighteners.
  • the coating compositions but in addition to one or more pigments and in addition to one or more Bindemitten and the optical brightener additionally thickener, line hardening agents, leveling agents, brightener, flow improvers, dispersants, wetting agents, lubricants, u.s.w.
  • the expert is grateful for any component whose properties he does not consider and which he does not have to incorporate into the coating.
  • Example C In the same reactor of Example C are first added 2.5 g of sodium bisulfite solution (40%) and then 32.4 g of sodium hydroxide solution (25%). The reaction mixture is heated to 80 ° C and stirred for 3 hours then cooled to 40 ° C and 22.4 g of hydrochloric acid (30%) was added, so that it reaches a pH of about 7. The slightly yellowish polymer solution has a degree of hydrolysis of 5.4% (enzymatic determination of the resulting formic acid).
  • Example 2 In the same reactor of Example 1 are first 2.5 g of sodium bisulfite solution (40%) and then 45 g of sodium hydroxide solution (25%) to. The reaction mixture is heated to 80 ° C and stirred for 3 hours then cooled to 40 ° C and 30.8 g of hydrochloric acid (30%) was added, so that a pH of about 7 is reached. The slightly yellowish polymer solution has a degree of hydrolysis of 4.3% (enzymatic determination of the resulting formic acid).
  • a commercially available wood-free base paper with the optical properties given in Table 1 was coated with 15 g / m 2 of a coating by means of a hand knife.
  • the coating contained 33% water.
  • the non-aqueous fraction consisted of 70 parts of calcium carbonate (Hydrocarb® 90 from Plüss-Staufer AG), 30 parts of kaolin (Amazon® 88, Kaolin International), 8 parts of a polymer dispersion based on styrene and butadiene as binder (Styronal® D 610 , BASF Aktiengesellschaft), 0.5 parts of a 1,3,5-triazinyl derivative of (4,4'-diaminostilbene-2,2'-disulphonic acid with 2 sulfonic acid groups Tinopal ® MC liquid from Ciba Specialty Chemicals) as an optical brightener and, if appropriate, 2 parts of a polyvinylformamide from Example D which acts as a rheological assistant, binding force
  • the coated paper was dried according to the prior art, calendered and examined as follows:
  • the white R 457 of the paper was determined according to DIN 53 145, part 2.
  • the CIE whiteness of the paper was measured according to ISO 2469.
  • a 10% strength aqueous solution of a polyvinylformamide having a K value of 45.9 and a degree of hydrolysis of 5.4% was applied to the coating base paper before coating with the coating composition in such a way that after drying, 2 g / m 2 of the polyvinylformamide remain on the paper.
  • the following papers were compared in Table 1: I: coating base II: Paper coated with the coating containing no activator. III: Paper coated with the coating composition which contains 2 parts of polyvinylformamide from Example D with a K value of 45.9 and a degree of hydrolysis of 5.4% as activator.
  • V Paper according to the process of the invention pretreated with polyvinylformamide and coated with a coating composition containing no activator.
  • V Paper according to the process of the invention which has been pretreated with polyvinylformamide but which additionally contains in the coating composition 2 parts of polyvinylformamide from Example D with a K value of 45.9 and a degree of hydrolysis of 5.4% as activator.
  • coating base 90.50 98.3 II Paper coated with coating (without activator) 91.19 100.4 III: paper coated with coating (including activator) 97.17 115.6 IV: paper pretreated with activator, coated with coating slip (without activator) (according to the invention) 100.62 124.4 V: Paper pretreated with activator, coated with coating slip (including activator) (according to the invention) 102.67 129.8
  • Example 2 The procedure was as in Example 1 with the difference that a 1,3,5-triazinyl derivative of 4,4'-diaminostilbene-2,2'-disulfonic acid with 4 sulfonic acid groups (Tinopal ® ABP-Z liquid from Ciba Specialty Chemicals) was used as optical brightener.
  • Teinopal ® ABP-Z liquid from Ciba Specialty Chemicals was used as optical brightener.
  • Table 2 White R 457 White CIE I: base paper 90.50 98.3 II: Paper coated with coating (without activator) 91.52 98.0 III: paper coated with coating (including activator) 99.14 117.7 IV: paper pretreated with activator, coated with coating slip (without activator) (according to the invention) 105.28 131.6 V: Paper pretreated with activator, coated with coating slip (including activator) (according to the invention) 107.07 136.1
  • Example 2 The procedure was as in Example 1 with the difference that a 1,3,5-triazinyl derivative of 4,4'-diaminostilbene-2,2'-disulfonic acid with 6 sulfonic acid groups (Tinopal ® SPP-Z liquid from Ciba Specialty Chemicals) was used as an optical brightener, and that optionally 1.5 parts of a functioning as a rheology aid, binding force enhancer and activator for the brightener unhydrolyzed polyvinylformamide from Example C were added with the K value 45.9.
  • Tinopal ® SPP-Z liquid from Ciba Specialty Chemicals
  • coating base 90.50 98.3 II Paper coated with coating (without activator) 94.02 107.3 III: paper coated with coating (including activator) 100.74 124.3 IV: paper pretreated with activator, coated with coating slip (without activator) (according to the invention) 105.98 136.8 V: Paper pretreated with activator, coated with coating slip (including activator) (according to the invention) 106.84 139.2
  • a 10% strength aqueous solution of a polyvinylformamide from Example D having a K value of 45.9 and a degree of hydrolysis of 5.4% (see above) was applied to the coating base paper before coating with the coating composition such that after drying, 2 g / m 2 of the polyvinylformamide remained on the paper.
  • Table 4 compares papers coated with coating compositions containing the various activators in varying amounts. Table 4 All coating base papers pretreated according to the invention with activator White R 457 White CIE I: base paper without activator 105.28 131.6 II: coating composition with 1.0 part of polyvinylformamide unhydrolysed as activator 105.87 134.4 III: coating composition with 1.5 parts of polyvinylformamide unhydrolysed as activator 106.12 135.4 IV: coating composition with 2.0 parts of polyvinylformamide unhydrolysed as activator 106.54 136.6 V: coating composition with 1.0 part of polyvinylformamide, degree of hydrolysis 5.4% as activator 105.50 133.1 VI: coating composition with 1.5 parts of polyvinylformamide, degree of hydrolysis 5.4% as activator 105.97 134.1 VII: coating composition with 2.0 parts of polyvinylformamide, degree of hydrolysis 5.4% as activator 107.07 136.1
  • a commercially available wood-free base paper with the optical properties given in Table 1 was coated with 15 g / m 2 of a coating by means of a hand knife.
  • the coating contained 33% water.
  • the non-aqueous fraction consisted of 70 parts of calcium carbonate (Hydrocarb® 90, Pluess-Staufer AG), 30 parts of kaolin (Amazon® 88, obtained from Kaolin International), 8 parts of a polymer dispersion based on styrene and butadiene as binder (Styronal® D 610, BASF Aktiengesellschaft) and 0.5 parts of a 1,3,5-triazinyl derivative of 4,4'-diaminostilbene-2,2'-disulfonic acid 6-sulfonic acid (Tinopal ® SPP-Z liquid from Ciba Specialty Chemicals ) as an optical brightener.
  • the coating base paper used was either not pretreated or various activators were applied to the coating base paper according to the technique described in Example 1.
  • Example 2 The procedure was as in Example 1 with the difference that a derivative of 4,4'-distyrylbiphenyl (Tinopal ® SK-B liquid from Ciba Specialty Chemicals) was used as an optical brightener, and that optionally 1.0 parts of a rheology aid , Binderkraftsverlutterer and activator for the brightener acting unhydrolyzed polyvinylformamide from Example C with a K value of 45.9 added to the coating slip.
  • Teopal ® SK-B liquid from Ciba Specialty Chemicals a derivative of 4,4'-distyrylbiphenyl
  • Binderkraftsverlutterer and activator for the brightener acting unhydrolyzed polyvinylformamide from Example C with a K value of 45.9 added to the coating slip.
  • Table 6 White R 457 White CIE I base paper 90.50 98.3 II: Paper coated with coating (without activator) 94,10 109.1 III: paper coated with coating (including activator unhydrolysed polyvinylformamide) 96.79 115.0 IV: paper pretreated with activator, coated with coating slip (without activator) (according to the invention) 99.75 121.6 V: paper pretreated with activator, coated with coating slip (including activator unhydrolysed polyvinylformamide) (according to the invention) 100.67 124.3
  • inventive method is also advantageous if optical brighteners of other chemical nature, eg. Based on derivatives of 4,4'-distyrylbiphenyl.
  • a paper already coated with a pigment-containing coating composition was provided with a top coat by coating with a pigment-containing coating composition containing 33% of water.
  • the non-aqueous content of the coating composition consists of 70 parts of calcium carbonate (Hydrocarb® 90 from Plüss-Staufer AG), 30 parts of kaolin (Amazon® 88, obtained from Kaolin International), 8 parts of a polymer dispersion based on styrene and butadiene as binder (Styronal® D 610 from BASF Aktiengesellschaft) and 0.5 part of a 1,3,5-triazinyl derivative of 4,4'-diamino-stilbene-2,2'-disulfonic acid having 6 sulfonic acid groups (Tinopal® SPP-Z liquid from Ciba Specialty Chemicals) as optical brightener.
  • the polymers specified in Table 7 are applied to the prepainted paper in a quantity of 1 g /
  • the topcoated paper is dried, calendered and tested according to the prior art.
  • the white R 457 of the paper was determined according to DIN 53 145, part 2.

Landscapes

  • Paper (AREA)

Claims (10)

  1. Procédé de réalisation de papier revêtu d'une bande contenant au moins un éclaircissant optique, caractérisé en ce qu'on traite du papier brut ou du papier prétraité avant l'application de la couche contenant l'éclaircissant optique avec au moins une substance renforçant l'efficacité des éclaircissants optiques.
  2. Procédé selon la revendication 1, caractérisé en ce que la couche contient au moins un pigment.
  3. Procédé selon les revendications 1 et 2, caractérisé en ce qu'on utilise pour le prétraitement un polymère ou un copolymère contenant au moins un amide d'acide N-vinylcarbonique monopolymérisé.
  4. Procédé selon les revendications 1 et 3, caractérisé en ce qu'on utilise pour le prétraitement du papier un polymère ou un copolymère contenant du N-vinyl formamide, du N-vinyl acétamide, du N-méthyl-N-vinyl formamide, du N-méthyl-N-vinyl acétamide, du N-vinylpyrrolidone ou du N-vinyle caprolactame sous forme monopolymérisée.
  5. Procédé selon la revendication 3 ou 4, caractérisé en ce que le copolymère ou polymère qui contient l'amide d'acide N-vinylcarbonique monopolymérisé est partiellement divisé.
  6. Procédé selon les revendications 3 à 4, caractérisé en ce que le copolymère ou polymère qui contient l'amide d'acide N-vinylcarbonique monopolymérisé est divisé de 0 à 30 %.
  7. Procédé selon les revendications 1 et 2, caractérisé en ce qu'on utilise pour le prétraitement du papier de l'alcool polyvinylique, du carboxyméthylcellulose, de l'amidon réduit anionique ou non ionique, de la caséine, des protéines de soja, un copolymérisat de styrène-acrylate hydrosoluble ou des copolymérisats contenant un ester acrylique.
  8. Procédé selon les revendications 1 à 7, caractérisé en ce que la couche contenant l'éclaircissant optique contient un (co)polymère contenant au moins un amide d'acide N-vinylcarbonique monopolymérisé.
  9. Papiers revêtus pouvant être obtenus selon le procédé des revendications 1 à 8.
  10. Utilisation de papier selon la revendication 9 dans un procédé d'imprimerie.
EP02767338A 2001-08-13 2002-08-07 Procede de fabrication de papier couche extremement blanc Expired - Lifetime EP1419298B8 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10138631A DE10138631A1 (de) 2001-08-13 2001-08-13 Verfahren zur Herstellung von beschichtetem Papier mit hoher Weiße
DE10138631 2001-08-13
PCT/EP2002/008813 WO2003016624A1 (fr) 2001-08-13 2002-08-07 Procede de fabrication de papier couche extremement blanc

Publications (3)

Publication Number Publication Date
EP1419298A1 EP1419298A1 (fr) 2004-05-19
EP1419298B1 true EP1419298B1 (fr) 2008-02-13
EP1419298B8 EP1419298B8 (fr) 2008-04-02

Family

ID=7694600

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02767338A Expired - Lifetime EP1419298B8 (fr) 2001-08-13 2002-08-07 Procede de fabrication de papier couche extremement blanc

Country Status (7)

Country Link
US (1) US7641765B2 (fr)
EP (1) EP1419298B8 (fr)
JP (1) JP2004538393A (fr)
AT (1) ATE386161T1 (fr)
CA (1) CA2456934C (fr)
DE (2) DE10138631A1 (fr)
WO (1) WO2003016624A1 (fr)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10138631A1 (de) * 2001-08-13 2003-02-27 Basf Ag Verfahren zur Herstellung von beschichtetem Papier mit hoher Weiße
WO2003021041A2 (fr) * 2001-09-03 2003-03-13 Basf Aktiengesellschaft Procede pour augmenter la blancheur du papier a l'aide de polyelectrolytes cationiques
DE10319741A1 (de) * 2003-04-30 2004-11-18 Basf Ag Verfahren zur Verbesserung der Bedruckbarkeit von Papier und Papierprodukten beim Bedrucken mit Hilfe des Tintenstrahldruckverfahrens
US20050025741A1 (en) * 2003-05-15 2005-02-03 Lau Aldrich N.K. Poly and copoly(N-vinylamide)s and their use in capillary electrophoresis
DE102004052957A1 (de) * 2004-10-29 2006-05-04 Basf Ag Verfahren zur Herstellung von gekrepptem Papier
US8246780B2 (en) * 2005-09-19 2012-08-21 Nalco Company Methods for enhancing brightness and resistance to thermal yellowing of bleached kraft pulp and paper
EP1712677A1 (fr) * 2005-04-08 2006-10-18 Clariant International Ltd. Solutions aqueuses d'azurants optiques
MY177088A (en) * 2005-04-08 2020-09-04 Nalco Co Improved compositions and processes for paper production
EP1752453A1 (fr) * 2005-08-04 2007-02-14 Clariant International Ltd. Solutions stable au stockage des azurants optiques
US7622022B2 (en) 2006-06-01 2009-11-24 Benny J Skaggs Surface treatment of substrate or paper/paperboard products using optical brightening agent
CN101605940B (zh) * 2007-02-08 2012-12-05 巴斯夫欧洲公司 用于涂纸浆液的水溶性粘合剂
US20090128808A1 (en) * 2007-11-15 2009-05-21 Alec Stewart Tindal Method for the communication and comparison of the whiteness of paper
US9127406B2 (en) 2008-12-08 2015-09-08 Hewlett-Packard Development Company, L.P. Surface coating composition for inkjet media
US9932709B2 (en) 2013-03-15 2018-04-03 Ecolab Usa Inc. Processes and compositions for brightness improvement in paper production
US8475630B2 (en) * 2009-04-16 2013-07-02 Nanopaper, Llc Retention systems and methods for papermaking
US20130189457A1 (en) 2012-01-23 2013-07-25 International Paper Company SEPARATED TREATMENT OF PAPER SUBSTRATE WITH MULTIVALENT METAL SALTS AND OBAs
CN111270561B (zh) * 2020-02-24 2022-03-25 亚太森博（山东）浆纸有限公司 一种高白度耐返黄涂布白卡纸及其制备方法
CN111851137B (zh) * 2020-07-24 2022-04-01 淄博圣泉纸业有限公司 一种低吸高效转移印花纸的制备方法

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1692854A1 (de) * 1967-11-29 1971-10-21 Hoechst Ag Verfahren zur Entwaesserung von Cellulosefaser-Suspensionen
GB1301661A (fr) * 1969-01-29 1973-01-04
DE3534273A1 (de) * 1985-09-26 1987-04-02 Basf Ag Verfahren zur herstellung von vinylamin-einheiten enthaltenden wasserloeslichen copolymerisaten und deren verwendung als nass- und trockenverfestigungsmittel fuer papier
GB2247030B (en) * 1990-07-03 1994-01-12 Grace W R & Co The enhancement of fluorescent whitening agents
DE4116593C1 (fr) * 1991-05-22 1993-01-07 Fa. Hermann Heye, 3063 Obernkirchen, De
US5373076A (en) * 1992-07-14 1994-12-13 Air Products And Chemicals, Inc. Functional oligomeric vinylformamides and vinylamines
GB2277749B (en) * 1993-05-08 1996-12-04 Ciba Geigy Ag Fluorescent whitening of paper
DE4409903A1 (de) * 1994-03-23 1995-09-28 Basf Ag N-Vinyleinheiten enthaltende Pfropfpolymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung
US6494990B2 (en) * 1995-08-25 2002-12-17 Bayer Corporation Paper or board with surface of carboxylated surface size and polyacrylamide
DE19616529A1 (de) * 1996-04-25 1997-11-06 Basf Ag Verwendung eines Polymerisats auf Basis von basischen Vinylheterozyklen zur Beschichtung von bedruckbaren Materialien
DE19618607C2 (de) * 1996-05-09 1999-07-08 Schoeller Felix Jun Foto Aufzeichnungsmaterial für Tintenstrahl-Druckverfahren
DE19627553A1 (de) * 1996-07-09 1998-01-15 Basf Ag Verfahren zur Herstellung von Papier und Karton
DE19727503A1 (de) * 1997-06-27 1999-01-07 Basf Ag Papierstreichmassen auf Basis von Bindemitteln mit N-Vinylformamidderivaten
JPH1193092A (ja) 1997-09-11 1999-04-06 Hymo Corp 紙用表面塗布剤
DE19815127A1 (de) * 1998-04-03 1999-10-07 Basf Ag Mittel mit Copolymerisaten aus N-Vinylcarbonsäureamiden und Monomeren mit hydrophobem Rest, und Verwendung dieser Copolymerisate
US6352341B2 (en) * 1998-12-18 2002-03-05 Eastman Kodak Company Ink jet printing process
DE19945580C5 (de) 1999-09-23 2007-03-15 Stora Enso Publication Paper Gmbh & Co. Kg Gestrichenes, optisch aufgehelltes Druckpapier und Verfahren zu dessen Herstellung
US6635319B1 (en) * 1999-12-01 2003-10-21 Eastman Kodak Company Glossy ink jet recording element
DE10044164A1 (de) * 2000-09-07 2002-03-21 Basf Ag Vinylamin-Verbindungen
DE10055592A1 (de) * 2000-11-09 2002-05-23 Basf Ag Papierstreichmassen
US6454404B1 (en) * 2001-01-26 2002-09-24 Eastman Kodak Company Ink jet printing method
JP2003039824A (ja) * 2001-05-22 2003-02-13 Fuji Photo Film Co Ltd インクジェット記録用シート
GB0115411D0 (en) * 2001-06-25 2001-08-15 Ciba Spec Chem Water Treat Ltd Manufacture of paper and paper board
DE10138631A1 (de) * 2001-08-13 2003-02-27 Basf Ag Verfahren zur Herstellung von beschichtetem Papier mit hoher Weiße
US6710175B2 (en) * 2001-08-31 2004-03-23 Kevin Ray Anderson Compositions suitable as additives in the paper industry, preparation; use; and, paper comprising such
WO2003021041A2 (fr) * 2001-09-03 2003-03-13 Basf Aktiengesellschaft Procede pour augmenter la blancheur du papier a l'aide de polyelectrolytes cationiques
US6605325B2 (en) * 2001-10-31 2003-08-12 Eastman Kodak Company Ink jet recording element
US7084200B2 (en) * 2001-11-24 2006-08-01 Basf Aktiengesellschaft Aqueous dispersions of water-soluble polymers of N-vinyl carboxylic acid amides, method for the production thereof and their use
DE10162052A1 (de) * 2001-12-17 2003-06-26 Basf Ag Verfahren zur Herstellung von Papier, Pappe und Karton
US6824650B2 (en) * 2001-12-18 2004-11-30 Kimberly-Clark Worldwide, Inc. Fibrous materials treated with a polyvinylamine polymer
US7041338B2 (en) * 2002-05-01 2006-05-09 Pixterra, Inc. Process for providing a coated paper, a resin coated paper, a polymeric film, and a flexible or inflexible woven fabric substrate by utilizing a coating composition containing a nitrogenous dye-fixing compound
PE20050740A1 (es) * 2003-09-30 2005-09-29 Basf Ag Procedimiento para el pretratamiento de textiles que contienen celulosa

Also Published As

Publication number Publication date
US20040154764A1 (en) 2004-08-12
EP1419298A1 (fr) 2004-05-19
EP1419298B8 (fr) 2008-04-02
CA2456934A1 (fr) 2003-02-27
DE10138631A1 (de) 2003-02-27
JP2004538393A (ja) 2004-12-24
DE50211691D1 (de) 2008-03-27
US7641765B2 (en) 2010-01-05
CA2456934C (fr) 2010-06-29
ATE386161T1 (de) 2008-03-15
WO2003016624A1 (fr) 2003-02-27

Similar Documents

Publication Publication Date Title
EP1419298B1 (fr) Procede de fabrication de papier couche extremement blanc
EP1438197B1 (fr) Procede pour augmenter la blancheur du papier a l'aide de polyelectrolytes cationiques
EP2370484B2 (fr) Procédé de production de dispersions polymères aqueuses à partir d'un composé vinylaromatique, d'un diène aliphatique conjugué et de nitrile carboxylique éthyléniquement insaturé
EP2531536B1 (fr) Épaississant associatif composé de monomère acide, monomère associatif et monomère non ionique
EP2291420B1 (fr) Agents de revêtement du papier contenant des pigments de sels métalliques et des dispersions aqueuses de copolymères solubles dans l'eau
EP2398831B1 (fr) Dispersion aqueuse de polymère à base d'un composé vinylaromatique, d'un diène conjugué aliphatique et d'un acide à insaturation éthylénique
EP1754829A1 (fr) Utilisation d'agents de blanchiment optiques pour la fabrication des melange d'enduisage
EP1337710B1 (fr) Pates a enduire le papier contenant du n-vinylformamide
WO2008095878A2 (fr) Liants hydrosolubles pour pâtes de couchage de papier
EP0724663B1 (fr) Utilisation de papier enduits avec certains melanges de liants pour l'impression offset
EP0742857B1 (fr) Utilisation de papiers enduits de masses de couchage specifiques pour l'impression offset
EP1242682B1 (fr) Matieres a retention d'eau elevee pour enduire le papier
EP0991681B1 (fr) Pates pour le couchage du papier a base de liants aux derives de n-vinylformamide
DE10150895A1 (de) Papierstreichmassen
EP0833752B1 (fr) Utilisation de matieres a enduire le papier a teneur elevee en butadiene en impression offset
CN112689645B (zh) 光学增亮的胶乳
DE10144131A1 (de) Papierstreichmassen
DE102004028431B3 (de) Streichmasse, deren Verwendung und Verfahren zur Herstellung von gestrichenen Papieren
WO2003022924A1 (fr) Dispersions polymeres contenant des copolymeres vinylamide
WO1999005188A1 (fr) Polymerisats blanchis et leur utilisation dans des pates a enduire pour recouvrir des substrats
DE10161157A1 (de) Verfahren zur Erhöhung der Weiße von Papier mit Hilfe von kationischen Polyelektrolyten

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040315

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: BASF SE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 50211691

Country of ref document: DE

Date of ref document: 20080327

Kind code of ref document: P

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: BASF SE

Effective date: 20080305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080524

ET Fr: translation filed
REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080213

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080213

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080213

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080714

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080213

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080513

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: CIBA HOLDING AG

Effective date: 20081110

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: CIBA HOLDING AG

Effective date: 20081110

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080831

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20080807

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080213

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080513

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

NLR1 Nl: opposition has been filed with the epo

Opponent name: CIBA HOLDING AG

PLBP Opposition withdrawn

Free format text: ORIGINAL CODE: 0009264

R26 Opposition filed (corrected)

Opponent name: CIBA HOLDING AG

Effective date: 20081110

PLBD Termination of opposition procedure: decision despatched

Free format text: ORIGINAL CODE: EPIDOSNOPC1

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080213

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080831

NLR1 Nl: opposition has been filed with the epo

Opponent name: CIBA HOLDING AG

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080213

PLBM Termination of opposition procedure: date of legal effect published

Free format text: ORIGINAL CODE: 0009276

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: OPPOSITION PROCEDURE CLOSED

27C Opposition proceedings terminated

Effective date: 20090620

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080807

NLR2 Nl: decision of opposition

Effective date: 20090620

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080807

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080213

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080514

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20101029

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20110829

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20110823

Year of fee payment: 10

Ref country code: FR

Payment date: 20110905

Year of fee payment: 10

Ref country code: AT

Payment date: 20110825

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20110829

Year of fee payment: 10

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20130301

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 386161

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120807

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120807

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130301

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120831

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120831

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20130430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120807

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120831

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50211691

Country of ref document: DE

Effective date: 20130301