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WO2003022924A1 - Dispersions polymeres contenant des copolymeres vinylamide - Google Patents

Dispersions polymeres contenant des copolymeres vinylamide Download PDF

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Publication number
WO2003022924A1
WO2003022924A1 PCT/EP2002/009834 EP0209834W WO03022924A1 WO 2003022924 A1 WO2003022924 A1 WO 2003022924A1 EP 0209834 W EP0209834 W EP 0209834W WO 03022924 A1 WO03022924 A1 WO 03022924A1
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Prior art keywords
polymer
paper
parts
vinyl
coating
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PCT/EP2002/009834
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German (de)
English (en)
Inventor
Thierry Blum
Friedrich Linhart
Heinrich Ullrich
Dieter Meck
Thomas Steinmacher
Steffen Geiger
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BASF SE
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BASF SE
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Priority claimed from DE2001144131 external-priority patent/DE10144131A1/de
Priority claimed from DE2001150895 external-priority patent/DE10150895A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of WO2003022924A1 publication Critical patent/WO2003022924A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof

Definitions

  • the invention relates to paper coating slips which contain a new binder, these binders, papers which are coated with the paper coating slips and the printing of papers which are coated with these coating slips.
  • Paper coating slips essentially consist of a mostly white pigment, dispersants, optical brighteners, polymeric binders and additives, which influence 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".
  • the main task of the Cobinder is to enhance the effect of the optical brightener.
  • the binder fixes the pigments on the paper and ensures the cohesion in the coating obtained.
  • the binders used in paper coating slips are usually styrene / butadiene copolymers or else acrylic copolymers.
  • dispersions of (co) polymers can be used which contain acrylic acid, acrylic acid ester, acrylonitrile, styrene, butadiene, vinyl acetate and ethylene in copolymerized form, e.g. (Co) polymers of acrylic ester and styrene, styrene and butadiene, vinyl acetate and ethylene or vinyl acetate.
  • Exemplary paper coating slips are described, for example, in WO 97/00776.
  • the main task of the binders is to bind the pigment particles evenly and finely distributed to the base paper in such a way that they do not detach from the paper when the paper is being processed, especially when printing.
  • the binders themselves generally do not themselves contribute to the desired increase in the whiteness of the paper, which is one of the most important goals which is aimed at by coating paper with coating slips.
  • Coating with paper coating slips gives base papers a smooth, uniform white surface.
  • the coating of paper with paper coating slips is well known nowadays, see for example "The Essential Guide to Aqueous Coating of Paper and Board", TWR Dean (ed.), Published by the Paper Industry Technical Association (PITA), 1997.
  • An increase in the whiteness of the coated paper can be achieved by a large number of different measures, for example by using a base paper with the highest possible degree of whiteness, which in turn can be obtained by using starting materials that are as white as possible.
  • Another very important measure is the selection of white pigments for the paper coating slip.
  • whiteners fluorescent or phosphorescent dyes
  • optical brighteners are usually added to the coating slip. These are dye-like, fluorescent compounds that absorb the short-wave ultraviolet light that is not visible to the human eye and emit it again as longer-wave blue light, which gives the human eye a higher whiteness and thus increases the whiteness.
  • optical brighteners only leads to the desired success if they have an optimal structure, conformation and distribution in the finished coating of the paper.
  • polymeric compounds are added to the paper coating slip, which reinforce the effect of the optical brightener and as "activator", "carrier” or
  • Carrier are called. An important function of the above-mentioned cobinder in coating colors is their brightening-activating effect.
  • Suitable cobinder can be water-soluble polymers, e.g. B. use polyvinyl alcohol, carboxymethyl cellulose, anionic or non-ionic degraded starches, casein, soy protein and (meth) acrylic acid-acrylate copolymers (see, for example, KP Kreuter, basic processes of paper production 2: interface processes when using chemical auxiliaries, H.-G. Völkel and R. Grenz
  • DE-A 197 27 503 discloses polymer dispersions for the production of paper coating slips which contain N-vinylformamide as the polymerized monomer component. These polymer dispersions are prepared by the main monomers usually used for the preparation of polymer dispersions, such as. As acrylic esters, styrene, acrylonitrile, butadiene, etc., on a polymer containing N-vinylformamide, which serves as a graft base, are graft-polymerized. An individual adaptation to the needs of different customers is only possible by changing the entire polymerization recipe and process, making it logistically and technically difficult to carry out. The polymer dispersions obtained in this way also do not enhance the optical brighteners in the coating slip.
  • the object of the present invention was to provide paper coating slips with improved properties with regard to increasing the whiteness and at the same time with regard to increasing the binding force, without having to incorporate an amplifier for the optical brightener into the coating slip as additional components.
  • At least one main monomer selected from the group comprising Ci to C o ⁇ alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 C atoms, vinyl aromatics with up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, Vinyl ethers or allyl ethers of alcohols containing 1 to 10 carbon atoms and aliphatic hydrocarbons with 2 to 8 carbon atoms and 1 or 2 double bonds, copolymerized containing (co) polymer A and
  • the (co) polymers A generally act as binders in the finished paper coating slips and are structured, for example, as follows:
  • auxiliary monomers 0 to 30% by weight of so-called auxiliary monomers, the total always giving 100% by weight.
  • the (co) polymer A is preferably composed of
  • the (co) polymer A is very particularly preferably composed of
  • (co) polymer is used in this document for polymer and copolymer.
  • Main monomers al) are selected from Ci to C 2 o-alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 C atoms, vinyl aromatics with up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers or allyl ethers of 1 alcohols containing up to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 carbon atoms and 1 or 2 double bonds or mixtures of these monomers.
  • (meth) acrylic acid alkyl ester with a C ⁇ -C ⁇ o ⁇ alkyl radical such as methyl methacrylate, ethyl methacrylate, methyl acrylate, n-butyl acrylate, n-octyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • acrylic acid is used for acrylic acid and methacrylic acid.
  • Vinyl esters of carboxylic acids with 1 to 20 carbon atoms are e.g. B. vinyl laurate, stearate, vinyl propionate, vinyl versatic acid and preferably vinyl acetate.
  • Suitable vinyl aromatic compounds are vinyl toluene ⁇ - and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are chlorine, fluorine or bromine-substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers examples include B. vinyl methyl ether, vinyl ethyl ether or vinyl isobutyl ether. Vinyl ethers of alcohols containing 1 to 4 carbon atoms are preferred.
  • hydrocarbons with 2 to 8 carbon atoms and one or two olefinic double bonds butadiene, isoprene and chloroprene, ethylene and propylene may be mentioned.
  • Cio-alkyl acrylates and methacrylates are preferred as main monomers, in particular C ⁇ ⁇ to Cs-alkyl acrylates and methacrylates, the acrylates being particularly preferred in each case.
  • Styrene, butadiene, acrylonitrile, vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate and mixtures of these monomers are very particularly preferred as monomers.
  • the (co) polymer A is preferably a (co) polymer based on acrylate, ie that the (co) polymer is composed of at least 60% by weight of C 1 -C 2 alkyl (meth) acrylates or mixtures thereof with vinyl aromatics such mixtures of alkyl (meth) acrylates and styrene are particularly preferred. Farther mixtures of alkyl (meth) acrylates, acrylonitrile and styrene are preferred.
  • a (co) polymer based on butadiene i.e. that at least 60% by weight of the (co) polymer consists of butadiene or mixtures thereof with vinylaromatics, such mixtures of butadiene and styrene are particularly preferred. Mixtures of butadiene, acrylonitrile and styrene are also preferred.
  • Secondary monomers a2) are monomers with carboxylic acid, sulfonic acid or phosphonic acid groups and their derivatives.
  • Carboxylic acid groups are preferred.
  • ethylenically unsaturated polymer preferably contains one or two, particularly preferably one, ethylenically unsaturated group.
  • the or one (if more than one) ethylenically unsaturated group is particularly preferably in the terminal position in the respective polymer chain.
  • the ethylenically unsaturated group is an acrylic or methacrylic group, preferably a methacrylic group.
  • the ethylenically unsaturated polymer preferably contains more than 2, particularly preferably more than 4, very particularly preferably more than 8 carboxylic acid groups.
  • the ethylenically unsaturated polymer is preferably composed of compounds which can be polymerized by free radicals, for example from the monomers or (meth) acrylic acid which are referred to here as main monomers a1), and can be obtained accordingly by free-radical polymerization of these compounds.
  • the ethylenically unsaturated polymer preferably consists of at least 50% by weight, particularly preferably 80% by weight, of Ci-Cio alkyl (meth) acrylates, (meth) acrylic acid and mixtures thereof.
  • the ethylenically unsaturated polymer is very particularly preferably composed of at least 50% by weight, in particular at least 80% by weight, of acrylic acid or methacrylic acid. Methacrylic acid is preferred.
  • the average molecular weight Mn of the ethylenically unsaturated polymer is preferably 800 to 20,000, particularly preferably 1,000 to 10,000 g / mol.
  • Mn is determined by gel permeation chromatography (polyacrylic acid standard and water as eluent).
  • the ethylenically unsaturated polymer is preferably made by radical polymerization in the presence of a transition metal complex as a molecular weight regulator, e.g. of a cobalt chelate complex.
  • a transition metal complex as a molecular weight regulator
  • This process is known as catalytic chain transfer polymerization (CCT) and is e.g. described in WO 95/04767.
  • secondary monomers are monomers containing (meth) acrylamide or hydroxyl groups, in particular C 1 -C 6 -hydroxyalkyl (meth) acrylates, such as e.g. 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2- or 3-hydroxypropyl acrylate or 4-hydroxybutyl vinyl ether.
  • auxiliary monomers a3) are phenyloxyethyl glycol mono- (meth) acrylate, glydidyl acrylate, glycidyl methacrylate, amino (meth) acrylates such as 2-aminoethyl (meth) crylate and N-vinylformamide.
  • Crosslinking monomers such as e.g. Trimethylolpropane triacrylate, pentaerythritol tetraacrylate, 1,3-propanediol diacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate or ethylene glycol diacrylate.
  • the glass transition temperature of the (co) polymer A is preferably below 50 ° C, in particular it is -40 to + 50 ° C, particularly preferably -20 to + 30 ° C and very particularly preferably -10 to + 25 ° C and in particular - 5 to + 20 ° C.
  • the glass transition temperature of a polymer can be determined by conventional methods such as differential thermal analysis or differential scanning calorimetry (see, for example, ASTM 3418/82, so-called “midpoint temperature”).
  • the (co) polymers B in the polymer dispersion according to the invention generally act as cobinder in the finished paper coating slip and are generally composed as follows:
  • Preferred (co) polymers B which are composed as follows:
  • the molecular weight of the (co) polymers B that can be used is not restricted. (Co) polymers B with K values between 20 and 110 are preferred, with K values between 30 and 90 being particularly preferred.
  • the K values are measured according to Fikentscher in 0.5% strength by weight aqueous saline solution at 25 ° C.
  • Preferred N-vinylcarboxamides B1) are those of the formula (I).
  • R 1 and R 2 independently of one another denote hydrogen or Ci to C o ⁇ alkyl, where the alkyl radical can be straight-chain or branched.
  • R 1 and R 2 are preferably independently of one another hydrogen or Ci to Cio-alkyl, particularly preferably hydrogen or 0 oder to C-alkyl, very particularly preferably hydrogen or methyl and in particular hydrogen.
  • R 1 and R 2 can also together form a straight-chain or branched chain containing 2 to 8 carbon atoms, preferably a 3 to 6 and particularly preferably a 3 to 5 carbon atom-containing chain.
  • one or more carbon atoms can 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, seJc-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,
  • N-vinylcarboxamides of the formula (I) are N-vinylformamide, N-vinylacetamide, N-vinylpropionic acid amide, N-vinylbutyric acid amide, N-vinylisobutyric acid amide, N-Vi nyl-2-ethylhexanoic acid amide, N-vinyldecanoic acid amide, N-vinyldodecanoic acid amide, N-vinylstearic acid amide, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide, N-methyl-N-vinylpropionic acid amide, N-methyl-N- Vinylbutyric acid amide, N-methyl-N-vinylisobutyric acid amide, N-methyl-N-vinyl-2-ethylhexanoic acid amide, N-methyl-N-vinyldecanoic acid amide, N-methyl-N-N-
  • N-n-butyl-N-vinyl dodecanoic acid amide N-n-butyl-N-vinyl stearic acid amide, N-vinyl pyrrolidone or N-vinyl caprolactam.
  • N-vinylformamide, N-vinyl acetamide, N-methyl-N-vinyl formamide, N-methyl-N-vinyl acetamide, N-vinyl pyrrolidone or N-vinyl caprolactam are preferred, and N-vinyl formamide is particularly preferred.
  • water-soluble cationic monomer b2) there can be used cationic groups, e.g. Ammonium sulfonium or phosphonium groups, and monomers bearing at least one copolymerizable, ethylenically unsaturated group, such as, for example, diallyldimethylammonium chloride, diallyldimethylammonium methosulfate, N- (2-trimethylmonium) ethylacrylamide methosulfate or N-2- (ethyldimethyl) copolymerize ammonium ethyl methacrylamide ethosulfate or mixtures thereof with the N-vinylcarboxamide B1), such as, for example in EP-Bl 464 043, and thus obtains cationic copolymers B.
  • cationic groups e.g. Ammonium sulfonium or phosphonium groups
  • monomers bearing at least one copolymerizable, ethylenically unsaturated group
  • Suitable monomers of the monoethylenically unsaturated carboxylic acids b3) having 3 to 8 carbon atoms and the water-soluble salts of these monomers are: acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylene malonic acid, allylacetic acid, vinyl acetic acid, crotonic acid, fumaric acid, Mesaconic acid and itaconic acid. From this group of monomers, preference is given to using acrylic acid, methacrylic acid, maleic acid or else mixtures of the carboxylic acids mentioned, in particular mixtures of acrylic acid and maleic acid. acid or mixtures of acrylic acid and methacrylic acid.
  • These monomers or mixtures thereof can either in the form of the free carboxylic acids or in part or in full, with ammonium, alkali or alkaline earth metal ions, such as, for example, ammonium, trimethylammonium, triethylammonium, tris (2-hydroxyethyl) ammonium,
  • Nonionic copolymers B of N-vinylcarboxamides with other vinyl monomers b4) can also be used in the polymer dispersions according to the invention.
  • the same monomers are used as are described as main monomers a1) in the (co) polymers A.
  • a common, but not the only method for the preparation of the (co) polymers mentioned above, preferably the (co) polymers B, is radical (co) polymerization in a solvent or diluent.
  • the free radical (co) polymerization of the monomers takes place, for example, in aqueous solution in the presence of polymerization initiators which decompose into free radicals under polymerization conditions.
  • the (co) polymerization can be carried out in a wide range
  • Temperature range if necessary under reduced or also under increased pressure, generally at temperatures up to 100 ° C.
  • the pH of the reaction mixture is usually adjusted in the range of 4 to 10.
  • the (co) polymerization can also be carried out in another manner known per se to the person skilled in the art, e.g. as solution, precipitation, water-in-oil emulsion or reverse suspension polymerization.
  • radical polymerization initiators e.g. Peroxides such as dibenzoyl peroxide or hydrogen peroxide, persulfates such as sodium, potassium and ammonium persulfate or peroxosulfate, hydroperoxides such as tert-butyl hydroperoxide or peroxyacetic acid, redox initiators such as
  • azo compounds which disintegrate into free radicals such as 2, 2 '-azobis (isobutyronitrile), 2, 2' -azobis- (2-amidino- propane) hydrochloride or 4,4'-azobis (4'-cyanopentanoic acid) (co) polymerized.
  • red-ox reduction-oxidation
  • the Red-Ox initiator systems consist of at least one mostly inorganic reducing agent and one inorganic or organic oxidizing agent.
  • the oxidation component is e.g. B. the initiators already mentioned above.
  • the reduction components are e.g. B. to alkali metal salts of sulfurous acid, such as. B. sodium sulfite,
  • Red-Ox initiator systems can be more soluble when used
  • Metal compounds whose metallic component can occur in several valence levels can be used.
  • Common Red Ox initiator systems are e.g. B. ascorbic acid / iron (II) sulfate / sodium peroxidisulf t, tert. -Butyl hydroperoxide / sodium disulfite, tert. -Butyl hydroperoxide / sodium hydroxymethanesulfinate.
  • the individual components e.g. the reduction component, can also be mixtures e.g. a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.
  • the monomers mentioned are mostly used in the form of aqueous solutions or dispersion, the lower concentration being determined by the amount of water which is acceptable in the (co) polymerization and the upper concentration being determined by the solubility or dispersibility of the compound in question in water.
  • the concentration is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably 1.0 to 10% by weight, based on the solution or, in the case of dispersion, 10-80% by weight. , preferably 10-70% by weight and particularly preferably 20 to 60% by weight.
  • the amount of initiators is generally 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the monomers to be (co) polymerized.
  • Several different initiators can also be used in the (co) polymerization.
  • Water or alcohols such as methanol, ethanol, n- or iso-propanol, n- or iso-butanol, or ketones, such as acetone, ethyl methyl ketone, diethyl ketone or iso-butyl methyl ketone, can serve as solvents or diluents, for example.
  • the (co) polymerization can be carried out in the presence of polymerization regulators such as hydroxylammonium salts, chlorinated hydrocarbons and thio compounds such as e.g. tert. -Butyl mercaptan, thioglycolic acid, ethyl acrylate, mercaptoethynol, mercaptopropyltrimethoxysilane, dodecyl mercaptan, tert-dodecyl mercaptan or alkali metal hypophosphites.
  • these regulators e.g. B. in amounts of 0 to 0.8 parts by weight, based on 100 parts by weight of the monomers to be (co) polymerized, by which the molecular weight of the resulting (co) polymer is reduced.
  • ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers can be used as surface-active compounds.
  • (co) polymerization gives (co) polymers of different molecular weights.
  • (Co) polymers B with a high K value e.g. above 80, are preferably prepared by (co) polymerizing the N-vinyl carboxamide in water.
  • (Co) polymers with 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.
  • saturated hydrocarbons for example hexane, heptane, cyclohexane, decalin or aromatic hydrocarbons, such as benzene, toluene, xylene and cumene
  • 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 B with a low K value, for example below 80 is obtained if the (co) polymerization is carried out in the presence of polymerization regulators or in a solvent which regulates the (co) polymerization, for example alcohols, such as methanol , Ethanol, n- or iso-propanol, or ketones, such as acetone, ethyl methyl ketone, diethyl ketone or is ⁇ -butyl methyl ketone.
  • polymerization regulators or in a solvent which regulates the (co) polymerization for example alcohols, such as methanol , Ethanol, n- or iso-propanol, or ketones, such as acetone, ethyl methyl ketone, diethyl ketone or is ⁇ -butyl methyl ketone.
  • ketones such as acetone, ethyl methyl ketone, diethyl ketone or is ⁇ -butyl
  • N-vinylcarboxamides for example of the formula (I) and especially N-vinylformamide, in (poly) -containing polymers B containing a polymerized form can be used according to the invention both in partially or completely cleaved and in uncleaved form.
  • Preferred is a degree of hydrolysis of the carboxylic acid group between 0 and 30 mol%, particularly preferably between 0 and 20 mol% and very particularly preferably between 0 and 10 mol%, based on the N-carboxylic acid id units contained in the (co) polymer.
  • the type of cleavage of the carboxylic acid or formyl group is not restricted, it can be carried out, for example, in the presence of acid or base; cleavage is preferred in the presence of bases, such as sodium hydroxide, potassium hydroxide, alkaline earth metal hydroxides, ammonia or amines.
  • bases such as sodium hydroxide, potassium hydroxide, alkaline earth metal hydroxides, ammonia or amines.
  • Partial hydrolysis e.g. of a copolymer containing (meth) acrylates and N-alkyl-N-vinylcarboxamides in polymerized form, amphoteric (co) polymers are formed.
  • Cationic polymers of N-vinylformamide can be obtained particularly easily by hydrolytically cleaving homopolymers of N-vinylformamide with defined amounts of acid or base to the desired degree of hydrolysis, as described in EP-B1 071 050.
  • the resulting amino groups on the polymer chain are more or less protonated depending on the pH of the solution and thus give the polymer a more or less cationic character.
  • the carboxylic acid group is split off in the hydrolysis 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 particularly preferably carried out in the temperature range from 70 to 90 ° C.
  • N-vinylformamide proceeds much faster than that of (co) polymers of other N-vinylcarboxamides, such as. B. of N-methyl-N-vinylformamide, and can therefore be carried out under gentler conditions, ie at lower temperatures and without a large excess of acids.
  • the hydrolysis of the carboxylic acid groups of the poly-N-vinylcarboxamide can also be carried out in an alkaline medium, e.g. in the pH range from 11 to 14.
  • This pH is preferably established by adding alkali metal bases, e.g. Sodium hydroxide solution or potassium hydroxide solution set.
  • alkali metal bases e.g. Sodium hydroxide solution or potassium hydroxide solution set.
  • ammonia, amines and / or alkaline earth metal bases for the alkaline hydrolysis, 0.05 to 1.5, preferably 0.4 to 1.0 equivalents of a base are used.
  • 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 can be carried out without acid or base. This is preferably carried out under conditions above the critical point, for example with supercritical water.
  • a solvent e.g. Water
  • Water can be carried out without acid or base. This is preferably carried out under conditions above the critical point, for example with supercritical water.
  • carboxylic acid group is split off from the poly-N-vinylcarboxylic acid amide in water in the presence of acids or bases; carboxylic acid, for example formic acid, or its salts is obtained as a by-product.
  • the solutions obtained are treated with ion exchangers, for example.
  • the residue separated from the hydrolysis products can then be used according to the invention.
  • the water solubility of the (co) polymers B which can be used according to the invention and which contain copolymerized N-vinylcarboxamides is generally at least 1% by weight at 20 ° C. until complete solubility.
  • the (co) polymers A and B differ from one another, for example, in that the (co) polymer B contains at least 30% by weight of an N-vinylcarboxamide, but the (co) polymer A up to 30% by weight of N-vinylformamide. Furthermore, the (co) polymer A is preferably obtainable by emulsion polymerization, while the (co) polymer B is preferably obtainable by solution polymerization.
  • At least one (co) polymer A which contains at least one main monomer selected from the group styrene, butadiene and (meth) acrylic acid ester in copolymerized form and
  • Polymer dispersions which are particularly preferred are those in
  • (Co) polymer B contain at least one N-vinylcarboxamide of the formula (I) in copolymerized form.
  • Polymer dispersions which contain copolymerized N-vinylformamide in the (co) polymer B are very particularly preferred.
  • Contain post-additives known to those skilled in the art, for example polyanions, such as Polyacrylic acid, which can be partially or fully neutralized, biocides, etc.
  • the present invention furthermore relates to those polymer dispersions mentioned above which additionally contain
  • optical brighteners C that can be used in the polymer dispersions are not limited.
  • brighteners such as those described in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2000 Electronic Release, OPTICAL BRIGHTENERS - Chemistry of Technical Products can be used.
  • Suitable optical brighteners C belong, for example, to the group of distyrylbenzenes, for example cyano-substituted 1,4-distyrylbenzenes with cyano groups in positions 2 'and 3''[CAS RegNr. 79026-03-2], or in position 2 'and 2''[13001-38-2],3' and 3 '' [36755-00-7], 3 'and 4''[79026-02-1 ] as well as 4 'and 4'' [13001-40-6], or amphoteric compounds, such as, for example, [84196-71-4], each in the 2 'and 2''position, a group
  • distyrylbiphenyls for example 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-sulfostyryl) biphenyl disodium salt [42380-62-1], 4,4 '-di (6-chloro-3-sulfostyryl) biphenyl disodium salt [60477-28-3], , 4 '-Di (2-methoxystyryl) biphenyl [40470-68-6] or a,' -di (styryl) biphenyl which has a group in position 2 on the styryl radical
  • 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 which carry a sulfonic acid in position 6 on the naphthol ring and in position 2 of the stilbene skeleton [ 2583-80-4], or on the stilbene structure in position 2 a cyano group and in position 4 'a chlorine group
  • Furans, benzo [b] furans and benzimidazoles such as 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-methyl-benzimidazole -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, 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-methyl-benzimidazole -2-yl)
  • 4, 4'-Distyrylbiphenyl derivatives or stilbene derivatives which are substituted with up to 6, particularly preferably with 2, 4 or 6, sulfonic acid groups can preferably be used, preferably the Blankophor® brands from Bayer AG, particularly preferably
  • Tinopal® brands 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, Leukophor® APN, UO, NS or SHR are particularly preferred.
  • optical brighteners can also be used, for example two, three or four, but preferably only one is used.
  • the invention furthermore relates to the use of the polymer dispersions mentioned in paper coating slips and in their preparation, in particular the use as binder in paper coating slips.
  • the invention furthermore relates to paper coating slips containing a polymer dispersion according to the invention, as described above.
  • An advantage of the coating slips according to the invention is that a process step in the paper mill, namely the incorporation of the cobinder into the coating slip, can be eliminated by using the polymer dispersions according to the invention in their manufacture. This not only saves time for the paper mill, but also reduces the logistical effort. In general, the manufacturers of coated papers obtain the individual components of the coating slips from different suppliers.
  • An important advantage of the coating slips according to the invention is that the paper mill has to incorporate one chemical less into the coating slip, and thus can do without a supplier, an order process, an incoming goods inspection, a storage container, a dosing system, etc. In the case of qualitative problems with the coating slip, there is one variable less when using the coating slip according to the invention, which can be considered as a possible cause of the problems.
  • Another advantage of the coating slips according to the invention for the paper manufacturer is that the handling of chemicals, even if they are relatively harmless polymers, is shifted back to the supplier.
  • the paper industry sees itself as a technical industry and usually endeavors to keep the handling of chemicals as low as possible and to employ as little personnel as possible trained in handling chemicals.
  • the new binders and coating slips according to the invention meet this aim.
  • the polymer dispersions used for the coating slips according to the invention have the further advantage that they can easily be prepared according to the individual needs of the paper manufacturer from polymer dispersions produced in large quantities by simple mixing after the polymerization and before delivery to the paper mill.
  • the amount of (co) polymer A and B contained in the polymer dispersions for the coating slips of the invention depends on the requirements of the paper manufacturer with regard to the strength and whiteness of the paper coating. The amount also depends on the viscosity that the new binder (polymer dispersion) gets from the addition of the (co) polymer B.
  • the proportion of (co) polymer B can be 1 to 50 parts.
  • the proportion of optical brightener can be 0 to 10, preferably 0.1 to 8 and particularly preferably 0.5 to 5 parts.
  • the polymer dispersions according to the invention for the coating slips according to the invention are prepared by mixing a dispersion of a (co) polymer A with a (co) polymer B, its dispersion, solution, suspension or emulsion, according to the prior art known for the preparation of mixtures of liquids ,
  • the (co) polymers B can also be incorporated as solids or gels in a dispersion of the (co) polymers A.
  • the optical brightener can be introduced as a solid, as a solution, for example in water, or as a suspension in the polymer dispersion, preferably as a solution. It is irrelevant whether it is added before or after components A and / or B. You can also first mix the optical brighteners with components B and combine these mixtures with the polymer dispersion. It makes sense to determine the optimal mixing sequence and mixing method by means of preliminary tests.
  • the mixtures can be produced continuously or batchwise and are not restricted. If the preparation is carried out batchwise, either (co) polymer B, its dispersion, solution, suspension or emulsion can be added to the dispersion of (co) polymer A or the dispersion of (co) polymer A to (co) polymer B, its dispersion , Solution, suspension or emulsion.
  • the smaller component is added to the larger component.
  • optical brightener or its mixture with component B as the last substance is particularly preferably added to the mixture of (co) polymers A and B or B and A or to the polymer dispersion A.
  • the (co) polymeric B is preferably present as a solution in a suitable solvent, especially water.
  • the mixture is preferably vigorously mixed, e.g. Stirring, pumping or the like.
  • the polymer dispersions according to the invention are generally produced with 5 polymer contents (sum (co) polymer A and B) of 15 to 75% by weight, preferably 20 to 60% by weight.
  • the viscosity of the polymer dispersion is generally 100 to 1500 mPas (measured by the Brookfield method at 20 rpm and 10 20 ° C. according to DIN 53019), preferably 100 to 1300 and particularly preferably 150 to 1200 mPas, or 50 to 1000 mPas (measured according to the Brookfield method at 100 rpm and 20 ° C.), preferably 50 to 750 and particularly preferably 100 to 600 mPas.
  • the paper coating slips according to the invention preferably contain the new binder in amounts of 1 to 30, in particular 5 to 15 parts by weight, based on the pigment content of the paper coating slips, the total amount of (co) polymers A and B being included under the amount of the binder understands.
  • the coating compositions of the invention are processed completely analogously to the processing of coating colors according to the prior art, e.g. according to "The Essential Guide to Aqueous Coating of Paper and Board", T.W.R. Dean (ed.), Published by the Paper
  • optical brighteners which can be used in conjunction with the coating slips according to the invention are not restricted.
  • optical brighteners 35 mentioned above can be used.
  • brighteners such as those described in Ulimann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2000 Electronic Release, OPTICAL BRIGHTENERS - Chemistry of Technical Products can be used.
  • the 4, 4'-distyrylbiphenyl derivatives or stilbene derivatives listed there which are substituted with up to 6, particularly preferably with 2, 4 or 6, sulfonic acid groups can preferably be used, particularly preferably the Blankophor® brands from Bayer AG, very particularly before -
  • Tinopal® brands from Ciba Specialty Chemicals, very particularly preferred Tinopal MC liquid, Tinopal® ABP-Z liquid, Tinopal ® SPP-Z liquid and Tinopal® SK-B liquid and more particularly preferably are the Leukophor® Mar- ken Clariant AG, very particularly preferably Leukophor® APN, UO, NS or SHR.
  • optical brightener per 100 parts by weight of pigment are added to the coating slip.
  • the pigments which can be used in the coating slips according to the invention are likewise not restricted.
  • satin white calcium carbonate in ground or precipitated form
  • barium sulfate in ground or precipitated form kaolin (clay)
  • calcined clay talc
  • zinc oxide silicates
  • organic pigments e.g. B. plastics in particle form
  • the paper coating slips can also e.g. Contain dispersants.
  • Suitable dispersants are polyanions, for example of polyphosphoric acids or of polyacrylic acids (polysalts), which are usually present in amounts of 0.1 to 3 parts by weight, based on the amount of pigment.
  • a cobinder can additionally be added to the coating slip according to the invention.
  • the co-polymers containing copolymerized (co) polymers as described in the German patent application with the file number 10055592.6, contain the cobinder corresponding to the prior art, e.g. Polyvinyl alcohol, carboxymethyl cellulose, anionic or non-ionic degraded starches, casein, soy protein and (meth) acrylic acid-acrylate copolymers in question.
  • the same to five times the amount of the optical brightener is usually added to the coating slip, ie 0.2 to 10 parts by weight, preferably 0.5 to 8 and particularly preferably 1 to 5 parts by weight, based on 100 parts by weight of pigment.
  • the presence of the new binders in the coating colors according to the invention also improves the effectiveness of additional cobinders with regard to the strengthening of the optical brightener.
  • another (co) polymer of N-vinylcarboxamide can also be used as an additional cobinder.
  • a thickener can be added.
  • conventional organic and inorganic thickeners such as hydroxymethylcellulose or bentonite are suitable as thickeners.
  • the paper coating slips can also contain further constituents known to the person skilled in the art.
  • Flow aids wetting aids for the pigments etc.
  • the ingredients are mixed in a known manner.
  • the application amount of the paper coating slip to the substrate to be coated can be chosen freely, as a rule, the application amount is 5 to 25 g / m 2 , preferably 7 to 20 g / m 2 and particularly preferably 9 to 15 g / m 2 .
  • the line can be applied to paper or cardboard on one or both sides, and one, two or more lines can be applied one after the other.
  • the paper putties are usually aqueous paper coating slips.
  • the water content can be adjusted depending on the desired viscosity or flow properties.
  • the water content in the paper coating slip is usually set to 25 to 75% by weight, based on the total paper coating slip (including water).
  • the paper coating slips according to the invention are suitable for coating e.g. of paper or cardboard.
  • the paper coating slip can then be applied to the papers or cardboard to be coated using customary methods (cf. Ullmann's Encyclopedia of Technical Chemistry, 4th edition, vol. 17, pp. 603 ff).
  • the papers coated with a paper coating slip according to the invention are also the subject of the present invention.
  • the papers, cardboard or cardboard coated with the paper coating slips according to the invention can be used in customary printing processes, for example offset, letterpress or gravure printing processes or modern digital printing processes such as, for example, 'laser printing or ink-jet.
  • 192 parts of a 50% dispersion of a copolymer of the main monomers butyl acrylate and styrene (Acronal S 504 from BASF Aktiengesellschaft) are 30 parts of a 20% aqueous solution of a homopolymer of N-vinylformamide, in which 5% of the formamido groups Hydrolysis were cleaved, mixed with the K value 30.
  • the binder obtained has a viscosity of 170 mPa-s (Brookfield, 20 U / min) or 108 mPa-s (Brookfield, 100 U / min). It can be used to produce the coating slips according to the invention.
  • 192 parts of a 50% dispersion of a copolymer of the main monomers butyl acrylate and styrene are 30 parts of a 20% aqueous solution of a homopolymer of N-vinylformamide, in which 5% of the formamido groups Hydrolysis were cleaved, mixed with the K value 50.
  • the binder obtained has a viscosity of 1150 mPa-s (Brookfield, 20 U / min) or 572 mPa-s (Brookfield, 100 rpm). It can be used to produce the coating slips of the invention.
  • Dispersions as are usually used as binders in paper coating slips, can be prepared by mixing with nonionic and cationic (co) polymers of N-vinylformamide, stable, new binders.
  • a paper coating slip is produced by intensively mixing 360 parts of a 77.7% suspension of calcium
  • Table 2 compares the same coating slip on an unsized and unlightened paper with the comparative examples.
  • the lightening of the paper was determined according to DIN 53 145, part 2.
  • the CIE whiteness of the paper was measured according to ISO 2469.
  • the color density when determining the wet pick resistance according to IGT with the specified Lorilleux color was determined with the Gretag densitometer.
  • a paper coating slip is produced by intensively mixing 360 parts of a 77.7% suspension of calcium carbonate (Hydrocarb® 90 from Plüss-Staufer AG), 160 parts of a 75% suspension of coating kaolin (Amazon® 88 from the company) kaolin International), 64 parts of a 50% dispersion of a copolymer of the principal monomers styrene and butadiene (Styronal ® D 610 from BASF Aktiengesellschaft), 20 parts of a 10% solution of carboxymethyl cellulose (CMC 7L2T derFirma Hercules GmbH), 4 Share a 50% solution of an optical brightener (Blankophor® PSG from Bayer AG) and 32.3 parts of water.
  • Hydrocarb® 90 from Plüss-Staufer AG
  • Amazon® 88 from the company
  • kaolin International kaolin International
  • a paper coating slip is produced by intensively mixing 360 parts of a 77.7% suspension of calcium carbonate (Hydrocarb 90 from Plüss-Staufer AG), 160 parts of a 75% suspension of coating kaolin (Amazon® 88 from Kaolin international), 64 parts of a 50% dispersion of a copolymer of the principal monomers styrene and butadiene (Styronal ® D 610 from BASF Aktiengesellschaft), 10 parts of a 20% aqueous solution of a homopolymer of N-vinylformamide having a K-value 50.4 parts of a 50% solution of an optical brightener (Blankophor® PSG from Bayer AG) and 42.3 parts of water.
  • Tables 1 and 2 show that the coating slip according to the invention, example 5, which contains the new binder, is significantly better in almost all properties than a classic coating slip, comparative example 1, with the cobinder carboxymethyl cellulose. It is also at least as good as the coating slip of Comparative Example 2, in which the (co) polymer of N-vinylformamide is not present in the binder, but is added separately as a cobinder.
  • coating slip according to the invention is applied with a solids content of 67.2% by weight to a sized wood-free paper with a basis weight of 70 g / m 2 , which contains optical brighteners, to a coat weight of 15 g / m 2 , dried and then satinized.
  • 7.5 parts of a 40% aqueous solution of a homopolymer of N-vinylformamide with the K value are in 96 parts of a 50% strength dispersion of a copolymer of the main monomers styrene and butadiene (Styronal D 610 from BASF Aktiengesellschaft)
  • the binder obtained has a viscosity of 495 mPa-s (Brookfield, 20 rpm) or 272 mPa-s (Brookfield, 100 rpm). It is intensively mixed with 537 parts of a 78.2% suspension of calcium carbonate (Hydrocarb 90 from Plüss-Staufer AG), 241 parts of a 74.8% suspension of coating
  • 7.5 parts of a 40% aqueous solution of a homopolymer of N-vinylformamide with a K value of 30 are placed in 96 parts of a 50% strength dispersion of a copolymer of the main monomers styrene and butadiene (Styronal D 610 from BASF Aktiengesellschaft) mixed.
  • the binder obtained has a viscosity of 495 mPa-s (Brookfield, 20 rpm) or 272 mPa-s (Brookfield, 100 rpm).
  • This coating slip according to the invention is applied with a solids content of 67.1% by weight to a glued wood-free paper with a basis weight of 70 g / m 2 , which contains optical brighteners, to a coat weight of 15 g / m 2 , dried and then satinized.
  • the properties of the coating slip and the paper coated with it can be found in Table 3.
  • the properties of the coating of a wood-free, unsized, brightener-free paper can be found in Table 4.
  • a paper coating composition is prepared by intensive mixing of 537 parts of a 78,2-% suspension of Calciumcar- carbonate (Hydrocarb ® 90 of the company Pluss-Staufer AG), 241 parts of a 74,8-% suspension of coating kaolin (Amazon ® 88 from Kaolin International), 96 parts of a 50% dispersion of a copolymer of the main monomers styrene and butadiene (Styronal® D 610 from BASF Aktiengesellschaft), 6 parts of a 50% solution of an optical brightener (blankophore
  • a paper coating slip is produced by intensive mixing of 537 parts of a 78.2% suspension of calcium carbonate (Hydrocarb® 90 from Plüss-Staufer AG), 241 parts of a 74.8% suspension of coating kaolin (Amazon® 88 from the company Kaolin International), 96 parts of a 50% dispersion of a copolymer of the main monomers styrene and butadiene (Styronal® D 610 from BASF Aktiengesellschaft), 6 parts of a 50% solution of an optical brightener (Blankophor PSG ® from Bayer AG), 30 parts of a 10% solution of carboxy ethyl cellulose (CMC Hercules 7L2T GmbH) and 65.9 parts of water.
  • Hydrocarb® 90 from Plüss-Staufer AG
  • Amazon® 88 from the company Kaolin International
  • 7.5 parts of a 40% aqueous solution of a homopolymer of N-vinylformamide with the K value are in 96 parts of a 50% strength dispersion of a copolymer of the main monomers styrene and butadiene (Styronal D 610 from BASF Aktiengesellschaft)
  • the binder obtained has a viscosity of 800 mPa-s (Brookfield, 20 rpm) or 411 mPa-s (Brookfield, 100 rpm). It is intensively mixed with 537 parts of a 78.2% suspension of calcium carbonate (Hydrocarb 90 der
  • This coating slip according to the invention is applied with a solids content of 67.3% by weight to a sized wood-free paper with a basis weight of 70 g / m 2 , which contains optical brighteners, to a coat weight of 15 g / m 2 , dried and then satinized.
  • the binder obtained has a viscosity of 800 mPa-s (Brookfield, 20 rpm) or 411 mPa-s (Brookfield, 100 rpm). It is intensively mixed with 537 parts of a 78.2% suspension of calcium carbonate (Hydrocarb® 90 der
  • This coating slip according to the invention is applied with a solids content of 67.1% by weight to a glued wood-free paper with a basis weight of 70 g / m 2 , which contains optical brighteners, to a coat weight of 15 g / m 2 , dried and then satinized.
  • This coating slip according to the invention is sized with a solids content of 67.3% by weight wood-free paper, with a basis weight of 70 g / m 2 , which contains optical brighteners, applied to a coat weight of 15 g / m 2 , dried and then satinized.
  • the properties of the coating slip and the paper coated with it can be found in Table 5 5.
  • the properties of the coating of a wood-free, unsized, brightener-free paper can be found in Table 6.
  • the binder obtained has a viscosity of 230 mPa-s (Brookfield, 20 U / min) or 150 mPa-s ⁇ (Brookfield, 100 U / min). It is intensively mixed with 537 parts of a 78.2% suspension of calcium carbonate (Hydrocarb 90 der
  • This coating slip according to the invention is applied with a solids content of 67.3% by weight to a sized wood-free paper with a basis weight of 70 g / m 2 , which contains optical brighteners, to a coat weight of 15 g / m 2 , dried and then satinized.
  • This example 13 shows that the process according to the invention can also be used to prepare a mixture of a polymer dispersion, a polymer copolymerized with a vinylcarboxamide and an optical brightener, and to process it in a coating slip for paper coating.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)

Abstract

L'invention concerne des dispersions polymères contenant I) au moins un monomère principal, sélectionné dans le groupe comprenant des acides carboxyliques contenant des alkyle C1-C20(méth)acrylates, des vinylaromatiques ayant jusqu'à 20 atomes de C, des nitriles insaturés éthyléniquement, des halogénures de vinyle, des vinyléthers ou des allyléthers d'alcools contenant entre 1 et 10 atomes de C et des hydrocarbures aliphatiques ayant entre 2 et 8 atomes de C et un (co)polymère A contenant 1 ou 2 liaisons doubles, sous forme intégrée par polymérisation et (ii) au moins un (co)polymère B contenant de l'amide d'acide N-vinylcarboxylique, sous forme intégrée par polymérisation.
PCT/EP2002/009834 2001-09-07 2002-09-03 Dispersions polymeres contenant des copolymeres vinylamide Ceased WO2003022924A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE10144131.2 2001-09-07
DE2001144131 DE10144131A1 (de) 2001-09-07 2001-09-07 Papierstreichmassen
DE2001150895 DE10150895A1 (de) 2001-10-18 2001-10-18 Papierstreichmassen
DE10150895.6 2001-10-18

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Publication Number Publication Date
WO2003022924A1 true WO2003022924A1 (fr) 2003-03-20

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08146555A (ja) * 1994-11-17 1996-06-07 Mitsubishi Paper Mills Ltd 写真印画紙用支持体
JPH11106695A (ja) * 1997-10-06 1999-04-20 Tombow Pencil Co Ltd 水性ボールペン用顔料インキ組成物
EP0960925A1 (fr) * 1998-05-22 1999-12-01 Showa Denko Kabushiki Kaisha Composition adhésive
WO2002038861A1 (fr) * 2000-11-09 2002-05-16 Basf Aktiengesellschaft Pâtes à enduire le papier contenant du n-vinylformamide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08146555A (ja) * 1994-11-17 1996-06-07 Mitsubishi Paper Mills Ltd 写真印画紙用支持体
JPH11106695A (ja) * 1997-10-06 1999-04-20 Tombow Pencil Co Ltd 水性ボールペン用顔料インキ組成物
EP0960925A1 (fr) * 1998-05-22 1999-12-01 Showa Denko Kabushiki Kaisha Composition adhésive
WO2002038861A1 (fr) * 2000-11-09 2002-05-16 Basf Aktiengesellschaft Pâtes à enduire le papier contenant du n-vinylformamide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199633, Derwent World Patents Index; Class A89, AN 1996-324990, XP002226168 *

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