FI64677B - LIMNINGSKOMPOSITION OCH FOERFARANDE FOER LIMNING AV PAPPER - Google Patents

Description

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Ma 11 UTLÄGGNINGSSKRIFT 6467 / -¾¾ C (45) ^ exam sylr .. ·: '.: · / 1? 12 1933 ^ T ^ (51) Kv.lk. ^ Int.Cl. ^ D 21 H 3A6 FINLAND - FINLAND (21) P «enUIh» kerou «- PaMnttnsöknlng 800027 (22) Hikemlipllvl— An * öknlng * dag 04.01. Ö0 ^ ^ (23) Alkuplivi - Glttighcodag 04. OH. Gö (41) Become public - Bllvlt off «ntllg qj ^

National Board of Patents and Registration Date of publication Date of publication. - J '',

Patent · och registrentyrelaen '' AnsOksn utlagd ech utl.skrlften publlcerad .31.UÖ.C., (32) (33) (31) Claim claimed privilege — Begird prlorltet (Ti) Hercules Incorporated, Wilmington, Delaware 19899, USA (US) (72) David Howard Dumas, Wilmington, Delaware, USA (US) (7 * 0 Oy Heinänen Ab (5 * 4) Adhesive mixture and method for gluing paper -

The present invention relates to an adhesive mixture in the form of an aqueous emulsion based on certain cationic polymers and to a process for impregnating paper 1 i using this 1 i detachable mixture.

In particular, the invention relates to the production of sizing paper and sizing board in which the sizing agent used is a hydrophobic, cellulose-reactive sizing agent, such as a ketene dimer-based sizing agent, and in which certain cationic polymers are further used as accelerators. that the cellulose-reactive sizing agent be used alone.

U.S. Pat. No. 3,840,4B proposes the use of water-soluble, heat-curable plastic compounds. They are obtained by a reaction involving Oisandiamide, an ammonium salt, formaldehyde and a water salt of a water-soluble aminoDO1amide, such as a water-soluble aminopolyamide 64677 obtained as a reaction product between adipic acid and diethylenetriamine. The plastic compositions or combinations of materials of U.S. Patent No. 3,840,486 accelerate the sizing process performed on paper using cellulose-reactive sizing agents such as ketene dimers, acid anhydrides, and organic isocyanates. By using the plastic combinations of materials of U.S. Patent No. 3,840-4-6 in conjunction with the aforementioned paper sizing agents, a greater post-paper gluing process can be achieved than would be accomplished using equivalent amounts of glue alone.

UK Patent 1,373,788 proposes the use of dicyandiamide-formaldehyde condensates as accelerators for the adhesion of ketene dimer sizing agents.

U.S. Pat. No. 3,409,500 proposes a process for making sized paper, which process comprises treating an aqueous anionic dispersion of carboxylic anhydride particles used in sizing hydrophobic organic and cellulose-reactive paper from a cellulose fiber suspension of the cellulose fiber. a native cationic polyamine having a molecular weight greater than 1000, wherein the amount of this polyamine is at least sufficient to cause the anhydride particles to adhere to the fibers and accelerate the rate at which this anhydride develops its sizing properties to cellulose fibers at about 88-121 ° C; a web that is dried at temperatures of 88-121 ° C.

U.S. Pat. No. 3,409,500, column 3, lines 61-70, discloses that the most effective cationic polymers are adipic acid dust 1 polyene polyamide-epi chlorohydrin polymers prepared by condensing adipic acid with polyalkylene. with polyamine to form polyamide-polyamine, after which this polymer is reacted with epichlorohydrin. Methods for making this type of agent have been proposed in U.S. Patent Nos. 2,926,116, 2,926,154 and 3,329,657.

The cationic polymers disclosed in U.S. Patent Nos. 3,646,767 and 2,926,154 have been found in U.S. Patent No. 3,463,077 to be useful adhesion aids for ketene dimer sizing agents, resulting in a better sizing effect compared to cationic starch sizing agents.

U.S. Pat. No. 3,575,796 proposes a method for gluing paper and pressed paperboard products, which method comprises intensively dispersing an aqueous pulp slurry or, alternatively, applying to the formed paper web an aqueous emulsion having an N-substituted azidirine-reacted compound prepared by an alpha-, beta-ethylenically unsaturated compound such as distearyl maleate and, on the other hand, an alkyleneimine such as ethyleneimine center. The sizing agent can be uniformly dispersed with a cationic emulsifier such as cationic starch to better adhere to the fibers. In U.S. Pat. No. 3,575,796, column 4, lines 1-44, it is proposed to use other cationic agents to promote the adhesion of the finishes of the invention, which are cationic thermosetting plastics such as reaction products with dibasic acids, polyalkylenem polyamines and epihalohydrins. Lines 45-62 of column 4 of this patent also show that cationic substances are also useful as emulsifiers for the sizing agent.

U.S. Patent No. 3,666,512 discloses compositions of matter containing hydrophobic carboxylic anhydrides reactive with cellulose suitable for sizing paper, and a catalyst that accelerates the rate at which the anhydride acquires its sizing properties after it decomposes. . The catalyst or accelerator of the anhydride sizing agent is a water-soluble cationic salt of a cellulose-substantiated water-soluble polyamine. Suitable cationic substances are shown in the table in column 7 of this patent publication. These cationic substances include aminopolyamide-epichlorohydrin plastic, wherein the aminopolyamide is derived from diethylenetriamine and ndi-p-nitric acid.

4 64677

U.S. Pat. .

U.S. Patent 3,046,186 discloses the preparation of sizing paper using a cholester addition process in which an aqueous cationic dispersion of a hydrophobic ketene dimer is added to an aqueous suspension of cellulose fibers. The glued paper is prepared by forming an aqueous suspension of cellulose pulp fibers and adding to it an emulsion of a hydrophobic ketene dimer in an aqueous medium containing a cationic dispersant, which may be monomeric or a high molecular weight hydrophilic or water-soluble basic nitrogen. Dispersants are disclosed in columns 3 and 4 of U.S. Patent 3,046,186.

U.S. Patent 3,006,806 proposes the use of an organic cationic polymer with a ketene dimer in paper sizing. Suggested polymers include melamine-formaldehyde plastics (as described in U.S. Patent Nos. 2,345,543 and 2,559,220), urea-formaldehyde plastics (as described in U.S. Patent No. 2,657,132), cationic starch, guanidine-formaldehyde vit (U.S. Patent 2,745,744), alkylene polyamine-halohydrin plastics (as described in U.S. Patent 2,601,597) and cationic urea-formaldehyde plastics (as disclosed in UK Patents 675,477 and 677,184). .

U.S. Pat. No. 3,084,092 discloses paper made using a hydrophobic organic isocyanate in combination with an amino mol. The sole oils described in U.S. Pat. No. 3,084,092 are polyfunctional halohydrin resins described in U.S. Pat. No. 2,595,935, dicyandiamide-formaldehyde amine polymers are described in U.S. Pat. , po lyami i ni - pc lyarni di -1 i nenari s ia polymers are described in U.S. Patent No. 2,729,560, poly-

II

Li

64677 I

mers formed from a copolymer of acrylamide and acrylic acid in a molar ratio of 9: 1 as well as sulfonated dimethylurea resins are described in U.S. Patent Nos. 2,528,840 and amino acid methylamine in U.S. Pat.

U.S. Patent No. 3,248,353 discloses water-soluble, cationically substantial, and chemically stable polymers having long molecular chains crosslinked together and useful as fixing aids in papermaking. The polymers are prepared by providing a substantially complete reaction to the point near the gel of the epichlorohydrin with a large relative amount of a water-soluble bifunctional amine such as a chain-forming component and a smaller relative amount of a component with a greater than a functional water-soluble multifunctional amine. which forms secondary amine bonds in this molecular chain, wherein the ratio of epi-chlorohydrin functionality to the total functionality of these amines is substantially 1: 1. Bifunctional amines include methylamine, ethylamine, ethanolamine, propylamine, [1, N'-dimethylethylenediamine, piperazine and aniline (see column 2, lines 3-16). Multifunctional amines have been proposed in column 2, lines 17-25 and 32-38, which are amines such as ammonium, ethylenediamine-N-methylenethylenediamine, diethylenetriaminine, tetraethylenepentamine, p-phenylenediamine, p, p '- 1-bis.ni-amine. , 3-diamino-2-propanol. Polymers are useful adjuvants for higher levels of fatty acid isocyanates, higher levels of fatty acid ketene dimers, and higher levels of fatty acids (see column 3, lines 10-51).

The sizing composition of the present invention is characterized in that it comprises a hydrophobic cellulose-reactive sizing agent and a cationic polymer selected from the group consisting of a cationic polymer prepared by reacting an epihalohydrin with a condensate which is disulfated by condensing with aminopropylpiperazine, or a cationic polymer prepared by condensing epihalohydrin with bis-aminopropyl-piperazine.

64677 The process for gluing paper internally or externally which is the subject of the present invention is further characterized in that the sizing composition used contains a hydrophobic cellulose-reactive sizing agent selected from the group consisting of ketene dimers, acid anhydrides and organic isocyanates, and the sizing composition further comprises which is a cationic polymer selected from the group consisting of a cationic polymer prepared by reacting epihalohydrin with a condensate prepared by condensing bis-aminopropylpiperazine and dicyandiamide with bis-aminopropylpiperazine and dicyandamide. in a molar ratio in the range of about 0.5: 1 to 1: 0-5, or with a condensate prepared to condense bis-aminopropylpiperazine and cyanamide in a molar ratio of bis-aminopropylpiperazine to cyanamide in the range of about 0.5 : 2-1: 1, the amount of epihalohydrin used is in the range of 0.3 to 2 moles per mole of amino nitrogen in the condensate, or a cationic polymer prepared by condensing bis-aminopropylpiperazine and epihalohydrin in a molar ratio of bis-aminopropylpiperazine to epihalohydrin in the range of 1: 3 to 1: The amount of the gluing event accelerator is such that it is sufficient to improve the gluing effect of the gluing agent on the paper exiting the paper machine.

Preferred sizing compositions are aqueous emulsions containing an emulsifier, a cellulose-reactive sizing agent and a cationic polymer as described above. The term "emulsion" as used herein means either a liquid-in-liquid type or a solid-in-liquid type dispersion.

The term "sizing effect on paper exiting the paper machine" refers to the level of sizing achieved when the paper leaves the paper machine, and not to the final level reached after the reaction between the sizing agent and the cellulose has been completed.

Joi 'u’san kun sr; a rv; A kt i oky ky J. s t e n hydrophobic absorbent water emulsions are already known in the art and 7 64677 are commercially available. To prepare the novel sizing compositions of this invention, an amount of cationic polymer sufficient to increase the sizing effect of the sizing agent is thoroughly mixed into the emulsion. It has been found by assays that 0.25 to 3 parts by weight of cationic polymer per part by weight of hydrophobic, cellulose-reactive finishing agent present in the emulsion gives good results.

The novel sizing compositions according to the present invention are thus aqueous emulsions which contain, as an essential ingredient, a hydrophobic, cellulose-reactive finishing agent such as a ketene dimer, at least one emulsifier and at least one new cationic polymer as an accelerator. The amount of emulsifier (s) used is such that it is sufficient to provide and maintain an emulsion that is stable over a relatively long period of time and is suitable for use by those skilled in the art.

The emulsifier used may be selected from those emulsifiers commonly used in the preparation of emulsions from cellulose-reactive sizing agents. Such emulsifiers are known per se in the art and include cationic starches, which are water-soluble starches having sufficient cationic amino groups, quaternary ammonium groups, or other cationic groups to make the starch entirely native to cellulose. An example of such a cationic starch is the cationic, amine-modified starch described in UK Patent 903,416.

Another emulsifier that can be used is the water-soluble cationic, thermosetting plastic prepared by reacting epichlorohydrin with a water-soluble aminopolyamide made from dicarboxylic acid and polyethylene polyamine. Plastics of this type are described in UK Patent Publication B65 727.

Those cationic polymers that are useful as gluing event accelerators are described below.

64677

The cationic polymer (1) is a nitrogen-containing dust polymer prepared by first condensing bis-aminopropylpiperazine with dicyandiamide or cyanamide. The condensation reaction results in a low molecular weight polymer which is then reacted with an epihalohydrin such as epichlorohydrin.

The cationic polymer (1) is prepared in two steps. First, the prepolymer condensate is prepared by condensing bis-aminopropylpiperazine (BAPP) and dicyandiamide in a molar ratio of BAPP to dicyandiamide in the range of about 0.5: 1 to 1:05. The recommended molar ratio is 1: 1. The reactants are mixed together and heated to a temperature in the range of about 150-220 ° C for 0.5-4 hours, with time varying inversely with temperature. Ammonia, evaporates during the reaction and the reaction is substantially complete when NH 4 ceases to evolve. The prepolymer in the aqueous medium is then reacted with epihalohydrin. The reaction with epihalohydrin is carried out at an elevated temperature, preferably in the temperature range of 50-80 ° C, until the viscosity of the reaction product is measured on a Gardner-Holdt scale between F and S. The amount of epihalohydrin used may be 0.3 to 2 moles, and preferably 1 to 1.5 moles per mole of amine nitrogen present in the prepolymer condensate. if cyanamide is used instead of dicyanamide, the molar amounts of cyanamide used should be twice the molar amount (s) of dicyandiamide.

In the following examples, all parts and percentages are parts by weight or percentages by weight unless otherwise indicated.

The following example illustrates the preparation of cationic polymer (1).

Example_1_ A 1 liter 3-neck round bottom flask equipped with a mechanical stirrer, heating mantle, thermostatic temperature controller and a condenser connected to a water cooling system was charged with 200 g (1 mole) of bis-aminopropylpiperazine -diarr.idia. Heating was started and continued to li 9 64677 160 ° C, whereupon ammonia evolved from the reaction mixture. The mixture was kept at 160 ° C for 3 hours during which time more than 1 mole of ammonia was recovered and then the reaction was quenched by the addition of 2-4 g of distilled water to give an aqueous dispersion with a total solids content of 44.4%. A 500 ml 3-necked, vortex-bottomed flask, also with a fourth large neck suitable for placing the pH on the electrode to monitor and adjust the reaction, was fitted with a mechanical stirrer, a condenser and a Spurlin-Spence viscometer (essentially a small-hole a tube fitted with a 5 ml container, which is filled by suction during the measurement and the time taken to reach a certain suction distance is measured). An aqueous solution of the condensation prepolymer 1) prepared above was charged to the reaction vessel (3 g) (50 g of prepolymer solids) (equivalent to 0.4 amine equivalents) and 87 g of distilled water to dilute the mixture to 25% solids. 46 g (0.5 mol) of epichlorohydrin were then added. At the beginning of the reaction, the pH of the mixture was 12.1. An exothermic or heat-generating reaction took place, which raised the temperature of the mixture to 60 ° C, after which the temperature of the mixture was maintained at 70 ° C by heating. The viscosity began to increase 45 minutes after the addition of epichlorohydrin to a pH of 7.0. The reaction mixture was heated for an additional 45 minutes, during which time the viscosity increased to 15 seconds using a Spurlin-Spence viscometer (corresponding to Gardner-Holdt viscosity N), then quenched with 234 g of distilled water and 14.4 g of formic acid, which lowered the pH of the product. to 4.0. The total amount of solids was 24.0%.

The cationic polymer (2) is a nitrogen-containing polymer obtained by condensing with an alkylenediamine epihalohydrin such as epichlorohydrin, wherein the molar ratio of alkylenediamine to epihalohydrin is 2: 1. This reaction product is reacted with a dicyandiamide or cyanamide in such a way as to form a low molecular weight polymer which is then reacted with an epi-halohydrin such as epichlorohydrin. Examples of alkylenediamines that can be used to prepare this cationic polymer (?) Include ethylenediamine, propylenediamine and hexamethylenediamine. Mixtures of two or more alkylamide amines may be used if desired.

10 64677

The cationic polymer [2) is prepared in three steps. First, the alkylenediamine is reacted with epihalohydrin in a molar ratio of 2: 1 at a temperature in the range of 50 ° C to 0 ° C for 1 to 3 hours (time vary inversely with temperature) to prepare the reaction product. This reaction product is then reacted with dicyandiamide at 15 ° C to 220 ° C for 0.5 to 4 hours, with the time varying inversely with temperature. the amount of dicyandiamide used is 1-2 moles for each mole of epichlorohydrin used in the reaction with the alkylene polyamine, with 1 mole being most preferred. This reaction product is then reacted with epihalohydrin at 2-2.5 moles per mole of epihalohydrin used in the reaction with α1-cyenediamine at temperatures of 25-7D ° C for 1-4 hours (time varies inversely). temperature).

If cyanamide is used instead of dicyandiamide, the molar amounts of cyanamides used are twice as high as the molar amount of dicyandiamide (Ct).

The following example illustrates the preparation of cationic polymer (2).

Example 2 A 500 ml round-bottomed 3-necked flask equipped with a heating mantle, a thermostatic regulator, a mechanical stirrer and a vertical condenser connected to water cooling was charged with 120 g of ethylenediamine (2 moles). This mixture was heated to 50 ° C and 92 g of epichlorohydrin (1 mol) was added dropwise over 2 hours. The temperature was allowed to rise to 60 ° C, after which it was raised to 80 ° C by heating. Dicyandiamide (64 g or 1 mole) was then added to the contents of the flask. The reaction mixture was heated to 150 ° C and maintained at this temperature for 2 hours. About 1.8 moles evaporated during the condensation reaction. 300 ml of water was added to make the reaction mixture 48% solids. 104 g of a 48% solids reaction mixture (50 g solids) was diluted with water to 25% solids, and 43 g of epichlorohydrin was added over 15 minutes. This reaction mixture was heated to 70 ° C and maintained at this temperature for 5 hours. The final product contained 32% by weight solids.

1 1 64677

The cationic polymer (3) is a nitrogen-containing polymer obtained by condensing 1,3-dicyanobenzene with polyalkylene polyamine to form a low molecular weight polymer. The resulting polymer is then reacted with an epihalohydrin such as epichlorohydrin. The polyalkylene polyamine used in the preparation of the cationic polymer (3) may be polyethylene polyamine, polypropylene polyamine, polybutylene polyamine and the like. Specific examples of such polyalkylene polyamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine and dipropylene triamine.

The cationic polymer (3) is prepared in two steps. First, 1,3-dicyanobenzene is condensed with poly (polyene) polyamine in a molar ratio of 1: 1 to give a condensation prepolymer. This condensation reaction is carried out at temperatures of 150-200 ° C for 1-4 hours. Time varies inversely with temperature. The condensation prepolymer is then reacted in an aqueous medium with epihalohydrin at an elevated temperature, preferably 50-90 ° C for about 1-4 hours. Time varies inversely with temperature. 1 mole of epihalohydrin is used for each mole of amine nitrogen present in the condensation prepolymer.

Example 3

The apparatus of Example 2 was used in this example.

54 g (G, 5 moles) of 1,3-dicyanobenzene and 51.5 g (0.5 moles) of diethylenetriamine were added to the flask to give a mixture which was heated to 165 ° C and maintained at this temperature for 4 hours. During this time, 0.5 moles of NH 4 evaporated. The reaction product was left at room temperature (about 23 ° C). 23 g of the reaction product (0.11 amine equivalents) were dissolved in 25 g of methanol, followed by the addition of 75 g of water, followed by 15 g (0.16 moles of epichlorohydrin), and the reaction mixture was heated to 90 ° C and maintained at this temperature for about 2 hours The product contained 29% by weight of solids.

The cationic polymer (4) is a nitrogen-containing polymer obtained by condensing bis-aminopropylpiperazine with an epihalohydrin such as epichlorohydrin.

64677

The cationic polymer (4) was prepared by a condensation reaction with bis-aminopropylpiperazine and epihalohydrin in a molar ratio of bis-aminopropylpiperazine to epihalohydrin in the range of 1: 3 to 1: 8 and preferably in a molar ratio of 1: 4. The reaction was carried out at temperatures of 50-90 ° C until the viscosity of the reaction product was such that it was between the limits F and S on the Gardner-Holdt scale. This usually requires 1-4 hours depending on the temperature used.

Example 4 In this example, the apparatus of Example 2 was used. 64 g (0.32 moles) of bis-aminopropylpiperazine were mixed with 354 g of water in a flask, and 125 g (1.34 moles) of epichlorohydrin was slowly added thereto over 15 minutes.

After the addition of epichlorohydrin, the temperature of the reaction mixture rapidly rose to 70 ° C and a cooling water bath was used to maintain the temperature at 70 ° C. When the addition of epichlorohydrin was complete, the cooling bath was removed and the temperature was maintained at 70 ° C using a heating mantle. The viscosity gradually increased over 1.5 hours to a viscosity of Gardner-Holdt N. The reaction was stopped by adding 398 g of water, 6 g of formic acid and cooling from the outside. The resulting solution contained 20% solids and had a pH of 5.

Acid anhydrides useful with cellulose-reactive sizing agents in papermaking are well known in the art and include (Λ) resin anhydride, cf. U.S. Pat. No. 3,582,464, (B) anhydrides of structural formula (I) wherein R 1 is a saturated or unsaturated hydrocarbon radical which is a straight or branched chain alkyl, aromatic substituted and alkyl substituted, alkyl substituted or alkyl substituted containing from 11 to 39 carbon atoms and fC) cyclic dicarboxylic anhydrides of structural formula 13 64677 O '

II

wherein R 'is -R' X05 wherein R 'is a dimethylene or trimethylene radical and wherein R "is a hydrocarbon radical containing 0-22 carbon atoms selected from the group consisting of alkyl, alkenyl, ararcyl or aracenyl. Substituted the cyclic dicarboxylic anhydrides of formula (II) above are substituted with succinic or glutaric anhydrides.

In the above formula (I), above each radical R 1 may be at the same time a hydrocarbon radical or each may be a different hydrocarbon radical.

Typical examples of anhydrides of formula (I) are myristoyl anhydride, pyrimoyl anhydride, oleoyl anhydride and stearoyl anhydride.

Typical examples of anhydrides of formula (II) are iso-octadenyl succinic anhydride, m-hexadenyl succinic anhydride, octenyl succinic anhydride and octyl ligutaric anhydride.

Hydrophobic organic isocyanates used as paper sizing agents are very well known in the art. The best results are obtained when the hydrocarbon chains of the isocyanates contain at least 12 carbon atoms, preferably 14 to 36 carbon atoms. Such isocyanates include resin isocyanate, dodecyl isocyanate, octadecyl isocyanate, tetradecyl isocyanate, 6-ethylidesyl isocyanate, 6-phenyldecyl isocyanate, and polyisocyanates such as 1,1-octadecyl diisocyanate. isocyanate, wherein the long chain alkyl group acts for two isocyanate radicals and imparts hydrophobic properties to the molecule as a whole.

The ketene dimers used as cellulose-reactive sizing agents are dimers of the formula (R "'CH = C = O) 2 14 64677 wherein R"' is a hydrocarbon radical such as alkyl having at least 0 carbon atoms, cycloalkyl having at least 6 carbon atom, aryl, ararchyl and alkaryl. In the phrase ketene dimers, the radical R ”’ is hereinafter referred to as “ketene dimer”. Thus, the phenyl ketene dimer is _ - (oy ch “c '° _ 2 and the benzyl ketene dimer is / ÖyCH2-CH = C = 0 ^ 2 and the decyl ketene dimer is ~ CH = C = 0) 2 · Examples of ketene dimers are octyl, desyl Dimesyl, tetradesyl, hexadesyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl beta-naphthyl and cyclohexyl ketene dimers, as well as ketene dimers prepared from montanic acid , naphthenic acid, Δ'-desylenic acid, Δ9,1ί-4-dodecenic acid, palmitoleic acid, oleic acid, ricinoleic acid, phthalic acid, linolenic acid and oleo-stearic acid such as those derived from them, as well as those obtained from natural ketene dimers coconut oil, babassu oil, palm kernel oil, palm oil, olive oil, peanut oil, rapeseed oil, beef lard, lard and leaf whale fat. Mixtures of all the above fatty acids with each other can also be used.

Example 5

A ketene dimer emulsion prepared from a mixture of palmitic and stearic acids was prepared by mixing ΘΒ0 parts of water, 60 parts of cationic starch and 10 parts of sodium lignin sulfate. The pH of the mixture was adjusted to about 3.5 using 90 L of sulfuric acid. The resulting mixture was kept at 90-9 ° C for about one hour. Water was then added to the mixture in an amount to give a mixture of 1750 parts (total parts by weight). About 240 parts of the ketene dimer were kept by mixing it into the mixture together with 2.4 parts of thiadiazine. Thiadiazine was used as a preservative. The resulting premix (at 65 ° C) was homogenized by passing it once through a homogenizer at a pressure of about 290 bar. The homogenized product is diluted with water to a content of solid ketene dimers of about 6%.

As is well known in the art, hydrophobic cellulose-reactive sizing agents have been used in the internal sizing of paper and also in the external sizing of paper. The accelerators of this invention may be used in conjunction with both of the adhesives of these methods.

Example 6

The products of Example and Example 5 were combined by adding water as needed to give an aqueous sizing containing 0.10% ketene dimer and 0.10% nitrogen-containing polymer according to Example 1.

Example 7

The products of Examples 2 and 5 were mixed together by adding the required amount of water to give an aqueous sizing mixture containing about 0.10% of the ketene dimer and 0.10% of the nitrogen-containing polymer of Example 2.

Example 8

The products of Examples 3 and 5 were mixed together by adding the required amount of water to give an aqueous sizing mixture containing 0.10% of the ketene dimer and 0.10% of the nitrogen-containing polymer of Example 3.

Example 9

The products of Examples 4 and 5 were mixed together with the required amount of water to give an aqueous sizing mixture containing 0.10% of the ketene dimer and 0.10% of the nitrogen-containing polymer of Example 4.

Example 10

The aqueous sizing mixture was prepared to give the mixture of Examples 6,7,8 and 9, with the exception that the nitrogen-containing polymer used in this case was aminopolyamide-epichlorohydrin plastic. The aminopolyamide was derived from adipic acid and diethylenetriamine. Experimental results show that this cationic polymer does not act as an accelerator of the ketene dimer.

The above-mentioned sizing compositions were applied to a non-sizing and filler-free sheet of paper having a basis weight of about 65 g / m 2. The sheet was made of such a so-called. co-rod: from a 50:50 softwood-cellulose blend using a "pilot paper machine". The pH of each adhesive mixture was adjusted to 7 before it was applied to the nip of the horizontal web press at the nip. The operating speed of this press was about 12 m / s and the degree of wet pickup was 70%. The adhesion residue, i.e. the amount of residue, of the ketene dimer sizing mixture is the same in all these treatment processes. The glued sheets were dried at 93 ° C for 20 seconds in a laboratory cylindrical dryer to contain 5% moisture. The quality of gluing was measured using the so-called Hercules-Size test using test solution no. 2 indicators to determine reflectance, i.e. reflectivity. The values outside the paper machine are obtained within two minutes of drying and the so-called values aged under natural conditions after 2-5 days of storage at room temperature. It is known to those skilled in the art that the ketene dimer adhesive develops substantially all of its sizing properties in paper within 3 days. Thereafter, the properties obtained on the paper by the gluing treatment remain essentially the same. The properties obtained by the paper treatment remain essentially the same. The off-mac-hirie result is a critical result in that it reflects, i.e. represents, the rate at which gluing develops. The application of sizing compositions to the surface eliminates or eliminates all retention phenomena of the cationic polymers used.

The results of the gluing treatment are shown in Table I below.

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Table I

_Hercules-liimaustesti_

Glue mixture After the paper machine. Naturally aged

Example for 80% reflectance to 85% reflectance 5 127 540 7 26 517 Θ 15 450 9 165 535 10 0 525 Reference sample 0 450 (ketene dimer only)

The foregoing description is intended to illustrate the present invention only and is not intended to limit its scope in any way.

Claims (8)

64677 1Ö A sizing composition in the form of an aqueous emulsion, characterized in that it comprises (A) a hydrophobic cellulose-reactive sizing agent and (B1) a cationic polymer selected from the group consisting of (1) a cationic polymer prepared reacting epihalohydrin with a condensate derived by condensing dicyandiamide or cyanamide with bis-aminopropylpiperazine, or (2) a cationic polymer prepared by condensing epihalohydrin with bis-aminopropylpiperazine. Sizing composition according to Claim 1, characterized in that the sizing agent is a ketene dimer and in that the cationic polymer is a polymer (1). Sizing composition according to Claim 2, characterized in that the epihalohydrin of the cationic polymer (1) is epichlorohydrin. Sizing composition according to Claim 1, characterized in that the sizing agent is a ketene dimer and in that the cationic polymer is a polymer (2). * Adhesive mixture according to Claim 4, characterized in that the epihalohydrin of the cationic polymer (2) is epichlorohydrin. A method of gluing a paner internally or externally using a gluing composition according to any one of the preceding claims, characterized in that the gluing composition used comprises a hydrophobic cellulose-reactive adhesive selected from the group consisting of ketene-cämoerlt, acid anhydrides and organic isocyanates, and that the adhesive mixture further comprises an adhesion accelerator which is a polymer selected from the group consisting of (1} cationic po 1 yrnce prepared by placing epihalohydrin to react with a condensate prepared by condensing bis-aminopropylpiperazine and dicyandiamide in a ratio of bis-aminepropylpiperazine to dicyandiamide, either in the range of about 0.5: 1 to 1: 0.5, or (ii) a condensate which 19 64677 is prepared by condensing bis-aminopropylpiperazine and cyanamide with moles of bis-aminopropylpiperazine and cyanamide in a ratio in the range of about 0.5: 2 to 1: 1, wherein the amount of n-lohohydrin used is in the range of 0.3 to 2 moles for each mole of condensed nitrogen in the condensate, or (2) a cationic polymer thereof. prepared by condensing bis-aminopropylpiperazine and epihalohydrin in a molar ratio of bis-aminopropylpiperazine to epihalohydrin in the range of 1: 3 to 1: 8, wherein the amount of accelerator used for the sizing process is such that it is sufficient to improve the sizing effect of the sizing agent. Process according to Claim 6, characterized in that the epihalohydrin used for the preparation of the cationic polymers (1) and (2) is epichlorohydrin. Process according to Claim 7, characterized in that the sizing composition used contains a hydrophobic cellulose-reactive sizing agent selected from the group consisting of ketene dimers, acid anhydrides and organic isocyanates, and in that the sizing composition further contains a cationic polymerizing accelerator. is selected from the group consisting of (1) a cationic polymer prepared by reacting epichlorohydrin with (i) a condensate prepared by condensing bis-aminopropylpiperazine and dicyandiamide in a molar ratio of 1: 1, or (ii) a condensate which is has been prepared by condensing bis-aminopropylpiperazine and cyanamide in a molar ratio of bis-aminopropylpiperazine to cyanamide of 1: 2, the amount of epihalohydrin used being in the range of 1 to 1.5 moles per mole of condensed amino nitrogen in the condensate, or (2) a cationic polymer prepared, bis-aminopropyylipiperats iin and epichlorohydrin in a molar ratio of bis-aminopropylpiperazine to epichlorohydrin of 1: 4, wherein the amount of gluing method used is sufficient to improve the sizing effect of the sizing agent on the paper leaving the paper machine. Process according to Claim 8, characterized in that the sizing agent is a ketene dimer and in that the sizing agent is a cationic polymer (1). 20 6 4 6 7 7 PATEN TKRAV