USE OF POLIVINYLAMINE TO IMPROVE THE APRESS OF OIL AND WATER IN CELLULOSIC PRODUCTS FIELD OF THE INVENTION This invention relates to an improvement in both sizing with oil / grease and water of cellulosic materials, especially paper products, through the use of a polyvinylamine in combination with both oil and water sizing agents. BACKGROUND OF THE INVENTION Sizing agents are used in papermaking processes to repel water or grease, i.e., oils, from adhering or penetrating to the paper, thereby weakening and / or stng the paper. The sizing agents can be classified into reactive agents or non-reactive agents. They can also be classified into internal sizing agents or as surface sizing agents. Reactive sizing agents are bound with paper fibers and are usually used for internal sizing. Sizing agents can be added to the paper supply before the supply enters the wet end of the papermaking machine. Alternatively, the same sizing agents can be sprayed or pressed towards the newly formed paper atas he passes through. If the sizing agent is added to the pulp suspension (that is, the provision) it should adhere to the pulp will not be retd on the paper. This can be achieved by using an agent that is oppositely charged with the pulp. Paper sizing agents prevent excess penetration of water or grease into paper. They are used where the resistance to water or grease is needed in the final use of the paper. There are no sizing agents that have adequate strength properties of both. The most efficient cellulose-based oil sizing agents, such as paper, contlong, linear fluorocarbon ch. Fluorocarbons in general have low surface energies and are not easily wetted by oil-based materials. Conversely, agents contng non-fluorinated hydrocarbon ch are good water sizing agents. However, when a combination of a fluorocarbon-based agent for oil resistance and a hydrocarbon-based product for water resistance are both used in papermaking processes, each has an adverse effect on the operation of the other. Consequently, more material or product must be used to compensate for the adverse loss of resistant properties.
As described by Bottorff in U.S. Patent No. 5,252,754, long chfluorocarbons are efficient oil sizing agents for cellulosic materials such as paper because of their low surface energy. However, these fluorocarbon-based sizing agents are generally inefficient for water resistance, especially if they conthydrophilic salt groups. On the other hand, hydrocarbon-based sizing products such as alkyl ketene dimer (AKD), are effective water sizing agents, but are inefficient for oil sizing purposes. When combinations of both hydrocarbon and fluorocarbon based materials are used, they have a negative impact on the mutual functioning of the paper. This adverse relationship generally results in inefficient treatment schemes because high product levels are required to achieve both oil and water resistance properties in the same paper. It has now been discovered that the presence of a polyvinylamine in a supply of paper or cardboard, whose supply cont both oil (or fat) and water sizing agents, the adverse effect is surprisingly counteracted.
SUMMARY OF THE INVENTION In one aspect, the invention is a papermaking or carton making process in which a provision cont both an oil sizing agent and a water sizing agent. The improvement being that the provision also cont a polyvinylamine. Another aspect to the invention is the order of addition of the agents to the provision. A water sizing agent is added to a paper supply. The polyvinylamine is then added to the paper supply either before or after the water sizing agent is added, followed by addition of the oil sizing agent. In addition, the invention provides a supply of paper containing at least one polyvinylamine, a water sizing agent, and an oil sizing agent. DETAILED DESCRIPTION OF THE INVENTION Adding a water-soluble cationic polyvinylamine when both an oil size and a water size are used in the papermaking process is an important aspect of the invention. The supply (i.e., pulp) is passed through a paper machine consisting of a head box, a sheet forming section and a paper section.of drying, everything in sequence. The polyvinylamines useful in this invention include but are not limited to those produced through polymerization of free radical solution of n-vinylformamide. The resulting nonionic polyvinylformamide can then be hydrolyzed in base, creating a primary amine cationic functionality in the polymer and sodium format as a byproduct. Products effective for the purpose include, but are not limited to, vinylamine polymers that have been reacted at a hydrolysis level of 35-100% speed 50-1005 with molecular weight ranging from 300,000-400,000 through chromatography Size exclusion (SEC) of polyvinylamine copolymers can be used. The comonomers include vinyl acetate or vinyl propionate monomers. The polyvinylamine polymers can be incorporated into the aqueous suspension of fibers used to form the weft, that is, the supply. By provision is meant the mixture of various materials that are mixed in the suspension of material from which paper or cardboard is made; The main constituents are fibrous material (pulp), sizing or strength materials, or other additives such asfillings and dyes. Pulp is understood to mean fibrous materials prepared from wood, cotton, grass, etc., by chemical or mechanical processes for use in the manufacture of paper, cardboard or cellulose products. By wire is meant a woven material made of plastic or metal for use in forming the paper or cardboard web of the diluted pulp suspension. By "headbox" is meant a flow control chamber that receives the diluted paper material or stock from the material preparation system and acts to disperse the flow uniformly throughout the entire width of the forming wire. By sheeting is meant the process by which the provision of diluted fiber is formed into a wet web through drainage effects by vacuum and gravity. By means of drying section is meant the part of the papermaking process that involves the removal of excess water from the wet paper or cardboard web through direct contact with heated drying cylinders. By plot, the sheet of paper is implied orcardboard that comes from a paper machine in its full width. Suitable water sizing agents include dimers of alkyl ketene (AKD) or alkenyl ketene dimer (AKD), alkenyl succinic anhydride (ASA), rosin-based sizing agents such as turpentine resin soap, disperse turpentine resin , and the like. Suitable oil sizing agents include fluorocarbon-containing polymers such as those having fluorinated alkyl groups. In a preferred process aspect of the invention, oil sizing and water sizing can be added to the supply in amounts of 0.005% to 1.0% (percent by weight) of active treatment solids based on the total supply solids. , and polyvinylamine may be present in an amount of between 0.001% and 1% of active treatment solids based on the total supply solids. The following Example A notes the typical adverse relationship between oil and water sizing agents in cellulose based systems that require high levels of water and oil sizing. EXAMPLE A To make manual sheets of paper, a trainer ofNoble and Wood laboratory was used to prepare 20 cm x 20 cm hand sheets at a base weight of 160 grams / square meter. A supply containing bleached softwood Kraft pulp and bleached quimitermomechanical pulp was obtained from commercial specialty manufacturers that require significant water and oil sizing properties. The pulps were mixed at a ratio of 1: 1 and refined in a laboratory cycle blender at 470 mi Canadian Standard Freeness (CSF). As outlined in Table A, commercial water and oil sizing agents were added in sequence to aliquots of the pulp. The agitation of material was achieved with a higher mixer set adjusted to 1,400 rpm. The oil sizing treatment was added to the pulp (provision), 30 seconds after the addition of the water sizing agent. The hand-paper preparation started after an additional 30 seconds of mixing time after the oil sizing treatment. The hand sheets were formed on a 100 mesh screen, passed through a roller press with adjusted filter of 2, 460 kg / cm2 (35 psi) (one pass), and dried at 3-4% humidity using a drum dryer. The performance test was conducted with botha Hot Water Cobb test and a Hot Oil Cobb test to demonstrate water and oil resistance properties on finished paper. The procedures for these tests are listed below. The Cobb Hot Water test involves paper samples cut to 12.5 cm x 12.5 cm, weighted to the nearest 0.01 g, and subsequently clamped within a 100-m Cobb ring device. A sample of 50 ml of water at 82 ° C (180 ° F) is then poured into the Cobb ring and onto the paper. After exactly two (2) minutes of contact time with the paper sample, water is quickly poured from the ring. - The moistened paper sample is separated from the apparatus and placed between two pieces of blotter paper (wet side up) . Excess water is removed from the paper sample by moving a Cobb hand roller once from one side to the other on the sample without exerting any additional force. The moistened paper sample is weighed again immediately to the nearest 0.01 g. The weight of water absorbed in grams per square meter is calculated by subtracting the conditioned weight of the sample from its final weight and multiplying by 100. The Cobb Hot Oil test is identical to the Cobb Hot Water Test, except that the oil (Wesson® Corn Oil) is used at 104 ° C (220 ° F) instead of water.
The only other difference in the oil test is that the Cobb hand roller is not used to remove excess oil but rather the moistened paper sample is hand pressed between blotting paper before the sample is gently rubbed with a Kimwipes® towel cleans. The Cobb Hot Oil test quantifies the weight of the hot oil absorbed in grams / square meter using the same calculation described under the Cobb Hot Water Test. In both Cobb Hot Water and Hot Oil tests, a higher result indicates a greater degree of absorption by the paper sample. Conversely, a lower Cobb test value is indicative of wetting and low surface penetration and better sizing properties. The data in Table a shows the typical negative impact of a water sizing agent on the permanence of an oil sizing product. For example, as the water level is increased, water sizing improves while the oil sizing property is reduced. The water sizing agent is comprised of alkyl ketene dimer while the oil squeeze is a product containing perfluoroalkyl. Table A: Water and Oil Sizing ResultsSizing Hot Water Sizing Commercial Water Oil Cobb Hot Oil Commercial Cobb (% by weight) (% by weight) (g / m *) (g / m *) 0.132 0.225. 162 89 0.155 0.225 71 118The following definitions apply for theTable A: AKD Commercial Water Sizing: Hercon® - Hercules Incoporated Commercial Oil Sizing: ImPress® FP-100 Hercules Incorporated% by Weight:% Addition of Active Treatment Solids Based on Total Solids Provision The following Examples are illustrative of surprising beneficial effect of polyvinylamine in both, resistance to water and oil in cellulose based systems that require high levels of water and oil sizing. EXAMPLE 1 The data of Example 1 is summarized in Table 1.
In this study, hand sheets were prepared using the same papermaking process described in ExampleA with the exception that the provision was comprised of refined commercial market pulps at 480 mi of Canadian Standard Freeness (CSF) of 560% Kraft of bleached soft wood from the south and 40% of Kraft of bleached hardwood from the north. The base weight of the goal was 248 grams / square meter. The chemical addition sequence as described in Example A, except that when polyvinylamine was included in the test, was added to the mixing provision 30 seconds before the addition of the water sizing agent. The manual sheet performance test was conducted using the same procedures as those described in Example A, except that an Ambient Saline Cbb 2% test is conducted instead of the Cobb Hot Water test. The salt used in the test is at room temperature and is derived from deionized water treated with NaCl at 2% by weight. Apart from these differences, the test procedure is identical to the Cobb Hot Water test method described in Example A. The data summarized in Table 1 show the simultaneous positive effect of polyvinylamine on both water and oil sizing test results. . The low values of Cobb's Salina and Agua Caliente test show that an effective balance in water and oil resistance is achieved through the addition of polyvinylamine. The agentof water sizing is comprised of alkyl ketene dimer while oil sizing is a product containing perfluoroalkyl. Polyvinylamine is a polymer in solution that has been reacted at a 50% hydrolysis level. Table 1: Results of Water and Oil SizingThe following definitions apply for theTable 1: Commercial Polyvinylamine: Hercules® PPD M-1189 - Hercules Incorporated AKD Commercial Water Squeeze: Hercon® 80 Hercules IncorporatedCommercial Oil Sizing: ImPress® FP-100 Hercules Incorporated% in Weight:% Addition of Solids for Acvtive Treatment Based on Total Provision Solids EXAMPLE 2 The data of Example 2 are summarized in Table 2. In this work, they were prepared manual sheets of 160 grams / square meter using the same papermaking process and furnish mixture described in Example A. The Canadian Standard Freeness goal for pulp refining was 470 mis. The chemical addition sequence was consistent with the description provided in Example A, except that when an anionic polymer was included in the test, it was added to the mixing provision 30 seconds after the addition of the water sizing agent and 30 seconds before the addition of the oil sizing material. When the polyvinylamine was included in the test, it was added to the mixing provision 30 seconds before the addition of the water sizing agent. The manual sheet performance test was conducted using the same procedures as described in Example A. The data in Table 2 further demonstrates the beneficial effect of polyvinylamine on both size sizing properties.water and oil since low Cobb values are achieved with the addition of polyvinylamine to the test provision. The water sizing agent is comprised of alkyl ketene dimer. Oil sizing is a product containing perfluoroalkyl, and polyvinylamine is a polymer in solution that has been reacted at a 50% hydrolysis level. The anionic polymer is a solution copolymer of acrylamide and acrylic acid (Hercobond 2000). The anionic polymer is used as a retention aid to improve the retention of fine solids in the web during the sheet forming process. Table 2: Water and Oil Sizing ResultsThe following definitions apply to Table 2: Commercial Polyvinylamine: Hercules® PPD M-1189 -Hercules incorporated Commercial Water Sanitizer (1): 60: 490 Mixture of ReTen® 204L / Hercon® 70 - Hercules Incorporated Commercial Water Sanitizer (2): Hercon® 70 Hercules Incorporated Commercial Anionic Polymer: ImPress® FP-100 Hercules Incorporated% 4in Weight_% Addition of Active Treatment Solids Based on Total Proportioning Solids. EXAMPLE 3 The data of Example 3 is summarized in Table 3. In this study, manual sheets were prepared using the same papermaking process as described in Example A with the exception that the provision was comprised of refined pulps of 70%. % Bleached softwood kraft from the south and 30% kraft from bleached hardwood from the north refined to 405 my CFanadian Standard Freeness. The base weight of the goal was 149 grams / square meter. The chemical addition sequence was consistent with the description provided in Example A, except that when anyof polyvinylamine or branched polyamines were included in the test, added to the mixing provision 30 seconds before the addition of the water sizing agent. In addition, the ionic polymer and colloidal silica were added in sequence order 30 seconds after the addition of the water size and 30 seconds before the addition of the oil sizing agent with 30 seconds of mixing time between each addition of product. The manual sheet performance test was conducted using the same procedures described in Example A. The data in the Table 3 reviews the positive effect of polyvinylamine on water and oil sizing results. The trends associated with polyvinylamine further demonstrate that it is possible to reduce the addition level of water and oil sizing agents while maintaining a low effective equilibrium of Cobb test values indicative of high water and oil resistance properties. The test data associated with the branched polyamines indicates that it is difficult to achieve the same effective balance in water and oil sizing properties compared to test conditions involving polyvinylamine. In this example, the branched polyamines is apolymer in solution with quaternary amine functionality. The polyvinylamine is a solution polymer reacted to a 50% hydrolysis level with a predominantly linear structure and primary amine functionality. The water sizing agent is comprised of alkyl ketene dimer, while oil sizing is a product containing perfluoroalkyl. The anionic polymer is an emulsion copolymer of acrylamide and acrylic acid. The silica component is an aqueous dispersion of colloidal silica particles. The anionic polymer and the colloidal silica are added to the supply with the purpose of increasing the retention of fine solids in the paper web in the formation process. Table 3: Results of Polishing Water and PoliPiliApresto Polysilice Apresto Cobb Cobb amine vinyl Water mere Colloid Water Acei¬Ramiamina ComerAniónico dal Oil Cate Caficada Comercial ComerComerComeriente lienteCommercial cial cial (% in (% in (% in (% in (% in (% in (gt / m2) (g / m) weight) weight) weight) weight) weight) weight 0.35 0. 0.14 0.29 0.09 0.15 49 950. 35 0 0.14 0.29 0.09 0.17 51 550. 35 0 0.14 0.29 0.09 0.19 47 390. 35 0 0.14 0.29 0.09 0.21 51 410. 35 0 0.14 0.29 0.09 0.23 76 390. 30 0 0.14 0.29 0.09 0.19 49 360. 40 0 0.14 0.29 0.09 0.19 57 390 0.15 0.14 0.29 0.09 0.19 39 470 0.20 0.14 0.29 0.09 0.19 39 350 0.20 0.12 0.29 0.09 0.17 39 340 0.20 0.10 0.29 0.09 0.15 40 33The following definitions apply for theTable 3: Branched Commercial Polyamine: Nalco 7607 - Nalco Polyvinylamine Commercial. Hercules® PPD M-11698 - Hercules Incorporated Commercial Water Squeeze: Hercon® 79 - HerculesIncorporated Commercial Anionic Polymer: PerForm® PA8137Hercules Incorporated Commercial Colloidal Silica: Positek 8691 - Nalco Commercial Oil Sizing: ImPress® FP-100Hercules Incorporated% in Weight_% of Addition of Solids of Active Treatment Based on Total Solids of Provision.