WO1997013033A1 - Procede de production de papier pourvu d'un appret resistant a l'etat sec et a l'etat humide - Google Patents

Procede de production de papier pourvu d'un appret resistant a l'etat sec et a l'etat humide Download PDF

Info

Publication number
WO1997013033A1
WO1997013033A1 PCT/EP1996/004202 EP9604202W WO9713033A1 WO 1997013033 A1 WO1997013033 A1 WO 1997013033A1 EP 9604202 W EP9604202 W EP 9604202W WO 9713033 A1 WO9713033 A1 WO 9713033A1
Authority
WO
WIPO (PCT)
Prior art keywords
paper
dry
polyisocyanates
strength
polymers
Prior art date
Application number
PCT/EP1996/004202
Other languages
German (de)
English (en)
Inventor
Friedrich Linhart
Werner Auhorn
Karl Häberle
Rudolf Schuhmacher
Rainer Dyllick-Brenzinger
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO1997013033A1 publication Critical patent/WO1997013033A1/fr

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
    • 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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D21H17/08—Isocyanates
    • 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
    • D21H21/18—Reinforcing agents

Definitions

  • the invention relates to a process for producing dry-strength and wet-strength paper by adding hydrophilically modified polyisocyanates and cationic polymers to the pulp and dewatering the pulp with sheet formation or by treating the surface of paper with hydrophilically modified polyisocyanates and cationic polymers.
  • US Pat. No. 4,421,602 discloses partially hydrolyzed, water-soluble polymers of N-vinylformamide which contain N-vinylformamide units and vinylamine units. The polymers are used as agents for increasing flocculation, retention and dewatering speed in the manufacture of paper.
  • copolymers containing vinylamine units which can be used as dry and wet strength agents in the production of paper are known, for example, from EP-B-0 251 182.
  • EP-A-0 564 912 discloses the use of water-dispersible polyisocyanates for the wet-strength finishing of paper.
  • the advantage of these wet strength agents is that they have no organically bound chlorine.
  • the water-dispersible polyisocyanates can also be used in a mixture of conventional retention or wet strength agents.
  • Polyamidoamine-epichlorohydrin resins are mentioned by way of example. However, such resins contain organically bound chlorine.
  • EP-A-0 582 166 discloses a process for the production of dry-strength and wet-strength finished and / or sized cellulose-containing material, the cellulose-containing material being treated with a water-dispersible polyisocyanate mixture which contains tertiary amino and / or ammonium groups becomes.
  • the water-dispersible polyisocyanate mixtures can also be used in combination with reactive sizing agents such as alkyldiketenes or alkenyl succinic anhydrides.
  • the polyisocyanate mixtures can optionally be used with cationic auxiliaries such as retention agents, fixing agents, dry strength agents and wet strength agents, for example polyamines, polyethyleneimines, polyamidoamines and polyacrylamides.
  • cationic polycondensates composed of polyamines and alkylene dihalides, preferably dichloroethane.
  • the invention has for its object to increase the effectiveness of dry and wet strength agents that do not contain organically bound chlorine.
  • the object is achieved according to the invention with a process for the production of dry-strength and wet-strength finished paper by adding hydrophilically modified polyisocyanates and cationic polymers to the paper stock and dewatering the paper stock with sheet formation or by treating the surface of paper with hydrophilically modified polyisocyanates and cat - Ionic polymers, if one uses polymers containing vinylamine units as cationic polymers.
  • hydrophilically modified polyisocyanates which are also referred to as water-dispersible polyisocyanates, are in the form of aqueous dispersions which are essentially free of organic solvents and other emulsifiers.
  • hydrophilically modified polyisocyanates used according to the invention are customary diisocyanates and / or usual higher-functional polyisocyanates with an average NCO functionality of 2.0 to 4.5. These components can be present alone or in a mixture.
  • customary diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanate hexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, 1,4-diisocyanate, or tetramate diisocyanate, or tetramate diisocyanate, or tetramate diisocyanate, or tetramate diisocyanate such as 1,3-diisocyanate 1,2-diisocyanatocyclohexane, 4,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3, 5-trimethyl-5- (isoeyanatomethyl) cyclohexane (isophorone di
  • aliphatic diisocyanates in particular hexamethylene diisocyanate and isophorone diisocyanate, are preferred.
  • suitable higher-functional polyisocyanates are triisocyanates such as 2,4,6-triisocyanatotoluene or 2,4,4'-triisocyanatodiphenyl ether or the mixtures of di-, tri- and higher polyisocyanates obtained by phosgenation of the corresponding aniline / formaldehyde Condensates are obtained and represent polyphenyl polyisocyanates having methylene bridges.
  • the corresponding isocyanato-isocyanates based on hexamethylene diisocyanate and isophorone diisocyanate are particularly preferred.
  • the present isocyanurates are, in particular, simple tris-isocyanatoalkyl or triisocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologues having more than one isocyanurate ring.
  • the isocyanato-isocyanurates generally have an NCO content of 10 to 30% by weight, in particular 15 to 25% by weight, and an average NCO functionality of 2.6 to 4.5.
  • uretdione diisocyanates with aliphatic and / or cycloaliphatic bound isocyanate groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
  • polyisocyanates containing biuret groups with aliphatically bound isocyanate groups in particular tris (6-isocyanato-hexyDbiuret or its mixtures with its higher homologues.
  • These polyisocyanates containing biuret groups generally have an NCO content of 18 to 25% by weight and a average NCO functionality from 3 to 4.5.
  • Polyisocyanates containing urethane and / or allophanate groups with aliphatically or cycloaliphatically bound isocyanate groups such as, for example, by reacting excess amounts of hexamethylene diisocyanate or isophorone diisocyanate with simple polyhydric alcohols such as trimethylolpropane, glycerol, 1, 2-dihydroxypropane or their mixture can be obtained.
  • These polyisocyanates containing urethane and / or allophanate groups generally have an NCO content of 12 to 20% by weight and an average NCO functionality of 2.5 to 3.
  • Polyisocyanates containing oxadiazinetrione groups preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Such polyisocyanates containing oxadiazinetrione groups can be prepared from diisocyanate and carbon dioxide.
  • Aliphatic diisocyanates and aliphatic higher-functional polyisocyanates are particularly preferred for the use according to the invention.
  • the described diisocyanates and / or higher functionalized polyisocyanates are converted to NCO-reactive compounds for conversion into non-ionically hydrophilically modified polyisocyanates, which are particularly preferred for the use according to the invention, and the hydrophilic structural elements with non-ionic groups or with polar Contain groups that cannot be converted into ion groups.
  • the diisocyanate or polyisocyanate is present in a stoichiometric excess so that the resulting hydrophilically modified polyisocyanate still has free NCO groups.
  • Hydroxyl group-terminated polyethers of the general formula I in particular come as such NCO-reactive compounds with hydrophilicizing structural elements
  • R 1 represents Cx to C 20 alkyl, in particular C 1 to C 4 alkyl, or C 2 to C 20 alkenyl, cyclopentyl, cyclohexyl, glycidyl, oxethyl, phenyl, tolyl, benzyl, furfuryl or tetrahydrofurfuryl, X denotes sulfur or in particular oxygen,
  • n stands for a number from 5 to 120, in particular 10 to 25,
  • Ci- to C 4 alkanol started ethylene oxide or propylene oxide polyethers having average molecular weights of from 250 to 7000, in particular from 450 to 1,500.
  • diisocyanates and / or more functionalized polyisocyanates it is also possible first of all by reaction with a deficit of hydroxyl-terminated polyesters, on other hydroxyl-terminated polyethers or on polyols, e.g. Generate ethylene glycol, trimethylolpropane or butanediol, prepolymers and then implement these prepolymers either subsequently or simultaneously with the polyethers I in deficit to the hydrophilically modified polyisocyanates with free NCO groups.
  • nonionically hydrophilically modified polyisocyanates from diisocyanate or polyisocyanate and polyalkylene glycols of the formula HO— (AO) n —H, in which A and n have the meanings given above. Both terminal OH groups of the polyalkylene glycol react with isocyanate.
  • non-ionically hydrophilically modified polyisocyanates are in the documents DE-A 24 47 135, DE-A 26 10 552, DE-A 29 08 844, EP-A 0 13 112, EP-A 019 844, DE-A 40 36 927, DE-A 41 36 618, EP-B 206 059, EP-A 464 781 and EP-A 516 361.
  • the described diisocyanates and / or higher functionalized polyisocyanates are converted into anionically hydrophilically modified polyisocyanates with NCO-reactive compounds which contain hydrophilic anionic groups, in particular acid groups such as carboxyl groups, sulfonic acid groups or phosphonic acid groups.
  • the diisocyanate or polyisocyanate is present in a stoichiometric excess so that the resulting hydrophilically modified polyisocyanate still has free NCO groups.
  • Such NCO-reactive compounds with anionic groups are, above all, hydroxyearonic acids such as 2-hydroxyacetic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid or hydroxypivalic acid and 2,2-bis- and 2,2,2-tris (hydroxymethyl) alkanoic acids, for example 2,2-bis (hydroxymethyl) acetic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid or 2,2,2-tris (hydroxymethyl) acetic acid.
  • the carboxyl groups can be partially or completely neutralized by a base in order to be present in a water-soluble or water-dispersible form.
  • the base used here is preferably a tertiary amine, which is known to be inert to isocyanate.
  • the described diisocyanates and / or more highly functionalized polyisocyanates can also be reacted with a mixture of nonionically hydrophilically modifying and anionically hydrophobically modifying compounds which are added in succession or simultaneously, for example with a deficiency of the polyethers I and the described hydroxyearonic acids .
  • anionically hydrophilically modified polyisocyanates are described in more detail in documents DE-A-40 01 783, DE-A-41 13 160 and DE-A-41 42 275.
  • the described diisocyanates and / or more highly functionalized polyisocyanates are converted into cationically hydrophilically modified polyisocyanates with NCO-reactive compounds which contain chemically incorporated alkylatable or protonatable functions with the formation of a cationic center.
  • NCO-reactive compounds which contain chemically incorporated alkylatable or protonatable functions with the formation of a cationic center.
  • such functions are tertiary nitrogen atoms, which are known to be inert to isocyanate and can be easily quaternized or protonated.
  • NCO-reactive compounds with tertiary nitrogen atoms are preferably amino alcohols of the general formula II
  • R 2 and R 3 are linear or branched C 1 to C 20 alkyl, in particular C 1 to C 5 alkyl, or together with the N atom form a five- or six-membered ring which is also an O atom or a tertiary one N atom can contain, in particular a piperidine, morpholine, piperazine, pyrrolidine, oxazoline or dihydrooxazine ring, where the radicals R 2 and R 3 can additionally carry hydroxyl groups, in particular in each case one hydroxyl group, and
  • R 4 denotes a C 2 - to Cio-alkylene group, in particular a C 2 - to C ⁇ -alkylene group, which can be linear or branched,
  • Particularly suitable amino alcohols II are N-methyldiethanolamine, N-methyldi (iso) propanolamine, N-butyldiethanolamine, N-butyldi (iso) propanolamine, N-stearyldiethanolamine, N-stearyldi (iso) propanolamine, N, N -Dimethylethanolamine, N, N-dimethyl (iso) propanolamine, N, N-diethylethanolamine, N, N-diethyl (iso) propanolamine, N, N-dibutylethanolamine, N, N-dibutyl (iso) propanolamine , Triethanolamine, tri (iso) propanolamine, N- (2-hydroxyethyl) morpholine, N- (2-hydroxypropyl) morpholine, N- (2-hydroxyethyl) piperidine, N- (2-hydroxypropyl) piperidine, N-methyl-N '- (2
  • NCO-reactive compounds with tertiary nitrogen atoms are preferably diamines of the general formula purple or IHb
  • R 2 to R 4 have the meanings given above and R 5 denotes Ci to Cs-alkyl or forms a five- or six-membered ring, in particular a piperazine ring, with R 2 .
  • Particularly suitable diamines are purple, N, N-dimethylethylene diamine, N, N-diethylethylene diamine, N, N-dimethyl-1,3-diamino-2,2-dimethylpropane, N, N-diethyl-1 , 3-propylenediamine, N- (3-aminopropyl) morpholine, N- (2-aminopropyl) morpholine, N- (3-aminopropyl) piperidine, N- (2-aminopropyl) piperidine, 4-amino-1 - (N, N-diethylamino) pentane, 2-amino-1- (N, N-dimethylamino) propane, 2-amino-1- (N, N-diethy
  • Particularly suitable diamines IIIb are N, N, N'-trimethylethylene diamine, N, N, N '-triethylethylene diamine, N-methylpiperazine or N-ethylpiperazine.
  • polyether (poly) ols with built-in tertiary nitrogen atoms which can be prepared by propoxylation and / or ethoxylation of starter molecules containing amine nitrogen, can also be used as NCO-reactive compounds.
  • Such polyether (poly) oles are, for example, the propoxylation and ethoxylation products of ammonia, ethanolamine, diethanolamine, ethylenediamine or N-methylaniline.
  • NCO-reactive compounds which can be used are polyester and polyamide resins having tertiary nitrogen atoms, polyols containing urethane groups and tertiary nitrogen atoms, and polyhydroxy polyacrylates having tertiary nitrogen atoms.
  • the described diisocyanates and / or higher functionalized polyisocyanates can also be reacted with a mixture of nonionically hydrophilically modifying and cationically hydrophilically modifying compounds which are added in succession or simultaneously, for example with a deficit of polyethers I and amino alcohols II or the diamonds purple or Illb. Mixtures of nonionically hydrophilically modifying and anionically hydrophilically modifying compounds are also possible.
  • the content of the hydrophilically modified polyisocyanates to be used in accordance with the invention in hydrophilicizing components which have reacted via their NCO-reactive groups with the described diisocyanates and / or higher-functionalized polyisocyanates to give the present products is generally 0.1 to 40% by weight, preferably 0.5 to 30% by weight, in particular 1.0 to 20% by weight, based on the weight of the product.
  • this content is generally 1 to 40% by weight, preferably 3 to 30% by weight, in particular 5 to 20% by weight
  • this content is generally 0.1 to 10% by weight, preferably 0.5 to 7% by weight, in particular 1.0 to 3% by weight.
  • hydrophilically modified polyisocyanates are used in aqueous media, the polyisocyanates must be sufficiently dispersible.
  • certain reaction products of di- or polyisocyanates and hydroxyl-terminated polyethers (polyether alcohols), such as the compounds I preferably act as emulsifiers for this purpose.
  • hydrophilically modified polyisocyanates are added to the paper stock in amounts of 0.05 to 20, preferably 0.5 to 5% by weight, based on dry fibers, or applied to the surface of the dry paper.
  • polymers containing vinylamine units are used as cationic polymers. Suitable polymers containing vinylamine units are known from the publications cited above, e.g. US-A-4 421 602, US-A-2 721 140, EP-B-0 216 387 and
  • Both hydrolyzed homopolymers of N-vinylformamide and hydrolyzed copolymers of N-vinylformamide with other monoethylenically unsaturated compounds can be used together with the hydrophilically modified polyisocyanates.
  • the vinylamine groups of the polymers can be in the form of salts or as a free base.
  • the hydrolysis or elimination of formyl groups from polymers which contain copolymerized N-vinylamide is preferably achieved by adding acids or bases and heating the reaction mixture to higher temperatures, for example in the temperature range from 20 to 200, preferably 50 to 90 ° C. .
  • Hydrolyzed homopolymers of N-vinylformamide or hydrolyzed copolymers of N-vinylformamide with vinyl acetate, vinyl propionate, C 1 -C 4 -alkyl vinyl ethers, N-vinyl pyrrolidone, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile and esters of acrylic acid and methacrylic acid are preferably used which are derived from alcohols having 1 to 18 carbon atoms and which can be obtained from the polymers by subsequent cleavage of 1 to 99, preferably 5 to 90 mol% of the formyl groups.
  • the copolymers contain, for example, 95 to 10 mol%
  • N-vinylformamide and 5 to 90 mol% of at least one ethylenically unsaturated monomer.
  • the hydrolysis of the copolymers of N-vinylformamide and vinyl formate, vinyl acetate and / or vinyl propionate can be carried out in this way, and the comonomers can also be partially or completely hydrolyzed, for example by hydrolysis of copolymers of N-vinylformamide and vinyl esters of saturated carboxylic acids with 1 to 3 carbon atoms split off 30 to 100 mol% of the formyl groups from the copolymerized N-vinylformamide units and 30 to 100 mol% from the polymerized vinyl ester units to form vinyl alcohol units.
  • the hydrolysis of homopolymers and copolymers of N-vinylformamide is preferably carried out in such a way that 20 to 50 mol% of the formyl groups of N-vinylformamide are hydrolyzed to form vinylamine units.
  • Suitable polymers containing vinylamine units are graft polymers which contain grafted N-vinylformamide and optionally other monoethylenically unsaturated monomers, for example graft polymers of N-vinylformamide onto polyalkylene glycols, for example polyethylene glycol with molar masses of about 400 to 100,000, preferably 1000 to 10000, block copolymers of ethylene oxide and propylene oxide, block copolymers of ethylene oxide and butylene oxide, block copolymers of ethylene oxide, propylene oxide and butylene oxide, it being possible for the block copolymers to contain the alkylene oxide units in any order.
  • addition products of alkylene oxides with alcohols, amines and carboxylic acids are suitable as the graft base. These addition products can optionally be end group-capped, for example etherified with a C 1 -C 22 -alkyl radical or esterified with carboxylic acids.
  • Polyalkylene glycols which are water-soluble and water-dispersible are preferably used.
  • the molar mass of the block copolymers and the addition products of alkylene oxides having 2 to 4 carbon atoms is preferably 200 to 100,000.
  • 0.1 to 20 preferably 1 to 10 parts by weight of N- are used per part by weight of the polyalkylene glycols used as the graft base.
  • Vinylformamide is preferably 1 to 10 parts by weight of N- are used per part by weight of the polyalkylene glycols used as the graft base.
  • the graft polymers are hydrolyzed by adding acids or bases in such a way that vinylamine units are formed from the grafted-on N-vinylformamides with elimination of the formyl group.
  • Polyvinyl esters or copolymers of such esters can also be used as the graft base for N-vinylformamide.
  • Preferred polyesters are, for example, polyvinyl formate and polyvinyl acetate. These copolymers can be used either directly or after hydrolysis, for example hydrolyzing 20 to 100, preferably 60 to 95% of the formate or acetate groups from the monopolymer cured vinyl esters to form vinyl alcohol units.
  • the molar mass of the hydrolyzed polyvinyl esters is, for example, 1000 to 1 million. 1 to 5, preferably 3 to 5 parts by weight of N-vinylformamide, if appropriate in a mixture with other monoethylenically unsaturated monomers, are grafted onto 1 part by weight of the non-hydrolyzed or hydrolyzed polyvinyl esters.
  • the graft polymers are converted into graft polymers containing vinylamine units by hydrolysis with acids or bases by elimination of formyl groups from the polymerized N-vinylformamide.
  • the grafted-on N-vinylformamide can be hydrolyzed to 10 to 100, preferably 20 to 50% by weight to form polymers containing vinylamine units.
  • the polymers containing vinylamine units described above are added to the paper stock in amounts of 0.05 to 20, preferably 0.1 to 5% by weight, based on dry fibers, or applied to the surface of the dry paper.
  • the polymers containing vinylamine units are preferably soluble in water. They have K values according to Fikentscher of 8 to 250, preferably 10 to 150 (measured in 1% by weight aqueous solution at 25 ° C. and pH 7).
  • the joint use of hydrophilically modified polyisocyanates and polymers containing vinyl lamin units in the production of dry-strength and wet-strength finished paper gives one
  • the combinations to be used according to the invention can be added to the paper stock prior to sheet formation, or applied to the surface of a paper sheet that has already been formed.
  • Per part by weight of hydrophilically modified polyisocyanates for example, 0.05 to 20, preferably 0.1 to 5 parts by weight of polymers containing vinylamine units are used, in each case based on the solids content.
  • the combinations to be used according to the invention have the advantage that they are practically not sensitive to impurities, i.e. they can also be used in paper factories with closed water circuits.
  • combinations of hydrophilically modified polyisocyanates and reaction products of polyamidoamines and / or polyamines and epichlorohydrin, for example are highly sensitive to impurities.
  • hydrophilically modified polyisocyanates and polymers containing vinylamine units to be used according to the invention are therefore preferred for the production of hygienic papers which are not exclusively made from fresh cellulose manufactured, but contain recycled fibers, and used in the manufacture of kraft paper.
  • Sulphite pulps which are known as TCF (totally chlorine free) and ECF (elemental chlorine free) qualities, are used for example for the production of hygiene papers.
  • TCF totally chlorine free
  • ECF electrochemical chlorine free
  • sulfate pulps can be used which are not washed as heavily or which are unbleached or half-bleached. Such sulfate pulps occur, for example, in integrated paper mills, in which pulp and paper are produced.
  • combinations to be used according to the invention can optionally be used together with customary auxiliaries, such as alkyldiketenes for sizing paper or with fixing agents.
  • the percentages in the examples mean% by weight, unless stated otherwise.
  • the K value of the polymers was determined according to H. Fikentscher, Zellulose-Chemie, Volume 13, pages 58 to 64 and 71 to 74 (1932), at a temperature of 25 ° C in 5% saline and a polymer concentration of 0.5 % By weight.
  • Homopolymer of N-vinylformamide with a K value of 85 from which 95 mol% of the formyl groups were split off by hydrolysis with hydrochloric acid, in a 12% aqueous solution with a pH value of 5.
  • Aqueous solution of a commercially available neutral wet strength resin based on a reaction product of epichlorohydrin and a polyamidoamine from diethylene triamine and adipic acid is a commercially available neutral wet strength resin based on a reaction product of epichlorohydrin and a polyamidoamine from diethylene triamine and adipic acid.
  • a pulp suspension with a fiber concentration of 0.5% was first prepared by introducing a mixture of 50% spruce sulfite pulp and 50% beech sulfite pulp in water.
  • the pH of the suspension was 7.8, the freeness 29 ° SR (Schopper-Riegler).
  • This pulp suspension was divided into 4 identical parts, which are referred to below as (a) to (d).
  • the additives shown in Table 1 were added to the substance suspensions (b) to (d).
  • leaves with a basis weight of 80 g / m 2 were produced from the material suspensions (a) to (d) on a Rapid-Köthen laboratory sheet former.
  • the wet tear length of the sheets obtained in each case was determined in the unaged condition and after aging for 5 minutes at a temperature of 110 ° C. The results are shown in Table 1.
  • Example 1 Additional wet tear length [m] of the leaves aged without aging
  • a pulp suspension with a concentration of 0.5% was prepared by introducing a fiber mixture of 50% spruce sulfite pulp and 50% beech sulfite pulp and 2% alum in water. The pH of the pulp suspension was 4.5 and the freeness was 29 ° SR. The stock suspension was then divided into 4 identical parts, and the additives shown in Table 2 were added to the stock suspensions (b) to (d). In each case, sheets with a basis weight of 80 g / m 2 were formed from the material suspensions obtained in this way on a Rapid Köthen sheet former. As stated in Example 1, the wet tear length was determined. The results are shown in Table 2.
  • a 0.5% pulp suspension was prepared by adding bleached pine sulphate pulp to water.
  • the pH of the suspension was 7.5, the freeness was 25 ° SR.
  • the pulp suspension was then divided into 8 equal parts, the substances described there being added to the suspensions given in Table 3 under (b) to (h). Thereafter, sheets with a basis weight of 80 g / m 2 were formed from the substance suspensions (a) to (h) in a Rapid Köthen laboratory sheet former.
  • the wet tear lengths of the leaves are given in Table 3.
  • Examples 3 (b) to (h) were repeated with the single exception that 1%, based on dry fiber, of a mixture of lignin sulfonate and humic acid in a weight ratio of 1: 1 was added to the paper stock. The results are shown in Table 4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)

Abstract

Le procédé décrit permet de produire du papier pourvu d'un apprêt résistant à l'état sec et à l'état humide par adjonction à la pâte à papier de combinaisons de polyisocyanates et de polymères contenant des unités de vinylamine modifiés afin de devenir hydrophiles, puis par déshydratation de la pâte à papier afin de former des feuilles, ou par traitement de la surface du papier avec des polyisocyanates et des polymères contenant des unités de vinylamine modifiés afin de devenir hydrophiles. L'invention concerne également l'utilisation de ces combinaisons de polyisocyanates et de polymères comme agents stabilisateurs à l'état sec et humide de papiers hygiéniques et de papiers kraft.
PCT/EP1996/004202 1995-10-05 1996-09-26 Procede de production de papier pourvu d'un appret resistant a l'etat sec et a l'etat humide WO1997013033A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1995137088 DE19537088A1 (de) 1995-10-05 1995-10-05 Verfahren zur Herstellung von trockenfest und naßfest ausgerüstetem Papier
DE19537088.0 1995-10-05

Publications (1)

Publication Number Publication Date
WO1997013033A1 true WO1997013033A1 (fr) 1997-04-10

Family

ID=7774085

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/004202 WO1997013033A1 (fr) 1995-10-05 1996-09-26 Procede de production de papier pourvu d'un appret resistant a l'etat sec et a l'etat humide

Country Status (2)

Country Link
DE (1) DE19537088A1 (fr)
WO (1) WO1997013033A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6616807B1 (en) * 1997-04-04 2003-09-09 Basf Aktiengesellschaft Method for producing high dry-strength paper, pulpboard and cardboard
US8349134B2 (en) 2004-11-23 2013-01-08 Basf Se Method for producing high dry strength paper, paperboard or cardboard
US9873983B2 (en) 2013-09-12 2018-01-23 Ecolab Usa Inc. Process and compositions for paper-making
US9873986B2 (en) 2013-09-12 2018-01-23 Ecolab Usa Inc. Paper-making aid composition and process for increasing ash retention of finished paper
CN114634610A (zh) * 2022-01-26 2022-06-17 合肥科天水性科技有限责任公司 一种用于纸张涂层的水性聚氨酯及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7147751B2 (en) 2002-12-20 2006-12-12 Kimberly-Clark Worldwide, Inc. Wiping products having a low coefficient of friction in the wet state and process for producing same
US6994770B2 (en) * 2002-12-20 2006-02-07 Kimberly-Clark Worldwide, Inc. Strength additives for tissue products
EP1999314B1 (fr) * 2006-03-16 2017-02-22 Basf Se Procédé de fabrication de papier et de carton présentant une grande résistance à sec
DE102006040771B3 (de) * 2006-08-31 2008-01-31 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Papiererzeugnis und Verfahren zu dessen Herstellung sowie dessen Verwendung

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1098023A (en) * 1964-05-07 1968-01-03 American Cyanamid Co Process of strengthening paper
US4784727A (en) * 1982-01-30 1988-11-15 Bayer Aktiengesellschaft Sizing agent and use thereof
US4957977A (en) * 1986-06-25 1990-09-18 Mitsubishi Kasei Corporation Vinylamine copolymer, flocculating agent etc.
DE4036927A1 (de) * 1990-11-20 1992-05-21 Basf Ag Nichtwaessrige polyisocyanatzubereitung
WO1995031492A1 (fr) * 1994-05-11 1995-11-23 Bayer Aktiengesellschaft Auxiliaires pour le finissage du papier

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1098023A (en) * 1964-05-07 1968-01-03 American Cyanamid Co Process of strengthening paper
US4784727A (en) * 1982-01-30 1988-11-15 Bayer Aktiengesellschaft Sizing agent and use thereof
US4957977A (en) * 1986-06-25 1990-09-18 Mitsubishi Kasei Corporation Vinylamine copolymer, flocculating agent etc.
EP0251182B1 (fr) * 1986-06-25 1991-11-27 Mitsubishi Kasei Corporation Copolymère de vinylamine, agent de floculation et agent d'amélioration du papier et son procédé de préparation
DE4036927A1 (de) * 1990-11-20 1992-05-21 Basf Ag Nichtwaessrige polyisocyanatzubereitung
WO1995031492A1 (fr) * 1994-05-11 1995-11-23 Bayer Aktiengesellschaft Auxiliaires pour le finissage du papier

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6616807B1 (en) * 1997-04-04 2003-09-09 Basf Aktiengesellschaft Method for producing high dry-strength paper, pulpboard and cardboard
US8349134B2 (en) 2004-11-23 2013-01-08 Basf Se Method for producing high dry strength paper, paperboard or cardboard
US9873983B2 (en) 2013-09-12 2018-01-23 Ecolab Usa Inc. Process and compositions for paper-making
US9873986B2 (en) 2013-09-12 2018-01-23 Ecolab Usa Inc. Paper-making aid composition and process for increasing ash retention of finished paper
CN114634610A (zh) * 2022-01-26 2022-06-17 合肥科天水性科技有限责任公司 一种用于纸张涂层的水性聚氨酯及其制备方法
CN114634610B (zh) * 2022-01-26 2024-03-19 合肥科天水性科技有限责任公司 一种用于纸张涂层的水性聚氨酯及其制备方法

Also Published As

Publication number Publication date
DE19537088A1 (de) 1997-04-10

Similar Documents

Publication Publication Date Title
EP0207414B1 (fr) Solutions ou dispersions aqueuses de produits d'addition de polyisocyanates, procédé pour leur préparation ainsi que leur utilisation comme matières à revêtement ou comme matières pour l'encollage de papier
DE3102038A1 (de) Polyurethanpolymeraminsalz als papieradditiv
EP0759041B1 (fr) Auxiliaires pour le finissage du papier
EP0582166B2 (fr) Résines multifonctionnelles sans chlore pour le finissage du papier
DE3822490A1 (de) Waessrige loesungen von polyamidoamin-epichlorhyrin-harzen, verfahren zu ihrer herstellung und ihre verwendung
DE2550860A1 (de) Verfahren zur herstellung von stabilen dispersionen
EP0828890B1 (fr) Procede de finition du papier au moyen de polyisocyanates a groupes anioniques
EP0564912B2 (fr) Procédé pour augmenter la resistance du papier à l'état humide
WO1997013033A1 (fr) Procede de production de papier pourvu d'un appret resistant a l'etat sec et a l'etat humide
EP0128399B1 (fr) Bande plâtrée et son procédé de fabrication
DE4436058A1 (de) Verfahren zur Herstellung trockenfest und/oder naßfest ausgerüsteter cellulosehaltiger Flächengebilde
EP0449041A2 (fr) Mélanges de cellulose et de polymères synthétiques, méthode d'obtention et applications
EP0929588B1 (fr) Isocyanates dispersibles dans l'eau a pouvoir d'absorption ameliore utilises comme agents auxiliaires pour le papier
DE2505344A1 (de) Verfahren zur herstellung in der waerme haertbarer harzemulsionen
EP0758417B1 (fr) Utilisation dans le domaine des textiles de polyisocyanates rendus hydrophiles par modification
DE4419572A1 (de) Mehrkomponenten-Systeme für die Papierveredelung
EP0985747B1 (fr) Procédé de fabrication de fibres de cellulose
DE4446334A1 (de) Wiederaufschließbare cellulosehaltige Materialien
DE1696280C3 (de) Mit Polymeren imprägniertes Papier
EP0823950B1 (fr) Procede de fabrication de papier a structure resistante
DE3205966A1 (de) Verfahren zur verbesserung der nasszugfestigkeit von papier
EP1070090B1 (fr) Preparations de polyisocyanates dispersables dans l'eau et destinees a la preparation de papier retriturable
DE4226110A1 (de) Chlorfreie Naßfestmittel für Papier
DE19548031A1 (de) Cellulosehaltige Materialien mit verbesserter Festigkeit
DE1916331C3 (de) Verfahren zum Veredeln von aus Wolle oder wollhaltigen Fasern bestehenden Textilmaterialien

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA