Aqueous oilproofing agent composition, method for producing aqueous oilproofing agent composition, method for oilproofing treatment of paper, and oilproof paper

Abstract

To provide a non-fluororesin-based aqueous oil-resistant agent composition which is an oil-resistant agent composition capable of obtaining oil-resistant paper having high oil resistance and high air permeability, does not contain a fluororesin and an organic solvent as components to be contained, and is considered in terms of health and environment.SOLUTION: A water-based oil resistant composition comprising (A) a polyvinyl alcohol (PVA) - based resin, (B) an addition-curable silicone emulsion, (E) water and (F) a platinum group metal-based catalyst, wherein the addition-curable silicone emulsion (B) comprises (G) an alkenyl group-containing organopolysiloxane, (H) an organohydrogenpolysiloxane, (I) a surfactant and (J) water.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an aqueous oil-proofing composition, a method for producing an aqueous oil-proofing composition, a method for treating paper with oil resistance, and oil-resistant paper. [Background technology]

[0002] Paper wrapping paper, packaging containers, food trays, and other paper coverings used for cooked foods such as fast food, fried foods, and baked foods that contain a lot of oil and water are made oil-resistant and water-resistant to prevent the oil and water from the food from penetrating and staining the surrounding area.

[0003] For grease-resistant paper or grease-resistant containers for food, polyethylene-laminated paper, which has a polyethylene film laminated to one side of a paper base, has been used, but polyethylene-laminated paper has problems such as low air permeability, which can lead to a deterioration in the flavor and storage stability of food, and the difficulty of removing the polyethylene film when recycling, making it poorly recyclable. There is also a strong movement to eliminate plastic, and there is a need for the development of grease-resistant paper that does not use polyethylene lamination. Conventionally, fluororesin-based oil-proofing agents have been widely used to impart oil resistance and water resistance to paper, and methods that have been adopted include coating the surface of a paper base material with a fluororesin-based oil-proofing agent to provide an oil-resistant layer, impregnating a paper base material with a fluororesin-based oil-proofing agent, or adding a fluororesin-based oil-proofing agent to a pulp slurry. However, fluororesin-based oil-proofing agents are undesirable from the standpoints of health and the environment due to their persistence in decomposition and bioaccumulation, and in recent years there has been a demand for oil-proofing agents that do not contain fluororesin (non-fluororesin-based oil-proofing agents).

[0004] Therefore, hydrophilic resins that form films, such as polyvinyl alcohol (PVA) resins and polysaccharides, are widely used as non-fluorine resin-based oil-resistant agents, and are known to provide excellent oil resistance. For example, Patent Document 1 discloses oil-resistant paper whose surface is coated with a composition containing a PVA resin and a silicone emulsion. In addition, acrylic and paraffin wax emulsions, as described in Patent Documents 2, 3, and 4, are also known to have excellent oil resistance. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-139418 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-237941 [Patent Document 3] Japanese Patent Publication No. 2020-122250 [Patent Document 4] Japanese Patent Application Publication No. 2022-188338 Summary of the Invention [Problem to be solved by the invention]

[0006] However, in the case of non-fluororesin-based oil-proofing agents, in order to achieve oil resistance while preventing the seepage of oil and fat components, it is necessary to either increase the density of the substrate or use a large amount of a filler or oil-proofing agent. While this increases oil resistance, it also reduces air permeability, which can lead to a decrease in the flavor and storage stability of food. For example, in order to impart oil and water resistance by applying the composition described in Patent Document 1 to a paper substrate, not only is a film-forming composition coated on the surface of the paper substrate, but a filler is also required for the paper substrate, which raises concerns about the reduced air permeability of the resulting grease-resistant paper. Although the grease-resistant papers described in Patent Documents 2, 3, and 4 have been confirmed to have air permeability, the amount of oil-proofing agent applied is large, and the air permeability is 100 seconds or more in all cases, which is inferior to that of fluororesin-based oil-proofing agents. As described above, no oil-resistant paper that uses a non-fluorine resin-based oil-resistant agent and that has both high oil resistance and high air permeability has yet been developed, and there is still room for improvement in this regard. Therefore, an object of the present invention is to provide an oil-proofing composition that can be used to obtain oil-resistant paper having high oil resistance and high air permeability, which is a non-fluorine resin-based water-based oil-proofing composition that does not contain a fluorine resin or an organic solvent and takes health and environmental aspects into consideration. [Means for solving the problem]

[0007] As a result of extensive research into achieving the above object, the present inventors have found that the following aqueous oil-proofing composition can solve the above problems, thereby completing the present invention. That is, the present invention provides the following oil-resistant composition and the like. [1] The following components (A), (B), (E) and (F): (A) Polyvinyl alcohol (PVA) resin with a viscosity of 2 to 80 mPa·s in a 4% aqueous solution at 20°C and a degree of saponification of 91 mol% or more: 100 parts by mass (B) Addition-curing silicone emulsion: 10 to 5,000 parts by mass (E) Water: 1,000~50,000 parts by mass (F) Platinum group metal catalyst: Catalyst amount A water-based oil-resistant composition comprising: The addition-curing silicone emulsion (B) is (G) an alkenyl group-containing organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and having a viscosity of 5 mPa·s or greater at 25°C, which accounts for 5 to 40 mass% of component (B), and the total alkenyl value of component (G) (the number of moles of silicon-bonded alkenyl groups contained in 100 g of component (G)) exceeds 0.1 mol / 100 g; (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms (SiH groups) per molecule: % by mass in which the number of moles of SiH groups in component (H) is 1 to 5 times the number of moles of alkenyl groups in component (G); (I) Surfactant: 0.1 to 10% by mass of component (B) (J) Water: 10-90% by mass in (B) component The water-based oil-resistant composition comprises: [2] The following components (A), (C), (D), (E) and (F): (A) Polyvinyl alcohol (PVA) resin with a viscosity of 2 to 80 mPa·s in a 4% aqueous solution at 20°C and a degree of saponification of 91 mol% or more: 100 parts by mass (C) Silicone emulsion: 5 to 2,500 parts by mass (D) Silicone emulsion (E) Water: 1,000~50,000 parts by mass (F) Platinum group metal catalyst: Catalyst amount A water-based oil-resistant composition comprising: The silicone emulsion (C) is (G) an alkenyl group-containing organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and a viscosity of 5 mPa·s or greater at 25°C, which accounts for 5 to 60 mass% of component (C), and the total alkenyl value of component (G) (the number of moles of silicon-bonded alkenyl groups contained in 100 g of component (G)) exceeds 0.1 mol / 100 g; (I) Surfactant: 0.1 to 10% by mass of component (C) (J) Water: 10~90% by mass in (C) component and The silicone emulsion (D) is (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule: 5 to 60% by mass of component (D); (I) Surfactant: 0.1 to 10% by mass of component (D) and (J) Water: 10-90% by mass in (D) component wherein the content of component (D) in the composition is such that the number of moles of SiH groups of component (H) in component (D) corresponds to 1 to 5 times the number of moles of alkenyl groups of component (G) in component (C). [3] The aqueous oil resistant composition according to [1] or [2], wherein the PVA resin as component (A) has a viscosity of 5 to 80 mPa·s in a 4% aqueous solution at 20°C and a degree of saponification of 95 mol % or more. [4] The aqueous oil resistant composition according to any one of [1] to [3], wherein the PVA resin as component (A) is at least one selected from polyvinyl alcohol and modified polyvinyl alcohol resins. [5] The aqueous oil-resistant composition according to any one of [1] to [4], wherein component (G) comprises at least two of a linear organopolysiloxane containing alkenyl groups only at both ends, and a linear organopolysiloxane containing alkenyl groups in side chains and at both ends. [6] The aqueous oil resistant composition according to any one of [1] to [5], wherein component (G) is a linear alkenyl group-containing organopolysiloxane represented by the following average composition formula (1-1): [ka] (In formula (1-1), R 1 are independently an alkenyl-containing organic group having 2 to 10 carbon atoms, and R 2 are independently one group selected from unsubstituted or substituted monovalent hydrocarbon groups that do not have a hydroxyl group, an alkoxy group, or an alkenyl group, and a, c, and d are each a number of 0 or greater that satisfies the relationships 0≦a≦3, 2≦2a+c, and 5≦c+d. [7] The aqueous oil-resistant composition according to any one of [1] to [6], wherein the ratio of the total number of hydrogen atoms bonded to silicon atoms to the total number of hydrogen atoms bonded to silicon atoms and groups bonded to silicon atoms in component (H) is 15 to 50%. [8] The aqueous oil-resistant composition according to any one of [1] and [3] to [7], wherein the silicone emulsion of component (B) further contains a polyvinyl alcohol (PVA)-based resin in an amount of 0.5 to 10 mass % in component (B). [9] The aqueous oil-resistant composition according to any one of [2] to [7], wherein at least one of the silicone emulsion of component (C) and the silicone emulsion of component (D) further contains a polyvinyl alcohol (PVA)-based resin in an amount of 0.5 to 10 mass % in component (C) or component (D).

[10] The aqueous oil resistant composition according to any one of [1] to [9], wherein the total mass of the components (G) and (H) is 60 to 2000 parts by mass per 100 parts by mass of the component (A).

[11] A method for producing the aqueous oil resistant composition according to any one of [1] and [3] to

[10] , (Step 1) A step of mixing and emulsifying the following components (G), (H), (I), and (J) to prepare (B) an addition-curable silicone emulsion: (G) an alkenyl-containing organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and a viscosity of 5 mPa·s or greater at 25°C: this comprises 5 to 40 mass% of component (B), and the total alkenyl value of component (G) (the number of moles of silicon-bonded alkenyl groups contained in 100 g of component (G)) exceeds 0.1 mol / 100 g (H) Organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms (SiH groups) per molecule: % by mass in which the number of moles of SiH groups in component (H) is 1 to 5 times the number of moles of alkenyl groups in component (G). (I) Surfactant: 0.1 to 10% by mass of component (B) (J) Water: 10-90% by mass in (B) component and (Step 2) A step of mixing the following components (A), (E), and (F) with 10 to 5,000 parts by mass of the addition-curable silicone emulsion (B) prepared in Step 1 above: (A) PVA resin having a viscosity of 2 to 80 mPa·s in a 4% aqueous solution at 20°C and a degree of saponification of 91 mol% or more: 100 parts by mass (E) Water: 1,000~50,000 parts by mass (F) Platinum group metal catalyst: Catalyst amount A method for producing a water-based oil-resistant composition comprising the steps of:

[12] A method for producing the aqueous oil resistant composition according to any one of [2] to

[10] , (Step 1') A step of mixing and emulsifying the following components (G), (I), and (J) to prepare (C) a silicone emulsion: (G) an alkenyl-containing organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and a viscosity of 5 mPa·s or greater at 25°C: this comprises 5 to 60 mass% of component (C), and the total alkenyl value of component (G) (the number of moles of silicon-bonded alkenyl groups contained in 100 g of component (G)) exceeds 0.1 mol / 100 g (I) Surfactant: 0.1 to 10% by mass of component (C) (J) Water: 10~90% by mass in (C) component (Step 1'') A step of mixing and emulsifying the following components (H), (I), and (J) to prepare (D) a silicone emulsion: (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule: 5 to 60% by mass of component (D); (I) Surfactant: 0.1 to 10% by mass of component (D) (J) Water: 10-90% by mass in (D) component and (Step 2') A step of mixing the following components (A), (E), and (F), 5 to 2,500 parts by mass of the (C) silicone emulsion prepared in step 1' above, and an amount of the (D) silicone emulsion prepared in step 1'' above, in which the number of moles of SiH groups in component (H) in component (D) corresponds to 1 to 5 times the number of moles of alkenyl groups in component (G) in component (C). (A) PVA resin having a viscosity of 2 to 80 mPa·s in a 4% aqueous solution at 20°C and a degree of saponification of 91 mol% or more: 100 parts by mass (E) Water: 1,000~50,000 parts by mass (F) Platinum group metal catalyst: Catalyst amount A method for producing a water-based oil-resistant composition comprising the steps of:

[13] A method for treating oil resistance of paper, comprising adding the aqueous oil-proofing agent composition according to any one of [1] to

[10] to a pulp slurry for internal treatment or to a paper substrate for external treatment.

[14]

[10] Grease-resistant paper treated with the aqueous oil-proofing composition according to any one of [1] to

[10] , which has an air permeability of 1,000 seconds or less according to the Oken air permeability test, measured in accordance with JAPAN TAPPI Paper and Pulp Test Method No. 5-2:2000. [Effects of the Invention]

[0008] The present invention combines the advantages of both materials by combining PVA resin, which has excellent compatibility with paper, with silicone, which has good water resistance and breathability. By treating a paper substrate with a composition that combines materials with a specific structure of the present invention under specific conditions and then curing it, it is possible to obtain oil-resistant paper that has excellent oil and water resistance and high breathability. Furthermore, the greaseproof paper of the present invention has high air permeability, so when food is packaged, it can prevent oil stains without impairing the flavor of the food. Furthermore, the PVA resin and silicone contained in the aqueous oil-proofing composition of the present invention are both highly environmentally safe and harmless materials, making them suitable for use as alternatives to organic fluorine compounds. Furthermore, because the aqueous oil-proofing composition of the present invention does not contain organic solvents, it can avoid the disadvantages associated with the use of organic solvents, such as environmental problems and biological hazards. Paper substrates treated with the composition of the present invention can be easily recycled and become products with low environmental impact, thereby resolving the harmful effects and environmental problems associated with fluorine compounds. DETAILED DESCRIPTION OF THE INVENTION

[0009] [Water-based oil-resistant composition] The aqueous oil-proofing composition of the present invention will be described in more detail below. In this specification, unless otherwise specified, "%" indicates a percentage by mass.

[0010] (A)PVA resin The PVA resin of component (A) is a polymer whose main structural unit is vinyl alcohol units, and constitutes the main component of the oil-proofing agent composition as an aqueous solution.

[0011] The properties of PVA-based resins are roughly defined by their degree of polymerization (or viscosity) and degree of saponification. The viscosity of the PVA-based resin used in the present invention is 2 to 80 mPa·s at 20°C for a 4% aqueous solution, and the degree of saponification is 91 mol% or higher. If the viscosity of a 4% aqueous solution of PVA-based resin at 20°C is less than 2 mPa·s, film-forming properties will be insufficient, and if it exceeds 80 mPa·s, coatability will be poor. From the viewpoint of film-forming properties and coatability, the viscosity of the PVA-based resin is preferably 5 to 80 mPa·s for a 4% aqueous solution at 20°C, more preferably 10 to 70 mPa·s, and even more preferably 20 to 60 mPa·s. The viscosity at 20°C is a value measured using a BM-type viscometer (e.g., manufactured by Tokyo Keiki Co., Ltd.). The rotor, rotation speed, and rotation time are selected appropriately according to the viscosity, based on standard methods (the same applies hereinafter). From the viewpoint of oil resistance and water resistance, the saponification degree of the PVA resin is 91 mol% or more, more preferably 95 mol% or more, and even more preferably 98 mol% or more. If the saponification degree of the PVA resin is less than 91 mol%, sufficient oil resistance and water resistance may not be obtained.

[0012] In the present invention, the PVA-based resin includes not only homopolymers (polyvinyl alcohols) having only vinyl alcohol units, but also copolymers having vinyl alcohol units and other polymerizable vinyl monomer units, and modified polyvinyl alcohol resins in which part of the side chains in the vinyl alcohol units have been substituted. The PVA resin used in the present invention can be a copolymer containing vinyl alcohol units and other polymerizable vinyl monomer units, i.e., a copolymer of polyvinyl alcohol with a known polymerizable vinyl monomer, typically 5 mol% or less, as long as the oil resistance effect is not impaired. Examples of polymerizable vinyl monomers include methacrylic acid esters such as methyl methacrylate, propyl methacrylate, and allyl methacrylate, acrylic acid esters such as methyl acrylate and butyl acrylate, butyl vinyl ether, ethylene, styrene, propylene, butene, butadiene, butenediol, acrylonitrile, acrylamide, maleic anhydride, vinyl chloride, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane. The molar ratio of vinyl alcohol to polymerizable vinyl monomer in the copolymer is 100:0 to 95:5 (vinyl alcohol:polymerizable vinyl monomer). The PVA resin used in the present invention may have a side chain partially substituted with a hydrocarbon group and a silyl group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups, aryl groups, and groups in which at least some of the hydrogen atoms of these groups have been substituted with silicon atom-containing groups.

[0013] In the present invention, any commercially available PVA resin can be used as long as it satisfies the above viscosity and degree of saponification, and specific examples include Kuraray Poval (manufactured by Kuraray Co., Ltd.), J-Poval (manufactured by Nippon Vinyl Acetate & Poval Co., Ltd.), Denka Poval (manufactured by Denka Co., Ltd.), Gohsenol (manufactured by Mitsubishi Chemical Corporation), etc. The PVA resin of component (A) may be used alone or in combination of two or more types. The content of component (A) in the composition of the present invention is preferably 10 to 90 mass %, more preferably 20 to 80 mass %, based on the total amount of components excluding water. The total amount of components excluding water is the combined amount of (E) water in the composition and the components other than (B) addition-curable silicone emulsion, (C) silicone emulsion, (D) silicone emulsion, and (J) water in the (K) catalyst composition, which will be described later.

[0014] The aqueous oil-resistant composition of the present invention comprises, as the silicone emulsion: <1> (B) Addition-curing silicone emulsion or <2> (C) Silicone emulsion and (D) Silicone emulsion Contains: (B) The addition-curable silicone emulsion contains (G) an alkenyl group-containing organopolysiloxane, (H) an organohydrogenpolysiloxane, (I) a surfactant, and (J) water. (C) Silicone emulsion contains (G) alkenyl group-containing organopolysiloxane, (I) surfactant, and (J) water. The (D) silicone emulsion contains an (H) organohydrogensiloxane, an (I) surfactant, and (J) water. Components (G) to (J) will be described later. In this specification, an aqueous oil-resistant composition containing the (B) addition-curable silicone emulsion may be referred to as the "aqueous oil-resistant composition <1>," and an aqueous oil-resistant composition containing the (C) silicone emulsion and the (D) silicone emulsion may be referred to as the "aqueous oil-resistant composition <2>." The emulsification to obtain components (B) to (D) may be carried out using a common emulsifying / dispersing machine. Examples of emulsifying / dispersing machines include high-speed rotation centrifugal radial mixers such as a Homodisper, high-speed rotation shear mixers such as a Homomixer, high-pressure jet emulsifying / dispersing machines such as a pressure homogenizer, colloid mills, and ultrasonic emulsifiers. The volume average particle size of each of the resulting emulsions of components (B) to (D), as measured using a laser diffraction / scattering particle size distribution analyzer, is preferably 50 to 10,000 nm, and more preferably 100 to 1,500 nm.

[0015] (B) Addition-curing silicone emulsion The amount of component (B) blended is 10 to 5,000 parts by mass, preferably 50 to 4,000 parts by mass, and more preferably 100 to 2,000 parts by mass, per 100 parts by mass of component (A). If the amount of component (B) blended is less than 10 parts by mass per 100 parts by mass of component (A), water resistance will be insufficient, and if it is more than 5,000 parts by mass, oil resistance will be insufficient.

[0016] The content of (G) in component (B) is 5 to 40 mass%, preferably 10 to 35 mass%, and more preferably 15 to 30 mass%. If it is outside this range, oil resistance and water resistance will be reduced.

[0017] The content of (H) in component (B) is 1 to 5 times, preferably 1.1 to 3 times, and more preferably 1.2 to 2.5 times by mass, the number of moles of SiH groups in component (H) relative to the number of moles of alkenyl groups in component (G). If the content is outside the above range, the oil resistance and water resistance will be reduced.

[0018] The content of (I) in component (B) is 0.1 to 10% by mass, preferably 0.2 to 5% by mass, and more preferably 0.3 to 3% by mass. If it is less than the lower limit, emulsification becomes difficult, and if it is more than the upper limit, oil resistance and water resistance decrease.

[0019] The content of (J) in component (B) is 10 to 90% by mass, preferably 20 to 80% by mass, and more preferably 30 to 70% by mass. If it is less than the lower limit, dispersion becomes difficult, and if it is more than the upper limit, the stability of the emulsion over time decreases.

[0020] In the aqueous oil-proofing composition <1>, the total mass of the component (G) and the component (H) is preferably 20 to 2,000 parts by mass, more preferably 30 to 1,000 parts by mass, and even more preferably 50 to 500 parts by mass, per 100 parts by mass of the component (A).

[0021] (C) Silicone emulsion containing organopolysiloxane having alkenyl groups The blend amount of component (C) is 5 to 2,500 parts by mass, preferably 25 to 2,000 parts by mass, and more preferably 50 to 1,000 parts by mass, per 100 parts by mass of component (A). If the blend amount of component (C) is less than 5 parts by mass per 100 parts by mass of component (A), water resistance will be insufficient, and if it is more than 2,500 parts by mass, oil resistance will be insufficient.

[0022] The content of (G) in component (C) is 5 to 60 mass %, preferably 10 to 50 mass %, and more preferably 15 to 40 mass %. If it is outside this range, oil resistance and water resistance will be reduced.

[0023] The content of (I) in component (C) is 0.1 to 10% by mass, preferably 0.2 to 5% by mass, and more preferably 0.3 to 3% by mass. If it is less than the lower limit, emulsification becomes difficult, and if it is more than the upper limit, oil resistance and water resistance decrease.

[0024] The content of (J) in component (C) is 10 to 90% by mass, preferably 20 to 80% by mass, and more preferably 30 to 70% by mass. If it is less than the lower limit, dispersion becomes difficult, and if it is more than the upper limit, the stability of the emulsion over time decreases.

[0025] (D) Organohydrogenpolysiloxane-containing silicone emulsion The amount of component (D) blended is 1 to 5 times, preferably 1.1 to 3.0 times, and more preferably 1.2 to 2.5 times, the molar number of SiH groups in component (D) relative to the molar number of alkenyl groups in component (C). If the amount of component (D) blended is outside the above range, the oil resistance and water resistance will be reduced.

[0026] The content of component (H) in component (D) is 5 to 60 mass%, preferably 10 to 50 mass%, and more preferably 15 to 40 mass%. If the content of component (H) in component (D) is outside the above range, the oil resistance and water resistance will be reduced.

[0027] The content of component (I) in component (D) is 0.1 to 10% by mass, preferably 0.2 to 5% by mass, and more preferably 0.3 to 3% by mass. If the content of component (I) in component (D) is less than the above lower limit, emulsification becomes difficult, and if it is more than the above upper limit, oil resistance and water resistance decrease.

[0028] The content of component (J) in component (D) is 10 to 90% by mass, preferably 20 to 80% by mass, and more preferably 30 to 70% by mass. If the content of component (J) in component (D) is less than the above lower limit, dispersion becomes difficult, and if it is more than the above upper limit, the stability of the emulsion over time decreases.

[0029] In the aqueous oil-proofing composition <2>, the total mass of the component (G) and the component (H) is preferably 20 to 2,000 parts by mass, more preferably 30 to 1,000 parts by mass, and even more preferably 50 to 500 parts by mass, per 100 parts by mass of the component (A).

[0030] (G) Alkenyl group-containing organopolysiloxane Component (G) is an organopolysiloxane that has at least two silicon-bonded alkenyl groups per molecule and has a viscosity of 5 mPa·s or greater at 25°C. The number of silicon-bonded alkenyl groups in component (G) per molecule is at least two, preferably 2 to 500, more preferably 2 to 100, and even more preferably 2 to 30. If the number of silicon-bonded alkenyl groups in component (G) per molecule is less than two, crosslinking is not possible, resulting in reduced oil resistance, which is undesirable. Furthermore, if the number of silicon-bonded alkenyl groups in component (G) per molecule is more than 500, curing may require a long time.

[0031] The viscosity of component (G) at 25°C is 5 mPa·s or greater, preferably 10 to 10,000 mPa·s, more preferably 20 to 5,000 mPa·s, and even more preferably 50 to 1,000 mPa·s. If the viscosity of component (G) at 25°C is lower than 5 mPa·s, emulsion preparation becomes difficult and oil resistance and stability may be reduced. There is no upper limit to the viscosity of component (G) at 25°C, but it can be set to, for example, 100,000 mPa·s. When multiple types of component (G) are used, the viscosity can be adjusted to fall within the above range by mixing a low-viscosity organopolysiloxane corresponding to component (G) with a high-viscosity or crude rubber-like organopolysiloxane corresponding to component (G).

[0032] The silicon-bonded alkenyl value in the total of component (G) exceeds 0.1 mol / 100 g, preferably 0.13 mol / 100 g or more, and more preferably 0.15 mol / 100 g or more. If the silicon-bonded alkenyl value in the total of component (G) is 0.1 mol / 100 g or less, crosslinkability and oil resistance will be reduced. There is no upper limit to the alkenyl value of component (G), but it can be set to, for example, 0.7 mol / 100 g. This alkenyl value is the number of moles of silicon-bonded alkenyl groups contained in 100 g of total of component (G). It can usually be calculated from the iodine value determined by the Hanus method (a method in which a compound is reacted with a Hanus reagent, followed by reaction with an aqueous potassium iodide solution, and the resulting iodine is titrated with sodium thiosulfate, in accordance with JIS K 0070) (the same applies hereinafter).

[0033] The molecular structure of component (G) is not particularly limited and may be any of a straight-chain, branched, or cyclic structure, but a straight-chain structure is preferred. The component (G) may be used alone or in combination of two or more. When two or more components (G) are used in combination, the average alkenyl value calculated from the total of the components (G) should exceed 0.1 mol / 100 g. Furthermore, when two or more components (G) are used in combination, their molecular structures are not particularly limited, but it is preferable to use in combination a linear organopolysiloxane containing alkenyl groups only at both ends and a linear organopolysiloxane containing alkenyl groups in the side chain and at both ends, and it is more preferable to use in combination organopolysiloxanes each having an alkenyl value of more than 0.1 mol / 100 g.

[0034] Component (G) is a component that provides oil resistance and water resistance to the composition, and specific examples thereof include those having a structure represented by average composition formula (1). [ka] (In formula (1), R 1 are independently an alkenyl-containing organic group having 2 to 10 carbon atoms, and R 2 are independently one type of group selected from unsubstituted or substituted monovalent hydrocarbon groups that do not have a hydroxyl group, an alkoxy group, or an alkenyl group, and a, b, c, d, e, f, and g are each independently a number of 0 or greater that satisfies 0≦a≦3, 1≦b, 2≦a b + c + e, and 5≦b+c+d+e+f+g.

[0035] R 1 R is an alkenyl-containing organic group having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 6 carbon atoms. 1 Examples of the alkyl group include alkenyl groups such as vinyl, allyl, and hexenyl.

[0036] R 2is one group selected from unsubstituted or substituted monovalent hydrocarbon groups that do not contain a hydroxyl group, an alkoxy group, or an alkenyl group. R 2 Examples of the alkoxy group represented by the formula (I) include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and the like. R 2 The unsubstituted or substituted monovalent hydrocarbon group having no alkenyl group, represented by the formula (I), preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms. Examples of the unsubstituted or substituted monovalent hydrocarbon group include alkyl groups preferably having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, and butyl; cycloalkyl groups preferably having 5 to 8 carbon atoms, such as cyclohexyl; aryl groups preferably having 6 to 10 carbon atoms, such as phenyl and tolyl; and aralkyl groups preferably having 7 to 10 carbon atoms, such as benzyl. Of these, the unsubstituted or substituted monovalent hydrocarbon group is preferably a methyl group or a phenyl group, with a methyl group being particularly preferred. The alkenyl group-containing organopolysiloxane represented by formula (1) is R 2 The ratio of the number of methyl groups to the total number of groups is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0037] In formula (1), a, b, c, d, e, f, and g are each independently a number of 0 or more. a is 0≦a≦3, preferably 0 or 1, and more preferably 1. b is a number greater than or equal to 1, and satisfies 2≦ab+c+e and 5≦b+c+d+e+f+g.

[0038] The alkenyl group-containing organopolysiloxane represented by formula (1) is particularly preferably linear, that is, one represented by the following formula (1-1) in which b=2 and e=f=g=0 in formula (1). [ka] In formula (1-1), R 1 and R 2are each defined as in formula (1), and a, c, and d are each numbers equal to or greater than 0, satisfying 0≦a≦3, 2≦2a+c, and 5≦c+d. Furthermore, in formula (1-1), when an alkenyl group is present in the side chain (1≦c), it is more preferable that 2≦c≦500, 3≦d≦4,000, further preferably that 5≦c≦100, 3≦d≦500, and particularly preferably that 10≦c≦50, 3≦d≦300. Furthermore, in formula (1-1), when there is no alkenyl group in the side chain (c=0), 3≦d≦30 is more preferable, and 3≦d≦20 is even more preferable.

[0039] Examples of component (G) include, but are not limited to, the following: In the following formulae, Me, Vi, and Ph represent a methyl group, a vinyl group, and a phenyl group, respectively. The bonding order of each siloxane unit shown in parentheses is not limited to the following: In each of the following formulae, the total number of siloxane repeating units is an average value. In the following formula, z1 to z39 are each a number of 0 or more. [ka] [ka] [ka] [ka]

[0040] (H) Organohydrogenpolysiloxane Component (H) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms (hereinafter referred to as SiH groups) per molecule. In component (H), the ratio of the total number of SiH groups to the total number of SiH groups and groups bonded to silicon atoms is preferably 15 to 50%, more preferably 20 to 45%, and even more preferably 30 to 40%. If the ratio of SiH groups in component (H) is less than 15%, the crosslink density may be low and oil resistance may be reduced, while if it is more than 50%, reactivity may be reduced and curing may take a long time.

[0041] The alkenyl groups in component (G) and the SiH groups in component (H) undergo an addition reaction to form a crosslinked structure. That is, component (H) functions as a crosslinking agent. From the viewpoint of crosslinking balance, the amount of component (H) to be blended is such that the ratio of the number of SiH groups in component (H) to the total number of alkenyl groups in component (G) is 1.0 to 5.0, more preferably 1.1 to 3.0, and even more preferably 1.2 to 2.5. If the amount of component (H) does not satisfy the above range, the crosslinking balance will be inappropriate, resulting in reduced oil resistance and water resistance.

[0042] The molecular structure of component (H) may be linear, branched, cyclic, or a three-dimensional network structure, or may be a mixture thereof. Furthermore, the SiH groups of component (H) may be located at either the terminal or intermediate positions of the molecular chain, or both. Component (H) is preferably a linear organohydrogenpolysiloxane represented by the following formula (2): [ka] (In formula (2), R 3 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms and not having a hydroxyl group or an aliphatic unsaturated bond. h is 0 or 1, and i and j are numbers that satisfy the conditions 0≦i≦200 and 0≦j≦200, and 2≦2h+i≦200 and 3≦i+j+2≦400.

[0043] In the above formula (2), R 3R are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms and not containing a hydroxyl group or an aliphatic unsaturated bond. 3 The monovalent hydrocarbon group having no aliphatic unsaturated bond is preferably an alkyl group or an aryl group, more preferably a methyl group, an ethyl group, a propyl group or a phenyl group, and particularly preferably a methyl group.

[0044] i is a number from 0 to 200, preferably from 3 to 150, and more preferably from 5 to 100. j is a number from 0 to 200, preferably from 0 to 100, and more preferably from 5 to 50. 2h+i is a number from 2 to 200, preferably from 4 to 150, more preferably from 5 to 100, and even more preferably from 10 to 80. i+j+2 is a number from 3 to 400, preferably from 5 to 200, and more preferably from 10 to 100.

[0045] Examples of organohydrogenpolysiloxanes represented by the above average composition formula (2) include methylhydrogensiloxane-dimethylsiloxane cyclic copolymers, dimethylsiloxane-methylhydrogensiloxane copolymers both ends blocked with trimethylsiloxy groups, dimethylpolysiloxanes both ends blocked with dimethylhydrogensiloxane groups, dimethylsiloxane-methylhydrogensiloxane copolymers both ends blocked with dimethylhydrogensiloxy groups, and methylhydrogensiloxane-diphenylsiloxane copolymers both ends blocked with trimethylsiloxy groups. , methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymers both ends blocked with trimethylsiloxy groups, methylhydrogensiloxane-methylphenylsiloxane-dimethylsiloxane copolymers both ends blocked with trimethylsiloxy groups, methylhydrogensiloxane-dimethylsiloxane-diphenylsiloxane copolymers both ends blocked with dimethylhydrogensiloxy groups, and methylhydrogensiloxane-dimethylsiloxane-methylphenylsiloxane copolymers both ends blocked with dimethylhydrogensiloxy groups. The component (H) may use one type alone, or two or more types in combination.

[0046] Examples of component (H) include, but are not limited to, linear or branched siloxanes represented by the following formulas: Me and Ph in the following formulas represent a methyl group and a phenyl group, respectively. The bonding order of each siloxane unit shown in parentheses is not limited to the following: In each of the following formulas, the total number of siloxane repeating units is an average value. In the following formulas, z42 to z73 are numbers such that the proportion of SiH groups in the organohydrogenpolysiloxane of each formula satisfies 15% to 50%. [ka] [ka] [ka]

[0047] (I) Surfactants Component (I) is a surfactant, and is not particularly limited as long as it can emulsify and disperse components (G) and (H) in water, but preferably contains a nonionic surfactant. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene-modified organopolysiloxanes, and polyoxyethylene polyoxypropylene-modified organopolysiloxanes. Among these, polyoxyethylene lauryl ether, polyoxyethylene oxypropylene lauryl ether, polyoxyethylene acetylene glycol ether, polyoxyethylene sorbitan monolaurate, and polyoxyethylene styrenated phenyl ether are preferred, and polyoxyethylene lauryl ether and polyoxyethylene styrenated phenyl ether are more preferred. The nonionic surfactants may be used alone or in combination of two or more. To obtain a stable emulsion composition, it is preferable that the single or two or more nonionic surfactants as a whole have an HLB of 10 to 15.

[0048] Anionic surfactants and cationic surfactants can also be used, but it is preferable to use them in combination with nonionic surfactants from the viewpoint of dispersibility. Examples of anionic surfactants include alkyl sulfate salts such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, alkyl benzene sulfonates, polyoxyethylene alkyl phenyl ether sulfonates, alkyl diphenyl ether disulfonates, alkanesulfonates, N-acyltaurate salts, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, polyoxyethylene alkyl ether sulfosuccinates, fatty acid salts, polyoxyethylene alkyl ether carboxylate salts, N-acylamino acid salts, monoalkyl phosphate salts, dialkyl phosphate salts, and polyoxyethylene alkyl ether phosphate salts. Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, polyoxyethylenealkyldimethylammonium salts, dipolyoxyethylenealkylmethylammonium salts, tripolyoxyethylenealkylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts, monoalkylamine salts, and monoalkylamidoamine salts.

[0049] In each silicone emulsion of components (B), (C), and (D), a water-soluble resin can be used in combination with a surfactant as an emulsifying aid to aid in the emulsification of components (G) and (H) and improve stability. Examples of water-soluble resins include PVA resins, cellulose derivatives, and carboxyvinyl polymers, with PVA resins being preferred. The PVA resin used as an emulsifying aid in each silicone emulsion of components (B), (C), and (D) may be the same as or different from component (A). Preferably, the PVA resin has a viscosity of 10 to 50 mPa·s in a 4% aqueous solution at 20°C and a degree of saponification of 85 to 95 mol%, more preferably a viscosity of 15 to 40 mPa·s and a degree of saponification of 86 to 92 mol%, and most preferably a viscosity of 20 to 30 mPa·s and a degree of saponification of 87 to 90 mol%, and is different from component (A). This water-soluble resin may also function as a thickener. In particular, it is preferable to select a water-soluble resin as an emulsification aid that has as little catalytic poisoning effect as possible on the platinum group metal catalyst of component (F), which will be described later. As with the surfactants described above, the amount of water-soluble resin is preferably the minimum amount necessary to ensure sufficient stability of the silicone emulsion. For example, it is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the combined total of components (G) and (H). If the amount of water-soluble resin is greater than the upper limit, the addition reaction may be inhibited, resulting in reduced oil resistance and water resistance. If the amount is less than the lower limit, it is difficult to obtain a stabilizing effect.

[0050] (J)Water Component (J) is water that becomes the continuous phase of the emulsion, and various types of water such as ion-exchanged water and purified water can be used.

[0051] Other ingredients In the present invention, each of the silicone emulsions (B), (C), and (D) can contain optional components other than those described above. Examples of such optional components include catalyst activity inhibitors (controllers) selected from various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, oxime compounds, and organic chloro compounds, for the purpose of suppressing the catalytic activity of platinum group metal catalysts. Examples of suitable additives include acetylenic alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, 2-phenyl-3-butyn-2-ol, and 1-ethynyl-1-cyclohexanol; acetylenic compounds such as 3-methyl-3-1-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; reaction products of these acetylenic compounds with alkoxysilanes, siloxanes, or hydrogensilanes; vinylsiloxanes such as tetramethylvinylsiloxane cyclics; organic nitrogen compounds such as benzotriazole and other organic phosphorus compounds; oxime compounds; and organic chloro compounds. The degree of curing inhibition effect of the addition reaction inhibitor varies depending on its chemical structure. Therefore, the amount of each addition reaction inhibitor used can be appropriately adjusted according to a conventionally known method. By adding an appropriate amount of an addition reaction inhibitor, the oil-proofing composition can be made superior in long-term storage stability at room temperature and heat curing properties.

[0052] (E)Water Component (E) is water, and the same as component (J) described above can be used. The content of component (E) in the aqueous oil-proofing composition of the present invention is 1,000 to 50,000 parts by mass, preferably 2,000 to 30,000 parts by mass, and more preferably 3,000 to 10,000 parts by mass, per 100 parts by mass of component (A). If the content of component (E) is less than 1,000 parts by mass per 100 parts by mass of component (A), handling will be impaired, while if it is more than 50,000 parts by mass, the coating weight will be reduced, resulting in insufficient oil resistance. Furthermore, the content of component (E) in the aqueous oil proofing composition of the present invention is preferably within the above range per 100 parts by mass of component (A), and is preferably 400 to 5,000 parts by mass, more preferably 1,000 to 3,000 parts by mass, and particularly preferably 1,500 to 2,000 parts by mass per 100 parts by mass of components (A), (G), and (H) combined. When the content of component (E) in the aqueous oil proofing composition is within the above range, handling properties are good and a good balance between oil resistance and coating weight is also achieved, which is preferred.

[0053] (F)Platinum group metal catalyst The platinum group metal catalyst of component (F) is a catalyst for promoting the addition reaction between components (G) and (H), and any catalyst known to those skilled in the art for promoting the so-called hydrosilylation reaction can be used. Examples of such platinum group metal catalysts include platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts, and among these, platinum-based catalysts are particularly preferred. Examples of such platinum catalysts include chloroplatinic acid, alcohol solutions or aldehyde solutions of chloroplatinic acid, complexes of chloroplatinic acid with various olefins or vinylsiloxanes, and complexes of platinum with various olefins or vinylsiloxanes.

[0054] The amount of platinum group metal catalyst added should be a catalytic amount. For example, from the standpoint of economic efficiency and to obtain a good cured coating, the amount of platinum group metal added is preferably in the range of 1 to 1,000 ppm, more preferably 10 to 500 ppm, and particularly preferably 20 to 200 ppm, based on the total mass of components (G) and (H). If the amount of component (F) is less than the lower limit, insufficient curing may occur, while if it is more than the upper limit, costs may increase.

[0055] The aqueous oil-proofing composition of the present invention may contain the component (F) as a mixture with the surfactant (I) and water (E). That is, the aqueous oil-resistant composition <1> is Components (A), (B), (E) and (K): (A) PVA resin having a viscosity of 2 to 80 mPa·s in a 4% aqueous solution at 20°C and a degree of saponification of 91 mol% or more: 100 parts by mass (B) Addition-curing silicone emulsion: 10 to 5,000 parts by mass (E) Water: 1,000~50,000 parts by mass (K) Catalyst composition A water-based oil-resistant composition comprising: The addition-curing silicone emulsion (B) is (G) an alkenyl group-containing organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and having a viscosity of 5 mPa·s or greater at 25°C, which accounts for 5 to 40 mass% of component (B), and the total alkenyl value of component (G) (the number of moles of silicon-bonded alkenyl groups contained in 100 g of component (G)) exceeds 0.1 mol / 100 g; (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms (SiH groups) per molecule: % by mass in which the number of moles of SiH groups in component (H) is 1 to 5 times the number of moles of alkenyl groups in component (G); (I) Surfactant: 0.1 to 10% by mass of component (B) (J) Water: 10-90% by mass in (B) component and The catalyst composition (K) is (F)Platinum group metal catalyst (I) surfactants and (J)Water The composition may be a water-based oil-proofing agent composition comprising: The aqueous oil-resistant composition <2> is Components (A), (C), (D), (E) and (K): (A) PVA resin having a viscosity of 2 to 80 mPa·s in a 4% aqueous solution at 20°C and a degree of saponification of 91 mol% or more: 100 parts by mass (C) Silicone emulsion: 5 to 2,500 parts by mass (D) Silicone emulsion (E) Water: 1,000~50,000 parts by mass (K) Catalyst composition A water-based oil-resistant composition comprising: The silicone emulsion (C) is (G) an alkenyl group-containing organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and a viscosity of 5 mPa·s or greater at 25°C, which accounts for 5 to 60 mass% of component (C), and the total alkenyl value of component (G) (the number of moles of silicon-bonded alkenyl groups contained in 100 g of component (G)) exceeds 0.1 mol / 100 g; (I) Surfactant: 0.1 to 10% by mass of component (C) (J) Water: 10~90% by mass in (C) component and The silicone emulsion (D) is (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule: 5 to 60% by mass of component (D); (I) Surfactant: 0.1 to 10% by mass of component (D) and (J) Water: 10-90% by mass in (D) component the content of component (D) in the composition is such that the number of moles of SiH groups of component (H) in component (D) corresponds to 1 to 5 times the number of moles of alkenyl groups of component (G) in component (C); The catalyst composition (K) is (F)Platinum group metal catalyst (I) surfactants and (J)Water The composition may be a water-based oil-proofing agent composition comprising:

[0056] The catalyst composition (K) is preferably an aqueous emulsion mixture of the components (F), (I), and (J), that is, an emulsion in which water is the continuous phase. The content of the component (F) in the catalyst composition (K) is preferably 0.1 to 10 mass %, more preferably 0.2 to 5 mass %, and even more preferably 0.3 to 3 mass %. The surfactant (I) used in the catalyst composition (K) can be exemplified by the same surfactants as those mentioned above. The surfactant (I) used in the catalyst composition (K) preferably contains a nonionic surfactant, similar to the surfactants used to emulsify the components (G) and (H). The content of component (I) in the catalyst composition (K) is preferably 0.1 to 5 mass%, more preferably 0.2 to 3 mass%, and even more preferably 0.3 to 2 mass%. If the content of component (I) in the catalyst composition (K) is more than 5 mass%, the addition reaction may be inhibited, resulting in reduced oil resistance and water resistance, while if it is less than 0.1 mass%, stability may be reduced. The content of component (J) in catalyst composition (K) is preferably 10 to 90 mass%, more preferably 20 to 85 mass%, and even more preferably 30 to 80 mass%. If the content of component (J) in catalyst composition (K) is less than 10 mass%, it may be difficult to disperse component (F), and if it is more than 90 mass%, the stability of the emulsion over time may be reduced. In order to obtain a stable emulsion, the (K) catalyst composition may contain, in addition to the above-mentioned components (F), (I), and (J), components that may be contained in the silicone emulsions of the above-mentioned components (B), (C), and (D).

[0057] The aqueous oil-proofing composition of the present invention may further contain preservatives, antifoaming agents, fragrances, thickeners, antioxidants, rust inhibitors, pigments, fillers, organic powders, inorganic powders, etc., within the range that does not impair the effects of the present invention. The amounts of these substances are selected from appropriate amounts for each. In order to further improve oil resistance, the aqueous oil-proofing composition of the present invention may further contain 0.5 to 10 mass % of a dicarboxylic acid, such as oxalic acid, malonic acid, succinic acid, glutaric acid, phthalic acid, or terephthalic acid, relative to the PVA resin. From the viewpoint of safety, it is preferable that the components of the aqueous oil-proofing composition of the present invention are composed only of compounds included in the positive list prescribed by the Ministry of Health, Labor and Welfare and the Japan Paper Association (Article 18, Paragraph 3 of the Revised Food Sanitation Act and Notification No. 370, Positive List of Chemical Substances for Paper and Paperboard Intended to Come into Contact with Food).

[0058] [Method of producing aqueous oil-resistant composition] The aqueous oil-resistant composition <1> of the present invention can be produced by mixing (A) a PVA resin, (B) an addition-curable silicone emulsion, (E) water, and (F) a platinum group metal catalyst. The order of adding the components is not particularly limited, but a preferred method for producing the aqueous oil-proofing composition <1> is as follows: (Step 1) A step of mixing and emulsifying components (G), (H), (I), and (J) to prepare (B) an addition-curable silicone emulsion. and (Step 2) A step of mixing the components (A), (E), and (F) with the addition-curable silicone emulsion (B) prepared in step 1 above. The method includes the following.

[0059] A more preferred method for producing the aqueous oil-proofing composition <1> is as follows: (Step 1) A step of mixing and emulsifying components (G), (H), (I), and (J) to prepare (B) an addition-curable silicone emulsion. (Step 2-1) A step of mixing components (A) and (E) to prepare an aqueous solution of component (A). (Step 2-2) A step of mixing the components (F), (I), and (J) to prepare the catalyst composition (K). and (Step 2-3) A step of mixing the addition-curable silicone emulsion (B) prepared in the above step 1, the aqueous solution of component (A) prepared in the above step 2-1, and the catalyst composition (K) prepared in the above step 2-2. The method includes the following.

[0060] The aqueous oil-resistant composition <2> of the present invention can be produced by mixing (A) a PVA resin, (C) a silicone emulsion, (D) a silicone emulsion, (E) water, and (F) a platinum group metal catalyst. The order of adding the components is not particularly limited, but a preferred method for producing the aqueous oil-proofing composition <2> is as follows: (Step 1') A step of mixing and emulsifying the components (G), (I), and (J) to prepare a silicone emulsion (C). (Step 1″) A step of mixing and emulsifying components (H), (I), and (J) to prepare a silicone emulsion (D). and (Step 2') A step of mixing the components (A), (E), and (F) with the silicone emulsion (C) prepared in the above step 1' and the silicone emulsion (D) prepared in the above step 1''. The method includes the following.

[0061] A more preferred method for producing the aqueous oil-proofing composition <2> is as follows: (Step 1') A step of mixing and emulsifying the components (G), (I), and (J) to prepare a silicone emulsion (C). (Step 1″) A step of mixing and emulsifying components (H), (I), and (J) to prepare a silicone emulsion (D). (Step 2'-1) A step of mixing components (A) and (E) to prepare an aqueous solution of component (A). (Step 2'-2) A step of mixing the components (F), (I), and (EJ) to prepare the catalyst composition (K). and (Step 2'-3) A step of mixing the (C) silicone emulsion prepared in the above step 1', the (D) silicone emulsion prepared in the above step 1'', the aqueous solution of the (A) component prepared in the above step 2'-1, and the (K) catalyst composition prepared in the above step 2'-2. The method includes the following.

[0062] (Step 1) (B) Preparation of addition-curing silicone emulsion Component (B) can be produced by known methods, such as mixing predetermined amounts of components (G), (H), and (I) with a portion of water (J) using a stirring device capable of high shear such as a planetary mixer, a combination mixer, or a high-pressure homogenizer, emulsifying by phase inversion, and diluting the mixture with the remainder of water (J). When preparing the (B) addition-curable silicone emulsion, predetermined amounts of components (A), (F), the water-soluble resin used as the emulsifying aid, and other components such as a catalyst activity inhibitor may be mixed in.

[0063] (Step 1') (C) Preparation of Silicone Emulsion Component (C) can be produced by known methods, such as mixing predetermined amounts of components (G) and (I) with a portion of water (J) using a stirring device capable of high shear such as a planetary mixer, a combination mixer, or a high-pressure homogenizer, emulsifying by phase inversion, and diluting the mixture with the remainder of water (J). When preparing the silicone emulsion (C), the components (A), (F), the water-soluble resin as the emulsifying aid, and other components such as the catalyst activity inhibitor may be mixed in predetermined amounts.

[0064] (Step 1'') (D) Preparation of Silicone Emulsion Component (D) can be produced by known methods, such as mixing predetermined amounts of components (H) and (I) with a portion of water (J) using a stirring device capable of high shear such as a planetary mixer, a combination mixer, or a high-pressure homogenizer, emulsifying by phase inversion, and diluting the mixture with the remainder of water (J). When preparing the silicone emulsion (D), the components (A), (F), the water-soluble resin as the emulsifying aid described above, and other components such as a catalyst activity inhibitor may be mixed in predetermined amounts.

[0065] (Step 2) Mixing components (A), (E), and (F) with component (B). (Step 2') Mixing components (A), (E), and (F), component (C), and component (D). In steps 2 and 2', the components may be mixed uniformly using a known mixing device. Mixing is preferably carried out at 10 to 30°C to ensure emulsion stability.

[0066] (Step 2-1), (Step 2'-1) Preparation of an aqueous solution of component (A) (Step 2-1) and (Step 2'-1) are steps in which component (A) is dissolved in water (E) to obtain an aqueous solution of the desired concentration. From the viewpoint of ease of handling, it is preferable that the PVA resin (A) is dissolved in water (E) before mixing with the other components, and that the resulting mixture of components (A) and (E) is mixed with the other components. The concentration of component (A) in the aqueous solution of component (A) obtained in this step is preferably 0.5 to 10 mass%.

[0067] (Step 2-2), (Step 2'-2) (K) Preparation of catalyst composition Component (F) may be mixed during the preparation of addition-curable silicone emulsion (B), but it is preferable to mix component (F), surfactant (I), and water (J) together before mixing with the other components, and then mix this mixture with the other components to form catalyst composition (K). The (K) catalyst composition may be produced using any device capable of mixing the components. Preferably, the components are mixed using a stirring device capable of high shear, such as a planetary mixer, a combination mixer, or a high-pressure homogenizer, and then emulsified by a phase inversion method to form an emulsion.

[0068] (Step 2-3) Mixing component (B), an aqueous solution of component (A), and component (K) (Step 2'-3) Mixing component (C), component (D), an aqueous solution of component (A), and component (K). Step 2-3 is preferably carried out immediately before using the aqueous oil-proofing composition <1> (for example, immediately before applying it to a paper substrate). Step 2'-3 is preferably carried out immediately before using the aqueous oil-proofing composition <2> (for example, immediately before applying it to a paper substrate). This not only inhibits dehydrogenation of the organohydrogensiloxane and provides an excellent shelf life, but also makes it easy to achieve a wide range of properties by changing the combination of emulsions to be mixed.

[0069] [Oil-resistant treatment method] The aqueous oil-proofing composition of the present invention can be suitably used to impart oil resistance and water resistance to paper substrates. The method for treating paper to be oil-resistant may be an internal treatment method in which the aqueous oil-proofing composition of the present invention is added to a pulp slurry, or an external treatment method in which the aqueous oil-proofing composition of the present invention is coated on a paper substrate after papermaking, or the paper substrate after papermaking is impregnated with the aqueous oil-proofing composition of the present invention and dried.

[0070] [Oil-resistant paper] The oil-resistant paper of the present invention can be produced by applying the above-mentioned oil-resistant treatment method to a paper substrate, and preferably can be obtained by coating or impregnating a paper substrate with the aqueous oil-proofing composition of the present invention.

[0071] Examples of paper substrates include those made on various paper machines using chemical pulps such as hardwood pulp and softwood pulp, mechanical pulps such as groundwood pulp and thermomechanical pulp, and recycled paper pulp. Specific examples include bleached kraft paper, unbleached kraft paper, fine paper, medium-quality paper, lightly coated paper, coated paper, semi-glossy paper, processed base paper, paperboard, white paperboard, liner, semi-glassine paper, glassine paper, parchment paper, etc. The pulp may also contain pH adjusters, sizing agents, paper strength agents, wet strength agents, retention aids, drainage aids, dyes, antifoaming agents, fillers, etc.

[0072] The aqueous oil-proofing agent composition is preferably applied to a paper substrate by external addition, and examples of such methods include application using a bar coater, knife coater, size press coater, roll coater, reverse roll coater, air knife coater, calendar, gate roll coater, blade coater, curtain coater, gravure coater, rod metering, two-roll size press, or the like. To increase the air permeability of oil-resistant paper, it is preferable to apply an external treatment in which the aqueous oil-proofing composition penetrates into the interior of the paper substrate, rather than to coat the aqueous oil-proofing composition only on the surface of the paper substrate. Impregnation treatment using a pond-type size press is particularly preferable. The amount of the aqueous oil-proofing composition (solid content after drying) is not particularly limited, but is preferably 0.1 to 10 g / m 2 , more preferably 0.5 to 3 g / m 2, and more preferably 0.5 to 2 g / m 2 If the amount of the aqueous oil-proofing composition is within the above range, the oil resistance and air permeability are excellent, which is preferable.

[0073] After the coating treatment, the paper substrate is subjected to a heat treatment to dry the aqueous oil-proofing composition. Examples of heat sources include a hot air dryer, an infrared heater, and a rotary dryer. Drying conditions include a temperature of preferably 80 to 180°C, more preferably 100 to 150°C, and even more preferably 120 to 150°C. From the viewpoints of productivity and the addition reaction of the aqueous oil-proofing composition, the drying time is preferably 0.1 to 180 minutes, more preferably 1 to 30 minutes, and even more preferably 2 to 5 minutes.

[0074] The air permeability of the grease-resistant paper of the present invention is the Oken air permeability measured in accordance with JAPAN TAPPI Paper and Pulp Testing Method No. 5-2:2000. The air permeability of the grease-resistant paper is not particularly limited as it depends on the paper base material and coating method, but is preferably 1000 seconds or less, more preferably 500 seconds or less, and even more preferably 5 to 300 seconds. There is no lower limit to the air permeability of the grease-resistant paper, but it can be set to, for example, 5 seconds. An air permeability of 1000 seconds or less is preferred because it does not deteriorate the flavor or storage stability of food packaged using the grease-resistant paper. [Example]

[0075] EXAMPLES The present invention will be specifically explained below using examples and comparative examples, but the present invention is not limited to these. The viscosities of component (A) and the PVA emulsification aid listed below are all values ​​measured using a BM-type viscometer at 20°C. The viscosities of component (G) listed below are all values ​​measured using a B-type rotational viscometer at 25°C. The vinyl value is measured using the Hanus method in accordance with JIS K 0070, and is a value calculated from the obtained iodine value. In the following, Me and Vi represent a methyl group and a vinyl group, respectively.

[0076] Component (A) (A-1) PVA resin with a viscosity of 28 mPa·s in a 4% aqueous solution at 20°C and a saponification degree of 98.5 mol% (manufactured by Kuraray Co., Ltd., product name: 28-98) (A-2) Ethylene-modified PVA resin with a viscosity of 27 mPa·s in a 4% aqueous solution at 20°C and a saponification degree of 98.0 mol% (manufactured by Kuraray Co., Ltd., product name: RS-2117) (A-3) PVA resin with a viscosity of 5.5 mPa·s in a 4% aqueous solution at 20°C and a saponification degree of 98.5 mol% (manufactured by Nippon Vinyl Acetate & Poval Co., Ltd., product name: JF-05) Comparative example (A) component (A'-1) PVA resin with a viscosity of 18 mPa·s in a 4% aqueous solution at 20°C and a saponification degree of 88.5 mol% (manufactured by Mitsubishi Chemical Corporation, product name: GM-14L)

[0077] (F) Component (F-1) Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex

[0078] (G) Component (G-1) (ViMe2SiO 1 / 2 )2(Me2SiO 2 / 2 ) 120 (ViMeSiO 2 / 2 ) 18 Vinyl value: 0.187 mol / 100 g, viscosity: 300 mPa·s (G-2) (ViMe2SiO 1 / 2 )2(Me2SiO 2 / 2 ) 10 Vinyl value: 0.211 mol / 100 g, viscosity: 9.0 mPa·s (G-3) (ViMe2SiO 1 / 2 )2(Me2SiO 2 / 2 ) 95 (ViMeSiO 2 / 2 )3 Vinyl value: 0.070 mol / 100 g, viscosity: 300 mPa·s (G-4) (ViMe2SiO 1 / 2 )2(Me2SiO 2 / 2) 43 Vinyl value: 0.063 mol / 100 g, viscosity: 60 mPa·s (G-5) (ViMe2SiO 1 / 2 )2(Me2SiO 2 / 2 ) x (ViMeSiO 2 / 2 ) y Vinyl value: 0.13 mol / 100 g, rubber-like at 25°C, viscosity of a solution dissolved in toluene to a concentration of 30% by mass is 7,000 mPa·s, x + y is a value that satisfies the viscosity, x / y=9 Comparative example (G) component (G'-1) (ViMe2SiO 1 / 2 )2(Me2SiO 2 / 2 ) 160 (ViMeSiO 2 / 2 )2 Vinyl value: 0.03 mol / 100 g, viscosity: 400 mPa·s (G'-2) (ViMe2SiO 1 / 2 )2(Me2SiO 2 / 2 ) 748 Vinyl value: 0.004 mol / 100 g, viscosity: 30,000 mPa·s

[0079] (H) Component (H-1)(MeSiO 1 / 2 )2(MeHSiO 2 / 2 ) 70 (MeSiO 2 / 2 ) 28 SiH group content: 1.08mol / 100g, viscosity: 122mPa·s (H-2)(MeSiO 1 / 2 )2(MeHSiO 2 / 2 ) 45 (MeSiO 2 / 2 ) 17 SiH group content: 1.10mol / 100g, viscosity: 44mPa·s (H-3)(MeSiO 1 / 2 )2(MeHSiO 2 / 2 )50 (MeSiO 2 / 2 ) 48 SiH group content: 0.75mol / 100g, viscosity: 117mPa·s (H-4)(MeSiO 1 / 2 )2(MeHSiO 2 / 2 ) 80 (MeSiO 2 / 2 ) 100 SiH group content: 0.65mol / 100g, viscosity: 370mPa·s (H-5)(MeSiO 1 / 2 )2(MeHSiO 2 / 2 ) 38 SiH group content: 1.60mol / 100g, viscosity: 20mPa·s (H-6)(MeSiO 1 / 2 )2(MeHSiO 2 / 2 )5(Me2SiO 2 / 2 ) 10 SiH group content: 0.42mol / 100g, viscosity: 10mPa·s

[0080] Component (I) (I-1) Polyoxyethylene styrenated phenyl ether (trade name: Noigen EA-137, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) HLB: 13.0 (I-2) Polyoxyethylene lauryl ether (trade name: Emulgen 109P, manufactured by Kao Corporation, HLB: 13.6) (I-3) Mixture of ethoxylated 2,4,7,9-tetramethyl-5-decyne-4,7-diol and sodium di-2-ethylhexyl sulfosuccinate (trade name: Surfynol PSA-336, manufactured by Evonik) emulsifying aid (I'-1) PVA resin (manufactured by Mitsubishi Chemical Corporation, product name: GM-14L) with a viscosity of 18 mPa·s in a 4% aqueous solution at 20°C and a saponification degree of 88.5 mol%.

[0081] A. Emulsion Preparation Preparation of addition-curing silicone emulsion (B) [Preparation Example 1] A 5-liter composite emulsifier (TK Combimix M model, product name: Primix Corporation) equipped with an anchor-type impeller capable of stirring the entire contents of the vessel and a rotatable disk with small teeth alternately provided on the periphery thereof was charged with 26.7 parts by mass of (G-1), 21.7 parts by mass of (G-2), 18.3 parts by mass of (H-1), 0.67 parts by mass of (I-1) as a surfactant, 22 parts by mass of a 15% aqueous solution of PVA (manufactured by Mitsubishi Chemical Corporation, product name: GM-14L, a 4% aqueous solution having a viscosity of 18 mPa s at 20°C and a degree of saponification of 88.5 mol%) as an emulsification aid, and 0.4 parts by mass of 1-ethynyl-1-cyclohexanol as a catalyst activity inhibitor. The mixture was stirred and mixed uniformly, and then 20 parts by mass of phase inversion water was added to cause phase inversion. The mixture was then stirred for 15 minutes. Next, 56.7 parts by mass of dilution water was added and stirred to obtain an addition-curing emulsion (B-1) with a silicone content of 40%. [Preparation Examples 2-16] Using the same method as in Preparation Example 1, emulsification was carried out with the compositions shown in Tables 1, 2, and 3 below to obtain addition-curable silicone emulsions (B-2 to 12 and B'-1 to B'-4).

[0082] Preparation of silicone emulsion (C) containing organopolysiloxane having alkenyl groups [Preparation Example 17] Using the same method as in Preparation Example 1, 26.7 parts by weight of (G-1), 21.7 parts by weight of (G-2), 0.49 parts by weight of (I-1), 16.2 parts by weight of a 15% aqueous solution of PVA (manufactured by Mitsubishi Chemical Corporation, trade name: GM-14L, 4% aqueous solution viscosity at 20 °C 18 mPa s, saponification degree 88.5 mol%) as an emulsification aid, and 0.4 parts by weight of 1-ethynyl-1-cyclohexanol as a catalyst activity inhibitor were charged into a composite emulsifier, stirred and mixed uniformly, and then 14.6 parts by weight of phase inversion water was added to induce phase inversion, followed by stirring for 15 minutes. Next, 41.4 parts by weight of dilution water was added and stirred to obtain an alkenyl-containing organopolysiloxane-containing silicone emulsion (C-1) with a silicone content of 40%.

[0083] Preparation of organohydrogenpolysiloxane-containing silicone emulsion (D) [Preparation Example 18] Using the same method as in Preparation Example 1, 18.3 parts by mass of (H-1), 0.17 parts by mass of (I-1), and 6 parts by mass of a 15% aqueous PVA solution (manufactured by Mitsubishi Chemical Corporation, product name: GM-14L, 4% aqueous solution viscosity at 20°C 18 mPa s, saponification degree 88.5 mol%) as an emulsification aid were charged into a complex emulsifier and mixed uniformly with stirring. After stirring, 5.4 parts by mass of phase inversion water was added to induce phase inversion, and stirring continued for 15 minutes. Next, 15.3 parts by mass of dilution water was added and stirred to obtain organohydrogenpolysiloxane-containing silicone emulsion (D-1) with a silicone content of 40%.

[0084] Preparation of catalyst composition (K) [Preparation Example 19] The catalyst composition was mixed with water and emulsified so that (F-1) and (I-2) were present in an amount of 0.4 mass % and 0.2 mass %, respectively, to obtain a platinum catalyst emulsion composition (K-1).

[0085] B. Preparation of Water-Based Oil-Resistant Composition and Oil-Resistant Paper [Example 1] 1,000 parts by mass of an aqueous solution of 10% PVA resin (A-1) previously dissolved in water, 166.7 parts by mass of an addition-curing silicone emulsion (B-1) with a silicone content of 40%, 3,067 parts by mass of water (E), and 8.3 parts by mass of platinum catalyst emulsion (K-1) (150 ppm platinum by weight relative to the silicone content) were added and thoroughly mixed to obtain a water-based oil-proofing composition. The prepared water-based oil-proofing composition was mixed with Advantec quantitative filter paper No. 5B (basis weight 108 g / m) as a paper substrate. 2 The filter paper was impregnated with a greaseproof paper (air permeability 3.6s), squeezed with a wringer, and then heated and dried in a dryer at 150°C for 3 minutes to obtain greaseproof paper.

[0086] [Examples 2 to 19, Comparative Examples 1 to 5] In the same manner as in Example 1, aqueous oil-proofing compositions were prepared according to the formulations shown in Tables 1 to 3 below, and paper substrates were treated with these compositions to obtain oil-resistant papers.

[0087] Comparative Example 6 With reference to Example 3 of Patent Document 1 (JP 2005-139418 A), (G'-1) was used as the (G) component, (H-5) as the H component, and (I-2) as the I component, and the composition shown in Table 4 was emulsified and blended in the same manner as in Preparation Example 1, and used as a treatment agent.

[0088] Comparative Example 7 With reference to Example 4 of JP 2015-532659 A, (G'-2) was used as the (G) component, (H-6) was used as the (H) component, and (I'-1) was used as the I component, and the composition shown in Table 4 was emulsified and blended in the same manner as in Preparation Example 1, and used as the treatment agent.

[0089] C. Evaluation items and methods The physical properties of each of the obtained greaseproof papers were evaluated according to the methods described below. The evaluation results are shown in Tables 1 to 4.

[0090] Oil resistance Using rapeseed oil (trade name: Nisshin Canola Oil) manufactured by Nisshin Oillio, one drop of oil was placed on greaseproof paper treated with the aqueous oil-proofing composition, and the state of penetration of the oil was visually checked 30 minutes after the drop was dropped. The criteria were as follows: ◎: (No oil stains or bleed-through after 30 minutes) 〇: (After 30 minutes, there are several pinhole-shaped oil stains) △: (Oil stains and bleed-through occur within 5 to 15 minutes) ×: (Oil stains and bleed-through occur within 5 minutes)

[0091] water resistance A drop of water was placed on the greaseproof paper treated with the aqueous oil-proofing composition, and the state of penetration of the water was visually observed 30 minutes after the drop. The criteria were as follows: 〇: (No water penetrates after 30 minutes) △: (Water penetrates within 5 to 15 minutes) ×: (Water penetrates within 5 minutes)

[0092] Air permeability Air permeability was measured in accordance with JAPAN TAPPI Paper and Pulp Test Method No. 5-2: 2000. The tester used was an Oken-type air permeability tester (model: 2040-C) manufactured by Kumagai Riki Kogyo Co., Ltd., and the air permeability was calculated as the average value of three different points.

[0093] [Table 1]

[0094] [Table 2]

[0095] [Table 3]

[0096] [Table 4]

[0097] As shown in Tables 1 to 3, paper impregnated with only a PVA resin (Comparative Example 1) or a silicone emulsion (Comparative Example 2) was poor in either oil resistance or water resistance. Furthermore, paper impregnated with a composition containing (A'-1) with a saponification degree of less than 91 mol% (Comparative Example 3) was poor in both oil resistance and water resistance, and paper impregnated with a composition in which the total alkenyl value in component (G) was 0.1 mol / 100 g or less (Comparative Examples 4 and 5) was poor in oil resistance. On the other hand, the oil-resistant paper obtained by impregnation with the aqueous oil-resistant composition of the present invention had excellent oil resistance and water resistance, and its air permeability was 15 seconds or less, which was appropriate for oil-resistant paper for food use. Furthermore, it was found that there was no significant difference in the performance of the resulting grease-resistant paper whether the silicone emulsion contained components (G) and (H) in the same emulsion (Examples 1 to 18) or in different emulsions (Example 19). In the present invention, the alkenyl value of component (G) is important, and it has been observed that as the alkenyl value of all components (G) blended in the composition decreases, oil resistance tends to decrease.

[0098] As shown in Table 4 above, the composition of Patent Document 1 (Comparative Example 6) did not exhibit oil resistance or water resistance, compared with the results of Example 1, which is also listed as an example of a composition of the present invention. In the examples of Patent Document 1, the composition was applied to the surface of a paper substrate containing a filler, dried, and a cured film was formed on the surface of the paper substrate, presumably imparting oil resistance. However, the results suggest that the alkenyl value (vinyl value) of the total of the (G) components in the composition is important when impregnating the interior of the paper substrate with the composition to exhibit oil resistance. Furthermore, a composition using a large amount of PVA resin as an emulsifier, such as that disclosed in JP-A-2015-532659 (Comparative Example 7), did not exhibit oil resistance, demonstrating the importance of subsequently adding a highly saponified PVA resin to the addition-curable silicone emulsion.

[0099] It has been found that the oil-resistant paper of the present invention achieves high oil resistance, water resistance, and air permeability because the oil-resistant PVA resin and the water-resistant, air-permeable organopolysiloxane are dispersed and physically entangled within the paper. In order to promote the physical entanglement of the PVA resin and organopolysiloxane, the crosslink density of the organopolysiloxane is important, and it is necessary to use an alkenyl-group-containing organopolysiloxane with a high alkenyl value. [Industrial Applicability]

[0100] Greaseproof paper treated with the aqueous oil-proofing composition of the present invention can achieve oil resistance, water resistance, and air permeability at the same time, and therefore can be suitably used as packaging paper, packaging containers, food trays, etc. for cooked foods such as fast food, fried foods, and baked foods that contain a lot of oil and water.

Claims

1. The following components (A), (B), (E), and (F): (A) Polyvinyl alcohol (PVA) resin having a viscosity of 2 to 80 mPa·s in a 4% aqueous solution at 20°C and a saponification degree of 91 mol% or more: 100 parts by mass (B) Addition-curing silicone emulsion: 10 to 5,000 parts by mass (E) Water: 1,000 to 50,000 parts by mass (F) Platinum group metal catalyst: catalyst amount A water-based oil-resistant composition comprising: The addition-curable silicone emulsion (B) is (G) an alkenyl group-containing organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and a viscosity of 5 mPa s or more at 25°C, which accounts for 5 to 40 mass% of component (B), and the total alkenyl value of component (G) (the number of moles of silicon-bonded alkenyl groups contained in 100 g of component (G)) exceeds 0.1 mol / 100 g; (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms (SiH groups) per molecule: % by mass in which the number of moles of SiH groups in component (H) is 1 to 5 times the number of moles of alkenyl groups in component (G); (I) Surfactant: 0.1 to 10% by mass of component (B), and (J) Water: 10 to 90% by mass in component (B) The water-based oil-resistant composition comprises:

2. The following components (A), (C), (D), (E) and (F): (A) Polyvinyl alcohol (PVA) resin having a viscosity of 2 to 80 mPa·s in a 4% aqueous solution at 20°C and a saponification degree of 91 mol% or more: 100 parts by mass (C) Silicone emulsion: 5 to 2,500 parts by mass (D) Silicone emulsion (E) Water: 1,000 to 50,000 parts by mass (F) Platinum group metal catalyst: catalyst amount A water-based oil-resistant composition comprising: The silicone emulsion (C) is (G) an alkenyl group-containing organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and a viscosity of 5 mPa s or more at 25°C, which accounts for 5 to 60 mass% of component (C), and the total alkenyl value of component (G) (the number of moles of silicon-bonded alkenyl groups contained in 100 g of component (G)) exceeds 0.1 mol / 100 g; (I) Surfactant: 0.1 to 10% by mass of component (C), and (J) Water: 10 to 90% by mass in component (C) and The silicone emulsion (D) is (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule: 5 to 60% by mass of component (D); (I) Surfactant: 0.1 to 10% by mass of component (D), and (J) Water: 10 to 90% by mass in component (D) wherein the content of component (D) in the composition is such that the number of moles of SiH groups of component (H) in component (D) corresponds to 1 to 5 times the number of moles of alkenyl groups of component (G) in component (C).

3. 3. The aqueous oil-resistant composition according to claim 1, wherein the PVA-based resin as component (A) has a viscosity of 5 to 80 mPa·s in a 4% aqueous solution at 20°C and a degree of saponification of 95 mol % or more.

4. 3. The aqueous oil-resistant composition according to claim 1, wherein the PVA-based resin (A) is at least one selected from the group consisting of polyvinyl alcohol and modified polyvinyl alcohol resins.

5. 3. The aqueous oil-resistant composition according to claim 1, wherein component (G) comprises at least two types of organopolysiloxanes: a linear organopolysiloxane containing alkenyl groups only at both ends; and a linear organopolysiloxane containing alkenyl groups in side chains and at both ends.

6. 3. The aqueous oil-resistant composition according to claim 1, wherein component (G) is a linear, alkenyl-containing organopolysiloxane represented by the following average composition formula (1-1): 【Chemistry 1】 (In formula (1-1), R 1 are independently an alkenyl-containing organic group having 2 to 10 carbon atoms, and R 2 are independently one type of group selected from unsubstituted or substituted monovalent hydrocarbon groups that do not have a hydroxyl group, an alkoxy group, or an alkenyl group, and a, c, and d are each a number of 0 or more that satisfies the conditions 0≦a≦3, 2≦2a+c, and 5≦c+d.

7. 3. The aqueous oil-resistant composition according to claim 1, wherein the ratio of the total number of silicon-bonded hydrogen atoms to the total number of silicon-bonded hydrogen atoms and silicon-bonded groups in component (H) is 15 to 50%.

8. 2. The aqueous oil-resistant composition according to claim 1, wherein the silicone emulsion of component (B) further contains 0.5 to 10% by mass of a polyvinyl alcohol (PVA) resin in component (B).

9. 3. The aqueous oil-resistant composition according to claim 2, wherein at least one of the silicone emulsion of component (C) and the silicone emulsion of component (D) further contains a polyvinyl alcohol (PVA)-based resin in an amount of 0.5 to 10 mass% in component (C) or component (D).

10. 3. The aqueous oil-resistant composition according to claim 1, wherein the total mass of components (G) and (H) is 60 to 2,000 parts by mass per 100 parts by mass of component (A).

11. A method for producing the aqueous oil resistant composition according to claim 1, comprising: (Step 1) A step of mixing and emulsifying the following components (G), (H), (I), and (J) to prepare (B) an addition-curable silicone emulsion: (G) an alkenyl group-containing organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and a viscosity of 5 mPa·s or greater at 25°C: this comprises 5 to 40 mass% of component (B), and the total alkenyl value of component (G) (the number of moles of silicon-bonded alkenyl groups per 100 g of component (G)) exceeds 0.1 mol / 100 g (H) Organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms (SiH groups) per molecule: % by mass in which the number of moles of SiH groups in component (H) is 1 to 5 times the number of moles of alkenyl groups in component (G) (I) Surfactant: 0.1 to 10% by mass of component (B) (J) Water: 10 to 90% by mass in component (B) and (Step 2) A step of mixing the following components (A), (E), and (F) with 10 to 5,000 parts by mass of the addition-curable silicone emulsion (B) prepared in Step 1 above: (A) PVA-based resin having a viscosity of 2 to 80 mPa·s in a 4% aqueous solution at 20°C and a saponification degree of 91 mol% or more: 100 parts by mass (E) Water: 1,000 to 50,000 parts by mass (F) Platinum group metal catalyst: catalyst amount A method for producing a water-based oil-resistant composition comprising the steps of:

12. A method for producing the aqueous oil-resistant composition according to claim 2, comprising the steps of: (Step 1') A step of mixing and emulsifying the following components (G), (I), and (J) to prepare a silicone emulsion (C): (G) an alkenyl group-containing organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and a viscosity of 5 mPa·s or greater at 25°C: this comprises 5 to 60 mass% of component (C), and the total alkenyl value of component (G) (the number of moles of silicon-bonded alkenyl groups per 100 g of component (G)) exceeds 0.1 mol / 100 g (I) Surfactant: 0.1 to 10% by mass of component (C) (J) Water: 10 to 90% by mass in component (C) (Step 1″) A step of mixing and emulsifying the following components (H), (I), and (J) to prepare (D) a silicone emulsion: (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule: 5 to 60% by weight of component (D); (I) Surfactant: 0.1 to 10% by mass of component (D) (J) Water: 10 to 90% by mass in component (D) and (Step 2') A step of mixing the following components (A), (E), and (F), 5 to 2,500 parts by mass of the silicone emulsion (C) prepared in the above step 1', and an amount of the silicone emulsion (D) prepared in the above step 1'' in which the number of moles of SiH groups of component (H) in component (D) corresponds to 1 to 5 times the number of moles of alkenyl groups of component (G) in component (C). (A) PVA-based resin having a viscosity of 2 to 80 mPa·s in a 4% aqueous solution at 20°C and a saponification degree of 91 mol% or more: 100 parts by mass (E) Water: 1,000 to 50,000 parts by mass (F) Platinum group metal catalyst: catalyst amount A method for producing a water-based oil-resistant composition comprising the steps of:

13. A method for oil-proofing paper, comprising adding the aqueous oil-proofing agent composition according to claim 1 or 2 to a pulp slurry as an internal treatment or adding the aqueous oil-proofing agent composition according to claim 1 or 2 to a paper substrate as an external treatment.

14. 3. The oil-resistant paper treated with the aqueous oil-proofing composition according to claim 1 or 2, wherein the air permeability measured by the Oken air permeability tester in accordance with JAPAN TAPPI Paper and Pulp Testing Method No. 5-2:2000 is 1,000 seconds or less.

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