EP0811091B1 - Dispersions aqueuses d'alkyldicetene et leur utilisation comme produits d'encollage pour papier - Google Patents
Dispersions aqueuses d'alkyldicetene et leur utilisation comme produits d'encollage pour papier Download PDFInfo
- Publication number
- EP0811091B1 EP0811091B1 EP96904005A EP96904005A EP0811091B1 EP 0811091 B1 EP0811091 B1 EP 0811091B1 EP 96904005 A EP96904005 A EP 96904005A EP 96904005 A EP96904005 A EP 96904005A EP 0811091 B1 EP0811091 B1 EP 0811091B1
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- EP
- European Patent Office
- Prior art keywords
- aqueous
- polyethyleneimines
- weight
- alkyldiketene
- protective colloid
- 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
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/17—Ketenes, e.g. ketene dimers
Definitions
- the invention relates to aqueous alkyldiketene dispersions which contain a C 14 -C 22 -alkyldiketene and 1 to 10% by weight of a polymeric protective colloid and to the use of the aqueous alkyldiketene dispersions as bulk sizes in the production of paper, cardboard and cardboard and for the hydrophobization of cellulose fibers.
- Alkyldiketenes are used in the form of aqueous dispersions as mass sizing agents used for paper. You will be in the presence of Emulsifiers or organic thickeners emulsified in water, see. US-A 2 627 477 and US-A 3 130 118. From the last mentioned literature is the preparation of aqueous alkyl diketene dispersions known with cationic strength. The one in it described low-concentration alkyl diketene dispersions are sufficiently stable in storage for use as sizing agents, however, aqueous alkyldiketene dispersions are used Concentrations of fatty alkyl diketenes of more than 12% relative quickly fixed.
- DE-A-2 514 128 discloses aqueous dispersions of ketene dimers known, the 1 to 30 wt .-%, based on ketene dimers, polyvinylpyrrolidone and / or contain polyvinyl caprolactam.
- You can also an emulsifier such as fatty alcohol sulfates or salts of Sulfonic acids by sulfonation of ethoxylated fatty alcohols are obtained or contain cationic emulsifiers, which, for example, by reacting oleylamine with ethylene oxide and quaternization with dimethyl sulfate.
- Alkyldiketene dispersions if you have alkyldiketenes in the presence of cationic strength and a cationic protective colloid dispersed in water, the protective colloid being a water-soluble Condensation product is that by grafting polyamidoamines with ethyleneimine and crosslinking those grafted with ethyleneimine Polyamidoamines with at least difunctional ones Crosslinkers is available.
- the alkyl diketene concentration in the aqueous Dispersions 6% by weight.
- a sizing agent mixture is known from EP-B-0 341 509, the essential components of an alkyl diketene and a hydrophilic Contains polymer that by polymerizing at least of a hydrophilic vinyl monomer in the presence of 0.01 to 10 mol% of an alkyl mercaptan with 6 to 22 carbon atoms in Molecule is available. According to Example 5 is a copolymer 97% acrylamide and 3% dimethylaminoethyl methacrylate as hydrophilic Vinyl polymer used.
- Stabilized aqueous alkyldiketene dispersions are known from EP-B 0 437 764 known to be a protective colloid in addition to an alkyl diketene and an ester of a long chain carboxylic acid and one long chain alcohol included.
- Preferred protective colloid come cationic strengths into consideration. Besides that, too Sorbitan esters, soaps, synthetic detergents and thickeners such as polymers of acrylamide, vinyl pyrrolidone and N-vinyl-2-methylimidazoline be used.
- the present invention has for its object, new aqueous To provide alkyldiketene dispersions that are available via have good storage stability and when used as Bulk sizing paper results in which the sizing effect immediately after paper production largely is trained.
- the invention also relates to the use of the aqueous Alkyldiketene dispersions as mass sizing agents in the manufacture of paper, cardboard and cardboard as well as for waterproofing of cellulose fibers.
- alkyldiketenes for example C 14 -C 22 -alkyldiketenes or mixtures of such alkyldiketenes are suitable.
- Alkyldiketenes are known and commercially available. They are produced, for example, from the corresponding carboxylic acid chlorides by splitting off hydrogen chloride with tertiary amines.
- the fatty alkyl diketenes can be characterized, for example, using the following formula: in which R 1 , R 2 denote the same or different C 14 to C 22 alkyl groups.
- Suitable fatty alkyldiketenes are, for example, tetradecyldiketene, hexadecyldiketene, octadecyldiketene, eikosyldiketene, docosyldiketene, palmityldiketene, stearyldiketene and behenyldiketene.
- Examples of compounds of the formula II in which the substituents R 1 and R 2 have different meanings are, for example, stearylpalmityldiketene, behenylstearyldiketene, behenyloleyldiketene or palmitylbehenyldiketene.
- stearyl diketene stearyl diketene, palmityldiketene or mixtures of stearyl diketene and palmityldiketene are preferably used.
- the diketenes are present in the aqueous emulsions in concentrations of 5 to 60, preferably 10 to 40,% by weight.
- Those aqueous alkyldiketene emulsions which have concentrations in the range from 10 to 20% by weight of a C 14 to C 22 alkyl diketene are particularly preferred.
- Dialkyldiketenes are emulsified in water in the presence of the protective colloids (a) and / or (b) given above.
- Protective colloid (a) are copolymers of N-vinylpyrrolidone and at least one quaternized N-vinylimidazole of the formula I given above.
- the anion can be, for example, a halogen ion, an alkyl sulfate ion or the remainder of an inorganic or organic acid.
- Examples of quaternized 1-vinyl imidazoles of the formula I are 1-vinylimidazole quaternized with C 1 to C 18 alkyl halides, salts of 1-imidazole with mineral acids such as sulfuric acid or hydrochloric acid quaternized 2-methyl with C 1 to C 18 alkyl halides -1-vinylimidazole, 3-methyl-1-vinylimidazolium chloride, 3-benzyl-1-vinylimidazolium chloride, 3-ethyl-1-vinylimidazolium metholsulfate and 2-methyl-1-vinylimidazolium methosulfate.
- copolymers of N-vinylpyrrolidone can also contain several different quaternized N-vinylimidazoles in copolymerized form, for example 1-vinylimidazolium chloride and 2-methyl-1-vinylimidazolium methosulfate.
- Copolymers of N-vinylpyrrolidone are preferably used and vinylimidazole and copolymers quaternized with methyl chloride from N-vinylpyrrolidone and quaternized with methyl chloride 2-methyl-1-vinylimidazole.
- the copolymers preferably contain 80 to 5 mol% of N-vinylpyrrolidone and 20 to 95 mol% of a quaternized vinyl imidazole of formula I.
- the K value of the copolymers is at least 20 and is preferably in the range of 40 to 80.
- the condensation products come into consideration as protective colloid (b), those described in WO-A 94/12560 cited at the outset are.
- These are amidated polyalkylene polyamines or their networking products.
- amidated polyethyleneimines are preferred.
- they are produced by a two-stage implementation, where in the first stage of the implementation of polyethyleneimines partially amidated with monocarboxylic acids.
- monocarboxylic acids are used, the 1 to 28, preferably contain 1 to 18 carbon atoms.
- the monocarboxylic acids can be saturated or one or optionally several ethylenically unsaturated non-conjugated double bonds exhibit.
- Suitable carboxylic acids are, for example, formic acid, Acetic acid, propionic acid, butyric acid, capric acid, 2-ethylhexanoic acid, benzoic acid, lauric acid, myristic acid, palmitic acid, Stearic acid, oleic acid, linoleic acid, arachidic acid, Erucic acid, marriage acid, valeric acid, decanoic acid, enanthic acid, Caprylic acid and fatty acid mixtures, for example from in naturally occurring fatty acid esters, e.g.
- the amidated polyethyleneimines can also be used, for example Use alkyldiketenes, e.g. Stearyl diketen, palmityldiketen, Lauryl diketene, oleyl diketene, behenyl diketene or mixtures of the above Diketenes.
- the polyethyleneimines are used in the process step (1) partially amidated so that, for example, 0.1 to 90, preferably 1 to 30% of the amidatable nitrogen atoms Polyethyleneimines are present as an amide group. Amidation there is no linkage of polyethyleneimine molecules. A such a link will only be made if applicable Implementation of the partially amidated polyethyleneimines with at least bifunctional crosslinkers achieved.
- Suitable crosslinkers are, for example, epihalohydrins, in particular epichlorohydrin, and also ⁇ , ⁇ -bis (chlorohydrin) polyalkylene glycol ethers and the ⁇ , ⁇ -bis (epoxides) of polyalkylene glycol ethers obtainable therefrom by treatment with bases.
- the chlorohydrin ethers are prepared, for example, by reacting polyalkylene glycols in a molar ratio of 1 to at least 2 to 5 with epichlorohydrin.
- Suitable polyalkylene glycols are, for example, polyethylene glycol, polypropylene glycol and polybutylene glycols and block copolymers of C 2 -C 4 -alkylene oxides.
- the average molar masses (M w ) of the polyalkylene glycols are, for example, 200 to 6000 and are preferably in the range from 300 to 2000 g / mol.
- ⁇ , ⁇ -bis (chlorohydrin) polyalkylene glycol ethers of this type are described, for example, in DE-C-2 434 816 specified in the prior art.
- the corresponding bisglycidyl ethers are formed from the dichlorohydrin ethers by treatment with bases.
- crosslinkers are ⁇ , ⁇ -dichloropolyalkylene glycols, which are known, for example, as crosslinkers from EP-B-0 025 515.
- crosslinkers are ⁇ , ⁇ - or vicinal dichloroalkanes, for example 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,4-dichlorobutane and 1,6-dichlorohexane.
- crosslinkers examples include the reaction products of at least trihydric alcohols with epichlorohydrin to give reaction products which have at least two chlorohydrin units, for example glycerol, ethoxylated or propoxylated glycerols, polyglycerols with 2 to 15 glycerol units in the molecule and optionally ethoxylated are used as polyhydric alcohols and / or propoxylated polyglycerols.
- Crosslinkers of this type are known, for example, from DE-C-2 916 356 given above.
- crosslinkers which contain blocked isocyanate groups for example trimethylhexamethylene diisocyanate blocked with 2,2,3,6-tetramethylpiperidinone-4.
- crosslinkers are known, for example, from DE-A-4 028 285 and crosslinkers containing aziridine units based on polyethers or substituted hydrocarbons, for example 1,6-bis-N-aziridinohexane, cf. US-A-3 977 923. It is of course also possible to use mixtures of two or more crosslinking agents to increase the molecular weight of the amidated polyalkylene polyamines.
- the amidated polyalkylene polyamines described under (1) are crosslinked with the crosslinking agents given under (2) at temperatures of 0 to 200, preferably 50 to 80 ° C.
- the reaction can be carried out in bulk or, preferably, in a solvent.
- the preferred solvent is water.
- alcohols for example C 1 to C 12 alcohols, such as methanol, ethanol, n-propanol, isopropanol and butanols and ethers, for example polyethylene glycol dimethyl ether, tetrahydrofuran and mixtures of these solvents with themselves or (and) water, are also suitable.
- Components (1) and (2) are preferably reacted in an aqueous medium.
- the pH during the reaction is usually in the range from 10 to 14, preferably 10 to 12.
- bases are, for example, sodium hydroxide solution, potassium hydroxide solution, calcium hydroxide, barium hydroxide, tertiary amines, for example triethylamine, triethanolamine or tri-n-propylamine.
- Sodium hydroxide is preferably used as the base.
- the condensation can be carried out continuously or batchwise.
- relatively high molecular weight polyethyleneimines for example those with average molecular weights (M w ) of 1,000 to 10,000, are reacted with bis-chlorohydrin ethers of polyalkylene glycols with a molecular weight of 300 to 6,000, preferably 800 to 1,500.
- Very high molecular weight condensation products also arise, for example, from the condensation of partially amidated polyethyleneimines with a molecular weight of at least 500,000 with epichlorohydrin.
- the protective colloids (a) and (b) are used, for example, in quantities from 1 to 20% by weight, based on alkyl diketene.
- the aqueous alkyldiketene dispersions are prepared in known manner in the equipment used for this by emulsifying the hydrophobic components in an aqueous Protection colloid solution.
- Suitable devices are, for example Homogenizers based on the high pressure relaxation principle work, e.g. LAB 100 from APV Gaulin.
- the procedure is such that the solid alkyl diketene is melted, added to an aqueous solution of the protective colloids (a) and / or (b) heated to 80 to 85 ° C. and the mixture is homogenized under the action of shear forces.
- the aqueous solution of the protective colloids is preferably adjusted to a pH below 7, for example to pH 3.5.
- the emulsion obtained is cooled to ambient temperature so that solid particles of alkyldiketene are in the form of a dispersion in water.
- the pH of the alkyldiketene dispersions is then, for example, in the range from 2 to 4.5.
- aqueous alkyldiketene dispersions contain, for example, 6 to 30, preferably 10 to 20 of a C 14 to C 22 alkyl diketene and 1 to 10, preferably 1 to 3, of a protective colloid (a) and / or (b).
- alkyl diketene dispersions In the production of the alkyl diketene dispersion, these can usually be used in the manufacture of such dispersions Auxiliaries are used, e.g. Common protective colloids such as cationic starch, sorbitan esters, anionic or nonionic emulsifiers, naphthalene-formaldehyde-sulfonic acid condensates and carboxylic acids. These excipients, usually are present in alkyldiketene dispersions are in the dispersions according to the invention used only in such amounts, that the stability of the dispersion is not disadvantageous being affected.
- Common protective colloids such as cationic starch, sorbitan esters, anionic or nonionic emulsifiers, naphthalene-formaldehyde-sulfonic acid condensates and carboxylic acids.
- aqueous alkyldiketene dispersions according to the invention have compared to the known starch-containing alkyl diketene dispersions special advantages in terms of storage stability and shear stability. They also have the advantage that those with the papers sized according to the invention almost the full sizing effect after production exhibit and practically no longer need ripening time, such as it is the case with the known alkyl diketene dispersions.
- a rapid glue development is especially for paper machines with integrated coating unit important because before the order the paper coating slip requires an immediate sizing of the paper is.
- the aqueous alkyldiketene dispersions according to the invention are used as bulk sizes in the manufacture of paper, Cardboard and cardboard as well as for the hydrophobization of cellulose fibers used. Compared to the known alkyl diketene dispersions the aqueous alkyldiketene dispersions according to the invention almost quantitative retention on the paper fibers. You own also an excellent sizing effect even in such Paper stocks that contain significant amounts of contaminants. Some of these contaminants come from recycled waste paper.
- the alkyldiketene dispersions according to the invention can be used for the preparation all paper, cardboard and cardboard qualities used e.g. Liners, papers for high-pressure / offset printing, so-called medium-fine writing and printing papers, natural gravure papers and also lightweight coating base papers.
- Liners papers for high-pressure / offset printing
- medium-fine writing and printing papers papers for high-pressure / offset printing
- natural gravure papers and also lightweight coating base papers.
- For the production such papers are used as the main raw material component sulfite and sulfate pulp
- both short and long fibers can, wood pulp, thermomechanical fabric (TMP), chemo-thermomechanical Fabric (CTMP) and pressure cut (PGW).
- TMP thermomechanical fabric
- CTMP chemo-thermomechanical Fabric
- PGW pressure cut
- the aqueous alkyl diketene dispersions can be used as a sizing agent for both Production of filler-free as well as filler-containing ones Papers are used.
- the filler content in the paper can up to max. 30 wt .-% and is, if filler-containing Papers are made, preferably in the range of 5 to 25% by weight filler.
- Suitable fillers are, for example Clay, kaolin, chalk, talc, titanium dioxide, calcium sulfate, barium sulfate, Alumina, satin white or mixtures of the above Fillers.
- the percentages in the examples are% by weight, which mean parts Parts by weight.
- the K values of the polymers were H. Fikentscher, Cellulose-Chemie, Volume 13, 58-64 and 71-74 (1932) in 0.5 M aqueous saline solution at a polymer concentration of 0.1 wt .-% and a temperature of 25 ° C.
- 215 g of an anhydrous polyethyleneimine containing 460 ethyleneimine units contains, with 6.1 g of benzoic acid at temperatures in the range of 150 to 180 ° C within 10 hours for the reaction brought.
- the reaction mixture is then cooled and in Water added.
- a 2% aqueous solution of the Benzoic acid amidated polyethyleneimine heats the solution to 80 ° C and sets the pH to 4 by adding acetic acid a.
- a stearyl diket melt is added to this solution, see above that the stearyl diketene content of the finished dispersion is 10% and homogenizes the mixture by applying high shear forces in a homogenizer.
- a device of the APV Gaulin company used. After 2 runs, the one obtained aqueous stearyl diketene dispersion within about 2 minutes Cooled to room temperature.
- the hot mixture is shown in the example 1 described homogenizer due to the action of high shear forces processed into a stearyl diketene dispersion. After The stearyldiketene dispersion is run within 2 passes Cooled to room temperature for 1 minute.
- a 2% aqueous solution of the cross-linked condensation product described above is heated to 80 ° C and by adding Acetic acid adjusted to a pH of 4. Then you give so much a stearyl diketene melt to the aqueous solution that the stearyl diketene content of the mixture is 12%. The mixture is then, as described in Example 1, by exposure to high Shear forces homogenized and cooled within 2 minutes.
- the effectiveness of the alkyldiketene dispersions according to the invention as a sizing agent was used in Examples 8 and 9 on 2 different Fabric models tested.
- the water intake was determined according to Cobb according to DIN 53 132 and the ink floating time (minutes) according to DIN 53 126.
- birch sulfate pulp Used on 100 parts of a wood-free birch sulfate pulp one 40 parts of chalk.
- concentration of birch sulfate pulp in the paper stock was 1.0%, based on dry fiber stock.
- the pH of the stock suspension was adjusted to 7.0.
- the mixture of materials was ground to a freeness of 35 ° SR (Schopper-Riegler) ground and with 0.025%, based on dry fiber, a commercially available retention agent based on a high molecular weight Polyacrylamids added.
- Waste paper from a mixture of 50 parts of newspapers and 50 parts of cardboard waste was just opened but not ground.
- the substance concentration was 1.0%, based on dry fiber.
- the pH of the pulp was 7.0. 0.025%, based on dry fibrous material, of a commercially available retention agent based on a high molecular weight polyacrylamide for stock suspension.
- Sheets of a basis weight of 80 g / m 2 were produced on a Rapid-Köthen sheet former using the amounts of stearyldiketene dispersion given in Table 1, which was obtained according to Example 3.
- Paper with a basis weight of 80 g / m 2 was produced on a test paper machine with a working width of 75 cm at a speed of 80 m / min.
- the composition of the material was 40 parts of TMP, 30 parts of bleached birch sulphate pulp, 30 parts of bleached pine sulphate pulp, 15 parts of chalk, 0.8% starch soluble in cold water and 0.02%, based on dry fibrous material, of a commercially available high molecular weight polyacrylamide.
- the increasing amounts of 12% stearyldiketene dispersion given in Table 2 and obtained in Example 7 were added to the paper stock.
- Examples a) to g) were repeated for comparison with a commercially available 12% stearyldiketene dispersion which contained 3% cationic starch as a protective colloid. Samples of the papers were tested immediately after production and after air conditioning for 24 hours under the conditions given in Example 8. The results are shown in Table 2. Ex. 9 12% stearyl diketene dispersion, ref. on dry fiber [%] Cobb values [g / m 2 ] directly 24 hours after production of the paper with stearyl ketene dispersion according to Ex. 7 Cf. Ex. 7 Cf.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Claims (4)
- Dispersions aqueuses d'alkyldicétène contenant un (alkyle en C14-C22)dicétène et 1 à 10% en poids d'un colloïde protecteur polymère, caractérisées en ce qu'elles contiennent en tant que colloïde protecteur(a) des copolymères de(1) N-vinylpyrrolidone et(2) au moins un N-vinylimidazole quaternisé de formule dans laquelle
- R, R1, R2 =
- H, groupement alkyle en C1-C4 ou phényle,
- R3 =
- H, groupement alkyle en C1-C18 ou benzyle et
- X⊖
- est un anion,
(b) des produits de condensation obtenus par(1) amidification partielle de polyéthylèneimines avec des acides monocarboxyliques et(2) condensation des polyéthyléneimines partiellement amidifiés avec des agents réticulants au moins bifonctionnels, présentant en tant que groupement fonctionnel un motif halogénohydrine, glycidyle, aziridine ou isocyanate ou un atome d'halogène, en polyéthyléneimines amidifiés réticulés, ayant une viscosité d'au moins 100 mPas dans une solution aqueuse à 20% en poids à 20°C, - Dispersions aqueuses d'alkyldicétènes selon la revendication 1, caractérisées en ce qu'elles contiennent en tant que colloïde protecteur (a) des copolymères de(1) N-vinylpyrrolidone et(2) de N-vinylimidazole quaternisé ou de 2-méthyl-1-vinylimidazole quaternisé.
- Dispersions aqueuses d'alkyldicétènes selon la revendication 1, caractérisées en ce qu'elles contiennent en tant que colloïde protecteur (b) des produits de condensation obtenus par(1) amidification partielle de polyéthyléneimines ayant 10 à 50 000 motifs éthylèneimine avec des acides monocarboxyliques et éventuellement(2) par condensation des polyéthylèneimines partiellement amidifiés avec de l'épichlorhydrine, des α,ω-bis(chlorhydrine)polyalkylèneglycoléthers, des α,ω-bis(glycidyl)éthers de polyalkylèneglycols, des α,ω-dichloropolyalkyléneglycols, des α,ω-dichloroalcanes ou des dichloroalcanes vicinaux ou leurs mélanges dans un rapport en poids (1) : (2) de 1 : 0,01 à 1 : 3.
- Utilisation des dispersions aqueuses d'alkyldicétènes selon l'une quelconque des revendications 1 à 3 en tant qu'agent d'encollage pour la fabrication de papier, de carton ainsi que pour les traitements rendant les fibres de cellulose hydrophobes.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19505751A DE19505751A1 (de) | 1995-02-20 | 1995-02-20 | Wäßrige Alkyldiketen-Dispersionen und ihre Verwendung als Leimungsmittel für Papier |
DE19505751 | 1995-02-20 | ||
PCT/EP1996/000500 WO1996026318A1 (fr) | 1995-02-20 | 1996-02-07 | Dispersions aqueuses d'alkyldicetene et leur utilisation comme produits d'encollage pour papier |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0811091A1 EP0811091A1 (fr) | 1997-12-10 |
EP0811091B1 true EP0811091B1 (fr) | 1998-08-19 |
Family
ID=7754490
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96904005A Expired - Lifetime EP0811091B1 (fr) | 1995-02-20 | 1996-02-07 | Dispersions aqueuses d'alkyldicetene et leur utilisation comme produits d'encollage pour papier |
Country Status (9)
Country | Link |
---|---|
US (1) | US5942588A (fr) |
EP (1) | EP0811091B1 (fr) |
JP (1) | JPH11500192A (fr) |
AT (1) | ATE169973T1 (fr) |
DE (2) | DE19505751A1 (fr) |
DK (1) | DK0811091T3 (fr) |
ES (1) | ES2119568T3 (fr) |
FI (1) | FI121121B (fr) |
WO (1) | WO1996026318A1 (fr) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10008930A1 (de) * | 2000-02-25 | 2001-08-30 | Basf Ag | Antiknitterausrüstung von cellulosehaltigen Textilien und Wäschenachbehandlungsmittel |
JP2002173895A (ja) * | 2000-09-25 | 2002-06-21 | Nippon Paper Industries Co Ltd | グラビア印刷用紙 |
US6426121B1 (en) * | 2000-10-17 | 2002-07-30 | Air Products Polymers, L.P. | Dual crosslinkable emulsion polymers at ambient conditions |
WO2003103656A1 (fr) * | 2002-06-06 | 2003-12-18 | 株式会社医薬分子設計研究所 | Derives hydroxyaryle o-substitues |
US8163133B2 (en) * | 2003-04-01 | 2012-04-24 | Akzo Nobel N.V. | Dispersion |
BRPI0410262A (pt) * | 2003-05-16 | 2006-05-16 | Basf Ag | material para embalagem, e, uso dos produtos de papel |
DE102004010447A1 (de) * | 2004-03-01 | 2005-09-22 | Basf Ag | Wässrige Dispersion von Reaktivleimungsmitteln, Verfahren zu ihrer Herstellung und ihre Verwendung |
CA2587527C (fr) | 2004-11-29 | 2015-04-28 | Basf Aktiengesellschaft | Agent d'encollage pour papier contenant de l'amidon cationique et du polmere lineaire a base d'azote |
US20080163993A1 (en) * | 2007-01-10 | 2008-07-10 | Varnell Daniel F | Surface sizing with sizing agents and glycol ethers |
DE102010038887A1 (de) | 2010-08-04 | 2012-02-09 | Wacker Chemie Ag | β-Ketocarbonylquatverbindungen und Verfahren zu deren Herstellung |
DE102010063696A1 (de) | 2010-12-21 | 2012-06-21 | Wacker Chemie Ag | Zusammensetzungen enthaltend Quatverbindungen und Organopolysiloxane |
US8486427B2 (en) | 2011-02-11 | 2013-07-16 | Kimberly-Clark Worldwide, Inc. | Wipe for use with a germicidal solution |
AT512143B1 (de) * | 2011-11-08 | 2013-12-15 | Chemiefaser Lenzing Ag | Cellulosefasern mit hydrophoben Eigenschaften und hoher Weichheit und der dazugehörige Herstellungsprozess |
CN103930618B (zh) | 2011-11-14 | 2016-06-08 | 凯米拉公司 | Akd组合物以及纸和纸板的生产 |
GB201215433D0 (en) | 2012-08-30 | 2012-10-17 | Rbp Associates Ltd | Door seal |
US20150315339A1 (en) * | 2012-12-05 | 2015-11-05 | Knauf Insulation Sprl | Binder |
CN111040103B (zh) * | 2019-12-27 | 2021-08-24 | 福建华夏蓝新材料科技有限公司 | 一种可再分散的水性聚氨酯粉末的制备方法 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2627477A (en) * | 1949-10-06 | 1953-02-03 | Hercules Powder Co Ltd | Higher alkyl ketene dimer emulsion |
US2901371A (en) * | 1957-06-12 | 1959-08-25 | American Cyanamid Co | Sizing compositions containing fatty acid |
NL131880C (fr) * | 1958-12-24 | |||
US3311532A (en) * | 1965-03-17 | 1967-03-28 | American Cyanamid Co | Ketene dimer paper sizing compositions including acyl compound extender and paper sized therewith |
DE2514128A1 (de) * | 1975-03-29 | 1976-10-14 | Basf Ag | Leimungsmittel fuer papier |
DE3025609A1 (de) * | 1980-07-05 | 1982-02-11 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von waessrigen epoxidharzdispersionen |
DE3316179A1 (de) * | 1983-05-04 | 1984-11-08 | Basf Ag, 6700 Ludwigshafen | Verfahren zur masseleimung von papier |
DE3343105A1 (de) * | 1983-11-29 | 1985-06-05 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von papier, karton und pappe mit hoher trocken-, nass- und laugenfestigkeit |
JPS61204034A (ja) * | 1985-03-08 | 1986-09-10 | Kao Corp | 水性分散液 |
JP2576586B2 (ja) * | 1987-08-12 | 1997-01-29 | 日本油脂株式会社 | 重合体非水分散液の製造方法、重合体非水分散液および塗料組成物 |
DE4001237A1 (de) * | 1990-01-18 | 1991-07-25 | Basf Ag | Stabilisierte waessrige alkyldiketenemulsionen |
DE4117487A1 (de) * | 1991-05-28 | 1992-12-03 | Wacker Chemie Gmbh | Aminooxy-vernetzer enthaltende waessrige dispersionen von carbonylgruppen enthaltenden copolymerisaten |
DE4229142A1 (de) * | 1992-09-01 | 1994-03-03 | Basf Ag | Papierleimungsmittelmischungen |
DE4240110A1 (de) * | 1992-11-28 | 1994-06-01 | Basf Ag | Kondensationsprodukte von Polyalkylenpolyaminen, Verfahren zu ihrer Herstellung und ihre Verwendung bei der Herstellung von Papier |
DE4306608A1 (de) * | 1993-03-03 | 1994-11-24 | Basf Ag | Wäßrige Pigmentanschlämmungen, Verfahren zu ihrer Herstellung und ihre Verwendung bei der Herstellung von füllstoffhaltigem Papier |
DE4335194A1 (de) * | 1993-10-15 | 1995-04-20 | Basf Ag | Wäßrige Pigmentanschlämmungen und ihre Verwendung bei der Herstellung von füllstoffhaltigem Papier |
DE4410198A1 (de) * | 1994-03-24 | 1995-09-28 | Basf Ag | Copolymerisate auf Basis von Diketenen, ethylenisch ungesättigten Dicarbonsäuren bzw. Dicarbonsäurederivaten und ethylenisch ungesättigten Kohlenwasserstoffen |
DE59602419D1 (de) * | 1995-05-03 | 1999-08-19 | Basf Ag | Verfahren zur Herstellung von lösungsmittelarmen Alkyldiketenen |
-
1995
- 1995-02-20 DE DE19505751A patent/DE19505751A1/de not_active Withdrawn
-
1996
- 1996-02-07 DE DE59600457T patent/DE59600457D1/de not_active Expired - Lifetime
- 1996-02-07 DK DK96904005T patent/DK0811091T3/da active
- 1996-02-07 JP JP8525342A patent/JPH11500192A/ja active Pending
- 1996-02-07 US US08/894,365 patent/US5942588A/en not_active Expired - Lifetime
- 1996-02-07 AT AT96904005T patent/ATE169973T1/de active
- 1996-02-07 EP EP96904005A patent/EP0811091B1/fr not_active Expired - Lifetime
- 1996-02-07 WO PCT/EP1996/000500 patent/WO1996026318A1/fr active IP Right Grant
- 1996-02-07 ES ES96904005T patent/ES2119568T3/es not_active Expired - Lifetime
-
1997
- 1997-08-19 FI FI973393A patent/FI121121B/fi not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
US5942588A (en) | 1999-08-24 |
JPH11500192A (ja) | 1999-01-06 |
FI121121B (fi) | 2010-07-15 |
WO1996026318A1 (fr) | 1996-08-29 |
ATE169973T1 (de) | 1998-09-15 |
FI973393A0 (fi) | 1997-08-19 |
DK0811091T3 (da) | 1998-12-14 |
ES2119568T3 (es) | 1998-10-01 |
MX9706207A (es) | 1997-10-31 |
EP0811091A1 (fr) | 1997-12-10 |
DE59600457D1 (de) | 1998-09-24 |
FI973393A (fi) | 1997-08-19 |
DE19505751A1 (de) | 1996-08-22 |
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