DK172016B1 - Process for the preparation of an emulsified sizing agent for use in the manufacture of glued paper products and a method for sizing paper and emulsion for use in the methods - Google Patents

Description

in DK 172016 B1

The invention relates to a process for preparing an emulsified sizing agent for use in the production of sealed paper products and a method for sizing paper as well as to an emulsion of a cyclic dicarboxylic anhydride in water containing a water-soluble cationic vinyl addition polymer for use in said processes.

Alkenyl succinic anhydrides (ASA), useful for gluing cellulose materials, have gained considerable commercial success. These materials were first fully described in U.S. Patent No. 3,102,064. This patent discloses a certain class of chemical materials which generally have the structural formula 15 0

II

wherein R is a dimethylene or trimethylene group and R 1 is a hydrophobic group containing more than 5 carbon atoms selected from alkyl, alkenyl, aralkyl and aralkenyl groups.

In describing the use of the ASA sizing agents 30 disclosed in this reference, the patentee states that for effective utilization, the sizing agents must be used with a material which is either cationic in nature or capable of ionized or dissociated in such a way as to produce one or more cations or other positively charged groups. The cationic agents as defined in this reference are described as "alum, aluminum chloride, long chain fatty acid amines, sodium aluminate, polyacrylamide, chromium sulfate, animal glue, cationic thermosetting resins and polyamide polymers". Patent 5 lists as particularly preferred cationic agents various cationic starch derivatives, including primary, secondary, tertiary or quaternary amine starch derivatives and other cationic nitrogen substituted starch derivatives, as well as cationic sulfonium and phosphonium starch derivatives. Such derivatives, as stated by the patent holder, can be prepared from all types of starches, including corn, tapioca, potato, etc.

With the growing commercial use of sizing agents of the type described above, there are serious, unresolved issues in the use of the sizing agents in pulp or pulp prior to their conversion into sheets or other useful forms. Part of the problem has been that the ASA sizing materials are not water-soluble and, as a result, must be uniformly suspended in the pulp so that the sizing agent can make appropriate contact with the cellulose fibers and thus create the desired effect on the end product.

25 Although the cationic agents disclosed in U.S. Patent No. 3,103,061 have been successful, there has been a need in the paper industry to produce a more effective "cationic" for ASA bonding. Furthermore, such a cationic agent would preferably support the retention of the sizing agent on the fiber and, where desired, would increase the wet and / or dry strength of the final sheet material.

The object of the invention is to provide an emulsified sizing agent containing an additive which will serve to emulsify or disperse the ASA glue in the pulp and enable retention of the glue on the fiber.

Accordingly, the invention provides a process for the preparation of an emulsified sizing agent for use in the preparation of glued paper products containing emulsion water, a cyclic dicarboxylic anhydride of the formula.

Wherein R is a dimethylene or trimethylene group and R 1 is a hydrophobic group containing more than 5 carbon atoms selected from alkyl, alkenyl, aralkyl and aralkenyl groups, as well as a water-soluble cationic vinyl addition polymer characterized by the cationic vinyl addition polymer has a molecular weight of from 50,000 to 150,000 and is made up of at least 10% by weight and up to 100% by weight of the polymer's mercury content from one or more 25 cationic or cationically modified vinyl addition monomers selected from a) methacrylamidopropyltrimethylammonium chloride , b) dimethylaminoethyl methacrylate; c) quaternary dimethylaminoethyl methacrylate compounds; d) dimethylaminoethyl acrylate; reaction, and DK 172016 Bl 4 i) quaternary Mannich-reacted ac rylamid compounds.

The invention also provides a method of sizing paper wherein the pulp is applied to an emulsion of a cyclic dicarboxylic anhydride of the formula I, wherein R is a dimethylene or trimethylene group and R 1 is a hydrophobic group containing more than 5 carbon atoms selected from alkyl, alkenyl, aralkyl and aralkenyl groups emulsified with a water-soluble cationic vinyl addition polymer, characterized in that the cationic vinyl addition polymer has a molecular weight of from 50,000 to 150,000 and is manufactured of at least 10% by weight and up to 100% by weight of the polymer's additional content from one or more cationic or cationically modified vinyl addition monomers selected from a) methacrylamidopropyltrimethylammonium chloride, b) dimethylaminoethyl methacrylate, c) quaternary dimethylaminoethyl methacrylate compounds, 30) dimethylaminoethyl acrylate, e) quaternary dimethylaminoethyl acrylate compounds, f) diethylaminoethyl acrylate, g) quaternary re-diethylaminoethyl acrylate compounds, h) acrylamide reacted with formaldehyde and a lower secondary amine 35 by the Mannich reaction, and i) quaternary Mannich acrylamide-reacted compounds.

DK 172016 B1 5

Finally, the invention provides an emulsion of a cyclic dicarboxylic anhydride of the formula 0, wherein R represents a dimethylene or trimethylene group and R 1 represents a hydrophobic group containing more than 5 carbon atoms selected from alkyl, alkenyl, aralkyl and aralkenyl groups in water for use in the aforementioned processes, the emulsion comprising: i) 50-99.9% by weight of water, ii) 0.01-40% by weight of said cyclic dicarboxylic anhydride, and iii) 0.001-10.0 % by weight of a water-soluble cationic vinyl addition polymer, characterized in that the cationic vinyl addition polymer has a molecular weight of from 50,000 to 150,000 and is made up of at least 10% by weight and up to 100% by weight of the polymer's additional content from one or more cationic or cationically modified vinyl addition monomers selected from a) methacrylamidopropyltrimethylammonium chloride, b) dimethylaminoethyl methacrylate, c) quaternary dimethylaminoethyl methacrylate compounds, d) (f) diethylaminoethyl acrylate, (g) quaternary diethylaminoethyl acrylate compounds, h) acrylamide reacted with formaldehyde and a lower secondary amine by the Mannich reaction, and 5 i) quaternary acrylic amide. compounds.

As stated above, the invention relates to the utilization of cationic water-soluble vinyl addition polymers having a molecular weight of between 50,000 and 150,000 as additives and 10 emulsifiers for ASA glue. The use of such cationic vinyl addition polymers serves to emulsify the ASA glue and further increases the retention of the glue on the cellulose sheet.

The ASA adhesives to which the invention may be applied include those mentioned in U.S. Pat.

3 102 061, 4 040 900, 3 968 005 and 3 821 069.

The ASA adhesives useful in the practice of the invention can generally be described by the following structural formula: 0 fl c 0 R - R1 25 X.

C

M

Wherein R represents a dimethylene or trimethylene group, 30 and R 1 represent a hydrophobic group containing more than 5 carbon atoms selected from alkyl, alkenyl, aralkyl and aralkenyl groups.

In a particularly preferred embodiment of the invention, a surfactant has also been used in the preparation of the ASA sizing agents of the invention. The agent of this surfactant may be anionic, nonionic or cationic. Surfactants used have usually been water-soluble and have had HLB values of between approx. 8 and approx. 30 or more, for 5 increments from approx. 8 to approx. 15. The surfactant is usually used to prepare the ASA sizing agent by simply mixing it with the raw ASA material. Accordingly, an ASA sizing agent used according to the invention in a preferred embodiment thereof will generally contain 75-99.5 parts by weight of ASA and preferably 90-99 parts by weight of ASA, with 0.5-25 parts by weight, preferably 0.75-10 parts by weight, and in particular 1.0-5 parts by weight of surfactant.

The surfactants are preferably added to ASA prior to emulsification in the aqueous medium. The surfactants may also be added to the aqueous medium prior to the addition of ASA.

The surfactants useful in the invention are further described in the aforementioned U.S. Patent No. 4,040,900.

Classes of materials useful as surfactants in connection with this invention include: ethoxylated alkylphenols such as nonylphenoxypolyethoxyethanols and octylphenoxypolyethoxyethanols; polyethylene glycols such as PEG-400 monooleate and PEG-600 dilaurate; as well as other materials, including certain one-30 hexylated phosphate esters.

Preferred surfactants for use in the invention are GAFAC® RM510 and GAFAC® RE610, both free acids of complex organic phosphate sterees produced by the GAF Corporation.

DK 172016 B1 8

Water-soluble polymers which are useful cationic agents of the invention include water-soluble vinyl addition homopolymers and copolymers having molecular weights between 50,000 and 150,000, wherein at least 10% by weight and up to 100% by weight of the polymer's additional content is a cationic monomer or a cationically modified monomer. Preferably, at least 15 and up to 95% by weight of the mer units in the polymer are cationic or cationically modified monomers. Most preferably, between 20 and 75% by weight of the mer units in the polymer or copolymer are cationic or cationically modified. These polymers are not ampholytic

Polymers usable in the practice of the invention include, but are not limited to, the following examples of copolymers and homopolymers: acrylamide-dimethylaminoethyl acrylate, quaternary acrylamide-dimethylamino-ethyl acrylate, acrylamide-diethylaminoethyl-acrylate, quaternary acrylic -diethylaminoethyl acrylate compounds, acrylamide-dimethylaminoethyl methacrylate, quaternary acrylamide-dimethylaminoethyl methacrylate for compounds, acrylamide-diallyldimethylammonium chloride, poly (dimethylaminoethyl methacrylate) and its quaternary compounds, poly (methacrylate)

Also used are acrylamide polymers and copolymers which have been subjected to a "Mannich" reaction with formaldehyde and a secondary (lower alkyl) amine. These polymers may optionally be quaternized.

As can be seen, all the polymers useful in the invention are cationically charged, non-ampholytic and water-soluble.

9 DK 172016 B1

The polymers used may be copolymers and even terpolymers of various vinyl addition monomers as previously mentioned. Although acrylamide is a preferred nonionic monomer for use in the preparation of copolymers useful in the present invention, other nonionic monomers such as methacrylamide can be used.

Polymers of the kind used in connection with this invention may be in the form of water-in-oil emulsions (such as those described in US Re 28,474 and 28,576), dry powders or dilute aqueous solutions.

15 To use the polymers in the emulsification of ASA glue, an aqueous solution of the polymer must first be prepared. In the case of the water-in-oil emulsions of vinyl addition polymers, it has been found that the water-soluble surfactants used to invert the water-in-20 oil emulsions have no detrimental effect on the activity of the polymer. used to emulsify the ASA glue. When preparing a polymer solution from a water-in-oil type emulsion polymer, a useful method or apparatus for forming the solution is exemplified in U.S. Patent No. 4,057,223, which describes a blending block.

Depending on the molecular weight and cationic charge of the polymer, from 0.01 to 25% by weight, preferably from 0.01 to 10% by weight, of the final glue emulsion to be added to the pulp may be polymer.

The ASA emissions applied to the pulp slurry of the invention will usually contain: 50 - 99.9% by weight of water 35 EN 172016 B1 10

0.01 - 50% by weight ASA

0.001 - 25.0% by weight of the water-soluble polymer

Preferably, these emulsions will contain: 50% - 99.9% by weight water

0.01 - 40% by weight ASA

Most preferably, the ASA emulsion contains 0.01 - 7.5 parts by weight and usually 0.01 -5.0 parts by weight of the polymer for each part by weight of ASA in the emulsion.

The polymers can be used to emulsify the ASA glue or they can be added to pre-formed ASA emulsions. In either case, the polymer will improve the properties of the emulsion as compared to emulsions that do not contain the polymer. When the polymer is added to an already formed ASA emulsion, conventional emulsifiers in addition to the polymer should be used. When the polymer is added or used during the preparation of the ASA emulsion, no additional emulsifier is needed.

To test the present invention, the following experiments were performed. The polymers listed below were obtained commercially or prepared in the form indicated.

EXAMPLE 1

A solution acrylamide copolymer of the type methyl acrylic amidopropyltrimethylammonium chloride (MAPTAC) was rated as ASA emulsifier and retention aid. The 35 new sizing agent was compared to conventional ASA emulsions in water or cationic starch, e.g.

DK 172016 B1 11 ASA particle size, physical stability of the emulsion and sizing ability. A description of this polymer is given in Table I. ASA emulsions in water are prepared by combining 95 parts of distilled water and 5 parts of ASA in an Eber-5 bach semimicroemulsion cup. The mixture was dispersed for 3 minutes at high speed. The emulsion formed was diluted with distilled water to 0.50% ASA dry matter and used in Experiment No. 1. Cationic starch ASA emulsions were prepared by first hydrating 5 parts of 10 a pregelatinized cationic potato starch in 95 parts of water and stirring. for 30 minutes. Sizing emulsions were then prepared by combining 75 parts of the starch solution with 25 parts of ASA in the emulsion cup and dispersing for 20 seconds. This emulsion was diluted to 0.50% ASA solids basis and used in Experiment No. 2. Finally, ASA emulsions in vinyl addition polymers were prepared by dispersing ASA in polymer solutions in a 5: 1 dry solids ratio. These emulsions were diluted to 0.50% ASA solids basis using the method described previously. Experiment # 3 illustrates the novel use of these addition polymers.

The ASA emulsions were tested separately in a paper slurry with a composition comprising 50% recycled, corrugated carton and 50% recycled newsprint. Other slurry parameters were 0.5% consistency, a grind degree (Canadian Standard Freeness) of 400 (pH 7.5 and 25 ° C) and 12.5 ppm hydrated aluminum sulfate was added. Manual sheets were prepared with a basis weight of 7.4 kg per square meter. 100 30 m2 in accordance with TAPPI T-205 procedures. The above sizing agents were added to the paper slurry shortly before formation of the wet web at doses of 0.10 and 0.15% based on paper solids. The manually made sheets were immediately dried on a rotary drum dryer to 98% dry matter. The results are shown in Table I.

DK 172016 B1 12 4-1

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Vinyl addition polymers, such as copolymers of acrylamide with quaternary dimethylaminoethyl methacrylate methyl chloride (DMAEM-MeCl quat) or methyl acrylamidopropyltrimethylammonium chloride (MAPTAC), were further rated as ASA emulsifying and retention aids. These new adhesives were compared to conventional ASA emulsions in water or cationic starch 10 m.h. particle size of the ASA emulsion, physical emulsion stability in aging and bonding ability. A description of these polymers is shown in Table II.

ASA emulsions in water were prepared by combining 15 95 parts of distilled water and 5 parts of ASA in a laboratory-type 237 ml Osterizer cup. The mixture was dispersed at high speed for 3 minutes. The emulsion formed was diluted with distilled water to 0.50% ASA on a solid basis and used in Experiment No. 4. ASA emulsions in 20 cationic starch solutions were prepared by first hydrating 5 parts of pregelatinized cationic potato starch in 95 parts of water and stirring for 30 minutes. minutes. Adhesive emulsions were then prepared by combining 95 parts of the starch solution with 5 parts of ASA in the Osterizer cup 25 and dispersing the adhesive for 25 seconds. This emulsion was diluted to 0.501 ASA on a dry solids basis and used in experiment # 5. ASA emulsions were prepared in vinyl addition polymers by dispersing ASA in the polymer solutions with a ratio of 1: 1 ASA to polymer solids in the Osterizer cup for 5 to 30 seconds. These emulsions were then diluted to 0.50% ASA on a solid basis, as described above. Experiments Nos. 6 and 7 illustrate the novel use of these vinyl addition polymers.

Each ASA emulsion was tested separately in a paper slurry of the composition: 50% bleached softwood kraft pulp and 50% bleached hardwood kraft pulp. The other slurry parameters were 0.5% consistency, a grinding degree (Canadian Standard Freeness) of 330 (pH 7.3 and 27 ° C). Manual sheets were prepared with a basis weight of 7.4 kg per square meter. 100 5 cm2 in accordance with TAPPI T-205 procedures. The sizing agents listed below were added to the paper slurry shortly before formation of the wet web at the dosage of 0.20% ASA dry solids calculated on paper solids. Manually made sheets were immediately pressed to approx. 50% residual moisture and dried on a rotating drum dryer to 98% paper solids. The results are shown in Table II.

DK 172016 B1 15

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The following comparative examples illustrate the use of acrylamide copolymers of the type quaternary dimethylaminoethyl methacrylate monoethyl sulfate (DMAEM-MeSQ), quaternary dimethylaminoethyl acrylate monoethyl sulfate (DMAEA-MeSQ), quaternary diethylamino ethyl acrylate molecular weights exceeding 1,000,000 as emulsifying and retention aids for alkenyl succinic anhydride sizing agents and conventional emulsions prepared from cationic starch.

For comparison, ASA emulsions were prepared in water by combining 95 parts of distilled water and 5 parts of ASA in an Eberbach semi-microemulsion cup and dispersing the glue for 60 seconds. The resulting emulsion was diluted with water to 0.50% ASA on a solids basis and used in Experiment No. 8. The ASA emulsions in cationic starch were prepared by first hydrating three parts of a pregelatinized cationic potato starch in 97 parts of stirred cold water. 30 minutes.

Emulsions with two ASA-dry solids ratios of 10: 1 and 3: 1 starch were then prepared by dispersing 30 parts of ASA and 70 parts of 3% cationic starch or 9 parts of ASA and 91 parts of 3% cationic starch, respectively, using the semi-microemulsion cup. . The resulting emulsions were diluted with water to 0.5% ASA on a solids basis and used accordingly in Experiments Nos. 10 and 11.

Polymer solutions were prepared by hydrating 0.6 parts (calculated as polymer solids) of each of the acrylamide copolymers listed below in 99.4 parts of water, using enough time and mixing to produce complete hydration. Emulsions were then prepared at two ratios of ASA to polymer of 10: 1 and 3: 1 by dispersing 6 parts ASA in 94 parts solution with 0.6% polymer solids or 1.8 parts ASA in 98.2 parts solution DK 172016 B1 17 with 0.6% polymer solids by means of the semimicroemulsion cup.

A further dilution to 0.5% ASA solids was then made. The following experimental results illustrate the advantages of the invention: the ability of these cationic water-soluble acrylamide copolymers to initiate an ASA emulsion and to make the ASA emulsion particles cellulose-substrate.

Each of the ASA emulsions listed below was added separately to a pulp slurry of 0.5% consistency, with the composition: 40% bleached hardwood sulfate pulp, 40% bleached softwood sulfate pulp and 20% calcium carbonate, and with a grinding grade (Canadian Standard Freeness ) of 300 (pH 8.2). He made manual sheets with a basis weight of 7.4 kg per day. 100 m2 in accordance with TAPPI T-205 procedures. Emulsions of ASA were added to the pulp slurry shortly before the wet web formation, at doses of 0.250 and 2.00% pulp solids.

The manual sheets were immediately dried on a rotary drum dryer to 98% dry matter (2% residual moisture). The results are shown in Table III.

This example clearly illustrates the new use of vinyl addition copolymers as ASA emulsifiers and retention aids. An improved water resistance to conventional ASA is obtained in water emulsions or emulsions with cationic starch. Second, the improved water resistance provided by the invention cannot simply be attributed to improved retention in the paper machine, as evidenced by separate additions of these same cationic polymers to the pulp.

The use of polymers in the high molecular weight range can lead to the formation of adhesive deposits and unstable emulsions. The use of polymers with molecular weights in the range from DK 172016 B1 18 50 000 to 150 000 led to the elimination of the aforementioned formation of precipitates and increased the stability of the ASA emissions thus produced.

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The effect of various other polymers on the emulsification of ASA sizing materials and the results obtained using such polymers were investigated. In this group of experiments, 3 different classes of polymers were used (see below). All of these materials were prepared as water-in-oil emulsions of the polymer. Aqueous solutions of the polymers were prepared to give an approximately 2% product-based or approximately 0.6% by weight aqueous polymer solution. The polymer solution was prepared by mixing 288 g of deionized water, 6.0 ml of a 2% by weight aqueous solution of an ethoxylated (9) nonylphenol surfactant followed by the addition of ca. 6 cc water-in-oil emulsion to the stirred mixture. The aqueous solutions were then adjusted to 2% by weight polymer product.

The ASA selected for this and all subsequent studies is a substituted (alkenyl) cyclic-dicarboxylic anhydride in which the alkenyl groups are derived from a mixture of 14-22 carbon atoms.

The ASA glue measurement used in these tests was prepared by mixing 196 g of the polymer solution with 4.0 g of a commercial grade alkenyl succinic anhydride glue available from Chevron Chemical Company containing 1.0 weight -% surfactant, "Gafac® RM-510", available from GAF Corporati-30on. The resulting mixture was then emulsified by mixing for 30 seconds in an Eberbach semimicroemulsion cup followed by final dilution to 0.5% ASA dry matter. The ASA emulsions were added to a commercial bleached power grade prescription with calcium carbonate as a filler, dosed in an amount of 0.25% pulp solids.

DK 172016 B1 21

The neutral ink penetration test describes the resistance of the paper to penetration of aqueous liquids and is a measure of the time (in seconds) it takes for the ink to penetrate the paper to a predetermined degree (end point: 80% reflectance). The longer the time, the greater the resistance of the paper to ink penetration. Those skilled in the art will readily recognize this test as the commonly practiced Hercules glue penetration test. The results are listed in Table IV.

10 __

Polymers Mole ratio P acrylamide-MAPTAC 97.5: 2.5 Q Q acrylamide-MAPTAC 95: 5 R acrylamide-MAPTAC 85:15 S acrylamide-DMAEA-Q 97.5: 2.5 T acrylamide-DMAEA-Q 95: 5 U acrylamide-DMAEA-Q 85:15 20 V acrylamide-DMAEM-Q 97.5: 2.5 W acrylamide-DMAEM-Q 95: 5 X acrylamide-DMAEM-Q 85:15 Y acrylamide-DMAEM-Q j 92, 3: 7.7 in DK 172016 B1 22

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The following examples further illustrate the novel use of DMAEM-MeSQ acrylamide copolymers as emulsifiers and retention aids for alkenyl succinic anhydride sizing agents. The ASA emulsions thus formed were compared with ASA water emulsions and conventional emulsions prepared from cationic starch with respect to particle size and bonding ability.

10

In comparison, ASA emulsions in water were prepared by combining 95 parts of distilled water and 5 parts of ASA in an Eberbach semi-microemulsion cup and dispersing the glue for 60 seconds. The resulting emulsion was diluted to 0.50% ASA solids basis with water and used for the two experiments. The ASA emulsions in cationic starch were prepared by first hydrating 3 parts of a pregelatinized cationic potato starch in 97 parts of stirred cold water for 30 minutes. 20 emulsions were then prepared at two ASA starch solids ratios of 10: 1 and 1: 1 by dispersing 30 parts ASA in 70 parts 3% cationic starch or 3 parts ASA in 97 parts 3% cationic starch by means of the semimicroemulsion cup. The resulting emulsions were diluted to 0.5% ASA solids basis with 25 water and used according to the following.

Polymer solutions were prepared by hydrating 0.6 parts (as polymers) of each of the 30 acrylamide copolymers listed below in 99.4 parts of water, using sufficient time and mixing to complete the hydration. Then, emulsions of ASA in polymer were prepared by dispersing 6 parts of ASA in 94 parts of 0.6% polymer for 60 seconds by means of the semimicroemulsion cup. A further dilution to 0.5% ASA solids was then made. This example, too, illustrates the advantages of this invention: the ability of these cationic water-soluble acrylamide copolymers to initiate and maintain a stable ASA emulsion in on and to make the ASA emulsion particles cellulosic. The 5 polymers tested include the following:

Polymer Mole percent (M%) of quaternary acrylamide copolymer 10

AA 3.5 M% DMAEM-MeSQ

BB 7.5 M% DMAEM-MeSQ

CC 10.9 M% DMAEM-MeSQ

15 1 Quaternary dimethylaminoethyl methacrylate methyl sulfate

Each of the ASA emulsions listed below was separately added to a pulp slurry of 0.5% consistency, with the composition: 40% bleached hardwood sulfate pulp, 40% bleached softwood sulfate pulp and 20% calcium carbonate and with a grind (Canadian) Standard Freeness) of 300 (pH 8.2). Manual sheets with a basis weight of 7.4 kg per 100 m2 was prepared in accordance with TAPPI T-205 procedures. Emulsions of ASA were added to the pulp slurry shortly before formation of the wet web at dosages of from 0.125 to 2.00%. The manual sheets were immediately dried on a rotary drum dryer to 98% dry matter (2% residual moisture). In another variation of this procedure, 0.025% of a polymer was added to the pulp slurry separately after addition of sizing emulsions. The results are shown in Table V.

This example clearly illustrates the new use of cationic vinyl addition copolymers as ASA emulsifiers and emulsion retention aids. Improved water resistance to conventional ASA-in-water or cationic starch emulsions is produced. Second, the improved water resistance provided by this invention cannot simply be attributed to improved retention in the paper machine, as evidenced by separate additions of these same cationic polymers to the paper recipe.

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Claims (7)

A process for the preparation of an emulsified sizing agent for use in the manufacture of glued paper products, which emulsion contains water, a cyclic di-carboxylic anhydride of the formula oc, wherein R is a dimethylene or trimethylene group, and R 1 is a hydrophobic group containing more than 5 carbon atoms selected from alkyl, alkenyl, aralkyl and aralkenyl groups, as well as a water-soluble cationic vinyl addition polymer, characterized in that the cationic vinyl addition polymer has a molecular weight of from 50 000 to 150,000 and is made up of at least 10% by weight and up to 100% by weight of the polymer's mercury content from one or more cationic or cationically modified vinyl addition monomers selected from a) methacrylamidopropyltrimethylammonium chloride, b) dimethylaminoethyl methacrylate, c) quaternary dimethylaminoethyl methacrylate d) dimethylaminoethyl acrylate, e) quaternary dimethylaminoethyl acrylate compounds, f) (g) quaternary diethylaminoethyl acrylate compounds; h) acrylamide reacted with formaldehyde and a lower secondary amine in the Mannich reaction; and i) quaternary Mannich-reacted acrylamide compounds. DK 172016 B1 28 Process according to claim 1, characterized in that the polymer is present in the alkenyl succinic anhydride sizing emulsion in a content of 0.01-10.0% by weight of the polymer solid. 5 Process according to claim 2, characterized in that the polymer is present in the alkenyl succinic anhydride sizing emulsion in a content of 0.01-5.0% by weight of the polymer solid. 10 Process according to any one of claims 1-3, characterized in that the polymer is added to the alkenyl succinic anhydride sizing emulsion in an amount such that there is 0.05-0.9 part by weight polymer for each part by weight of alkenyl succinic anhydride which is present in the emulsion. A method of sizing paper, wherein the pulp is applied to an emulsion of a cyclic dicarboxylic anhydride of formula 0 Λ. X is a dimethylene or trimethylene group and R 1 is a hydrophobic group containing more than 5 carbon atoms selected from alkyl, alkenyl, aralkyl and aralkenyl groups emulsified with a water-soluble cationic vinyl addition polymer , characterized in that the cationic vinyl addition polymer has a molecular weight of from 50,000 to 150,000 and is made up of at least 10% by weight and up to 100% by weight of the polymer's additional content from one or more cationic or cationically modified vinyl addition monomers selected from a) methacrylamidopropyltrimethylammonium chloride, b) dimethylaminoethyl methacrylate, c) quaternary dimethylaminoethyl methacrylate compounds, d) dimethylaminoethylacrylate, e) quaternary dimethylaminoethylacrylate compounds formaldehyde and a lower secondary amine in the Mannich reaction, and 15 i) quaternary re Mannich-reacted acrylamide compounds. Process according to claim 5, characterized in that the emulsion containing the water-soluble polymer is added to the pulp. 20 7. Emulsion of a cyclic dicarboxylic anhydride of formula C 25 30 C wherein R represents a dimethylene or trimethylene group and R1 represents a hydrophobic group containing more than 5 35 carbon atoms selected from alkyl, alkenyl, aralkyl and aralkenyl groups in water for use in the process of claim 1 or claim 5, which comprises: 5 i) 50-99.9% by weight of water, ii) 0.01-40% by weight of said cyclic dicarboxylic anhydride and iii) 0.001-10.0% by weight of a water-soluble cationic vinyl addition polymer, characterized in that the cationic vinyl addition polymer has a molecular weight of from 50,000 to 150,000 and is made up of at least 10% by weight and up to 100% by weight of the polymer's additional content from one or more cationic 15 or cationically modified vinyl addition monomers selected from a) methacrylamidopropyltrimethylammonium chloride, b) dimethylaminoethyl methacrylate, c) quaternary dimethylaminoethyl methacrylate compounds, d) dimethylaminoethyl acrylate, e) quaternary dimethylaminoeth g) quaternary diethylaminoethyl acrylate compounds, 25 h) acrylamide reacted with formaldehyde and a lower secondary amine in the Mannich reaction, and i) quaternary Mannich-reacted acrylamide compounds.