EP0105028B1 - Procédé d'encollage du papier avec des agents d'encollage anioniques hydrophobes et des agents de rétention cationiques - Google Patents

Procédé d'encollage du papier avec des agents d'encollage anioniques hydrophobes et des agents de rétention cationiques Download PDF

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EP0105028B1
EP0105028B1 EP83810373A EP83810373A EP0105028B1 EP 0105028 B1 EP0105028 B1 EP 0105028B1 EP 83810373 A EP83810373 A EP 83810373A EP 83810373 A EP83810373 A EP 83810373A EP 0105028 B1 EP0105028 B1 EP 0105028B1
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Prior art keywords
sizing
carbon atoms
sizing agent
formula
agents
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EP0105028A1 (fr
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Michael Dr. Bernheim
Peter Rohringer
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Novartis AG
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Ciba Geigy AG
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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
    • D21H17/03—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 present invention is based on the object of providing the paper manufacturer with easily accessible and easily obtainable sizing agents which, with the use of conventional, cationic retention aids in a novel combination, are suitable for achieving good sizing in paper production from fiber suspensions.
  • reaction products of ketene dimers and di- or oligoamines are used according to the invention as sizing agents of this type.
  • a process for sizing paper is known from US Pat. No. 2,961,367, in which, however, a ketene dimer (in contrast to reaction products of ketene dimers and di- or oligoamines) is used as the anionic, hydrophobic sizing agent in the presence of a polymeric, cationic retention agent.
  • the sizing agents (A) used according to the invention which are obtainable from components (a) and (b), have 1 to 6, preferably 2 to 6, potentially anionic groups, which are generally in the form of acidic groups are available.
  • the ability of the potentially anionic substituents to form anions in an aqueous medium is another essential characteristic of the sizing agent.
  • the formation of anions takes place at the pH values of the fiber suspensions which are usually present in papermaking.
  • the cationic retention agents (B) are also capable of forming cations.
  • the ability of the sizing agents or the retention agents to form anions or cations under the conditions of paper production can also be described as anion-active or cation-active.
  • the anionic sizing agents and the cationic retention agents can also be called anion-active sizing agents and cation-active retention agents.
  • the sizing agents (A) which are obtainable from components (a) and (b), have 2 to 12, preferably 4 to 12 hydrophobic, only carbon and hydrogen-containing substituents with at least 5, preferably 8 to 22, carbon atoms , e.g. B. C 5 -C 2 cycloalkyl or C e -C lo aryl, alkaryl or aralkyl radicals.
  • Preferred hydrophobic substituents are, however, alkyl or alkenyl radicals which are generally derived from fatty acids having at least 6, preferably 8 to 22, carbon atoms.
  • the type of linkage with which these hydrophobic substituents are bonded forms a further characteristic of the sizing agents (A).
  • the connecting members via which at least two of the hydrophobic groups are connected, namely preferably have 2 to 18 carbon atoms and at least 2 heteroatoms each, preferably at least 2 nitrogen atoms in the main chain. Links each having 2 to 12 carbon and two nitrogen atoms are preferred.
  • the sizing agents contain 1 to 5 connecting members of the type specified.
  • Sizing agents (A) of the type indicated which are preferably used have molecular weights of from about 1,000 to about 4,000.
  • R, and R, ' are identical or different and each represent a hydrophobic substituent with at least 5 carbon atoms, provided that at least one of the radicals R 1 and R,' has at least 8 carbon atoms.
  • Dimers of the ketenes of the formulas are preferred and wherein R 2 and R 2 'are the same or different and are each alkyl or alkenyl having 5 to 22 carbon atoms, cycloalkyl having 5 to 12 carbon atoms or aryl, alkaryl or aralkyl having 6 to 10 carbon atoms, provided that at least one of the radicals R 2 and R 2 'has at least 8 carbon atoms.
  • R 2 and R 2 in the definitions of R 2 and R 2 , in the formulas (3) and (4) as representatives of C S -C 12 cycloalkyl z.
  • B cyclopentyl, cyclododecyl and especially cyclohexyl and as representatives of C 6 -C 10 aryl, alkaryl or aralkyl z.
  • the unsaturated or saturated C 6 -C 22 , preferably C 8 -C 22 fatty acids from which the ketenes of the formulas (5) and (6) are derived are, for. B. capronic, preferably caprylic, capric and arachic acid, especially lauric, myristic, palmitic, stearic and behenic acid or myristoleic, palmitoleic, elaeostearic, clupanodonic acid, especially oil, elaidic, erucic , Linoleic and linolenic acid. Lauric, palmitic, stearic, oleic and behenic acids are of particular importance here. Stearic acid is the focus of interest and is mainly used in combination with the other last-mentioned fatty acids. Ketenes which are derived from industrial mixtures of the saturated and / or unsaturated fatty acids mentioned are particularly preferred.
  • ketene dimers of the type specified are known per se and, for. B. described in U.S. Patent 4,317,756. Their manufacture, e.g. B. from the corresponding acid halides, especially fatty acid chlorides, and strong tertiary bases, especially trialkylamines, z. B. disclosed in U.S. Patent 2,383,863.
  • R has the meaning given.
  • cyclic representations for ketene dimers are also possible, that of the formula correspond in which R I and R I 'are the same or different and have the meaning given.
  • Component (b) from which the sizing agent (A) is obtainable are aliphatic, cycloaliphatic, aromatic, araliphatic or heterocyclic di- or oligoamines with 2 to 6 nitrogen atoms and 2 to 36 carbon atoms.
  • the oligoamines are primarily aliphatic amines, in particular polyalkylene polyamines with a maximum of 6 nitrogen atoms and 2 or 3 carbon atoms in each alkylene bridge member.
  • aromatic or araliphatic bridge members preferably having 6 to 16 carbon atoms or heterocyclic bridge members, preferably the piperazine series, as well as aliphatic bridge members having preferably 2 to 8 carbon atoms or cycloaliphatic bridge members having preferably 5 to 12 carbon atoms are possible between the two nitrogen atoms .
  • a 1 is alkylene, hydroxyalkylene or alkenylene, it is a matter of both branched and straight-chain bridge members.
  • Alkenylene radicals generally have 3 to 8 carbon atoms and 3 or 2 double bonds or preferably only one double bond. Alkylene is preferred over alkenylene and generally has 2 to 9, in particular 2 to 6, carbon atoms. Alkylene radicals can be unsubstituted or substituted by preferably at most 2 hydroxyl groups, in particular only one hydroxyl group. Such hydroxyalkylene residues are generally straight-chain. Cyclodecylene, cyclododecylene and especially cyclopentylene and in particular cyclohexylene may be mentioned as representatives of cycloalkylene radicals.
  • D 1 is an alkyl or alkenyl radical, it is preferably derived from the above-mentioned C 6 -C 22, preferably C 8 -C 22 fatty acids.
  • D 1 preferably represents alkyl or alkenyl radicals only insofar as A 1 is alkylene.
  • Ethylene is the meaning of E 1 and E 1 ' prefers.
  • n and n 2 each represent 1 or 2 and n 3 and n 4 each represent 1.
  • Preferred representatives of the formula (9.1) are toluylene and especially aflem xylylene and phenylene and the formula (9.2) preferably represents diphenylene ether.
  • di- or oligoamines which are of primary interest, correspond to the formula wherein A 2 is unsubstituted, straight-chain or branched alkylene or straight-chain alkylene substituted by hydroxy with 2 to 9 carbon atoms, cyclopentylene, cyclohexylene, phenylene, tolylene, xylylene, diphenylene ether, or D 2 is hydrogen, or if A 2 is alkylene, D 2 is also an alkyl or alkenyl radical derived from a fatty acid having 8 to 22 carbon atoms and m is an integer from 1 to 4, and in particular of the formula wherein A 3 is unsubstituted or substituted by at most one methyl or hydroxyl radical, straight-chain alkylene with a total of 2 to 6 carbon atoms, cyclohexylene, phenylene, diphenylene ether, xylylene or the rest of the formula (10.1), D 3 is hydrogen or, if A 3 is alkylene
  • the sizing agents (A) used according to the invention are characterized in that they are obtainable from the above-mentioned ketene dimers as component (a) and di- to oligoamines as component (b).
  • dimers of the ketenes of the formulas (1) and (2) or ketene dimers of the formula (1.1) or (1.2) are used as component (a) and di- or oligoamines of the formula (9) are used as component (b)
  • the sizing agents (A) or their salts correspond to one of the probable formulas where formula (12) applies if diamines are used as starting component (a) and formula (13) applies if oligoamines are used as starting component (a), and in formulas (12) and (13)
  • reaction preferably 1 to 1.1 equivalents, in particular 1.0 equivalent, per mole of component (a) are used per mole of component (b), the reaction generally being in the melt or preferably in at least one organic solvent, ie. H. in a single solvent or in a solvent mixture, at preferred temperatures of about 10 to about 140 ° C.
  • the solvents used must be each of the starting components (a) and (b) as well as the end product, i.e. H. be inert to the reaction products from (a) and (b).
  • a solvent such.
  • B. optionally halogenated hydrocarbons into consideration, which have a boiling point of at most 140 ° C, preferably between about 80 ° and about 140 ° C, such as benzene, especially toluene, chlorobenzene, o-, m- and p-xylene, a technical Xylene mixture or mixtures of the hydrocarbons mentioned are preferred. however, lower boiling, e.g. B.
  • halogenated hydrocarbons for example dichloroethane, carbon tetrachloride or especially chloroform are preferred. It is particularly expedient to carry out the reaction at the reflux temperature of the solvent of the type specified in each case.
  • the sizing agents Before they are used as component (A) in the paper sizing process according to the invention, the sizing agents generally do not need to be cleaned and recrystallized after production, but can generally be used directly.
  • the sizing agent (A) and the retention agent (B) are added separately (in any order) to the fiber suspension in the process according to the invention for sizing paper or cardboard, it is expedient to use the sizing agent partially in salt form. If necessary, such salts can be obtained by, after the reaction of components (a) and (b) has ended, the reaction products obtained by adding, inter alia, an alkylamine or alkanolamine having a total of at most 6 carbon atoms, for. B.
  • an alkali metal hydroxide e.g. As potassium or especially sodium hydroxide or especially ammonia usually used in the form of their diluted, about 1 to 10 weight percent aqueous solution.
  • reaction products of the formula (12) or (13) it is expedient to use at most 2 mol, especially at most 1 mol, preferably 0.1 to 0.9, in particular 0.1 to 0.7 mol of ammonia or alkali metal hydroxide per group of the formula present of the reaction products of the formula (12) or (13).
  • the reaction products thus present as salts correspond to the formula (12) or (13), the acidic groups at least partially into the corresponding anions are transferred, the negative charge S of which is neutralized by the corresponding amine, ammonium or alkali metal cations.
  • the paper sizing process according to the invention always uses a polymeric, cationic retention agent (B) which generally has a molecular weight of at least 1,000, especially at least about 2,500, preferably from about 2,000 to about 2,000,000, more preferably from about 5,000 to about 2,000,000.
  • Retention agents with molecular weights in the range of 10,000 to 100,000 are particularly preferred. In principle, any commercially available retention agent can be considered for use in the process according to the invention.
  • Examples of conventional retention agents (B) which are particularly suitable for use together with the sizing agent (A) in the paper sizing process according to the invention are polyalkyleneimines, epihalohydrin adducts of reaction products from polyalkylene polyamides . NEN and from aliphatic dicarboxylic acids or from reaction products from polyalkylene polyamines, from dicyandiamide and optionally from unesterified or esterified with alkanols, organic dicarboxylic acids.
  • Preferred epichlorohydrin adducts of reaction products of polyalkylene polyamines and aliphatic dicarboxylic acids are r.
  • Preferred cationically modified starches and carbohydrates from locust bean or guar gum are alkylene oxide adducts of these starches or carbohydrates, the alkylene oxide used having 2 or 3 carbon atoms in the alkylene radical and quaternary ammonium groups.
  • Copolymers based on polyamide amines have molecular weights of 10 3 to 10 5 , preferably 10 3 to 10 ° and are, for. B.
  • reaction products from epihalohydrins and polymerized diallylamines preferably have molecular weights of 1,000 to 2,000 and are e.g. For example, see U.S. Patents 3,700,623 and 4,279,794.
  • retention agents (B) which are in the foreground of interest for use together with the sizing agents (A) in the paper sizing process according to the invention, is a maize or potato starch modified with a propylene oxide containing quaternary ammonium groups, the 25% strength of which is suspended in distilled water at 20 ° C has a pH of 4.2 to 4.6, a polyethyleneimine which has a molecular weight of 10,000 to 100,000, an epichlorohydrin adduct of a reaction product of triethylene tetramine and dicyandiamide, an epichlorohydrin adduct of a reaction product of diethylene triamine, dicyandiamide and dimethyl adipate , a reaction product of dicyandiamide, formaldehyde, ammonium chloride and ethylenediamine, an epichlorohydrin adduct of a poly-N-methyldiallylamine and a copolymer of adipic acid and dimethylamino-
  • 0.02 to 3, preferably 0.1 to 3, in particular 0.2 to 0.8, percent by weight of the sizing agent (A) and 0.02 to 3, preferably 0.1 to 3, in particular 0.2, are generally used up to 0.4 percent by weight of the retention agent (B), based in each case on the dry matter of (A) and (B) and on the solids content of the fiber suspension.
  • sizing agent (A) and the retention agent (B) are sufficient only for the so-called “size press control", which cannot be determined with conventional sizing tests (see, for example, the article "Control and understanding of size press pickup by DR Dill in the journal TAPPI (Proceedings of the Technical Association of the Pulp and Paper Industry), Volume 57, No. 1 of January 1974, pages 97 to 100).
  • the fiber suspension to which the sizing agents (A) and the retention agents (B) are added, generally has a solids content of 0.1 to 5, preferably 0.3 to 3, in particular 0.3 to 1 percent by weight and a Schopper- Riegler freeness from 20 to 60 °, preferably 20 to 45 °, in particular 25 to 35 °. It usually contains pulp, especially those made of softwood, e.g. B. pine wood, or hardwood, d. H. Hardwood z. B. beech wood, which by conventional methods, for. B. the sulfite or especially the sulfate process. In addition, the fiber suspension may contain groundwood. Waste paper containing alum can also be contained in the fiber suspension.
  • the fiber suspension can also contain organic or mineral fillers.
  • organic fillers come u. a. synthetic pigments, e.g. B. polycondensation products of urea or melamine and formaldehyde with large specific surfaces, which are in highly dispersed form and u. a. in British patents 1,043,937 and 1,318,244 are described as mineral fillers and. a. Montmorillonite, titanium dioxide, calcium sulfate and especially talc, kaolin and / or chalk (calcium carbonate).
  • the fibrous suspension contains 0 to 40, preferably 5 to 25, in particular 15 to 20 percent by weight, based on the solids content of the fibrous suspension, of dry matter of the fillers of the type specified.
  • the pH of the fiber suspension can be in a wide range, z. B. Values from 3.5 to about 10 may be present.
  • alkaline fiber suspensions are obtained with a pH of about 7 to about 9, preferably 7.5 to 8.5.
  • Acidic fiber suspensions with a pH of 3.5 to 7, preferably 5 to 7, in particular 5 to 6, can in the absence of calcium carbonate by adding acids, e.g. B. sulfuric or formic acid or especially z.
  • B. latent acidic sulfates such as aluminum sulfate (alum) can be obtained.
  • Fibrous suspensions that contain no filler can be used in a wide pH range of e.g. B. 3.5 to 10 are present.
  • Preferred are fiber suspensions, optionally by adding chalk have a pH of about 7 to about 9 and are advantageous insofar as possible signs of corrosion on the sensitive paper machines are excluded.
  • the fibrous suspension can also contain additives such as. B. starch or its degradation products. which increase the fiber / fiber or fiber / filler bond.
  • High molecular weight polymers of the acrylic acid series e.g. B. polyacrylamides with molecular weights above 1,000,000 can be added to the fiber suspensions as an aid to retain the finest cellulose fiber particles, with minimal amounts of about 0.005 to 0.02 percent by weight, based on the dry matter of the high polymer and the solids content of the fiber suspensions, being sufficient .
  • the fibrous suspension is processed further in a manner known per se on sheet formers or, preferably, continuously on paper machines of conventional design to give paper or cardboard. After drying at about 100 to 140 ° C for about 0.5 to 10 minutes, papers with a variable basis weight of z. B. 50 to 200 g / m 2 obtained.
  • the aqueous composition for carrying out the paper sizing process according to the invention contains, in addition to optional customary additives, the sizing agent (A), provided that the sizing agent (A) and the retention agent (B) are added separately to the fiber suspension.
  • the preparation preferably contains the sizing agent partly in the form of its salts (obtained using, for example, ammonia, an alkyl- or alkanolamine or an alkali metal hydroxide of the type mentioned in the ratios given above).
  • such compositions contain 5 to 30, preferably 5 to 20 percent by weight of dry matter of the sizing agent, which is partially in salt form, based on the weight of the aqueous composition.
  • the aqueous compositions of the type mentioned may contain surface-active compounds, e.g. B. dispersants or further emulsifiers and / or water-soluble organic solvents.
  • surface-active compounds e.g. B. dispersants or further emulsifiers and / or water-soluble organic solvents.
  • dispersants and emulsifiers come, for. B. conventional lignin sulfonates, ethylene oxide adducts of alkylphenols, fatty amines, fatty alcohols or fatty acids, fatty acid esters of polyhydric alcohols, substituted benzimidazoles or condensation products of aromatic sulfonic acids and formaldehyde into consideration.
  • Other surface-active compounds are preferably the anionic surfactants, especially sulfate surfactants, e.g. B.
  • diethanolamine lauryl sulfate or ethoxylated lauryl sulfates Possible water-soluble, organic solvents are aliphatic ethers with 1 to 10 carbon atoms, e.g. B. dioxane, methylene glycol n-butyl ether or diethylene glycol monobutyl ether or alcohols with 1 to 4 carbon atoms, e.g. B. isopropanol, ethanol or methanol.
  • compositions are prepared in a conventional manner by combining the sizing agent (A) together with the retention agent (B) or the sizing agent (A) e.g. B. partially in the form of its salt alone either in the molten state or preferably in the solid state, in particular in powdered form, usually in the presence of glass beads and, if necessary, emulsifiers (in the case of sizing agents in the molten state) or dispersants (in the case of sizing agents in powder form) ) stirred at a maximum of 90 ° C, preferably about 50 to 85 ° C for emulsions, in particular at about 15 to 25 ° C for dispersions, storage-stable, homogeneous emulsions or preferably dispersions being obtained.
  • emulsifiers in the case of sizing agents in the molten state
  • dispersants in the case of sizing agents in powder form
  • the sizing agents together with the retention aids or the sizing agents which are partially present as salts are generally self-dispersing or self-emulsifying, the use of dispersing agents or emulsifying agents is generally not necessary. This also applies to the optional addition of solvents and / or surfactants, which are only used if the dispersions or emulsions have insufficient storage stability.
  • fiber suspensions of the most varied types can be processed in a simple manner with relatively small amounts of sizing and retention agent into paper, which has good sizing properties (ink floating time and above all water absorption according to Cobb).
  • the paper sized according to the process has good mechanical properties, ie good strengths, in particular good tear strength. Good reproducibility of the process is guaranteed.
  • pulp suspensions containing wood pulp or waste paper can be processed.
  • the compatibility of the sizing agent used according to the invention with a wide variety of fillers and their additives, such as. B. kaolin or alum in acidic areas of the fiber suspensions is advantageous.
  • the sizing agents also have advantageous compatibility with optical brighteners.
  • the degree of whiteness of the glued paper is not significantly influenced by the gluing and can even u. U. be improved.
  • the surprisingly high storage stability of the sizing agent dispersions of the type indicated is of great advantage.
  • This advantageous storage stability applies both to dispersions of sizing agents (A) alone and to dispersions of mixtures of sizing agents (A) and retention aids (B).
  • Example 2 The procedure described in Example 1 is followed, except that 51 parts (0.1 mol) of the dimer from the ketenes of the formula (16) and (17) and 3.6 parts (0.025 mol) of triethylenetetramine are used. 54.6 parts (100% of theory) of the crude reaction product of the formula are obtained
  • Example 1 The procedure described in Example 1 is followed, except that 35.4 parts (0.07 mol) of the dimer from the ketenes of the formulas (16) and (17) and 2.7 parts (0.014 mol) of tetraethylene pentamine are used. 38.1 parts (100% of theory) of the crude reaction product of the formula are obtained q and q 'as indicated in formula (18).
  • Example 1 The procedure described in Example 1 is followed, except that 35.4 parts (0.07 mol) of the dimer from the ketenes of the formulas (16) and (17) and 2.8 parts (0.012 mol) of pentaethylene hexamine are used. 38.2 parts (100% of theory) of the crude reaction product of the formula are obtained
  • Example 2 The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 1.5 parts (0.025 mol) of 1,2-diaminoethane are used. 26.8 parts are obtained (100% of theory) of the raw reaction product of the formula q and q 'as indicated in formula (18).
  • Example 2 The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 2.2 parts (0.017 mol) of bis (3-aminopropyte) are used. amine a. 27.5 parts (100% of theory) of the crude reaction product of the formula are obtained
  • Example 2 The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 2.2 parts (0.013 mol) of 1,2-bis (3 -aminopropylamino) -ethane. 27.5 parts (100% of theory) of the crude reaction product of the formula are obtained
  • the crude product mixture is recrystallized from acetone.
  • the recrystallized product mixture is in the form of a yellowish powder. It is also free of unreacted ketene dimer.
  • Example 2 The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 2.7 parts (0.025 mol) of 1,3-diaminobenzene are used. 28.0 parts (100% of theory) of the crude reaction product of the formula are obtained
  • Example 2 The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 5.0 parts (0.025 mol) of 4,4'-diamino diphenyl ether. 30.3 parts (100% of theory) of the crude reaction product of the formula are obtained
  • Example 2 The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 2.3 parts (0.025 mol) of 1,3-diamino-2 are used -propanol. 27.6 parts (100% of theory) of the crude reaction product of the formula are obtained
  • Example 2 The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 1.8 parts (0.025 mol) of 1,2-diaminopropane are used. 27.1 parts (100% of theory) of the crude reaction product of the formula are obtained
  • the crude product is recrystallized from ethyl acetate for analysis purposes.
  • the recrystallized product is in the form of a colorless powder. It is also free of unreacted ketene dimer.
  • Example 2 The procedure described in Example 1 is followed, except that 25.3 parts (0.05 mol) of the dimer from the ketenes of the formulas (16) and (17) and 2.9 parts (0.025 mol) of 1,4-diaminocyclohexane are used. 28.2 parts (100% of theory) of the crude reaction product of the formula are obtained q and q 'as indicated in formula (18).
  • the percentages relate to dry matter of auxiliaries and fillers, based on the solids content of the fiber suspension.
  • Formulations of the sizing agent are prepared by in each case 7% of the reaction products indicated as a crude product in powder form as a sizing agent, each with 3.5% POLYMIN P ® (polyethyleneimine having a molecular weight from 10,000 to 100,000) as a retention agent in the presence of deionized water and glass beads having a diameter of 2 mm.
  • POLYMIN P ® polyethyleneimine having a molecular weight from 10,000 to 100,000
  • the dispersions obtained are homogeneous, pourable and stable in storage. The percentages relate to the dry matter of sizing and retention agent, based on the total weight of the formulation.
  • the aqueous formulation of the sizing agent and the retention aid is added to the fibrous suspension in such a way that an amount of 0.5% dry matter of the sizing agent, based on the solids content of the fibrous suspension, is formed.
  • the fiber suspension is then processed in a laboratory sheet former to paper sheets which, after a first drying at 130 ° C. for 3 minutes, have a basis weight of 80 g / m 2 .
  • the paper sheet thus obtained is subjected to an additional heat treatment at 140 ° C for 3 minutes.
  • Both surfaces of the paper sheets obtained ie the surface obtained on the screen side of the sheet former and the opposite or top side, are checked for their sizing properties.
  • the water absorption according to Cobb is measured after 30 seconds of exposure (WA Cobb 30 ) according to DIN 53 132.
  • the results of the WA Cobb 30 measurements in g / m 2 of the sieve side (SS) and top side (OS) before and after the heat treatment at 140 ° C and before and after storage for one day at 20 ° C are in the table below I specified.
  • WA Cobb 30 values over 100 correspond to a completely unsatisfactory sizing of the paper.

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  • Paper (AREA)
  • Electroluminescent Light Sources (AREA)
  • Inert Electrodes (AREA)
  • Cell Separators (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Claims (6)

1. Procédé pour l'encollage du papier ou du carton, dans lequel on ajoute, dans un ordre quelconque ou simultanément, à des suspensions aqueuses de matières fibreuses, contenant éventuellement des charges, au moins
(A) un agent d'encollage anionique hydrophobe et
(B) un agent de rétention polymère cationique,

caractérisé par le fait que l'agent d'encollage (A) utilisé peut être préparé à partir
(a) de dimères de cétènes, dont les substituants hydrophobes, qui ne contiennent que du carbone et de l'hydrogène, comportent au moins 5 atomes de carbone, et
(b) de di- ou oligo-amines ayant de 2 à 6 atomes d'azote et de 2 à 36 atomes de carbone.
2. Procédé selon la revendication 1, caractérisé par le fait que l'on utilise comme composant (a) un dimère des cétènes de formules R1―CH=C=0 et R1'―CH=C=0, dans lesquelles R1 et Ri' sont identiques ou différents l'un de l'autre et représentent chacun un substituant hydrophobe ayant au moins 5 atomes de carbone, étant entendu qu'au moins un des restes R1 et Ri' comporte au moins 8 atomes de carbone.
3. Procédé selon l'une des revendications 1 ou 2, caractérisé par le fait que l'on utilise comme composant (b) une di- ou oligo-amine de formule D1―NH―A1―NH2, dans laquelle A1 représente un radical alkylène, hydroxyalkylène, alcénylène ou cycloalkylène ayant 12 atomes de carbone au maximum, un radical naphtylène ou un reste correspondant à l'une des formules
Figure imgb0072
Figure imgb0073
D1 représente un atome d'hydrogène ou un reste alkyle ou alcényle dérivant d'acides gras ayant de 8 à 22 atomes de carbone ; El et E1' représentent chacun un groupe éthylène ou n-propylène ; n1, nz, n3 et n4 représentent chacun 1, 2 ou 3 ; et m est un nombre entier allant de 1 à 4.
4. Composition aqueuse pour la mise en oeuvre du procédé selon l'une des revendications 1 à 3, l'agent d'encollage (A) et l'agent de rétention (B) étant ajoutés séparément, dans un ordre quelconque, à la suspension de matières fibreuses, caractérisée par le fait qu'elle contient l'agent d'encollage (A) au moins en partie sous forme de sels, et éventuellement des additifs usuels.
5. Composition aqueuse pour la mise en œuvre du procédé selon l'une des revendications 1 à 3, dans lequel l'agent d'encollage (A) et l'agent de rétention (B) sont ajoutés simultanément à la suspension de matières fibreuses, caractérisée par le fait qu'elle contient
(A) de 2 à 40 % en poids d'agent d'encollage,
(B) de 0,1 à 20 % en poids d'agent de rétention,


par rapport, respectivement, à la matière sèche de (A) et de (B) et au poids de la composition aqueuse, et éventuellement des additifs usuels.
6. Utilisation du composant (A) selon l'une des revendications 1 à 3, pour l'encollage du papier ou du carton.
EP83810373A 1982-08-25 1983-08-19 Procédé d'encollage du papier avec des agents d'encollage anioniques hydrophobes et des agents de rétention cationiques Expired EP0105028B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83810373T ATE23584T1 (de) 1982-08-25 1983-08-19 Verfahren zum leimen von papier mit anionischen, hydrophoben leimungsmitteln und kationischen retentionsmitteln.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH506282 1982-08-25
CH5062/82 1982-08-25

Publications (2)

Publication Number Publication Date
EP0105028A1 EP0105028A1 (fr) 1984-04-04
EP0105028B1 true EP0105028B1 (fr) 1986-11-12

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EP83810373A Expired EP0105028B1 (fr) 1982-08-25 1983-08-19 Procédé d'encollage du papier avec des agents d'encollage anioniques hydrophobes et des agents de rétention cationiques

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Country Link
EP (1) EP0105028B1 (fr)
JP (1) JPS5959998A (fr)
AT (1) ATE23584T1 (fr)
CA (1) CA1238324A (fr)
DE (1) DE3367639D1 (fr)
FI (1) FI74075C (fr)
ZA (1) ZA836255B (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0673989B2 (ja) * 1985-02-01 1994-09-21 富士写真フイルム株式会社 感熱記録紙
DE4032660A1 (de) * 1990-10-15 1992-04-16 Basf Ag Verfahren zur masseleimung von papier, pappe und karton
US5886223A (en) * 1998-04-08 1999-03-23 American Cyanamid Company Process for the preparation of substituted β-ketoanilide compounds
US6175022B1 (en) * 1998-12-30 2001-01-16 Hercules Incorporated Alcohol-terminated ketene multimer sizing agents
DE102010038887A1 (de) * 2010-08-04 2012-02-09 Wacker Chemie Ag β-Ketocarbonylquatverbindungen und Verfahren zu deren Herstellung
EP4400554A1 (fr) * 2022-11-09 2024-07-17 Daikin Industries, Ltd. Agent répulsif

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2323938A (en) * 1940-07-25 1943-07-13 Du Pont Product and synthesis thereof
US2462358A (en) * 1946-06-21 1949-02-22 Eastman Kodak Co Amides of acetoacetic acid and process for their preparation
US2961367A (en) * 1957-02-27 1960-11-22 Hercules Powder Co Ltd Sized paper and method of making same
US3736178A (en) * 1971-01-14 1973-05-29 Mc Graw Edison Co Cellulose material treated with a cellulose derivative,diglycolamine and an alkylketene dimer
US4317756A (en) * 1977-08-19 1982-03-02 Hercules Incorporated Sizing composition comprising a hydrophobic cellulose-reactive sizing agent and a cationic polymer

Also Published As

Publication number Publication date
ATE23584T1 (de) 1986-11-15
FI74075C (fi) 1987-12-10
JPS5959998A (ja) 1984-04-05
FI832999A0 (fi) 1983-08-22
DE3367639D1 (en) 1987-01-02
ZA836255B (en) 1985-02-27
CA1238324A (fr) 1988-06-21
EP0105028A1 (fr) 1984-04-04
FI832999A (fi) 1984-02-26
FI74075B (fi) 1987-08-31

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