Water-resistant agent kit for papermaking, water-resistant paper and its manufacturing method

Abstract

To provide a water resistant agent kit for paper making, capable of suitably producing water resistant paper, when used in paper making.SOLUTION: The water resistant agent kit for paper making, comprising a first agent consisting of a cationic polymer coagulant and a second agent consisting of a non-fluorine type water resistant agent, is for imparting water resistance to a paper substrate prepared by paper making of a paper material, by blending a paper material with the first agent and subsequently with the second agent at a time of using the kit.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a waterproofing agent kit for papermaking, waterproof paper, and a method for producing the same. [Background technology]

[0002] Paper that has been given water resistance, oil resistance, etc., such as waterproof paper and oil resistance paper, is used in various fields. Various methods have been proposed as methods for producing such modified paper.

[0003] For example, Patent Document 1 discloses a paper substrate having at least C of (meth)acrylic acid. 12 ~C 40 A method for modifying a paper substrate has been proposed in which the substrate is coated with a polymer having alkyl esters as polymerized units.

[0004] Furthermore, Patent Document 2 proposes a water-repellent and oil-resistant paper in which at least one of the oil-resistant layers contains a methacrylic acid-acrylic acid alkyl ester-styrene copolymer water repellent.

[0005] Patent Document 3 also proposes a resin-containing paper that contains a resin component consisting of a synthetic resin with a glass transition point of 20°C or higher and a water repellent, the content of the resin component being 2% by mass or more and less than 30% by mass, and the weight ratio of synthetic resin / water repellent being 80 / 20 to 98 / 2.

[0006] Furthermore, Patent Document 4 proposes a coated cellulose article having excellent oil and fat resistance, water resistance, or moisture permeability, in which an aqueous dispersion of a melt-kneaded mixture of an ethylene-based thermoplastic polymer and at least one type of polymer stabilizer is coated on a cellulose-based substrate. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2000-154493 A [Patent Document 2] JP 2015-151647 A [Patent Document 3] JP 2004-308094 A [Patent Document 4] JP 2016-65352 A Summary of the Invention [Problem to be solved by the invention]

[0008] The main object of the present invention is to provide a waterproofing agent kit for papermaking that can be used in papermaking to suitably produce waterproof paper. Another object of the present invention is to provide a method for producing waterproof paper using the waterproofing agent kit for papermaking, and waterproof paper. [Means for solving the problem]

[0009] The present inventors have conducted intensive studies to solve the above problems. As a result, they have found that a kit comprising a first agent made of a cationic polymer coagulant and a second agent made of a non-fluorine-based water-resistant agent can be prepared, and that the kit can be used to mix the paper stock with the first agent and the second agent in sequence when used, and then the paper stock is made, thereby suitably imparting water resistance to a paper base material. Furthermore, they have also found that when a cationic polymer coagulant having a cationic charge density within a specific range is used, water resistance can be suitably imparted to a paper base material, regardless of whether the non-fluorine-based water-resistant agent is anionic or cationic. They have also found that water resistance can be suitably imparted to a paper base material, even when a paper stock with a high content of recycled paper (i.e., a paper stock with a high content of fine fibers) is used. The present invention is an invention that has been completed based on such findings and through further intensive studies.

[0010] That is, the present invention provides the following configuration. Item 1. A first agent comprising a cationic polymer coagulant; A second agent consisting of a non-fluorinated water resistant agent; Equipped with A water-resistant agent kit for papermaking, which is used to sequentially mix the paper stock with the first agent and the second agent when used to impart water resistance to a paper base material from which the paper stock is made. Item 2. The papermaking waterproofing agent kit according to Item 1, wherein the non-fluorinated waterproofing agent has a charge density of −100.0 to +200.0 μeq / g. Item 3. The waterproofing agent kit for papermaking according to Item 1 or 2, wherein the non-fluorine-based waterproofing agent is at least one selected from the group consisting of a long-chain acrylate-based waterproofing agent, a long-chain acrylate-silicone macromonomer copolymer-based waterproofing agent, a hybrid emulsion-based waterproofing agent, a long-chain acrylate-halogenated olefin copolymer-based waterproofing agent, a blend-based waterproofing agent of a long-chain acrylate copolymer and a long-chain alkyl-modified silicone polymer, a blend-based waterproofing agent of a long-chain acrylate copolymer, a vinyl chloride polymer, and a silicone resin, a blend-based waterproofing agent of an amino-modified silicone, a silicone resin, and a polyfunctional isocyanate, a polyurethane-based waterproofing agent, a polyurea-based waterproofing agent, and a polyurethane dendrimer-based waterproofing agent. Item 4. The papermaking waterproofing agent kit according to any one of Items 1 to 3, wherein the cationic polymer coagulant has a cationic charge density of +100.0 to +10000.0 μeq / g. Item 5. The waterproofing agent kit for papermaking according to any one of Items 1 to 4, wherein the cationic polymer coagulant is at least one selected from the group consisting of polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, cationic starch, cationic polyacrylamide, cationic modified polyvinyl alcohol, polydiallyldimethylammonium chloride or a derivative thereof, a copolymer of diallyldimethylammonium chloride and another monomer, polyamine, polyallylamine, polyvinylamine, polyethyleneimine, 2-(methacryloyloxy)ethyltrimethylammonium chloride polymer, N-vinylformamide-vinylamine copolymer, melamine resin, polyamide epoxy resin, polyamide polyamine resin, dimethylamine epichlorohydrin resin, and dimethylamine-ethylenediamine epichlorohydrin copolymer. Item 6. Waterproof paper, in which at least a cationic polymer coagulant and a non-fluorine-based waterproofing agent are contained in a paper base material. Item 7. Waterproof paper, which is obtained by subjecting a paper base material to a waterproofing treatment using the waterproofing agent kit for papermaking according to any one of items 1 to 5. Item 8. The Cobb water absorption measured in accordance with JIS P8140:1998 (Paper and paperboard - Water absorption test method - Cobb method) is 25.0 g / m 2 Item 6 or 7. The waterproof paper according to item 6 or 7, which is as follows: Item 9. The total content of the cationic polymer coagulant and the non-fluorine-based waterproofing agent is 0.05 to 10.0 g / m 2 Item 9. The waterproof paper according to any one of items 6 to 8, Item 10. The waterproof paper according to any one of Items 6 to 9, wherein the content of the cationic polymer coagulant is 0.05 to 10.0 mass %, and the content of the non-fluorine-based waterproofing agent is 0.5 to 20.0 mass %. Item 11. A process 1 for mixing a first agent consisting of a cationic polymer coagulant with a paper stock; A step 2 of mixing the mixture obtained in the step 1 with a second agent comprising a non-fluorinated water-resistant agent; Step 3 is a papermaking process using the mixture obtained in step 2; A method for producing waterproof paper comprising the steps of: Effect of the Invention

[0011] According to the present invention, it is possible to provide a waterproof agent kit for papermaking that can be used in papermaking to suitably produce waterproof paper. Also, according to the present invention, it is possible to provide a method for producing waterproof paper using the waterproof agent kit for papermaking, and waterproof paper. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The waterproofing agent kit for papermaking of the present invention is characterized in that it comprises at least a first agent consisting of a cationic polymer coagulant and a second agent consisting of a non-fluorine-based waterproofing agent, and is used to impart water resistance to a paper base material from which the paper stock is made by sequentially mixing the first agent and the second agent when used. By having such a configuration, the waterproofing agent kit for papermaking of the present invention can suitably impart water resistance to a paper base material.

[0013] The waterproof paper of the present invention can be suitably manufactured by using the waterproofing agent kit for papermaking of the present invention. That is, the waterproof paper of the present invention is characterized in that the paper base material is waterproofed using the waterproofing agent kit for papermaking of the present invention. In the waterproof paper of the present invention, at least a cationic polymer coagulant and a non-fluorine-based waterproofing agent are contained in the paper base material. By having such a configuration, the waterproof paper of the present invention can exhibit excellent waterproofness.

[0014] The method for producing waterproof paper of the present invention is a method for producing waterproof paper using the waterproofing agent kit for papermaking of the present invention, and is characterized by comprising at least step 1 of mixing a first agent consisting of a cationic polymer coagulant with paper stock, step 2 of mixing the mixture obtained in step 1 with a second agent consisting of a non-fluorinated waterproofing agent, and step 3 of making paper from the mixture obtained in step 2. The method for producing waterproof paper of the present invention, having such a configuration, can suitably produce waterproof paper.

[0015] The papermaking waterproofing agent kit, waterproof paper, and method for producing waterproof paper of the present invention will be described in detail below.

[0016] In the present invention, the "charge density" is a value determined by adding a standard titrant having an opposite charge to that of the sample to the sample until the charge amount becomes zero. Generally, sodium polyethylene sulfonate (PES-Na) or potassium polyvinyl sulfate (PVSK) is used as the anion titrant, and polydiallyldimethylammonium chloride (PolyDADMAC) is used as the cation titrant.

[0017] Further, the term "stock slurry" refers to a dispersion of stock in a liquid medium, and for example, "pulp slurry" refers to a dispersion of pulp in a liquid medium.

[0018] In addition, the term "anionic group" refers to a group that has a negative charge when the cation dissociates, and includes an acid type in which the cation is a proton, and a salt type in which the cation is an alkali metal ion, ammonium ion, or the like.

[0019] Additionally, "(meth)acrylate" is a general term for acrylate and methacrylate.

[0020] Moreover, "containing" as a "main component" means that the component is contained in an amount of 50% by mass or more.

[0021] [Waterproofing agent kit for papermaking] The water-resistant agent kit for papermaking of the present invention includes a cationic polymer coagulant as the first agent and a non-fluorine-based water-resistant agent as the second agent. The water-resistant agent kit for papermaking of the present invention is used as follows. That is, a mixture is obtained by mixing a paper stock described below with a cationic polymer coagulant as the first agent. Next, the mixture obtained is mixed with a non-fluorine-based water-resistant agent as the second agent to obtain a mixture. By subjecting the mixture obtained in this manner to papermaking, a paper base material in which the non-fluorine-based water-resistant agent is suitably attached to the paper base material is obtained, and water resistance is imparted to the paper base material.

[0022] (Cationic polymer coagulant) The cationic polymer coagulant may be a cationic paper strength enhancer used in normal papermaking, etc. The cationic polymer coagulant may be used alone or in combination of two or more kinds.

[0023] The cationic polymer coagulant preferably has a cationic charge density of about +100.0 to +10000.0 μeq / g. If the cationic polymer coagulant has a cationic charge density equal to or higher than the lower limit of the above range, anionic stock (i.e., cellulose, etc.) can be suitably cationized even when a stock containing a large amount of fine fibers is used, such as a stock with a high recycled paper content (e.g., a stock with a recycled paper content of 60% or more). If the cationic charge density of the cationic polymer coagulant is equal to or lower than the upper limit of the above range, fine fibers can be suitably captured by the cationic polymer coagulant during papermaking, even when a stock containing a large amount of fine fibers is used, such as a stock with a high recycled paper content. By satisfying these cationic charge densities, the non-fluorine-based waterproofing agent described below can be fixed to the stock surface with high uniformity, whether it is anionic (anionic non-fluorine-based waterproofing agent) or cationic (i.e., cationic non-fluorine-based waterproofing agent).

[0024] Specific examples of cationic polymer coagulants include polyamine epichlorohydrin resins, polyamide epichlorohydrin resins, cationic starch, cationic polyacrylamides (acrylamide-allylamine copolymers, acrylamide-dimethylaminoethyl (meth)acrylate copolymers, acrylamide-diethylaminoethyl (meth)acrylate copolymers, acrylamide-quaternary dimethylaminoethyl (meth)acrylate copolymers, acrylamide-quaternary diethylaminoethyl (meth)acrylate copolymers, etc.), cationic modified polyvinyl alcohol, polydiallyldimethylammonium chloride or derivatives thereof, copolymers of diallyldimethylammonium chloride and other monomers, polyamines, polyallylamine, polyvinylamine, polyethyleneimine, 2-(methacryloyloxy)ethyltrimethylammonium chloride polymers, N-vinylformamide-vinylamine copolymers, melamine resins, polyamide epoxy resins, polyamide polyamine resins, dimethylamine epichlorohydrin resins, dimethylamine-ethylenediamine epichlorohydrin copolymer resins, etc.

[0025] The proportion of the cationic polymer coagulant used relative to 100.0 parts by mass of the paper stock (solid content) is preferably about 0.05 to 10.0 parts by mass, and more preferably about 0.1 to 5.0 parts by mass.

[0026] In addition, in the waterproofing agent kit for papermaking of the present invention, the ratio of the cationic polymer coagulant as the first agent to the non-fluorine-based waterproofing agent as the second agent (first agent:second agent (mass ratio)) is preferably about 1:0.5-100, and more preferably about 1:1-50.

[0027] (Non-fluorinated waterproofing agent) As the fluorine-based waterproofing agent, either anionic non-fluorine-based waterproofing agents or cationic non-fluorine-based waterproofing agents can be used, but from the viewpoint of the fixing efficiency of the non-fluorine-based waterproofing agent to the paper stock, cationic non-fluorine-based waterproofing agents are preferred. Only one type of non-fluorine-based waterproofing agent may be used, or two or more types may be mixed and used.

[0028] Specific examples of non-fluorine-based water-resistant agents include long-chain acrylate-based water-resistant agents, long-chain acrylate-silicone macromonomer copolymer-based water-resistant agents, hybrid emulsion-based water-resistant agents, long-chain acrylate-halogenated olefin copolymer-based water-resistant agents, blend-based water-resistant agents of long-chain acrylate copolymers and long-chain alkyl-modified silicone polymers, blend-based water-resistant agents of long-chain acrylate copolymers, vinyl chloride polymers and silicone resins, blend-based water-resistant agents of amino-modified silicones, silicone resins and polyfunctional isocyanates, polyurethane-based water-resistant agents, polyurea-based water-resistant agents and polyurethane dendrimer-based water-resistant agents.

[0029] The charge density of the non-fluorinated waterproofing agent is preferably about −100.0 to +200.0 μeq / g.

[0030] (Paper materials) The paper stock to be treated by the waterproofing agent kit for papermaking of the present invention is not particularly limited as long as it is used for papermaking, and may be, for example, uncoated paper stock. Pulp is generally used as the paper stock. Examples of pulp include those containing plant cellulose (wood, grass, bamboo, rice straw, reed, bagasse, palm, etc.). Recycled pulp produced by treating waste paper may also be used. Only one type of pulp may be used, or two or more types may be mixed together.

[0031] Specific examples of pulp include bleached softwood kraft pulp (NBKP), bleached hardwood kraft pulp (LBKP), groundwood pulp (GP), thermomechanical pulp (TMP), chemi-thermomechanical pulp (CTMP), deinked pulp (DIP), etc. As described above, the waterproofing agent for papermaking of the present invention is particularly suitable for use in the manufacture of paper using pulp with a high recycled paper content (e.g., pulp with a recycled paper content of 60% or more). Examples of recycled paper pulp used in the present invention include disintegrated recycled paper pulp, disintegrated and deinked recycled paper pulp (DIP), or disintegrated, deinked and bleached recycled paper pulp, etc., which are manufactured from brown recycled paper, kraft envelope recycled paper, magazine recycled paper, newspaper recycled paper, flyer recycled paper, office recycled paper, cardboard recycled paper, white recycled paper, Kent recycled paper, imitation recycled paper, and land-registered recycled paper.

[0032] The water resistance agent kit for papermaking of the present invention is preferably used in the papermaking process. Therefore, it is preferable that the paper stock is in a slurry (preferably pulp slurry) state and mixed in sequence with the first agent and the second agent of the water resistance agent kit for papermaking of the present invention. In general, in the papermaking process in papermaking, the paper stock is dispersed in water and diluted, and then the obtained slurry of the paper stock is placed on a wire (net) and the water is removed to make paper (wire part). In the water resistance agent kit for papermaking of the present invention, the first agent (cationic polymer coagulant) is added to the paper stock slurry in the papermaking process, so that the first agent is suitably attached to the paper stock, and further, the second agent (non-fluorine-based water resistance agent) is also suitably attached to the paper stock due to the first agent being attached to the paper stock, so that the outflow of the non-fluorine-based water resistance agent in the wire part is suppressed, and water resistance can be suitably imparted to the paper base material after papermaking. The impartation of such water resistance can exhibit a particularly remarkable effect when the paper stock is made of pulp containing a large amount of fine fibers and having a high recycled paper content. In the present invention, when the cationic charge density of the cationic polymer coagulant is within the above range, it is particularly effective in achieving the above effect.

[0033] In the papermaking process using the waterproofing agent kit for papermaking of the present invention, other additives may be added in addition to the first and second agents. The additives may be those used in the papermaking process of known paper manufacturing methods, such as softeners, sizing agents, fixing agents, dry strength agents, wet strength agents, aluminum sulfate, retention aids, dyes, pigments, etc. For example, the sizing agents may be cationic sizing agents, anionic sizing agents, rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents, etc.), styrene-acrylic acid-based copolymers, alkenyl succinic anhydrides, alkyl ketene dimers, etc. The amount of additives used may be adjusted as appropriate. For example, the amount of sizing agent may be about 0.001 to 5.0 parts by mass per 100 parts by mass of paper material (solid content).

[0034] [Water-resistant paper manufacturing method] The method for producing waterproof paper of the present invention includes step 1 of mixing a first agent consisting of a cationic polymer coagulant with paper stock, step 2 of mixing the mixture obtained in step 1 with a second agent consisting of a non-fluorine-based waterproofing agent, and step 3 of making paper from the mixture obtained in step 2.

[0035] The waterproof paper of the present invention can be suitably produced by using the waterproofing agent kit for papermaking of the present invention described above, for example.

[0036] In step 1, the first agent consisting of a cationic polymer coagulant is mixed with the paper stock. Details of the cationic polymer coagulant and the paper stock are as described above.

[0037] When pulp is used as the paper material, known pulping methods can be used for pulping vegetable cellulose, etc., such as mechanical pulping, thermomechanical pulping, chemi-thermomechanical pulping, kraft pulping, sulfite pulping, deinking pulping, and recycled pulping.

[0038] As described above, it is preferable that the stock is dispersed in water to form a slurry, and the first agent is added to and mixed with the slurry. The stock slurry can be prepared by disintegrating the stock in a liquid medium by a known method. Examples of the disintegration method include a method using a disintegrator. The liquid medium is preferably an aqueous medium containing water as the main component. In terms of handling and safety and hygiene, the aqueous medium is preferably water or an azeotropic mixture containing water and an organic solvent that forms an azeotropic mixture with water. Examples of the organic solvent include propylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and diacetone alcohol.

[0039] The lower limit of the stock concentration in the slurry is preferably 0.3% by mass, more preferably 0.7% by mass, and even more preferably 1.0% by mass. The upper limit of the stock concentration in the slurry is preferably 6.0% by mass, more preferably 5.0% by mass, and even more preferably 4.0% by mass. When the stock concentration is equal to or higher than the lower limit of the above range, the effects of the present invention are fully exhibited. When the stock concentration is equal to or lower than the upper limit of the above range, the fine fibers are even less likely to aggregate. Therefore, the surface of the fine fibers can be more uniformly cationized by the cationic polymer coagulant.

[0040] In step 1, the mixing ratio of the cationic polymer coagulant is preferably 0.3 to 5.0 parts by mass, more preferably 1.0 to 4.0 parts by mass, relative to the stock (100.0 parts by mass of solids). If the mixing ratio of the cationic polymer coagulant is equal to or greater than the lower limit of the above range, the fine fibers can be cationized more sufficiently by the cationic polymer coagulant. If the mixing ratio of the cationic polymer coagulant is equal to or less than the upper limit of the above range, the stock is less likely to be agglomerated by the cationic polymer coagulant even if, for example, the waste paper content in the slurry is high. Therefore, the fine fibers can be cationized more uniformly by the cationic polymer coagulant.

[0041] In step 2, the mixture of the stock and the first agent obtained in step 1 is mixed with the second agent consisting of a non-fluorine-based waterproofing agent. Details of the non-fluorine-based waterproofing agent are as described above. As described above, it is preferable that the stock is dispersed in water to form a slurry, the first agent is added to the slurry and mixed in step 1, and the second agent is further added in step 2.

[0042] In step 2, the mixing ratio of the non-fluorine-based waterproofing agent is preferably 0.5 to 20.0 parts by mass, more preferably 1.0 to 15.0 parts by mass, and particularly preferably 1.0 to 10.0 parts by mass, relative to the paper material (100.0 parts by mass of solid content). If the mixing ratio of the non-fluorine-based oil-proofing agent is equal to or higher than the lower limit of the above range, waterproof paper with even more excellent water resistance can be obtained. If the content ratio of the non-fluorine-based oil-proofing agent is equal to or lower than the upper limit of the above range, it is advantageous in terms of cost.

[0043] In steps 1 and 2, the above-mentioned additives can be mixed within the range that does not impair the effects of the present invention. The first and second agents and the above-mentioned additives, which are mixed as necessary, can be mixed at any stage in the papermaking process in step 3 described below, as long as it is before the stock is supplied onto the wire. Specifically, it can be mixed in the pulp manufacturing process, stock preparation process, etc., and is preferably mixed in the stock preparation process.

[0044] In step 3, the mixture obtained in step 2 is made into paper. The papermaking method can be a known method used in papermaking, and is generally carried out using a papermaking machine. The papermaking machine may be any device capable of dewatering the stock slurry on a wire. In addition to continuous papermaking machines such as Fourdrinier papermaking machines, the papermaking machine also includes batch-type molding machines in which the stock slurry is added onto a molding frame formed by a wire, and then dewatered from below the wire to produce a molded body.

[0045] According to the method for producing waterproof paper of the present invention, waterproof paper is produced in which the cationic polymer coagulant and the non-fluorine-based waterproof agent are dispersed throughout the entire paper base material, as described above. In other words, since the entire waterproof paper of the present invention contains the cationic polymer coagulant and the non-fluorine-based waterproof agent, it is possible to suitably suppress the deterioration of water resistance due to folds and wrinkles in the waterproof paper, as compared with waterproof paper in which water resistance is imparted only to the surface portion of the paper base material.

[0046] [Water-resistant paper] The waterproof paper of the present invention includes at least a paper base material, a cationic polymer coagulant, and a non-fluorine-based waterproof agent. As described above, the waterproof paper of the present invention can be a waterproof paper in which the cationic polymer coagulant and the non-fluorine-based waterproof agent are dispersed throughout the paper base material.

[0047] The method for producing the waterproof paper of the present invention is not particularly limited, but for example, the waterproof paper can be suitably produced by waterproofing a paper base material using the waterproofing agent kit for papermaking of the present invention described above. Specifically, the waterproof paper can be suitably produced by employing the manufacturing method of the present invention described above.

[0048] The cationic polymer coagulant, non-fluorine-based waterproofing agent, paper stock, additives mixed as required, and the like contained in the waterproof paper are as described above.

[0049] In the waterproof paper of the present invention, the content of the cationic polymer coagulant is preferably 0.05 to 10.0% by mass, more preferably 0.1 to 5.0% by mass. The content of the non-fluorine-based waterproof agent is preferably 0.5 to 20.0% by mass, more preferably 1.0 to 15.0% by mass, and particularly preferably 1.0 to 10.0% by mass. In the waterproof paper of the present invention, the total content of the cationic polymer coagulant and the non-fluorine-based waterproof agent is preferably 0.05 to 10.0 g / m 2 , more preferably 0.1 to 5.0 g / m 2 It is.

[0050] The waterproof paper of the present invention has a Cobb water absorption of 25.0 g / m2 or less, as measured in accordance with JIS P8140:1998 (Paper and paperboard-Water absorption test method-Cobb method). 2 It is preferable that the thickness is 21.0 g / m or less. 2 It is more preferable that:

[0051] In the waterproof paper of the present invention, the paper base material may be in the form of a long web, cut into sheets, or molded articles (containers, etc.) obtained using a pulp molding machine.

[0052] In the waterproof paper of the present invention, a layer different from the paper base may be provided on the surface of the paper base, such as a coating layer in so-called coated paper, which is formed by applying a paint containing a pigment to the surface of the paper base. EXAMPLES

[0053] The present invention will be described in detail below with reference to examples, comparative examples, and reference examples, but the present invention is not limited to the examples.

[0054] (charge density) The charge density was measured using a particle charge meter (Paticle Charge Detector PCD03) manufactured by BTG. The measurement sample was diluted with water so that the titration volume was 0.1 to 1.0 ml, and 10.0 ml of the diluted sample was measured into a measurement container using a measuring pipette. When measuring a cationic sample, the anionic titrant was used, and when measuring an anionic sample, the cationic titrant was used. The charge density was calculated from the titration volume.

[0055] (Cationic polymer coagulant) The following cationic polymer coagulants were used: Cationic polymeric coagulant (A1): Polyamide epichlorohydrin, Kymene 557H manufactured by Hercules, charge density 2010 μeq / 1g (solids) Cationic polymer coagulant (A2): Cationic polyacrylamide, Aromafix PT manufactured by Meisei Chemical Industry Co., Ltd., charge density 550μeq / 1g (solid content) Cationic polymer coagulant (A3): Polydiallyldimethylammonium chloride, Meisei Chemical Co., Ltd. AG Fix M-80, charge density 6200 μeq / 1g (solid content)

[0056] (Non-fluorinated waterproofing agent) The following non-fluorine-based waterproofing agents were used: Non-fluorinated water resistant agent (B1): Long-chain acrylate-silicone copolymer water resistant agent, charge density 88.0 μeq / 1 g (solids) Non-fluorinated water resistant agent (B2): Long-chain acrylate-vinyl chloride copolymer water resistant agent, charge density 100.6 μeq / 1 g (solid content) Non-fluorinated water resistant agent (B3): Hybrid emulsion water resistant agent, charge density 5.2μeq / 1g (solid content) Non-fluorinated water resistant agent (B4): Long-chain acrylate-silicone copolymer water resistant agent, charge density - 58.0 μeq / 1 g (solid content) Non-fluorinated water resistant agent (B5): Long-chain acrylate water resistant agent, charge density -568.0μeq / 1g (solid content)

[0057] Example 1 The waste corrugated paper pulp was dispersed in water to adjust the pulp concentration to 1% by mass, and a chemical-free waste corrugated paper pulp slurry was obtained. A cationic polymer coagulant (A1) was added to the chemical-free waste corrugated paper pulp slurry in an amount of 0.2 parts by mass per 100.0 parts by mass of pulp in the pulp slurry, and the mixture was stirred for 5 minutes. Further, a non-fluorine-based waterproofing agent (B1) was added in an amount of 5.4 parts by mass per 100.0 parts by mass of pulp in the pulp slurry, and the mixture was stirred for 5 minutes, after which the basis weight was adjusted to 50 g / m 2 Thus, the waterproof paper according to the present invention was obtained.

[0058] Example 2 Waterproof paper was obtained in the same manner as in Example 1, except that the amount of cationic polymer coagulant (A1) added was changed to 3.6 parts by mass per 100.0 parts by mass of pulp in the pulp slurry.

[0059] Example 3 Waterproof paper was obtained in the same manner as in Example 1, except that the cationic polymer coagulant (A1) was changed to the cationic polymer coagulant (A2).

[0060] Example 4 Waterproof paper was obtained in the same manner as in Example 3, except that the amount of cationic polymer coagulant (A2) added was changed to 3.6 parts by mass per 100.0 parts by mass of pulp in the pulp slurry.

[0061] Example 5 Waterproof paper was obtained in the same manner as in Example 1, except that the cationic polymer coagulant (A1) was changed to the cationic polymer coagulant (A3).

[0062] Example 6 Waterproof paper was obtained in the same manner as in Example 1, except that the non-fluorine-based waterproof agent (B1) was changed to the non-fluorine-based waterproof agent (B2).

[0063] Example 7 Waterproof paper was obtained in the same manner as in Example 1, except that the non-fluorine-based waterproof agent (B1) was changed to the non-fluorine-based waterproof agent (B3).

[0064] Example 8 Waterproof paper was obtained in the same manner as in Example 7, except that the amount of the non-fluorinated waterproofing agent (B3) added was changed to 3.6 parts by mass per 100.0 parts by mass of pulp in the pulp slurry.

[0065] Example 9 Waterproof paper was obtained in the same manner as in Example 7, except that the amount of the non-fluorinated waterproofing agent (B3) added was changed to 7.2 parts by mass per 100.0 parts by mass of pulp in the pulp slurry.

[0066] Example 10 Waterproof paper was obtained in the same manner as in Example 1, except that the non-fluorine-based waterproof agent (B1) was changed to the non-fluorine-based waterproof agent (B4).

[0067] Example 11 Waterproof paper was obtained in the same manner as in Example 10, except that the amount of cationic polymer coagulant (A1) added was changed to 2.4 parts by mass per 100.0 parts by mass of pulp in the pulp slurry.

[0068] Example 12 Waterproof paper was obtained in the same manner as in Example 11, except that the amount of the non-fluorinated waterproofing agent (B4) added was changed to 3.6 parts by mass per 100.0 parts by mass of pulp in the pulp slurry.

[0069] (Example 13) Hardwood bleached kraft pulp (LBKP) and softwood bleached kraft pulp (NBKP), which had been refined to a Canadian standard freeness of 140 ml, were mixed in a dry mass ratio of LBKP:NBKP = 70:30, dispersed in water, and the pulp concentration was adjusted to 1 mass%, to obtain a virgin pulp slurry without added chemicals.

[0070] A cationic polymer coagulant (A1) was added to a virgin pulp slurry containing no chemicals in an amount of 0.2 parts by mass per 100.0 parts by mass of pulp in the pulp slurry, and the mixture was stirred for 5 minutes. A non-fluorine-based waterproofing agent (B1) was then added to the pulp slurry in an amount of 5.4 parts by mass per 100 parts by mass of pulp in the pulp slurry, and the mixture was stirred for 5 minutes until the basis weight reached 50 g / m. 2 Thus, waterproof paper was obtained.

[0071] Example 14 Waterproof paper was obtained in the same manner as in Example 13, except that the non-fluorine-based waterproof agent (B1) was changed to a non-fluorine-based waterproof agent (B3) and the amount of the non-fluorine-based waterproof agent added was changed to 1.8 parts by mass per 100.0 parts by mass of pulp in the pulp slurry.

[0072] Comparative Example 1 Waterproof paper was obtained in the same manner as in Example 1, except that the cationic polymer coagulant (A1) was not added in the production of waterproof paper in Example 1.

[0073] Comparative Example 2 Waterproof paper was obtained in the same manner as in Example 1, except that the non-fluorinated waterproofing agent (B1) was not added in the production of waterproof paper in Example 1.

[0074] Comparative Example 3 Waterproof paper was obtained in the same manner as in Example 13, except that the cationic polymer coagulant (A1) was not added in the production of waterproof paper in Example 13.

[0075] Comparative Example 4 Waterproof paper was obtained in the same manner as in Example 13, except that the non-fluorinated waterproofing agent (B1) was not added in the production of waterproof paper in Example 13.

[0076] (Reference example 1) Waterproof paper was obtained in the same manner as in Example 5, except that the amount of cationic polymer coagulant (A3) added was changed to 1.6 parts by mass per 100.0 parts by mass of pulp in the pulp slurry.

[0077] (Reference example 2) Waterproof paper was obtained in the same manner as in Example 1, except that the non-fluorine-based waterproof agent (B1) was changed to the non-fluorine-based waterproof agent (B5).

[0078] The waterproof paper thus obtained was subjected to the following evaluations, and the evaluation results are shown in Table 1.

[0079] (Water absorption) According to JIS P 8140:1998 "Paper and paperboard-Water absorption test method-Cobb method", the water absorption of the test paper was measured at a contact time of 60 seconds and a test time of 22°C.

[0080] [Table 1]

[0081] Examples 1 to 14, which used both a cationic polymer coagulant and a non-fluorine-based water-resistant agent, had superior water resistance compared to Comparative Examples 1 to 4, which did not use a cationic polymer coagulant or a non-fluorine-based water-resistant agent.

Claims

1. A first agent comprising a cationic polymer coagulant; a second agent comprising at least one non-fluorine-based water resistant agent selected from the group consisting of a long-chain acrylate-silicone macromonomer copolymer-based water resistant agent, a hybrid emulsion-based water resistant agent, a long-chain acrylate-halogenated olefin copolymer-based water resistant agent, a blend-based water resistant agent of a long-chain acrylate copolymer and a long-chain alkyl-modified silicone polymer, a blend-based water resistant agent of a long-chain acrylate copolymer, a vinyl chloride polymer and a silicone resin, a blend-based water resistant agent of an amino-modified silicone, a silicone resin and a polyfunctional isocyanate, a polyurethane-based water resistant agent, a polyurea-based water resistant agent and a polyurethane dendrimer-based water resistant agent, and having a charge density of −100.0 to +200.0 μeq / g; Equipped with The water-resistant agent kit for papermaking is for imparting water resistance to a paper base material from which the paper material is made by sequentially mixing the paper material with the first agent and the second agent in an amount such that the cationic polymer coagulant is added to 100.0 g of pulp in the paper material so that the charge amount is 110 to 7236 μeq when used.

2. The papermaking waterproofing agent kit according to claim 1, wherein the cationic polymer coagulant has a cationic charge density of +100.0 to +10000.0 μeq / g.

3. The waterproofing agent kit for papermaking according to claim 1 or 2, wherein the cationic polymer coagulant is at least one selected from the group consisting of polyamide epichlorohydrin resin, cationic polyacrylamide, and polydiallyldimethylammonium chloride or a derivative thereof.

4. A paper base material from which paper stock is made, The waterproof paper contains in its base material at least a cationic polymer coagulant in an amount such that the charge amount per 100.0 g of pulp in the paper stock is 110 to 7236 μeq, and at least one non-fluorine-based waterproof agent selected from the group consisting of a long-chain acrylate-silicone macromonomer copolymer-based waterproof agent, a hybrid emulsion-based waterproof agent, a long-chain acrylate-halogenated olefin copolymer-based waterproof agent, a blend-based waterproof agent of a long-chain acrylate copolymer and a long-chain alkyl-modified silicone polymer, a blend-based waterproof agent of a long-chain acrylate copolymer, a vinyl chloride polymer, and a silicone resin, a blend-based waterproof agent of an amino-modified silicone, a silicone resin, and a polyfunctional isocyanate, a polyurethane-based waterproof agent, a polyurea-based waterproof agent, and a polyurethane dendrimer-based waterproof agent, and has a charge density of -100.0 to +200.0 μeq / g.

5. A waterproof paper obtained by subjecting a paper base material to a waterproofing treatment using the papermaking waterproofing agent kit according to any one of claims 1 to 3.

6. The Cobb water absorption measured in accordance with JIS P8140:1998 (Paper and paperboard-Water absorption test method-Cobb method) is 25.0 g / m 2 6. The waterproof paper according to claim 4 or 5, wherein:

7. The total content of the cationic polymer coagulant and the non-fluorine-based waterproofing agent is 0.05 to 10.0 g / m 2 The waterproof paper according to any one of claims 4 to 6,

8. The waterproof paper according to any one of claims 4 to 7, wherein the content of the cationic polymer coagulant is 0.05 to 10.0 mass% and the content of the non-fluorine-based waterproofing agent is 0.5 to 20.0 mass%.

9. A method for producing a paper stock comprising the steps of: mixing a first agent consisting of a cationic polymer coagulant with a paper stock in an amount such that the charge amount of the cationic polymer coagulant is 110 to 7236 μeq per 100.0 g of pulp in the paper stock; a step 2 of mixing the mixture obtained in the step 1 with a second agent comprising at least one non-fluorine-based water resistant agent selected from the group consisting of a long-chain acrylate-silicone macromonomer copolymer-based water resistant agent, a hybrid emulsion-based water resistant agent, a long-chain acrylate-halogenated olefin copolymer-based water resistant agent, a blend-based water resistant agent of a long-chain acrylate copolymer and a long-chain alkyl-modified silicone polymer, a blend-based water resistant agent of a long-chain acrylate copolymer, a vinyl chloride-based polymer, and a silicone resin, a blend-based water resistant agent of an amino-modified silicone, a silicone resin, and a polyfunctional isocyanate, a polyurethane-based water resistant agent, a polyurea-based water resistant agent, and a polyurethane dendrimer-based water resistant agent, and having a charge density of −100.0 to +200.0 μeq / g; Step 3: making paper from the mixture obtained in step 2; A method for producing waterproof paper comprising the steps of:

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