EP1337710A1 - Paper coating slip containing n-vinyl formamide - Google Patents
Paper coating slip containing n-vinyl formamideInfo
- Publication number
- EP1337710A1 EP1337710A1 EP01993722A EP01993722A EP1337710A1 EP 1337710 A1 EP1337710 A1 EP 1337710A1 EP 01993722 A EP01993722 A EP 01993722A EP 01993722 A EP01993722 A EP 01993722A EP 1337710 A1 EP1337710 A1 EP 1337710A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- paper
- coating slips
- paper coating
- parts
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—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 new paper coating slips.
- the invention further relates to the use of paper coating slips and papers which are coated with these paper coating slips.
- Paper coating slips essentially consist of a mostly white pigment, a polymeric binder 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 binder fixes the pigments on the paper and ensures the cohesion in the coating obtained.
- Coating with paper coating slips gives raw papers a smooth, uniform white surface.
- the paper coating slips also improve the printability of the paper.
- a variety of different measures can be taken to increase the whiteness of the coated paper. These include, for example, the use of raw 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 measure is the selection of white pigments for the paper coating slip. In most cases, however, these measures alone do not meet today's consumer demands for the whiteness of paper. Therefore, so-called “whiteners” (fluorescent or phosphorescent dyes) or “optical heaters” are added to the coating slip. These are dye-like fluorescent dyes 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, so that the whiteness is increased.
- Suitable cobinder can be water-soluble polymers, e.g. B. Polyvinyl alcohol, carboxymethyl cellulose, anionic or non-ionic degraded starches, casein, soy protein and water-soluble styrene-acrylate copolymers (see e.g. KP Kreutzer, basic processes of paper production 2: interface processes when using chemical auxiliaries, H.-G. Völkel and R. réelle (ed.), PTS Kunststoff, 2000, PTS manuscript: ' PTS-GPE - SE 2031-2).
- the activation of the optical brightener is not possible with all water-soluble polymers, e.g. not with certain polysaccharides, e.g. B. dextran, or with anionic polyacrylamides to activate the optical brightener.
- water-soluble polymers which contain cationic groups, in particular amino or ammonium groups e.g. Polyamine / epichlorohydrin or polyamidoamine / epichlorohydrin resins, polyamines or polyethyleneimines not only do not strengthen the whitener, they even deactivate it, so that the brightening is deleted (K. P. Kreutzer, op. Cit., Pp. 8-22).
- polymers or copolymers hereinafter referred to as (co) polymers
- the polymers or copolymers can be subjected to a cleavage in which the carboxylic acid groups (formyl groups) are partly split off before use in a coating slip of the invention.
- the (co) polymers incorporated into the paper coating slip also have the property that they also increase the dry pick resistance and the wet pick resistance of the coated paper, and this also more than other cobinders. It has also surprisingly been found that papers which have been finished with the coating slips according to the invention give a higher gloss than papers with coating slips which contain cobinder according to the prior art.
- the preparation of the polymers of N-vinylformamide which can be used for the coating slips according to the invention has been known for a long time (see, for example, ⁇ P-Bl 71 050, corresponds to US 44 21
- Cationic copolymers which contain N-vinylformamide in copolymerized form can also be used according to the invention.
- cationic copolymers from N-vinylformamide 10 and a water-soluble basic monomer, such as, for example, N-trialkylammonium alkyl acrylamides, N-trialkylammonium alkyl methacrylamides and / or diallyldialkyl ammonium salts, and their use as flocculation and drainage aids for the treatment of waste water and sludge -Bl 464 043 15 (corresponds to US 52 25 088).
- a water-soluble basic monomer such as, for example, N-trialkylammonium alkyl acrylamides, N-trialkylammonium alkyl methacrylamides and / or diallyldialkyl ammonium salts
- diallyldimethylammonium chloride diallyldimethylammonium methosulfate, N- (2-trimethylammonium) ethyl acrylamide methosulfate or 20 N-2- (ethyl-dimethyl) ammonium ethyl methacrylamide ethosulfate or mixtures thereof
- N-vinylformamide 46 as in EP-Bl 46 043 describes and thus obtains cationic copolymers which are suitable for use in the coating colors of the invention.
- split vinylformamides can also be used for the coating slips according to the invention, in which the amino functions released, bound in the polymer, form an ammonium formate with the split-off formic acid.
- Suitable monomers of the onoethylenically unsaturated carboxylic acids 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, 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 or mixtures of acrylic acid and methacrylic acid. These monomers or mixtures thereof can either be in the form of the free carboxylic acids or be used in partially or completely neutralized form in the copolymerization.
- the weight ratio of vinylformamide to monoethylenically unsaturated carboxylic acid with 3 to 8 carbon atoms and / or their alkali metal, alkaline earth metal or ammonium salts in the monomer mixture can vary between 100: 0 and 70:30, with weight ratios between 100: 0 and 80:20, but especially between 100: 0 and 90:10 are preferred.
- Nonionic copolymers of N-vinylformamide with other water-soluble vinyl monomers can also increase the effectiveness of the optical heat-up agent in the paper coating slips of the invention.
- N-vinyl pyrrolidone and other N-vinyl lactams such as e.g. N-vinyl caprolactam
- N-vinyl-N-alkyl carboxamides or N-vinyl carboxamides such as.
- B N-vinyl acetamide, N-vinyl-N-methylformamide and N-vinyl-N-methylacetamide, into consideration. Mixtures of these can also be used.
- N-vinylpyrrolidone is preferred as the monomer.
- composition of the (co) polymers is generally as follows:
- Acrylic acid or methacrylic acid and / or their salts or mixtures thereof 0-30 parts by weight, preferably 1-20, particularly preferably 2-10
- a free-radical (co) polymerization in a solvent or diluent is a common, but not the only method for the preparation of the (co) polymers mentioned above.
- the radical (co) polymerization of such monomers is carried out at ⁇ play, 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 temperature range.
- reaction mixture 15 rich, 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, however, 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. Solution polymerization is preferred.
- the N-vinylformamide is used using radical polymerization initiators, e.g. radical-decomposing azo compounds, such as 2, 2'-azobis (isobutyronitrile), 2, 2 'azobis (2-amidinopropane) hydrate chloride or 4,' azobis (4 'cyan) -pentanoic acid) (co) polymerized.
- radical-decomposing azo compounds such as 2, 2'-azobis (isobutyronitrile), 2, 2 'azobis (2-amidinopropane) hydrate chloride or 4,' azobis (4 'cyan) -pentanoic acid) (co) polymerized.
- the compounds mentioned are mostly used in the form of aqueous solutions, the lower concentration due to the amount of water which is acceptable in the (co) polymerization and the upper concentration due to the solubility of the compound in question in water.
- the concentration is generally 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.
- the amount of initiators is generally 0.1 to 40 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.
- solvents or diluents which can be used are 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 iso-butyl methyl ketone.
- 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 ercaptan 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 as surface-active compounds.
- the (co) polymerization gives (co) polymers of different molecular weights, which are described in EP-Bl 71 050 and subsequently with the aid of the K values according to Fikentscher (measured in 0.5% by weight aqueous cook - Saline solution at 25 ° C) is characterized.
- (Co) polymers with a high K value, e.g. above 80, are preferably prepared by (co) polymerizing the N-vinylformamide in water.
- (Co) polymers with a high K value and high molecular weights 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
- 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, 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 iso-butyl methyl ketone.
- polymerization regulators for example alcohols, such as methanol, Ethanol, n- or iso-propanol
- ketones such as acetone, ethyl methyl ketone, diethyl ketone or iso-butyl methyl ketone.
- K values with low molecular weights and correspondingly low K values continue to be obtained .
- the molecular weight of the (co) polymers which can be used according to the invention is not restricted, but it should not be too high so that the coating slip does not become too high in viscosity.
- (Co) polymers with K values between 10 and 80 are preferred, with K values between 30 and 70 being particularly preferred.
- vinylformamide-containing (co) polymers can be used both in partially or completely cleaved and in uncleaved form. A degree of hydrolysis of between 0 and 30% is preferred, particularly preferably between 0 and 20% and very particularly preferably between 0 and 10%.
- the type of waste cleavage of the formyl group is not limited, it may for example be effected in the presence of acid or base, forthcoming 'Trains t is the' cleavage in the presence of bases such as sodium hydroxide, potassium hydroxide, alkaline earth metal hydroxides, ammonia or amines.
- Partial hydrolysis for example of a copolymer containing (meth) acrylates and vinylformamides in copolymerized form, can give rise to amphoteric (co) polymers.
- Cationic copolymers of vinyl formamide can be obtained particularly simply by hydrolytically cleaving homopolymers of vinyl formamide with defined amounts of acid or base to the desired degree of hydrolysis, as described in EP-Bl 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 formyl group is split off in the hydrolysis at temperatures in the range from 20 to 200, preferably 40 to 180 ° C., if appropriate in the presence of acids or bases.
- the hydrolysis is preferably carried out in the temperature range from 70 to 90 ° C.
- About 0.05 to 1.5 equivalents of an acid, such as hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, are required for the acid hydrolysis per ' formyl group equivalent in the poly-N-vinylformamide.
- the pH in acidic hydrolysis is in the range from 2 to 0, preferably from 1 to 0.
- the hydrolysis proceeds much faster than that of (co) polymers of other N-vinylcarboxamides, such as, for example, 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 formyl groups of the poly-N-vinylformamide can also be carried out in an alkaline medium, e.g. in the pH range from 11 to 14 .
- This pH is preferably adjusted by adding sodium hydroxide solution or potassium hydroxide solution.
- ammonia, amines and / or alkaline earth metal bases are used for 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.
- hydrolysis i.e. the formyl group is split off from the poly-N-vinylformamide in water in the presence of acids or bases, and formic acid or salts of formic acid are obtained as a by-product.
- the solutions obtained can be used without further work-up, but the hydrolysis or solvolysis products can also be separated off.
- the solutions obtained are treated, for example, with ion exchangers.
- the residue separated from the hydrolysis products can then be incorporated into the coating slips.
- the amount of (co) polymers of vinylformamide that is added to the paper coating slip according to the invention depends on the amount of the brightener in the coating slip. Normally, 0.2 to 2 parts by weight of optical brightener per 100 parts by weight of pigment are added to the coating slip. Of the (co) polymer, the same to five times the amount of the optical brightener is usually added to the coating slip, ie 0.2 to 10 5 parts by weight, preferably 0.5 to 8 and particularly preferably 1 to 5 parts by weight.
- the paper coating slips according to the invention preferably contain at least one optical brightener.
- 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 Indus-
- the paper coating slips according to the invention also contain at least one white pigment and at least one binder.
- 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.
- optical brighteners which can be used in conjunction with the coating slips according to the invention are not restricted.
- the commercially available stilbene derivatives which are substituted with up to 6 sulfonic acid groups e.g. Blankophor PSG from Bayer AG, or their derivatives, or 4, 4 '-distyryl-biphenyl derivatives can be used.
- 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
- ⁇ 0 kate chalk or coating clay or organic pigments, e.g. B. plastics in particle form can be used.
- the binders ((co) polymeric binders) which can be used in the coating slips according to the invention are likewise not restricted.
- casein, starch, soy protein, carboxymethyl cellulose, alginate and / or polyvinyl alcohol or dispersions which contain acrylic acid, acrylic acid ester, vinyl acetate and / or styrene in polymerized form, for example (co) polymers made from acrylic ester / styrene, styrene / butadiene or vinyl acetate.
- the paper coating slips can also contain, for example, dispersants. Suitable dispersants are polyanions, for example of polyphosphoric acids or of polyacrylic acids (poly salts), which are usually present in amounts of 0.1 to 3% by weight, based on the amount of pigment.
- the constituents are mixed in a known manner, the (co) polymer generally being used in the form of a dispersion, suspension or solution.
- 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 slip can be applied to the papers to be coated by customary methods (cf. Ullmann's Encyclopedia of Technical Chemistry, 4th edition, vol. 17, pp. 603 ff).
- a thickener can be added.
- conventional organic and inorganic thickeners such as hydroxymethylcellulose or bentonite are suitable as thickeners.
- the paper coating slips are mostly aqueous ' paper coating slips.
- the water content can be adjusted depending on the desired viscosity or flow properties.
- the components can be mixed in a known manner.
- 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 by customary methods.
- the papers or cardboards coated with the paper coating slips according to the invention can be prepared in conventional processes, e.g. Offset, letterpress or gravure printing processes can be printed.
- a coating slip with the following composition was produced: 5
- CMC 7L2T carboxymethyl cellulose
- PVFA polyvinylformamide
- the coating colors were applied with a solids content of 68.1% by weight to an oil-free paper with a basis weight of 70 g / m 2 to a coat weight of 16 g / m 2 and then satinized.
- 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 coating slips according to the invention which contain a polyvinylformamide (PVFA), experience a stronger optical brightening and have a higher whiteness according to CIE than the coating slips which contain carboxymethyl cellulose as cobinder according to the prior art. It can also be seen that polyvinylformamides, which are hydrolyzed to a certain extent and are therefore cationic, bring about a higher lightening and CIE whiteness than non-ionic PVFA. In addition, it is seen that the coating compositions which contain a polyvinylformamide properties have both in the dry pick as significantly better in the wet pick resistance egg ', than those which contain CMC as cobinder. Finally, the coating slips according to the invention also give a significantly higher gloss.
- PVFA polyvinylformamide
- a coating slip with the following composition was produced:
- CMC 7L2T carboxymethyl cellulose
- PVFA polyvinylformamide
- Example 1 ben beschrie ⁇ .
- a coating slip with the following composition was produced:
- PVFA polyvinylformamide
- the coating slips were processed as described in Example 1.
- a coating slip with the following composition was produced:
- CMC 7L2T carboxymethyl cellulose
- CMC 7L2T carboxymethyl cellulose
- PVFA polyvinylformamide
- the coating slips were processed as described in Example 1.
- the lightening and whiteness of the satinized paper and their 10 dry and wet picking strengths were determined as described in Example 1.
- PVFA polyvinyl formamide
- HG degree of hydrolysis
- the coating slips were processed as described in Example 1.
- Blister resistance was determined by immersing the coated paper in hot oil (240 ° C). The blistering was rated from 1 (no bubbles) to 6 (very many bubbles).
- a coating slip with the following composition was produced:
- CMC 7L2T carboxymethyl cellulose
- VFA / AS 0.5 part of a copolymer of vinyl formamide and acrylic acid
- the coating slips were processed as described in Example 1.
- a coating slip with the following composition was produced:
- PVFA polyvinyl formamide
- the coating slips were processed as described in Example 1.
- Table 7 shows that the addition of nonionic and cationic polyvinylformamides with a low molecular weight (K value) to coating slips results in papers with greater optical brightening than can be achieved by the addition of co-binders according to the prior art.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Sanitary Thin Papers (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10055592A DE10055592A1 (en) | 2000-11-09 | 2000-11-09 | Paper coating composition, used for paper is used in printing, contains N-vinylformamide polymer or copolymer with water-soluble ionic monomer, e.g. (meth)acrylic acid or salt, as cobinder |
DE10055592 | 2000-11-09 | ||
PCT/EP2001/012685 WO2002038861A1 (en) | 2000-11-09 | 2001-11-02 | Paper coating slip containing n-vinyl formamide |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1337710A1 true EP1337710A1 (en) | 2003-08-27 |
EP1337710B1 EP1337710B1 (en) | 2005-08-24 |
Family
ID=7662723
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01993722A Expired - Lifetime EP1337710B1 (en) | 2000-11-09 | 2001-11-02 | Paper coating slip containing n-vinyl formamide |
Country Status (8)
Country | Link |
---|---|
US (1) | US6969444B2 (en) |
EP (1) | EP1337710B1 (en) |
JP (1) | JP2004513262A (en) |
AT (1) | ATE302878T1 (en) |
AU (1) | AU2002215999A1 (en) |
CA (1) | CA2428356C (en) |
DE (2) | DE10055592A1 (en) |
WO (1) | WO2002038861A1 (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10161158A1 (en) | 2001-02-23 | 2002-09-05 | Basf Ag | Composition for coating ink-jet recording materials, comprises nonionic or cationic polymer containing N-vinylformamide functioning as a binder, flow agent and fixative |
DE10138631A1 (en) | 2001-08-13 | 2003-02-27 | Basf Ag | Process for the production of coated paper with high whiteness |
WO2003020808A1 (en) * | 2001-09-03 | 2003-03-13 | Basf Aktiengesellschaft | Reinforcement of the effect of optical brighteners by means of polymers |
US20040182533A1 (en) * | 2001-09-03 | 2004-09-23 | Thierry Blum | Method for increasing the whiteness of paper by means of cationic polyelectrolytes |
WO2003022924A1 (en) * | 2001-09-07 | 2003-03-20 | Basf Aktiengesellschaft | Polymer dispersions comprising vinylamide copolymers |
DE102004045172A1 (en) * | 2004-09-17 | 2006-03-23 | Basf Ag | Process for the preparation of single or multiple coated substrates with a coating composition comprising a binder before adhesion |
DE102004045171A1 (en) * | 2004-09-17 | 2006-03-23 | Basf Ag | Process for the preparation of mono- and / or multicoated substrates |
US7731820B2 (en) * | 2004-10-27 | 2010-06-08 | Ciba Specialty Chemicals Corporation | Compositions of fluorescent whitening agents |
DE102004052957A1 (en) * | 2004-10-29 | 2006-05-04 | Basf Ag | Process for producing creped paper |
FR2911884B1 (en) * | 2007-01-31 | 2010-02-26 | Arjowiggins Licensing Sas | OFFSET-PRINTING WHITE SHEET WHICH HAS A HIGH FLUORESCENCE POWER AND METHOD FOR MANUFACTURING THE SAME |
CN101605940B (en) * | 2007-02-08 | 2012-12-05 | 巴斯夫欧洲公司 | Water-soluble binders for paper coating slips |
CA2692297C (en) * | 2007-07-05 | 2019-04-02 | Basf Se | Aqueous slurries of finely divided fillers, a process for their preparation and their use for the production of papers having a high filler content and high dry strength |
US8613834B2 (en) | 2008-04-03 | 2013-12-24 | Basf Se | Paper coating or binding formulations and methods of making and using same |
US8475630B2 (en) * | 2009-04-16 | 2013-07-02 | Nanopaper, Llc | Retention systems and methods for papermaking |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1692854A1 (en) * | 1967-11-29 | 1971-10-21 | Hoechst Ag | Process for dewatering cellulose fiber suspensions |
CA1283748C (en) * | 1986-06-25 | 1991-04-30 | Takaharu Itagaki | Vinylamine copolymer, flocculating agent and paper strength increasingagent using the same, as well as process for producing the same |
US5026507A (en) * | 1989-05-04 | 1991-06-25 | Westvaco Corporation | Fluorescent whitening agents, products comprising the agent and method of use thereof |
DE4001045A1 (en) * | 1990-01-16 | 1991-07-18 | Basf Ag | Paper, paste-board and cardboard prodn. - by draining pulp contg. retention agent and as fixing agent, min. 60 per cent-hydrolysed homo- or copolymer of N-vinyl-formamide |
GB2247030B (en) * | 1990-07-03 | 1994-01-12 | Grace W R & Co | The enhancement of fluorescent whitening agents |
GB2277749B (en) * | 1993-05-08 | 1996-12-04 | Ciba Geigy Ag | Fluorescent whitening of paper |
DE4409903A1 (en) * | 1994-03-23 | 1995-09-28 | Basf Ag | Graft polymers containing N-vinyl units, process for their preparation and their use |
DE19727503A1 (en) | 1997-06-27 | 1999-01-07 | Basf Ag | Paper coating slips based on binders with N-vinylformamide derivatives |
JPH1193092A (en) | 1997-09-11 | 1999-04-06 | Hymo Corp | Surface coating agent for paper |
ATE269440T1 (en) | 1999-05-05 | 2004-07-15 | Landqart | PRINTED AND PRINTABLE SUBSTRATES |
-
2000
- 2000-11-09 DE DE10055592A patent/DE10055592A1/en not_active Withdrawn
-
2001
- 2001-11-02 DE DE50107224T patent/DE50107224D1/en not_active Expired - Lifetime
- 2001-11-02 EP EP01993722A patent/EP1337710B1/en not_active Expired - Lifetime
- 2001-11-02 CA CA002428356A patent/CA2428356C/en not_active Expired - Fee Related
- 2001-11-02 JP JP2002541169A patent/JP2004513262A/en not_active Withdrawn
- 2001-11-02 AU AU2002215999A patent/AU2002215999A1/en not_active Abandoned
- 2001-11-02 AT AT01993722T patent/ATE302878T1/en active
- 2001-11-02 US US10/415,338 patent/US6969444B2/en not_active Expired - Fee Related
- 2001-11-02 WO PCT/EP2001/012685 patent/WO2002038861A1/en active IP Right Grant
Non-Patent Citations (1)
Title |
---|
See references of WO0238861A1 * |
Also Published As
Publication number | Publication date |
---|---|
ATE302878T1 (en) | 2005-09-15 |
WO2002038861A1 (en) | 2002-05-16 |
DE10055592A1 (en) | 2002-05-23 |
US20040020615A1 (en) | 2004-02-05 |
EP1337710B1 (en) | 2005-08-24 |
JP2004513262A (en) | 2004-04-30 |
AU2002215999A1 (en) | 2002-05-21 |
DE50107224D1 (en) | 2005-09-29 |
US6969444B2 (en) | 2005-11-29 |
CA2428356A1 (en) | 2002-05-16 |
CA2428356C (en) | 2009-06-16 |
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