EP1210480B1 - Procede de production de papier, carton-pate et carton - Google Patents
Procede de production de papier, carton-pate et carton Download PDFInfo
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- EP1210480B1 EP1210480B1 EP00965878A EP00965878A EP1210480B1 EP 1210480 B1 EP1210480 B1 EP 1210480B1 EP 00965878 A EP00965878 A EP 00965878A EP 00965878 A EP00965878 A EP 00965878A EP 1210480 B1 EP1210480 B1 EP 1210480B1
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- Prior art keywords
- paper
- acid
- condensates
- increasing
- paper stock
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- 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
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/22—Proteins
-
- 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
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
Definitions
- the invention relates to a method for producing paper, Cardboard and cardboard by draining paper stock in the presence of polymers.
- paper consists essentially of fibers consisting of wood and / or cellulose and optionally of mineral fillers, in particular calcium carbonate and / or aluminum silicate, and that the essential process in papermaking consists of a separation of this fiber - And fillers consists of a dilute aqueous suspension of these substances by means of one or more movable screens. It is also known that certain chemicals are added to the suspension of fiber and fillers in water both to improve this separation process and to achieve or improve certain properties of the paper.
- cationic water-soluble polymers or, in other words, cationic polyelectrolytes or polycations with preferably medium or high molecular mass.
- These products are added to the very thin paper pulp before the paper sheet is formed on the sieve. Depending on their composition, they cause, for example, more fine material to remain on the sieve, or that the water on the sieve is separated more quickly, or that certain substances are fixed to the paper fibers and thus do not get into the white water, with the latter property both
- the cleanliness of the white water can be in the foreground, as well as the effect of the fixed substances, such as dyes or sizing agents, on the properties of the finished paper.
- polycations can also increase the strength of the paper or give the paper improved residual strength when wet.
- polycations are generally used which additionally carry reactive groups, which react with the paper constituents or with themselves with the formation of a network and which make the paper more resistant to water due to the covalent bonds formed.
- thermosetting resins based on Polyamidoamines known to crosslink by reaction with epichlorohydrin and by Heating can be hardened. Resins of this type are used, for example, as wet strength agents used in the manufacture of paper.
- polysaccharides with a very narrow activity profile polysaccharides with a very narrow activity profile.
- the main one cationic strengths are used to increase the dry strength of the paper used and to a lesser extent Dimensions also as a retention aid.
- the object of the invention is based on further substances to provide natural raw materials that are used in the Paper production, for example, anionic substances in paper fix and improve the retention of fillers.
- connections of groups (a) and (b) are, for example, in molar ratio of 100: 1 to 1:20, preferably 100: 1 to 1: 5 and usually in a molar ratio of 10: 1 to 1: 2 in the condensation used.
- the basic amino acids lysine, arginine, ornithine and tryptophan which can be considered as a compound of group (a) in the condensation can be in the form of the free bases, the hydrates, the esters with C 1 - to C 4 -alcohols and the salts such as sulfates, Hydrochlorides or acetates can be used in the condensation.
- Lysine hydrate and aqueous solutions of lysine are preferably used.
- Lysine can also be used in the form of the cyclic lactam, ⁇ -amino- ⁇ -caprolactam.
- Lysine mono- or dihydrochloride or mono- or dihydrochloride of lysine esters can also be used.
- salts of compounds of group (a) are used, equivalent amounts of inorganic bases, for example sodium hydroxide solution, potassium hydroxide or magnesium oxide, are preferably used in the condensation.
- the alkobol component of mono- and dihydrochlorides of lysine esters are derived, for example, from low-boiling alcohols, for example methanol, ethanol, isopropanol or tert-butanol.
- L-lysine dihydrochloride, DL-lysine monohydrochloride and L-lysine monohydrochloride are preferably used in the condensation.
- co-condensable compounds of group b) are aliphatic or cycloaliphatic amines, preferably methylamine, Ethylamine, propylamine, butylamine, pentylamine, hexylamine, Heptylamine, octylamine, nonylamine, decylamine, undecylamine, Dodecylamine, tridecylamine, stearylamine, palmitylamine, 2-ethylhexylamine, Isononylamine, hexamethylene diamine, dimethylamine, Diethylamine, dipropylamine, dibutylamine, dihexylamine, ditridecylamine, N-methylbutylamine, N-ethylbutylamine, cyclopentylamine, cyclohexylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine and Dicyclohexylamine.
- triamines and tetraamines are preferably suitable Ethylene diamine, propylene diamine, butylene diamine, neopentyl diamine, Hexamethylene diamine, octamethylene diamine, imidazole, 5-amino-1,3-trimethylcyclohexylmethylamine, diethylene triamine, Dipropylenetriamine and tripropyltetraamine.
- Suitable amines are 4,4'-methylenebiscyclohexylamine, 4,4'-methylenebis (2-methylcyclohexylamine), 4,7-dioxadecyl-1,10-diamine, 4,9-dioxadodecyl-1,12-diamine, 4,7,10-trioxatridecyl-1,13-diamine, 2- (ethylamino) ethylamine, 3- (methylamino) propylamine, 3- (cyclohexylamino) propylamine, 3- (2-aminoethyl) aminopropylamine, 2- (diethylamino) ethylamine, 3- (dimethylamino) propylamine, dimethyldipropylenetriamine, 4-aminomethyloctane-1,8-diamine, 3- (diethylamino) propylamine, N, N-diethyl-1,4-pentanediamine,
- Aliphatic amino alcohols are, for example, 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 2- (2-aminoethoxy) ethanol, 2 - [(2-aminoethyl) amino] ethanol, 2-methylaminoethanol, 2- (ethylamino) ethanol, 2-butylaminoethanol, diethanolamine, 3 - [(hydroxyethyl) amino] -1-propanol, Diisopropanolamine, bis (hydroxyethyl) aminoethylamine, Bis (hydroxypropyl) minoethylamin, Bis (hydroxyethyl) aminopropylamine and bis (hydroxypropyl) aminopropylamine.
- Further co-condensable compounds b) are, for example, saturated Monocarboxylic acids, unsaturated monocarboxylic acids, polybasic Carboxylic acids, carboxylic anhydrides, diketenes, monohydroxycarboxylic acids, monobasic polyhydroxycarboxylic acids and Mixtures of the compounds mentioned.
- saturated monobasic carboxylic acids are formic acid, acetic acid, propionic acid, Butyric acid, valeric acid, caproic acid, octanoic acid, Nonanoic acid, lauric acid, palmitic acid, stearic acid, arachidic acid, Behenic acid, myristic acid, 2-ethylhexanoic acid and all naturally occurring fatty acids and mixtures thereof.
- Examples of unsaturated monobasic carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, sorbic acid, oleic acid, linoleic acid and erucic acid.
- Examples of polybasic carboxylic acids are oxalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, itaconic acid, adipic acid, aconitic acid, azelaic acid, pyridinedicarboxylic acid, furandicarboxylic acid, phthalic acid, terephthalic acid, diglycolic acid, glutaric acid, C substituted 4-dicarboxylic acids, sulfosuccinic acid, C 1 - to C 6 - Alkyl succinic acids, C 2 -C 26 alkenyl succinic acids, 1,2,3-propane tricarboxylic acid, 1,1,3,3-propane tetracarboxylic acid, 1,1,2,2-ethane t
- carboxylic anhydrides are mono- and dianhydrides of butanetetracarboxylic acid, phthalic anhydride, acetylcitric anhydride, maleic anhydride, succinic anhydride, itaconic anhydride and aconitic anhydride.
- alkyldiketenes with 1 to 30 carbon atoms in the alkyl group and diketene itself.
- alkyldiketenes are methyldiketene, hexyldiketene, Cyclohexyldiketene, octyldiketene, decyldiketene, dodecyldiketene, Palmityldiketene, stearyldiketene, oleyldiketene, octadecyldiketene, Eicosyldiketen, Docosyldiketen and Behenyldiketen.
- monohydroxycarboxylic acids examples include malic acid, citric acid and isocitric acid.
- polyhydroxycarboxylic acids for example tartaric acid, gluconic acid, bis (hydroxymethyl) propionic acid and hydroxylated unsaturated fatty acids such as Dihydroxystearic.
- component b) further include non-proteinogenic amino acids into consideration, such as anthranilic acid, N-Methylaminosubstitusammlung acids such as N-methylglycine, dimethylaminoacetic acid, ethanolaminoacetic, N-Carboxymethylaminocarbonklare, nitrilotriacetic acid, ethylenediamine acetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylenediaminotriacetic, diaminosuccinic acid, C 4 - to C 26 aminoalkyl carboxylic acid such as 4-aminobutyric acid, 6-aminocaproic acid and 11-aminoundecanoic acid.
- the acids can be used in the form of the free acids and also in the form of their salts with alkali metal bases or amines in the condensation.
- component b) are alcohols, for example monohydric alcohols having 1 to 22 carbon atoms in the molecule, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, hexanol, 2 -Ethylhexanol, cyclohexanol, octanol, decanol, dodecanol, palmityl alcohol and stearyl alcohol.
- alcohols for example monohydric alcohols having 1 to 22 carbon atoms in the molecule, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, hexanol, 2 -Ethylhexanol, cyclohexanol,
- Suitable alcohols are, for example, ethylene glycol, propylene glycol, glycerol, polyglycerols with 2 to 8 glycerol units, erythritol, pentaerythritol and sorbitol.
- the alcohols can optionally be alkoxylated. Examples of such compounds are the addition products of 1 to 200 moles of a C 2 -C 4 -alkylene oxide to one mole of an alcohol.
- Suitable alkylene oxides are, for example, ethylene oxide, propylene oxide and butylene oxides.
- Ethylene oxide or propylene oxide is preferably used, or both ethylene oxide and propylene oxide are added to the alcohols in the form of blocks, it being possible first to add a sequence of ethylene oxide units and then propylene oxide units to the alcohols, or first to add propylene oxide and then ethylene oxide to the alcohols.
- a statistical addition of ethylene oxide and propylene oxide and a different arrangement of the blocks in the alkoxylated products is also conceivable.
- the alcohols can optionally contain a double bond, such as oleyl alcohol.
- component (b) it is also possible to use alkoxylated amines which are derived, for example, from the amines given above and which can be obtained by reaction with ethylene oxide and / or propylene oxide.
- alkoxylated amines which are derived, for example, from the amines given above and which can be obtained by reaction with ethylene oxide and / or propylene oxide.
- the addition products of 5 to 30 mol ethylene oxide with 1 mol stearylamine, oleylamine or palmitylamine may be mentioned.
- component (c) are naturally occurring amino sugars such as chitosan or chitosamine and compounds which can be obtained from carbohydrates by reductive amination, for example aminosorbitol.
- the condensation products can optionally contain, in condensed form, carbohydrates such as glucose, sucrose, dextrin, starch and degraded starch, maltose and sugar carboxylic acids such as gluconic acid, glutaric acid, glucuronactone and glucuronic acid.
- carbohydrates such as glucose, sucrose, dextrin, starch and degraded starch
- maltose and sugar carboxylic acids such as gluconic acid, glutaric acid, glucuronactone and glucuronic acid.
- the above components can be in the form of free Bases (such as amines) or in the form of the corresponding salts, e.g. the ammonium salts with inorganic or organic acids be used in the condensation.
- free Bases such as amines
- the condensation can be carried out in bulk, in an organic solvent or in an aqueous medium.
- the reaction can advantageously be carried out in an aqueous medium at concentrations of the compounds of groups (a) and (b), for example 10 to 98% by weight, at temperatures of 120 to 300 ° C.
- the condensation is carried out in water at concentrations of component (a) and (b) from 20 to 70% by weight under pressure at temperatures from 140 to 250 ° C.
- the condensation can also be carried out in an organic solvent such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide, glycol, polyethylene glycol, propylene glycol, polypropylene glycol, monohydric alcohols, addition products of ethylene oxide and / or propylene oxide with monohydric alcohols, with amines or with carboxylic acids.
- an organic solvent such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide, glycol, polyethylene glycol, propylene glycol, polypropylene glycol, monohydric alcohols, addition products of ethylene oxide and / or propylene oxide with monohydric alcohols, with amines or with carboxylic acids.
- the water can optionally also be distilled off before or during the condensation.
- the condensation can be carried out under normal pressure with removal of water.
- the water formed during the condensation is preferably removed from the reaction mixture.
- the condensation can be carried out under increased pressure, under normal pressure or under reduced pressure.
- the condensation time is,
- the condensation can optionally also in the presence of Mineral acids can be carried out as a catalyst.
- concentration of mineral acids is, for example, 0.001 to 5, preferably 0.01 to 1 wt .-%, based on the basic amino acids.
- suitable mineral acids as a catalyst are hypophosphorous acid, hypodiphosphoric acid, phosphorous Acid, hydrochloric acid, sulfuric acid or mixtures of the mentioned acids.
- the alkali, ammonium and alkaline earth metal salts of the acids can be used as a catalyst.
- crosslinking agents ⁇ , ⁇ - or vicinal dichloroalkanes, epihalohydrins, Bischlorohydrin ethers of polyols, bischlorohydrin ethers of polyalkylene glycols, Esters of chloroformic acid, phosgene, diepoxides, Polyepoxides, diisocyanates and polyisocyanates.
- Suitable crosslinkers of group (1) are ethylene carbonate, Propylene carbonate and urea. From this group of monomers propylene carbonate is preferably used. The crosslinker of this group react to form urea compounds containing amino groups.
- Suitable halogen-free crosslinkers of group (2) are, for example, monoethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid and the amides, esters and anhydrides derived therefrom.
- the esters can be derived from alcohols having 1 to 22, preferably 1 to 18, carbon atoms.
- the amides are preferably unsubstituted, but can carry a C 1 -C 22 -alkyl radical as a substituent.
- Suitable dicarboxylic anhydrides are, for example, maleic anhydride, Itaconic anhydride and succinic anhydride.
- the Crosslinking of compounds of the component containing amino groups (a) with the halogen-free crosslinking agents mentioned above takes place with the formation of amide groups or amides such as adipic acid diamide by Umamidierung.
- Maleic acid ester, monoethylenic Unsaturated dicarboxylic acids and their anhydrides can both by formation of carboxamide groups as well as by addition of NH groups of the component to be crosslinked (e.g. polyamidoamines) networking like a Michael addition cause.
- At least dibasic saturated carboxylic acids include for example tri- and tetracarboxylic acids such as citric acid, Propane tricarboxylic acid, ethylenediaminetetraacetic acid and butanetetracarboxylic acid. Also come as crosslinkers of group (2) the salts derived from the aforementioned carboxylic acids, Esters, amides and anhydrides are considered.
- Suitable crosslinkers of group (2) are also polycarboxylic acids, by polymerizing monoethylenically unsaturated Carboxylic acids or anhydrides are available.
- monoethylenic unsaturated carboxylic acids come e.g. Acrylic acid, Methacrylic acid, fumaric acid, maleic acid and / or itaconic acid in Consideration.
- Suitable crosslinkers are e.g. polyacrylic acids, Copolymers of acrylic acid and methacrylic acid or copolymers from acrylic acid and maleic acid.
- crosslinkers (2) are prepared, for example, by polymerizing anhydrides such as maleic anhydride in an inert solvent such as toluene, xylene, ethylbenzene, isopropylbenzene or solvent mixtures in the presence of initiators which form free radicals.
- Peroxyesters such as tert-butyl per-2-ethylhexanoate are preferably used as initiators.
- copolymers of maleic anhydride are suitable, for example copolymers of acrylic acid and maleic anhydride or copolymers of maleic anhydride and a C 2 to C 30 olefin.
- copolymers of maleic anhydride and isobutene or copolymers of maleic anhydride and diisobutene are preferred.
- the copolymers containing anhydride groups can optionally be modified by reaction with C 1 -C 20 alcohols or ammonia or amines and can be used in this form as crosslinking agents.
- the molecular weight M w of the homopolymers and copolymers is, for example, up to 10,000, preferably 500 to 5,000.
- Polymers of the type mentioned above are described, for example, in EP-A-0 276 464, US Pat. No. 3,810,834, GB-A-1 411 063 and US-A-4 818 795.
- the at least dibasic saturated carboxylic acids and the polycarboxylic acids can also be used as crosslinking agents in the form of the alkali metal or ammonium salts.
- the sodium salts are preferably used.
- the polycarboxylic acids can be partially, for example 10 to 50 mol%, or completely neutralized.
- Compounds of group (2) which are preferably used are tartaric acid dimethyl esters, Tartaric acid diethyl ester, adipic acid dimethyl ester, Diethyl adipate, dimethyl maleate, diethyl maleate, Maleic anhydride, maleic acid, acrylic acid, Acrylic acid methyl ester, acrylic acid ethyl ester, acrylamide and methacrylamide.
- the polyether diamines are, for example, by reacting Polyalkylene glycols made with ammonia.
- the polyalkylene glycols can be 2 to 50, preferably 2 to 40 alkylene oxide units contain. This can be, for example, polyethylene glycols, Polypropylene glycols, polybutylene glycols or block copolymers from ethylene glycol and propylene glycol, block copolymers from ethylene glycol and butylene glycol or block copolymers from ethylene glycol, propylene glycol and butylene glycol act.
- block copolymers are also suitable for Preparation of the polyether diamines, random copolymers from ethylene oxide and propylene oxide and optionally Butylene oxide.
- Polyether diamines are also derived from polytetrahydrofurans which have 2 to 75 tetrahydrofuran units.
- the polytetrahydrofurans are also reacted with Converted ammonia into the corresponding ⁇ , ⁇ -polyether diamines.
- Preferably used for the preparation of the polyether diamines Polyethylene glycols or block copolymers of ethylene glycol and Propylene glycol.
- alkylenediamines examples include ethylenediamine, propylenediamine, 1,4-diaminobutane and 1,6-diaminohexane.
- Suitable polyalkylene polyamines are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, bisaminopropylethylenediamine and polyethyleneimines having molecular weights up to 5000.
- the compounds of formula (II) are, for example, thereby available that alkylene glycols, polyethylene glycols, polyethyleneimines, Polypropyleneimines, polytetrahydrofurans, ⁇ , ⁇ -diols or ⁇ , ⁇ -diamines with maleic anhydride or those given above other monoethylenically unsaturated carboxylic acids or Implemented carboxylic acid derivatives.
- the for the production of the Crosslinker II have suitable polyethylene glycols preferably molecular weights from 62 to 10,000, the molecular weights of the polyethyleneimines are preferably 129 to 50,000 that of the polypropylene imines 171 to 50,000.
- Suitable alkylene glycols are, for example Ethylene glycol, 1,2-propylene glycol, 1,4-butanediol and 1,6-hexanediol.
- ⁇ , ⁇ -diamines are ethylenediamine and ⁇ , ⁇ -diamines derived from approx. 400 to 5,000 each of molecular weights M w of molecular weights M w of polyethylene glycols or of polytetrahydrofurans.
- crosslinkers of the formula II are reaction products of maleic anhydride with ⁇ , ⁇ -polyether diamines a molecular weight of 400 to 5000, the reaction products of polyethyleneimines with a molecular weight of 129 to 50,000 Maleic anhydride and the reaction products of ethylenediamine or triethylenetetramine with maleic anhydride in a molar ratio of 1: at least 2.
- Polyether diamines, alkylenediamines and polyalkylene polyamines can also react with maleic anhydride or the ethylenically unsaturated carboxylic acids or their derivatives with addition to the double bond in the manner of a Michael addition.
- crosslinkers of the formula (III) bring about crosslinking with the compounds containing amino groups via their terminal carboxyl or ester groups, with the formation of an amide function.
- This class of crosslinking system also includes the reaction products of monoethylenically unsaturated carboxylic acid esters with alkylenediamines and polyalkylene polyamines, for example the addition products of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and of polyethyleneimines with molar masses of, for example, 129 to 50,000 of acrylic acid or methacrylic acid or methacrylic acid or methacrylic acid 1 mol of the amine component uses at least 2 mol of the acrylic acid or methacrylic acid ester.
- the C 1 to C 6 alkyl esters of acrylic acid or methacrylic acid are preferably used as esters of monoethylenically unsaturated carboxylic acids.
- Acrylic acid methyl ester and acrylic acid ethyl ester are particularly preferred for the preparation of the crosslinking agents.
- the crosslinkers which are prepared by Michael addition of polyalkylene polyamines and ethylenically unsaturated carboxylic acids, esters, amides or anhydrides can have more than two functional groups. The number of these groups depends on the molar ratio in which the reactants are used in the Michael addition.
- 2 to 10, preferably 2 to 8 moles of ethylenically unsaturated carboxylic acids or their derivatives can be added to one mole of a polyalkylene polyamine containing 10 nitrogen atoms in the manner of a Michael addition.
- At least 2 to at most 4 mol of the ethylenically unsaturated carboxylic acids or their derivatives can be added to 1 mol of polyalkylenediamines and alkylenediamines in the manner of a Michael addition.
- the secondary NH groups in the compounds of formula IV can optionally with acrylic acid, acrylamide or acrylic esters react like a Michael addition.
- the compounds are preferably used as crosslinking agent of group (3) of the formula II, which contain at least 2 carboxyl groups and by reacting polyether diamines, ethylenediamine or polyalkylene polyamines available with maleic anhydride are or at least 2 ester addition-containing Michael products from polyether diamines, polyalkylene polyamines or Ethylene diamine and esters of acrylic acid or methacrylic acid with each monohydric alcohols containing 1 to 4 carbon atoms.
- Suitable halogen-free crosslinkers of group (4) are reaction products which are prepared by reacting dicarboxylic acid esters which are completely esterified with monohydric alcohols having 1 to 5 carbon atoms with ethyleneimine.
- Suitable dicarboxylic acid esters are, for example, dimethyl oxalate, diethyl oxalate, dimethyl succinate, diethyl succinate, dimethyl adipate, diethyl adipate and dimethyl glutarate.
- the reaction of diethyl oxalate with ethyleneimine gives bis- [ ⁇ - (1-aziridino) ethyl] oxalic acid amide.
- the dicarboxylic acid esters are reacted with ethyleneimine, for example in a molar ratio of 1 to at least 4.
- Reactive groups of these crosslinkers are the terminal aziridine groups.
- crosslinkers described above can be used either alone or in Mix when reacting with the water-soluble specified above Condensates of basic amino acids are used. The In all cases, the crosslinking reaction is at most as far led that the resulting products are still water-soluble, e.g. should at least 10 g of the crosslinked polymer in 1 1 Dissolve water at a temperature of 20 ° C.
- the condensates of basic amino acids are at least bifunctional crosslinkers preferably in aqueous solution or implemented in water-soluble organic solvents.
- suitable Water-soluble organic solvents are, for example, alcohols such as methanol, ethanol, isopropanol, n-propanol and butanols, Glycols such as ethylene glycol, propylene glycol or butylene glycol or Polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol and dipropylene glycol and tetrahydrofuran.
- the Concentration of the starting products in the solvents is in each case chosen so that reaction solutions are formed, for example Contain 5 to 50 wt .-% of cross-linked reaction products.
- the crosslinking is preferably carried out in aqueous solution.
- the temperatures during the reaction are 20 to 180, preferably 40 to 95 ° C. If the reaction temperature is above the Should be the boiling point of the solvent used, the reaction is carried
- homopolymers and copolymers based on lysine which is also 2,6-diaminohexanoic acid or 2,6-diaminocaproic acid may differ from most common process chemicals for papermaking not only because it derived from a natural product. They unfold after the addition several different effects on paper stock, and differentiate differs from the usual process chemicals and also from those based on the natural product starch.
- the Polymers to be used according to the invention bring about solidification of the paper in the dry as well as in the wet state, they increase the retention of fillers and fine substances, they accelerate the dewatering of the paper stock on the paper machine screen, they increase the effectiveness of anionic retention agents, they help anionic retention aids significant drainage effect, they improve the fixation of anionic paper dyes, they are capable of undesirable anionic Oligomers and polymers, commonly known as contaminants act to fix on the paper fibers and thus from the circulating water to remove the paper machine. They also increase the absorbency of the paper.
- wet strength of paper is desirable when the paper is inadvertently or in contact with water contrary to its intended purpose comes and should not dissolve or after drying to show its original properties again. In such In some cases you can glue the paper additionally or alternatively, i.e. partially hydrophobic with a paper chemical and thus slow down the penetration of water into the fiber structure. It but there are many types of paper with the fastest possible Water penetration is desired, maintaining the fiber structure must stay. Examples of such papers are paper towels, Sanitary papers, paper tissues, paper napkins, Toilet paper and filter paper.
- paper made with polymers based on Lysine is wet solidified, has a very high absorbency, which is higher than that which is more commercially available when used Wet strength agent is obtained, and also higher than that of the wet strength agent-free Paper with otherwise identical raw materials.
- absorbency of paper for example by watering or spraying the Paper web with wetting agents or hydrophilic substances, e.g. Polygykolen.
- these known methods reduce strength of the paper in the dry state.
- the polymeric derivatives of Natural product lysine according to the inventive method however increase the absorbency of the paper at the same time Increase in dry strength.
- the strength that the paper has is sufficient Because of its fiber composition, its filler content and of its manufacturing process. This will be in the course the growing environmental awareness and the increasing Use of waste paper, which has a far lower strength potential than fresh paper fibers, particularly blatant. But The natural strength is sufficient even when using fresh fibers often not, especially if the paper contains a lot of filler should. In such cases, the papermaker tries to Strength of its product through the addition of certain chemicals to increase. Most of the time, the paper surface is after the actual paper production with suitable chemicals, preferably treated with degraded starch.
- the application rates of polymers required for the effects described based on lysine condensates vary widely Differentiate limits depending on the desired effect but does not fundamentally differ from the application rates of one commercial paper chemicals used for each specific effect.
- To get wet hardening one should 0.1 - 5% by weight, preferably 0.5-2% by weight, based on dry Use paper stock on polymers based on lysine.
- To increase the dry strength of the paper you need e.g. 0.2 - 2% by weight, based on dry paper stock, of the lysine polymers.
- For fixation, retention and drainage effects if, for example, 0.01-1% by weight, preferably 0.02-, is used 0.2% by weight of polylysine derivatives, with the fixing of Dyes the necessary amounts up to 2%, each based on dry paper stock.
- the K value of the polycondensate is 64.5, the molecular weight M w is 960,000.
- the K value of the polycondensate is 52.2.
- the K value of the polycondensate is 69.
- test results are shown in Table 1. They show that a similar wet strength can be achieved with the polymers based on lysine as with the products of the prior art.
- the absorbency of the paper increases with an increasing amount of the lysine polycondensate, while it decreases with an increasing amount of the epichlorohydrin resin. Drying at 90 ° C for 10 min; additionally aged at 130 ° C for 5 min.
- the test results are shown in Table 3. They show that when the polymers based on lysine are used in paper production, the same dry strength of the paper is obtained as when using cationic starches. In contrast to the cationic starches, the polylysine derivatives additionally increase the wet strength of the paper. without Cationic strength Lysinpolykondensat I II G B Amount added (% active substance, based on dry paper stock) 1 1 1 1 1 Dry tear length (m) 3246 3544 3447 3541 3459 Wet tear length (m) 109.3 106.8 108.8 444.3 390.4 rel. Wet strength (%) 3.4 3.0 3.2 12.5 11.3
- the white water that has passed through becomes one Turbidity measurement subjected. The clearer the white water is, the more The combination of chemicals has a stronger impact. For comparison a paper sheet is also checked, but without condensate made in the presence of anionic polyacrylamide has been. The test results are shown in Table 5.
- Example 5 The procedure is as described in Example 4, but with the difference that the polylysine derivatives are compared with two commercially available cationic starches.
- the test results are shown in Table 5. They show that the lysine polycondensates in combination with an anionic polyacrylamide significantly accelerate the dewatering of a wood-free paper stock, while combinations of cationic starches and anionic polyacrylamide do not. It can also be seen that said combinations with lysine polycondensates have a better retention effect than combinations with cationic starches.
- Example 6 The procedure is as described in Example 4, but with the difference that TMP (thermomechanical pulp) is used as the fiber and kaolin (China Clay) as the filler, and a high molecular weight cationic polyacrylamide (Polymin® KE 78 from BASF Aktiengesellschaft) is used as the retention agent.
- TMP thermomechanical pulp
- kaolin China Clay
- Polymin® KE 78 from BASF Aktiengesellschaft
- Table 6 The test results are shown in Table 6. They show that the use of lysine polycondensates in paper production can significantly increase the dewatering and retention effectiveness of high molecular weight cationic polyacrylamides, and more so than with commercially available fixatives.
- Example 4 The procedure is as described in Example 4, but with the difference that cationic starches are also tested as comparative products.
- the test results are shown in Table 9. They show that lysine polycondensates have a significantly better drainage and retention effectiveness than cationic starches in paper production even when used alone. Lysinpolykondensat Cationic strength G G H H I I II II Add retention aid, based on dry paper stock % 0.2 0.4 0.2 0.4 0.2 0.4 0.2 0.4 0.4 0.4 0.4 Drainage time for 600 ml sec. 55 15 13 19 15 50 48 44 38 Turbidity measured at 588 nm 1,195 0,298 0.261 0.410 0,330 1,149 1,037 0,961 0.837
Claims (8)
- Procédé de préparation de papier, de carton-pâte et de carton par déshydratation d'une pâte de papier en présence de polymères, avec formation de feuilles, caractérisé en ce que, comme polymères, on met en oeuvre des produits de condensation réticulés qui peuvent être obtenus par réaction(i) d'homocondensats d'aminoacides basiques, de condensats d'au moins deux aminoacides basiques et/ou de cocondensats d'aminoacides basiques et de composés cocondensables, avec(ii) au moins un agent de réticulation comportant au moins deux groupes fonctionnels.
- Procédé suivant la revendication 1, caractérisé en ce qu'on met en oeuvre des condensats réticulés qu'on peut obtenir avec un agent de réticulation (ii) du groupe des dichloroalcanes α,ω ou vicinaux, des épihalogénhydrines, des éthers de bischlorhydrine de polyols, des éthers de bischlorhydrine de polyalkylèneglycols, des esters de l'acide chloroformique, du phosgène, des diépoxydes, des polyépoxydes, des diisocyanates et des polyisocyanates.
- Procédé suivant l'une des revendications 1 et 2, caractérisé en ce qu'on met en oeuvre les condensats en des quantités de 0,01 à 5% en poids par rapport à la pâte de papier sèche.
- Procédé suivant l'une des revendications 1 à 3, caractérisé en ce qu'on met en oeuvre les condensats en des quantités de 0,02 à 2% en poids, par rapport à la pâte de papier sèche, pour augmenter la résistance à sec du papier, pour augmenter le pouvoir absorbant du papier et pour fixer des colorants anioniques dans le papier.
- Procédé suivant l'une des revendications 1 à 4, caractérisé en ce qu'on met en oeuvre les condensats en des quantités de 0,02 à 0,2% en poids pour fixer des substances perturbatrices, pour augmenter la vitesse de déshydratation de la pâte de papier et pour augmenter la rétention de matières fines et de remplissage lors de la fabrication du papier.
- Procédé suivant l'une des revendications 1 à 5, caractérisé en ce qu'on met en oeuvre les condensats en des quantités de 0,02 à 0,2% en poids par rapport à la pâte de papier sèche, en combinaison avec des agents de rétention anioniques synthétiques pour augmenter l'action de déshydratation et l'action de rétention des agents de rétention anioniques synthétiques.
- Procédé suivant l'une des revendications 1 à 6, caractérisé en ce qu'on met en oeuvre les condensats en des quantités de 0,02 à 0,2% en poids par rapport à la pâte de papier sèche, en combinaison avec des agents de rétention cationiques synthétiques pour augmenter l'action de déshydratation et l'action de rétention des agents de rétention cationiques synthétiques.
- Utilisation de condensats réticulés d'aminoacides basiques, qui peuvent être obtenus par réaction(i) d'homocondensats d'aminoacides basiques, de condensats d'au moins deux aminoacides basiques et/ou de cocondensats d'aminoacides basiques et de composés cocondensables, avec(ii) au moins un agent de réticulation comportant au moins deux groupes fonctionnels,
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19940955 | 1999-08-28 | ||
DE19940955A DE19940955A1 (de) | 1999-08-28 | 1999-08-28 | Verfahren zur Herstellung von Papier, Pappe und Karton |
PCT/EP2000/007984 WO2001016425A1 (fr) | 1999-08-28 | 2000-08-16 | Procede de production de papier, carton-pate et carton |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1210480A1 EP1210480A1 (fr) | 2002-06-05 |
EP1210480B1 true EP1210480B1 (fr) | 2003-05-14 |
Family
ID=7919971
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00965878A Expired - Lifetime EP1210480B1 (fr) | 1999-08-28 | 2000-08-16 | Procede de production de papier, carton-pate et carton |
Country Status (9)
Country | Link |
---|---|
US (1) | US6673206B1 (fr) |
EP (1) | EP1210480B1 (fr) |
JP (1) | JP2003508642A (fr) |
AT (1) | ATE240434T1 (fr) |
AU (1) | AU7647300A (fr) |
CA (1) | CA2382672A1 (fr) |
DE (2) | DE19940955A1 (fr) |
ES (1) | ES2200943T3 (fr) |
WO (1) | WO2001016425A1 (fr) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JP4675009B2 (ja) * | 2001-09-21 | 2011-04-20 | 日華化学株式会社 | 紙用嵩高剤及び嵩高紙の製造方法 |
US6723204B2 (en) * | 2002-04-08 | 2004-04-20 | Hercules Incorporated | Process for increasing the dry strength of paper |
CA2755586C (fr) * | 2009-03-20 | 2015-06-23 | Fpinnovations | Materiaux de cellulose dotes de nouvelles proprietes |
EP2497757A1 (fr) | 2011-03-11 | 2012-09-12 | Sika Technology AG | Retardateur de prise pour liants formant un hydrate |
AU2014211681B2 (en) * | 2013-01-31 | 2017-12-07 | Glatfelter Gernsbach Gmbh | Crosslinking/functionalization system for a paper or non-woven web |
JP2015137433A (ja) * | 2014-01-21 | 2015-07-30 | 日本製紙クレシア株式会社 | 衛生薄葉紙 |
CN115821640B (zh) * | 2022-11-22 | 2023-08-18 | 启东欣联壁纸有限公司 | 一种防水耐污型墙纸及其制备方法 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE268357C (fr) | ||||
US3086961A (en) * | 1959-12-07 | 1963-04-23 | American Cyanamid Co | Water-soluble dibasic acid-polyalkylenepolyamine-alkylene glycol crosslinked polymer |
US3250664A (en) * | 1963-10-24 | 1966-05-10 | Scott Paper Co | Process of preparing wet strength paper containing ph independent nylon-type resins |
US3526608A (en) * | 1968-02-13 | 1970-09-01 | Pfizer & Co C | Use of polyamides derived from iminodiacetic acid and related compounds in improving the wet and dry strength of paper |
DE1771043C3 (de) * | 1968-03-27 | 1979-05-23 | Bayer Ag, 5090 Leverkusen | Selbstvernetzende wasserlösliche Produkte und deren Verwendung als Naßfestmittel für Papier |
US3535288A (en) * | 1968-04-30 | 1970-10-20 | Diamond Shamrock Corp | Cationic polyamide-epichlorohydrin resins |
DE1771814C2 (de) * | 1968-07-16 | 1974-05-09 | Bayer Ag, 5090 Leverkusen | Hilfsmittel-Verwendung für die Papierfabrikation |
DE1802435C3 (de) * | 1968-10-11 | 1979-01-18 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von vernetzten Harzen auf der Basis von basischen Polyamidoaminen und deren Verwendung als Entwässerungs-, Retentions- und Flockungsmittel bei der Papierherstellung |
US3761350A (en) * | 1971-06-23 | 1973-09-25 | Houghton & Co E | Thermosetting wet strength resin |
US3869342A (en) * | 1973-06-07 | 1975-03-04 | Houghton & Co E F | Cationic thermosetting resin composition for improving wet strength of paper |
DE2353430C2 (de) * | 1973-10-25 | 1982-04-15 | Wolff Walsrode Ag, 3030 Walsrode | Verfahren zur Herstellung von kationischen Polyaminopolyamiden und deren Verwendung als Papiererzeugungshilfsmittel |
US4035229A (en) * | 1974-11-04 | 1977-07-12 | Hercules Incorporated | Paper strengthened with glyoxal modified poly(β-alanine) resins |
DE2756431C2 (de) * | 1977-12-17 | 1985-05-15 | Bayer Ag, 5090 Leverkusen | Amidgruppenhaltige Polyamine |
DD268357A3 (de) * | 1986-10-13 | 1989-05-31 | Akad Wissenschaften Ddr | Verfahren zur herstellung von hydrolysierenden polykationischen verbindungen |
CA2132112A1 (fr) * | 1993-09-21 | 1995-03-22 | David Elliott Adler | Methode de catalysation acide pour l'obtention de polymeres d'acide amine |
-
1999
- 1999-08-28 DE DE19940955A patent/DE19940955A1/de not_active Withdrawn
-
2000
- 2000-08-16 WO PCT/EP2000/007984 patent/WO2001016425A1/fr active IP Right Grant
- 2000-08-16 AU AU76473/00A patent/AU7647300A/en not_active Abandoned
- 2000-08-16 US US10/069,719 patent/US6673206B1/en not_active Expired - Fee Related
- 2000-08-16 ES ES00965878T patent/ES2200943T3/es not_active Expired - Lifetime
- 2000-08-16 CA CA002382672A patent/CA2382672A1/fr not_active Abandoned
- 2000-08-16 DE DE50002206T patent/DE50002206D1/de not_active Expired - Fee Related
- 2000-08-16 JP JP2001519958A patent/JP2003508642A/ja not_active Withdrawn
- 2000-08-16 AT AT00965878T patent/ATE240434T1/de not_active IP Right Cessation
- 2000-08-16 EP EP00965878A patent/EP1210480B1/fr not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
WO2001016425A1 (fr) | 2001-03-08 |
CA2382672A1 (fr) | 2001-03-08 |
AU7647300A (en) | 2001-03-26 |
EP1210480A1 (fr) | 2002-06-05 |
JP2003508642A (ja) | 2003-03-04 |
ATE240434T1 (de) | 2003-05-15 |
DE19940955A1 (de) | 2001-03-01 |
US6673206B1 (en) | 2004-01-06 |
ES2200943T3 (es) | 2004-03-16 |
DE50002206D1 (de) | 2003-06-18 |
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