MXPA98000482A - Synthetic cationic polymers as promoters for apresting with alkenil-succin anhydride - Google Patents

Abstract

Synthetic cationic polymers are used as promoters for the preparation with alkenyl succinic anhydride. The addition of certain synthetic cationic polymers which are reactive with the alkenyl succinic anhydride, is shown to improve the dressing efficiency of the hydrophobic cellulose preparation material in papermaking. It is intended that synthetic cationic polymers replace starch as an effective promoter in the manufacture of pap

Description

SYNTHETIC CATIONIC POLYMERS AS PROMOTERS FOR APRESTING WITH ALKENIL-SUCCINIC ANHYDRIDE TECHNICAL FIELD This invention relates to emulsions using synthetic cationic polymers, as promoters for the preparation with alkenyl succinic anhydride, and more specifically to an emulsion containing alkenyl succinic anhydride and a synthetic cationic polymer which improves the efficiency of preparation, and a method to use the same.

BACKGROUND OF THE INVENTION Dressing agents in the papermaking process are used to promote the reduced absorption of water and ink in the paper product, as well as to resist acidic and alkaline aqueous solutions. As used herein, the term "paper" is contemplated to include any sheet-like masses and molded products made from fibrous cellulosic materials that can be derived from natural and synthetic sources.

REF: 26145 Paper is frequently prepared with various materials to increase water resistance, as well as other types of aqueous solutions. These materials are referred to as sizing or dressing, and can be introduced during actual papermaking processes. Alternatively, sizing or priming can be applied to the surface of the net or finished sheet. An example of a sizing agent is alkenyl succinic anhydride ("ASA"). The ASA, useful in the preparation of cellulosic materials, has gained considerable commercial success in the manufacture of paper, particularly as an alternative to the conventional dressing system of alum-turpentine resin. The use of ASA as a sizing agent is well known in the art, as described in Farley and Wasser, "Sizing with Aikenyl Succinic Anhydride" in The Sizing of Paper, W.F. Reynolds, Ed., TAPPI, 1989, Chapter 3. See also US Patent No. 3,968,005, which is incorporated by reference herein. ASA is insoluble in water and hydrolytically unstable. Therefore, it must be emulsified in the paper mill before use. Specifically, the art requires that for retention, the sizing agents be used in conjunction with a material that is cationic by nature, or that is capable of producing one or more cations or other positively charged groups. Emulsification is normally achieved by passing the ASA and a protective colloid, starch and / or synthetic polymer, through a device such as a homogenizer, a high-cut turbine pump, etc. Cationic starch plays several important roles in the preparation with ASA. First, it helps the generation of ASA emulsions of small particle size. Small particle size, in the range of microns, is required for good sizing efficiency. Second, it imparts good physical stability to the emulsion. ASA emulsions must be stable, in order to prevent deposits and adhesion in the press once they have been added to the paper raw material. Third, it retains the emulsion on the surfaces of the fibers and promotes the efficiency of preparation. The preparation levels for a given amount of ASA are found to increase several times as the amount of cationic starch in the pulp feedstock increases. Typically, cationic starch is used at a ratio of 2 to 4 times that of the ASA to give the optimum sizing efficiency. However, certain problems arise with the use of cationic starch. For example, the starch must be cooked in the mill, thus requiring large-scale cooking equipment and storage tanks. More importantly, starch is susceptible to biological degradation, resulting in silt growth and the creation of deposits on the paper mill equipment, causing problems in the ability to run in the form of adhesion to the press, filling the endless belt and poor consistency control in the cylindrical tank. It may be desirable, in some cases, to perform the function of the dressing system with ASA independently of the cationic starch. Variation in the viscosity of the batch-to-batch starch and the solids, and the need to cool the starch prior to emulsification, can lead to undesirable variation in the particle size of the ASA emulsion. Some paper mills do not like to use starch due to the difficult cooking and handling requirements. Others, where fine grades of paper are made, and where many of the ASA sizes are currently being used, require cationic starch for dry strength, but mills prefer to use lower cost cationic corn starches. In general, the cheaper cationic potato starch gives better results for the preparation with ASA. Synthetic polymers have been studied as alternatives to cationic starch for the emulsification of ASA, and specifically to overcome the problems associated with cationic starch. The synthetic cationic polymers of the art as alternatives to starch are not reactive with ASA. For example, U.S. Patent No. 4,657,946 teaches improved emulsification of the ASA sizing agent by the use of water-soluble, cationic, charged vinyl addition polymers. The '946 patent teaches a paper and emulsion preparation method using water-soluble, cationically charged vinyl addition polymers, and condensation polymers that provide improved emulsification of the alkenyl succinic anhydride preparation agents. U.S. Patent No. 5,224,993 teaches a saponified sizing agent for the paper, derived from the dehydration condensation of an alkenyl succinic anhydride and an organic carboxylic acid, with a polyalkylene polyamine and the saponification of the remaining carboxyl groups with alkali after of dehydration condensation. U.S. Patent No. 4,629,655 teaches a sizing composition as a solid product produced by mixing a cationic polymer suitable to function as an assistant for the retention of the sizing, and an adequate preparation for sizing a substrate. The process for preparing a substrate in the patent * 655 comprises dispersing the solid in an aqueous mixture, applying the resulting mixture to a substrate, and causing the size to be fixed thereto to the substrate. However, the synthetic cationic polymers of the art have only been marginally successful as an appropriate replacement for starch. None of these synthetic cationic polymers contain functional groups that are reactive with ASA. The synthetic cationic polymers of the art, which serve as additives and co-emulsifying agents for the preparation with ASA, do not improve the preparation (or do not serve as good promoters). Various patents that describe polymers that are reactive with ASA do not teach the use to promote the efficiency of the sizing agent. For example, these patents include U.S. Patent No. 5,232,553, which teaches a process for making paper using polyvinylamine in which the paper product obtained from the pulp suspension contains fine particles of material. The '553 patent relates to the use of the poly (vinylamine) and the aldehyde to increase the retention of the fine particles in the paper product. In developing an alternative to starch in ASA emulsions, it is generally found that the production of a cationic synthetic polymer that has high viscosity to generate emulsions of small particle size and acting as a retention aidIt is not particularly difficult. The difficulty lies in developing a synthetic cationic polymer that promotes the efficiency of the ASA preparation by providing reactive ASA groups that can anchor the ASA to the surface of the fiber. Various other patents make use of similar synthetic cationic polymers, but do not teach an increase in the efficiency of papermaking readiness. An anhydride dispersion of a polyelectrolyte in a liquid reactive sizing is claimed in European Patent EP-A-0, 200, 504. U.S. Patent No. 4,217,214 teaches the use of high molecular weight polyvinylamine hydrochloride for flocculation of suspended solids in wastewater clarification or water purification systems. U.S. Patent No. 4,957,977 teaches a flocculating agent and the agent for increasing the strength of the paper, using a vinylamine copolymer and a process for the production of the vinylamine polymer. British Patent Application GB 2,268,758A teaches an improvement of the wet strength of the paper by the addition of wet or dry end of a polyvinyl alcohol with amine functional group, and a reactive sizing with cellulose which is a cyclic ester of 4 or 5 members or an anhydride having one or more alkyl or alkenyl substituents of 4 or more carbon atoms, and having a total of at least 8 carbon atoms in the substituents. In fact, patents that are directed to synthetic cationic polymers in the art do not specifically refer to increasing the efficiency of paper sizing. While the synthetic agents of the prior art have met with some success, there is still a need in the paper industry to produce a more effective cationic agent that is useful as a promoter for the dressing, to avoid the problems generally associated with the cationic starch.

Such a cationic agent could be reactive with ASA and could significantly ove the sizing efficiency.

BRIEF DESCRIPTION OF THE INVENTION According to the present invention, papermaking methods are provided to ove the sizing efficiency of a hydrophobic cellulose sizing material, which comprises adding thereto a synthetic cationic polymer that is reactive with the sizing material. dressing Groups that are reactive with ASA include primary amine and hydroxyl. The preferred finishing material is alkenyl succinic anhydride. The preferred synthetic cationic polymer comprises a primary amine polymer. Also provided is a synthetic cationic polymer which contains one or more non-sizing reactive monomers, particularly, non-ASA reactive monomers, such as acrylic acid. For purposes of this invention, the term non-sizing reactive monomer (or non-ASA reactive monomer) refers to a monomer that does not result in a significant reaction with a sizing material. The synthetic cationic polymer can be a copolymer of vinyl alcohol and vinylamine. The synthetic cationic polymer can also be a copolymer of acrylamide and vinylamine. A method is also provided in papermaking to ove the sizing efficiency of a hydrophobic cellulose sizing material, which comprises adding to a cellulose sizing agent an effective amount of a synthetic cationic polymer containing hydroxyl groups and / or primary amine. Preferably, the polymer comprises about 50 to about 99 mol% vinyl alcohol and about 50 to about 1 mol% vinylamine. A method for making paper is provided to ove the sizing efficiency of an alkenyl succinic anhydride which comprises adding to it a synthetic cationic polymer of from about 20 to about 90 mol% acrylamide and about 80 to about 10 mol% of vinylamine This invention discloses an alkaline emulsion emulsion for oving sizing efficiency in papermaking, comprising a cellulose, hydrophobic sizing material and a cationic vinylamine copolymer that is reactive with the sizing material. Preferably, the finishing material is alkenyl succinic anhydride. It is preferable to have a copolymer comprising a synthetic polymer of about 20 to about 90 mol% acrylamide and about 80 to about 10 mol% vinylamine. It is also preferable to have a copolymer comprising a synthetic polymer of from about 50 to about 99 mol% vinyl alcohol and about 50 to about 1 mol% vinylamine. An alkaline priming emulsion comprising an alkenyl succinic anhydride preparation material, and an effective amount of a synthetic cationic polymer reactive with the sizing material, wherein the polymer contains primary hydroxyl and / or amine groups is also provided. As provided herein, the term "effective amount" is defined as the amount of material necessary to increase the dressing efficiency of a sizing agent.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES Various synthetic cationic polymers were evaluated as replacements for the cationic starch which is normally used in the paper dressing process with ASA. Cationic starch has been shown to be a good promoter of preparation for ASA. To demonstrate the effects of the various synthetic cationic polymers on the preparation with ASA, the promotion performance was evaluated based on an increase in the dressing efficiency using cationic starch, compared to a variety of different synthetic cationic polymers. It should be noted that starch is different from synthetic cationic polymers, because starch is a natural substance, instead of synthetic. Paper test sheets containing the size and promoter were prepared and used for the evaluation of the preparation. For purposes of this invention, a test sheet is comprised of pulp, fillers, sizing agent (ASA) and promoter (a cationic starch or a synthetic cationic polymer).

Emulsification of ASA using cationic polyacrylamide: For the evaluation of each test sheet, an ASA emulsion is prepared in deionized water. The emulsification process proceeds as follows: 24.0 g of deionized water were weighed into a small stainless steel mixing vessel (approximately 35 ml capacity). 1 g of ASA (heavy by difference) was added and the mixer was run at high speed for five minutes. Based on the calculated concentration of ASA, the sample was immediately diluted to 0.25% with cold deionized pH 3 water to minimize hydrolysis. The sample was kept on ice until it was used for the evaluation of the test sheet. It was estimated that the particle size was in the range of 1.5 to 2 microns. A variety of synthetic cationic polymers containing amide copolymers and amine groups, as well as alcohol and amine groups, are within the scope of the invention. Each of the polymers and copolymers was selected for evaluation, because each contains functional groups (eg, primary amine or hydroxyl) that can react with ASA.

The cationic polyvinyl alcohol can contain 6 mol% of the vinylamine groups (PVOH / PVA) and have a molecular weight in the range of 80 to 140 kilodaltons. The copolymer was prepared by hydrolysis of a copolymer of vinyl acetate and N-vinyl formamide. Polyvinylamine (PVA) and polyvinylamine hydrochloride (PVA / HCl) are contemplated as being useful in this invention. The PVA is of low molecular weight and is supplied as a 12.8% solution. The PVA. HCl can be a powder of intermediate molecular weight. Polyallylamine hydrochloride (PAA) and allylamine copolymer and diallylamine hydrochloride (PAA / PDAA) are also contemplated as being useful in this invention. The PAA has an average molecular weight of approximately 100 kilodaltons and is supplied as a 40% aqueous solution. The PAA and the PDAA have a weight average molecular weight of 50 kilodaltons. Hofmann's degradation of polyacrylamide using sodium hypochlorite introduces primary amine and carboxyl groups. Samples were separated containing approximately 40 mol% primary amine, using polyacrylamide samples of four different molecular weights, in the range of 14 to 200 kilodaltons, using the Tanaka procedure (see, H. Tanaka, J. Polymer Science: Polymer Letters, Edition 16, 87-89 (1978)). Table I presents the Hofmann degradation products of polyacrylamide. In analyzing the amine and carboxyl content of the Hofmann degradation products, it is shown that the variation in molecular weights does not significantly change the concentration of the amine content, the carboxyl content or the isoelectric pH.

Table I Molecular weight% mol% mol Eü Example (kdalones) amine carboxyl isoelectric 1 200 40 14 9 2 77 47 24 9 3 47 60 24 8 4 14 47 14 8.5 In addition to the synthetic cationic polymers reactive with ASA, various synthetic cationic polymers not reactive with ASA were considered as promoters, for example, the acrylamide / methacryloxyethyltrimethylammonium copolymer (acrylamide / Q6), polyethyleneimine (polymer with average molecular weight of 50 to 60 kilodaltons, containing mainly amine secondary groups), Mannich quaternary of polyacrylamide, and terpolymers of acrylamide, acryloxyethyltrimethylammonium chloride (Q9) and alkyl methacrylate. The ASA mainly used is ACCOSIZE® 18 (available from Cytec Industries Inc.).

Advancement promotion with ASA: The level of preparation achievable with ASA is significantly increased (promoted) as the amount of cationic starch in the system increases. The magnitude of the increase and readiness continues to increase even with a relatively large amount of cationic starch, up to a ratio of 3: 1 to ASA. Because of this effect, a high proportion of cationic starch is used to ASA in current commercial practice. It does not matter if the cationic starch is part of the ASA emulsion or if it is added separately to the raw material. As shown in this invention, the level of preparation of an ASA preparation level can also be significantly increased, by increasing the concentration of the synthetic cationic polymers that are reactive with ASA.

Evaluation of the polymer test sheet as ASA promoters Experiments are performed with test sheets using the following procedure. The raw material is a 50/50 blend of bleached pulps for brown paper, in a hard and soft way, beaten at a Canadian Standard Refining of 500 to which 15% by weight of precipitated calcium carbonate is added, and the pH is adjusted to 7.5. While stirring, a batch of 0.6% consistency material containing 10 g of fiber is treated with the promoter, followed by a given dose of ASA emulsion, then with 0.453 g / ton (1.0 lb / ton) of anionic polyacrylamide retention aid. 15 seconds of contact time between each addition is allowed. Three test sheets of 2.8 g (22.68 kg (50 lbs / Tappi reams)) are formed, pressed with 1-1 / 2 weights, and dried one minute on a rotary drum dryer at 115.5 ° C (240 ° F) ). Base weight and dressing are measured on the leaves after conditioning for at least 24 hours at 23 ° C and 50% relative humidity. The test sheets are tested for ink penetration using a dressing test of the type described in the Tappi Standard T-530 pm-83. This measures the time elapsed after the contact of one side of the paper with the ink, so that the reflectance of the opposite side drops to 80% of its initial value. The ink is the same as the one described in T-530 pm-83, but it does not contain formic acid and is buffered at pH 7. The tests are normalized to a base weight of 22.68 kg (50 lbs / reps Tappi), assuming that the readiness is proportional to the cube of the base weight. While it is apparent that the invention described herein is very well calculated to describe the invention set forth above, it should be well appreciated that numerous modifications and modalities may be considered by those skilled in the art, and it is understood that the appended claims cover all modifications and modalities that fall within the true spirit and scope of the present invention.

EXAMPLES 5 TO 14 (Comparative) Example 5 of Table II shows the results of an ink penetration evaluation of an ASA emulsion made with a 90/10 molar ratio of AMD / Q6 copolymer. This same emulsion was then post-diluted either with additional copolymer of AMD / Q6 (a synthetic cationic polymer) or with cationic starch. The ASA dose was 0.15% on the fiber in all the examples. Post-dilution with the additional copolymer AMD / Q6 (Examples 6 to 9) shows that the sizing efficiency does not increase appreciably, since the copolymer is not reactive with ASA. Examples 10 to 14 show that AMD / Q6 copolymer post-diluted with cationic starch, provided marked increase in sizing efficiency. As used herein, ink penetration is provided in seconds. It is shown that the effect of the increase in dressing efficiency is attributed to the cationic starch (which is reactive with ASA) and not to the AMD / Q6 copolymer (which is not reactive with ASA).

Table II Example Post-dilution Post-dilution Penetration with Polymer with Starch the ink (sec.) Cationic Cationic (Proportion at (ASA Proportion) ASA) 5 (emulsion 0.13 - 70 initial) 6 0.5 - 138 7 1.0 - 117 Table II ( below) Example Post-dilution Post-dilution Penetration with Polymer with Starch the ink (sec.) Cationic Cationic (Proportion at (ASA Proportion) ASA) 8 2.0 - 64 9 3.0 - 86 10 - 0.5 187 11 - 1.0 254 12 - 2.0 329 13 - 3.0 349 14 _ 4.0 396 EXAMPLES 15 TO 23 (Comparative) Table III presents the results of an evaluation that is similar to that presented in Table II. The 90/10 molar ratio of the AMD / Q6 copolymer of these examples is carried out by inverse emulsion techniques. Example 15 shows the preparation obtained with the ASA emulsion made using the copolymer AMD / Q6. The dose of ASA is 0.15% on fiber in all the examples. This same emulsion is then post-diluted either with additional AMD / Q6 copolymer (Examples 16 to 18) or with cationic starch (Examples 19 to 23). These examples (Examples 15 to 18) show that the addition of the reverse emulsion AMD / Q6 copolymer does not increase the efficiency of preparation, since the copolymer is not reactive with ASA. Examples 19 to 23 show that inverted or inverted AMD / Q6 copolymer, diluted with cationic starch, provided marked increase in sizing efficiency. It is shown that the effect of the increase in dressing efficiency is attributed to the cationic starch (which is reactive with ASA) and not to the AMD / Q6 copolymer (which is not reactive with ASA).

Table III Example Post-dilution Post-dilution Penetration with Polymer with Starch ink (Cationic Cation sec. (Proportion at (ASA Proportion) ASA) 15 (emulsion 0.13 62 initial) 16 0.5 78 17 1.0 35 18 2.0 11 19 0.5 - 130 1.0 189 21 2.0 257 Table I I I (continued) Example Post-dilution Post-dilution Penetration with Polymer with Starch ink (sec.) Cationic Cationic (Proportion at (ASA Ratio) ASA) 22 - 3. 0 290 23 - 4. 0 340 EXAMPLES 24 TO 32 (Comparative) Table IV shows the results of an evaluation that is similar to those presented in Tables II and III. In this case, the synthetic cationic copolymer is a 99/1 molar ratio of AMD / Q9. An ASA emulsion is prepared using water alone, Example 24. The dose of ASA was 0.125% fiber in all the examples. This same emulsion is then post-diluted either with AMD / Q9 copolymer (Examples 25 to 27) or with cationic starch (Examples 28 to 32). These examples demonstrate that the addition of the AMD / Q9 copolymer does not increase the efficiency of the dressing, since the copolymer is not reactive with ASA. Post-dilution with cationic starch provides a marked increase in the efficiency of the preparation. It is shown that the effect of the increase in the efficiency of the dressing is attributed to the cationic starch (which is reactive with ASA) and not to the AMD / Q9 copolymer (which is not reactive with ASA).

Tabl a IV Example Post-dilution Post-dilution Penetration with Polymer with Starch ink (sec.) Cationic Cationic (Proportion at (ASA Proportion) ASA) 24 (emuls ion - -iniial) 25 0. 5 - 8 26 1. 0 - 4 27 2. 0 - 5 28 0.35 40 29 0.6 77 30 1.2 89 31 2.4 157 32 4.8 179 EXAMPLES 33 TO 41 (Comparative Table V shows the results of a screening assessment as a function of the promoter dose for several promoters. Each of the examples in Table V is conducted using 0.2% fiber on the ASA. Examples 33 to 35 use a terpolymer of 18/20/2 mole percent of acrylamide terpolymer / Q9 / dodecyl methacrylate. This is a non-reactive polymer with ASA. Examples 36 to 38 use cationic potato starch as the promoter. Examples 39 to 41 use PVOH / PVA as the promoter. The penetration of the ink is provided in seconds. These examples show that the promotion effect of PVOH / PVA, a polymer reactive with ASA, increases the efficiency of the preparation by increasing the dose.

Table V Example Dose of Cationic Polymer Penetration of (% on fiber) Ink (sec.) 33 0.05 2 34 0.10 2 35 0.20 2 36 0.05 10 37 0.10 5 38 0.20 58 39 0.05 44 40 0.10 48 41 0.20 195 EXAMPLES 42 TO 49 (Comparative) Table VI presents the results of a screening assessment as a function of the promoter dose for various promoters. Each of the examples in Table VI are conducted using 0.15% on the fiber. Examples 42 to 45 use cationic potato starch as the promoter. Examples 46 to 49 use PVOH / PVA as the promoter. Other parameters of this analysis are similar to those of Table V (Examples 33 to 41). Table VI demonstrates that PVOH / PVA is a more effective promoter than cationic potato starch (in the range of 34 to 204 g / ton (0.075 to 0.45 lbs) / ton). These examples show that the efficiency of the promoter is a function of the concentration of the promoter. Here, PVOH / PVA is a much more effective promoter than cationic potato starch when the concentration of the cationic polymer (either the synthetic cationic polymer or the starch) is less than about 0.45% on the fiber.

Table VI Example Dose of Pol: Cationic Cation Penetration of Ink (% on fiber) (sec.) 42 0.075 160 43 0.15 157 44 0.30 194 45 0.45 222 46 0.075 251 47 0.15 269 48 0.30 315 49 0.45 214 EXAMPLES 50 TO 55 (Comparative) Table VII presents the results of a screening assessment as a function of the promoter dose for various promoters, as in Table V (Examples 33 to 41). The emulsions of Table VII are prepared in the presence of either PVOH / PVA or cationic potato starch at a 0.5 / 1 ratio of ASA. After the emulsification, PVOH / PVA or additional cationic potato starch is added to the raw material, to give a dose of 0.075, 0.15 or 0.3% on the fiber. Examples 50 to 52 use cationic potato starch as the promoter. Examples 53 to 55 use PVOH / PVA, a polymer reactive with ASA, as the promoter. These examples demonstrate that the efficiency of the promoter is a function of the concentration of the preparation and the reactivity of the promoter with the sizing material.

Table VII Example Dose of the Polymer Penetration of the Cationic (% on Ink (sec.) Fiber) 50 0.075 140 51 0.15 232 52 0.30 171 53 0.075 208 54 0.15 254 55 0.30 314 EXAMPLES 56 TO 70 (Comparative) Table VIII shows the results of a screening assessment as a function of the promoter dose for various promoters, such as Table VI (Examples 42 to 49). Examples 56 to 59 use polyethyleneimine as the promoter. The examples 60 to 63 use a Hofmann degradation product as the promoter (Table I, Example 1). Examples 64 to 66 use cationic potato starch as the promoter. Examples 67 through 70 use PVOH / PVA as the promoter. These examples show that synthetic cationic copolymers reactive with ASA (PVOH / PVA and the Hofmann degradation product) provide a promoter effect to the preparation of ASA. Polyethyleneimine, which is not reactive with ASA, does not provide that effect.

Table VI I I Example Dose of the Polymer Penetration of the Cationic (% on Ink (sec.) Fiber) 56 0. 075 2 57 0. 15 4 58 0. 30 2 59 0. 45 2 60 0.075 28 61 0.15 92 62 0.30 242 63 0.45 184 Table VIII (continued) Example Dose of the Polymer Penetration of the Cationic (% on Ink (sec.) Fiber) 64 0.075 111 65 0.15 144 66 0.45 282 67 0.075 225 68 0.15 285 69 0.30 434 70 0.45 350 EXAMPLES 71 TO 82 (Comparative) Table IX shows the results of a screening assessment as a function of the promoter dose for various promoters, as in Table VI (Examples 42 to 49). The dose of ASA is 0.2% on dry fiber. Examples 71 through 73 use a Mannich polyacrylamide quaternary as the promoter. Examples 74 to 76 use cationic potato starch as the promoter. Examples 77 to 79 use PVOH / PVA as the promoter. Examples 80 to 82 use a Hofmann degradation product as the promoter (Table I, Example 1). This experiment shows that the two synthetic cationic polymers reactive with ASA (PVOH / PVA and the Hofmann degradation product) provide a promoter effect to the preparation. The Mannich polyacrylamide quaternary, which is not reactive with ASA, does not provide it.

Table IX Example Dose of the Polymer Penetration of the Cationic (% on Ink (sec.) Fiber) 71 0.075 2 72 0.15 2 73 0.30 2 74 0.15 7 75 0.30 24 76 0.45 101 77 0.0375 40 78 0.075 45 79 0.15 129 80 0.075 73 81 0.15 72 82 0.30 177 EXAMPLES 83 TO 106 (Comparative) Table X shows the results of a screening assessment as a function of the promoter dose for various promoters, as in Table VI (Examples 42 to 49). 0.15% ASA is used on the fiber. Examples 83 to 85 use PAA / PDAA of 50 kilodaltons of molecular weight as the promoter. Examples 86 to 88 use PAA of 100 kilodaltons of molecular weight as the promoter. Examples 89 to 91 use a Hofmann degradation product of 14 kilodaltons of molecular weight (Table 1, Example 4) as the promoter. Examples 92 through 94 use a Hofmann degradation product of 47 kilodaltons of molecular weight (Table I, Example 3) as the promoter. Examples 95 to 97 use a Hofmann degradation product of 77 kilodaltons of molecular weight (Table I, Example 2) as the promoter. Examples 98 to 100 use a Hofmann degradation product of 200 kilodaltons of molecular weight (Table I, Example 1) as the promoter. Examples 101 to 103 use a cationic potato starch as the promoter. Examples 104 to 106 use PVOH / PVA as the promoter. These examples show that the promotion effect of the Hofmann degradation products increases as the molecular weight increases. Also, these examples show that the promoter effect of the Hofmann degradation products increases with the increase of the amount of the promoter with the sizing material.

Table X Example Dose of the Polymer Penetration of the Cationic (% on Ink (sec.) Fiber) 83 0.075 11 84 0.15 40 85 0.30 29 86 0.075 2 87 0.15 1 88 0.30 3 89 0.075 2 90 0.15 1 91 0.30 7 92 0.075 2 93 0.15 2 94 0.30 2 Table X (continued) Example Dose of Polymer Penetration of Cationic (% on Ink (sec.) Fiber) 95 0.075 15 96 0.15 20 97 0.30 111 98 0.075 71 99 0.15 194 100 0.30 236 101 0.15 236 102 0.30 312 103 0.45 373 104 0.075 308 105 0.15 491 106 0.30 389 EXAMPLES 107 TO 130 (Comparative) Table XI shows the comparative results of an evaluation of ink penetration as a function of the promoter dose for various promoters, as in Table X (Examples 83 to 106).

Examples 107 to 109 use a Hofmann degradation product of 14 kilodaltons of molecular weight (Table I, Example 4) and Examples 110 to 112 use a Hofmann degradation product of 47 kilodaltons of molecular weight (Table I, Example 3). ) as the promoter. Examples 113 to 115 use a Hofmann degradation product of 77 kilodaltons (Table I, Example 2) as the promoter. Examples 116 to 118 use a Hofmann degradation product of 200 kilodaltons of molecular weight (Table I, Example 1) as the promoter. Examples 119 to 121 use PVA as the promoter. Examples 122 to 124 use PVA. HCl as the promoter. Examples 125 to 127 use PVOH / PVA as the promoter. Examples 128 to 130 use potato cationic starch as the promoter. These examples show that PVA and PVA. HCl are effective promoters for ASA. Both are reactive with ASA. It shows that PVOH / PVA is an effective promoter, and that the effectiveness of Hofmann degradation products increases as molecular weight increases.

Table XI Example Dose of the Polymer Penetration of the Cationic (% on Ink (sec.) Fiber) 107 0 0..3300 4 108 00..4455 5 109 00..6600 60 110 0 0..3300 111 00..4455 112 00..6600 113 0 0..1155 6 114 00..3300 24 115 00..4455 127 116 00..007755 194 117 00..1155 153 118 00..222255 240 119 00..1155 258 120 00..3300 449 121 00..4455 260 122 00..1155 129 123 00..3300 477 Table XI (continued) Example Dose of the Polymer Penetration of the Cationic (% on Ink (sec.) Fiber) 124 0.45 406 125 0.0375 178 126 0.075 280 127 0.15 337 128 0.15 108 129 0.30 334 130 0.45 326 EXAMPLES 131 TO 154 (Comparative) Table XII presents an additional comparative evaluation of the PVOH / PVA polymer as a preparation promoter for ASA. The performance of the PVOH / PVA polymer as a sizing promoter is compared to the use of the cationic starch as the promoter. The synthetic polymer is evaluated under variation of the mole percent of PVA in the PVA / PVOH polymer, as well as under the variation of molecular weight and the dose of PVA / PVOH. Each evaluation is conducted using 0.15 mol% on the ASA fiber. It is shown that the higher the content in% mol of PVA (for example, at 6 or 18 mol%), the PVOH / PVA promoter is more efficient than the cationic starch. At levels of 3 mol% PVA or less, the copolymer is not effective as a promoter. It is also shown that better efficiency is obtained with samples of higher molecular weight.

Table XII% mol Starch Weight Dose Penetration Example PVA Cationic Molecular (% on top of the ink (on the (dalton) fiber) (sec.) Fiber) 131 < 1 - 50-120 0.15 1 132 < 1 - 50-120 0.30 1 133 < 1 - 50-120 0.45 1 134 3 50-120 0.15 1 135 3 50-120 0.30 1 136 3 50-120 0.45 1 137 6 36 0.0375 5.5 138 6 36 0.075 21 139 6 36 0.15 48 140 6 95 0.0375 1 141 6 95 0.075 23 142 6 95 0.15 98 Table XII (continued)% mole of Starch Weight Dose Penetration Example PVA Molecular cationic (% on top of the ink (% on the (kdaltons) fiber) (sec.) Fiber) 143 6 - 80-140 0.0375 47 144 6 - 80-140 0.075 119 145 6 _ 80-140 0.15 378 146 18 75 0.0375 30 147 18 75 0.075 259 148 18 75 0.15 204 149 -. 149 - 0.15 - - 34 150 - 0.15 - - 13.6 151 -. 151 - 0.30 - - 239 152 - 0.30 - - 271 153 - 0.45 - - 275 154 - 0.45 - - 540 EXAMPLES 155 TO 159 (Comparative) The paper used for the examples in Table XIII is prepared on a pilot paper machine. The ASA is emulsified either with a copolymer of quaternary salt of acrylamide / methyl chloride of dimethylaminoethyl methacrylate (AMD / Q6) or with cationic potato starch. The emulsion is added to the pulp in the lower leg of the raw material box. The dose of ASA is kept constant at 0.175%. The raw material is hard wood / soft wood at 70/30 bleached with 25% (in dry fiber) of precipitated calcium carbonate, aggregate. In Example 155, polymer AMD / Q6 is provided at a final ASA ratio of 0.13 / 1. In Example 156, the total copolymer of AMD / Q6 is provided as in Example 155, but with the addition of additional polymer bringing the final ratio of AMD / Q6 to ASA as 1.0 / 1. In Example 157, the ASA emulsion is made using an AMD / Q6 90/10 reverse emulsion copolymer, with a final polymer / ASA ratio of 0.13 / 1. The result of these three examples shows the average readiness for Examples 155, 156 and 157 as 20, 41 and 5 seconds, respectively. This shows that the readiness was low, in relation to standard emulsions. Increasing the copolymer level from 0.13: 1 to 1: 1 resulted in only a small increase in the dressing. It is shown that synthetic cationic polymers do not give preparation (or increase sizing efficiency) if the polymer is not reactive with the sizing material. In comparison, Examples 158 and 159 are ASA emulsions made using a cationic starch in an ASA ratio of 2.1 / 1. The much higher readout values show the promoter effect of the cationic starch reactive with ASA.

Table XIII Example Proportion of Starch Proportion of Cationic Penetration Cationic Polymer of Ink (sec.) 155 -. 155 - 0.13 20 156 - 1.0 41 157 - 0.13 5 158 2.1 - 225 159 2.1 - 219 It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, property is claimed as contained in the following:

Claims (10)

1. An improved process for the manufacture of paper, which comprises the provision of a paper raw material or network of paper comprised of fiber and adding alkenyl succinic anhydride to it, the improvement is characterized in that it comprises increasing the efficiency of preparation of the anhydride alkenyl succinic, by adding to said raw material paper or network of paper, an amount greater than 0.0375%, based on the fiber, of a synthetic polymer comprised of the hydroxyl groups and / or primary amine groups, which is reactive with the alkenyl succinic anhydride, to provide on the paper formed from said paper stock or paper web, an increased level of readiness, which is greater than the readiness level obtained if 0.0375% was used based on the fiber, of the polymer.

2. A process according to claim 1, characterized in that (c) is polyvinylamine.

3. A process according to claim 1, characterized in that (c) is comprised of hydroxyl groups.

4. A process according to claim 1, characterized in that (c) has a molecular weight of at least 47,000 and is composed of i) carboxyl groups and ii) primary amine groups.

5. A process according to claim 4, characterized in that (c) is a Hofmann degradation product of polyacrylamide.

6. An improved preparation composition comprising alkenyl succinic anhydride which is added to a paper raw material or paper web comprised of fiber, the improvement is characterized in that it comprises increasing the efficiency of the preparation of said alkenyl succinic anhydride, by adding to the sizing composition, of an amount greater than 0.0375%, based on the fiber, of a synthetic polymer comprised of hydroxyl groups and / or primary amine groups that are reactive with the alkenyl succinic anhydride, to provide in the formed paper from the paper raw material or from the paper web, an increased dressing level that is greater than the dressing level obtained if 0.0375%, based on the fiber, of the polymer was used.

7. A composition according to claim 6, characterized in that (c) is polyvinylamine.

8. A composition according to claim 6, characterized in that (c) is comprised of hydroxyl groups.

9. A composition according to claim 6, characterized in that (c) has a molecular weight of at least 47,000 and is comprised of i) carboxyl groups and ii) primary amine groups.

10. A composition according to claim 9, characterized in that (c) is a Hofmann degradation product of polyacrylamide.