Aqueous oil-resistant agent composition, method for producing aqueous oil-resistant agent composition, method for oil-resistant treatment for paper, and oil-resistant paper

Abstract

Provided is a non-fluorinated resin-based aqueous oil-resistant agent composition by which an oil-resistant paper having high oil-resistance and high air permeability can be obtained, wherein the components contained in the composition do not include any fluorine-based resin or organic solvent, and health aspects and environmental aspects are taken into consideration. This aqueous oil-resistant agent composition contains (A) a polyvinyl alcohol (PVA)-based resin, (B) an addition-curable silicone emulsion, (E) water, and (F) a platinum group metal-based catalyst, wherein (B) the addition-curable silicone emulsion contains (G) an alkenyl group-containing organopolysiloxane, (H) an organohydrogen polysiloxane, (I) a surfactant, and (J) water.

Description

Water-based oil-proofing composition, method for producing water-based oil-proofing composition, method for treating paper with oil resistance, and oil-resistant paper

[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.

[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] Grease-resistant paper for food or grease-resistant containers has traditionally been made of polyethylene-laminated paper, which has a paper substrate laminated to one side with a polyethylene film. However, polyethylene-laminated paper has problems such as poor air permeability, which can lead to a deterioration in the flavor and storage stability of food, and the difficulty of removing the polyethylene film during recycling, making it poorly recyclable. There is also a strong movement toward a plastic-free society, and the development of grease-resistant paper without polyethylene lamination is desired. Furthermore, fluororesin-based oil-proofing agents have traditionally been widely used to impart oil and water resistance to paper. For example, methods include coating the surface of a paper substrate with the fluororesin-based oil-proofing agent to form an oil-resistant layer, impregnating a paper substrate with the fluororesin-based oil-proofing agent, or adding the fluororesin-based oil-proofing agent to a pulp slurry. However, fluororesin-based oil-proofing agents are undesirable from health and environmental perspectives due to their persistence and bioaccumulation. Therefore, 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, as non-fluorine resin-based oil-resistant agents, for example, hydrophilic resins that form films, such as polyvinyl alcohol (PVA)-based resins and polysaccharides, are widely used, 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-based resin and a silicone-based emulsion. In addition, acrylic and paraffin wax-based emulsions such as those described in Patent Documents 2, 3, and 4 are also known to have excellent oil resistance.

[0005] JP 2005-139418 A JP 2013-237941 A JP 2020-122250 A JP 2022-188338 A

[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 results in insufficient air permeability, which can lead to a deterioration 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 demonstrated air permeability, they all require a large amount of oil-proofing agent applied, resulting in air permeabilities of 100 seconds or more, which are inferior to those of fluororesin-based oil-proofing agents. As such, no grease-resistant paper capable of combining high oil resistance and high air permeability using a non-fluororesin-based oil-proofing agent has yet been developed, leaving 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.

[0007] As a result of extensive research to achieve the above object, the present inventors have found that the following aqueous oil-resistant composition can solve the above problems, and have thus completed the present invention. That is, the present invention provides the following oil-resistant composition, etc. [1] An aqueous oil-resistant composition comprising the following components (A), (B), (E), and (F): (A) 100 parts by mass of a polyvinyl alcohol (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; (B) 10 to 5,000 parts by mass of an addition-curable silicone emulsion; (E) 1,000 to 50,000 parts by mass of water; and (F) a catalytic amount of a platinum group metal catalyst, wherein the (B) addition-curable silicone emulsion is The aqueous oil-resistant composition comprises: (G) an alkenyl-containing organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and having a viscosity of 5 mPa s or more at 25°C: 5 to 40 mass% in component (B), and having a total alkenyl value of component (G) (the number of moles of silicon-bonded alkenyl groups per 100 g of component (G)) of greater than 0.1 mol / 100 g; (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms (SiH groups) per molecule: 1 to 5 times the number of moles of SiH groups in component (H) relative to the number of moles of alkenyl groups in component (G); (I) a surfactant: 0.1 to 10 mass% in component (B); and (J) water: 10 to 90 mass% in component (B).[2] An aqueous oil-resistant composition comprising the following components (A), (C), (D), (E), and (F): (A) 100 parts by mass of a polyvinyl alcohol (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; (C) 5 to 2,500 parts by mass of a silicone emulsion; (D) 1,000 to 50,000 parts by mass of water; and (F) a catalytic amount of a platinum group metal catalyst, wherein the (C) silicone emulsion 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 more at 25°C: 5 to 60 mass% in component (C), and the alkenyl value of component (G) in total (the number of moles of silicon-bonded alkenyl groups per 100 g of component (G)) exceeds 0.1 mol / 100 g; (I) a surfactant: 0.1 to 10 mass% in component (C); and (J) water: 10 to 90 mass% in component (C), wherein the (D) silicone emulsion comprises: (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule: 5 to 60 mass% in component (D), (I) a surfactant: 0.1 to 10 mass% in component (D), and (J) water: 10 to 90 mass% in component (D).

[0013] The aqueous oil-resistant composition according to any one of [1] to [3], 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.

[0014] The aqueous oil-resistant composition according to any one of [1] to [3], wherein the PVA-based resin as component (A) is at least one selected from the group consisting of 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-containing organopolysiloxane represented by the following average composition formula (1-1): (In formula (1-1), R １ are independently an alkenyl-containing organic group having 2 to 10 carbon atoms, and R ２are independently one group selected from unsubstituted or substituted monovalent hydrocarbon groups that are free of hydroxyl groups, alkoxy groups, and alkenyl groups, and a, c, and d are each numbers equal to or greater than 0 and satisfy the relationships 0≦a≦3, 2≦2a+c, and 5≦c+d.) [7] The aqueous oil resistant composition of any one of [1] to [6], 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] The aqueous oil resistant composition of 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% by 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 comprises a polyvinyl alcohol (PVA) 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 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 proofing composition according to any one of [1] and [3] to

[10] , wherein (Step 1) the following components (G), (H), (I), and (J) are mixed and emulsified 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 having a viscosity of 5 mPa·s or more at 25°C: (G) accounts for 5 to 40 mass% of component (B), and the alkenyl value of the total of components (G) (the number of moles of silicon-bonded alkenyl groups contained in 100 g of components (G)) exceeds 0.1 mol / 100 g: (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms (SiH groups) per molecule: (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms (SiH groups) per molecule, in a mass % equivalent to 1 to 5 times the number of moles of SiH groups in component (H) relative to the number of moles of alkenyl groups in component (G); (I) a surfactant: 0.1 to 10 mass % in component (B); (J) water: 10 to 90 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: (A) 100 parts by mass of 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; (E) water: 1,000 to 50,000 parts by mass; and (F) a platinum group metal-based catalyst: a catalytic amount.

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

[10] , wherein: (Step 1') is a step of mixing and emulsifying the following components (G), (I), and (J) to prepare (C) a silicone emulsion: (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 more at 25°C: 5 to 60 mass% in component (C), and the alkenyl value of all components (G) (the number of moles of silicon-bonded alkenyl groups contained in 100 g of all components (G)) exceeds 0.1 mol / 100 g; (I) a surfactant: 0.1 to 10 mass% in component (C); and (J) water: 10 to 90 mass% in component (C). (Step 1'') is 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 mass% in component (D); (I) a surfactant: 0.1 to 10 mass% in component (D); (J) water: 10 to 90 mass% in component (D); and (Step 2') a step of mixing the following components (A), (E), and (F), 5 to 2,500 mass parts of the silicone emulsion (C) prepared in step 1' above, and an amount of the silicone emulsion (D) prepared in step 1'' above, in which the number of moles of SiH groups in component (H) of component (D) corresponds to 1 to 5 times the number of moles of alkenyl groups in component (G) of component (C); (A) 100 parts by mass of a PVA-based resin having a viscosity of 2 to 80 mPa s as a 4% aqueous solution at 20°C and a degree of saponification of 91 mol% or more. (E) water: 1,000 to 50,000 parts by mass, and (F) platinum group metal catalyst: catalytic amount.

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

[10] to a pulp slurry or externally adding the aqueous oil proofing composition according to any one of [1] to

[10] to a paper substrate.

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

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

[0008] The present invention combines the advantages of both materials by combining a PVA resin, which has excellent compatibility with paper, with a silicone, which has good water resistance and air permeability. By treating a paper substrate with a composition obtained by combining materials having a specific structure according to the present invention under specific conditions and then curing the composition, greaseproof paper with excellent oil and water resistance and high air permeability can be obtained. Furthermore, the high air permeability of the greaseproof paper of the present invention prevents oil stains without impairing the flavor of food when packaged in the paper. Furthermore, the PVA resin and silicone contained in the aqueous oilproofing composition of the present invention are both environmentally safe and harmless materials, making them suitable for use as alternatives to organic fluorine compounds. Furthermore, because the aqueous oilproofing composition of the present invention does not contain organic solvents, it avoids the environmental problems and biological hazards associated with the use of organic solvents. Paper substrates treated with the composition of the present invention can be easily recycled and become environmentally friendly products, thereby resolving the harmful effects and environmental problems associated with fluorine compounds.

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

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

[0011] The properties of a PVA-based resin are roughly defined by its 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 the PVA-based resin at 20°C is less than 2 mPa·s, the film-forming ability will be insufficient, and if it exceeds 80 mPa·s, the coatability will be poor. From the viewpoint of film-forming ability and coatability, the viscosity of the PVA-based resin is preferably 5 to 80 mPa·s, more preferably 10 to 70 mPa·s, and even more preferably 20 to 60 mPa·s, for a 4% aqueous solution at 20°C. 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-based 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-based 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 a homopolymer having only vinyl alcohol units (polyvinyl alcohol), but also a copolymer having vinyl alcohol units and other polymerizable vinyl monomer units, and a modified polyvinyl alcohol resin in which part of the side chain of the vinyl alcohol unit is substituted, etc. The PVA-based resin used in the present invention may also be a copolymer having vinyl alcohol units and other polymerizable vinyl monomer units, i.e., a PVA-based resin obtained by copolymerizing polyvinyl alcohol with a known polymerizable vinyl monomer in an amount of up to 5 mol % within a range that does not impair the oil resistance effect. 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 vinyl alcohol:polymerizable vinyl monomer = 100:0 to 95:5. The side chains of the PVA resin used in the present invention may be partially substituted with a hydrocarbon group having 1 to 20 carbon atoms and a silyl group. Examples of hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups, aryl groups, and groups in which at least a portion of the hydrogen atoms of these groups are substituted with a silicon-containing group.

[0013] In the present invention, any commercially available PVA-based resin can be used as long as it satisfies the above-mentioned viscosity and degree of saponification. 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.), and Gohsenol (manufactured by Mitsubishi Chemical Corporation). The PVA-based resin (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% by mass, and more preferably 20 to 80% by mass, based on the total amount of components excluding water. The total amount of components excluding water refers to the combined amount of (E) water and the components other than (J) water in the composition, including (B) addition-curable silicone emulsion, (C) silicone emulsion, (D) silicone emulsion, and (K) catalyst composition, which will be described later.

[0014] The aqueous oil-proofing composition of the present invention contains, as a silicone emulsion, <1> (B) an addition-curable silicone emulsion or <2> (C) a silicone emulsion and (D) a silicone emulsion. The (B) addition-curable silicone emulsion contains (G) an alkenyl group-containing organopolysiloxane, (H) an organohydrogenpolysiloxane, (I) a surfactant, and (J) water. The (C) silicone emulsion contains (G) an alkenyl group-containing organopolysiloxane, (I) a surfactant, and (J) water. The (D) silicone emulsion contains (H) an organohydrogensiloxane, (I) a surfactant, and (J) water. Each of the components (G) to (J) will be described below. In this specification, an aqueous oil-proofing composition containing an addition-curable silicone emulsion (B) may be referred to as the "aqueous oil-proofing composition <1>," and an aqueous oil-proofing composition containing a silicone emulsion (C) and a silicone emulsion (D) may be referred to as the "aqueous oil-proofing composition <2>." The emulsification to obtain the components (B) to (D) may be carried out using a general emulsifying disperser. Examples of the emulsifying disperser include a high-speed rotation centrifugal radial mixer such as a Homodisper, a high-speed rotation shear mixer such as a Homomixer, a high-pressure jet emulsifying disperser such as a pressure homogenizer, a colloid mill, and an ultrasonic emulsifier. The volume-average particle size of the resulting emulsions of the 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-Cure Silicone Emulsion The blending amount of component (B) 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 blending amount of component (B) 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% by mass, preferably 10 to 35% by mass, and more preferably 15 to 30% by mass. If it is outside this range, the oil resistance and water resistance will be reduced.

[0017] The content of (H) in component (B) is a mass % corresponding to 1 to 5 times, preferably 1.1 to 3 times, and more preferably 1.2 to 2.5 times 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% by mass, preferably 10 to 50% by mass, and more preferably 15 to 40% by mass. If it is outside this range, the 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 blending amount of component (D) is a mass % corresponding to 1 to 5 times the number of moles of SiH groups in component (D) relative to the number of moles of alkenyl groups in component (C), preferably 1.1 to 3.0 times, and more preferably 1.2 to 2.5 times. If the blending amount of component (D) is outside the above range, oil resistance and water resistance will be reduced.

[0026] The content of component (H) in component (D) is 5 to 60% by mass, preferably 10 to 50% by mass, and more preferably 15 to 40% by 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, whereas 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, whereas 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 having at least two silicon-bonded alkenyl groups per molecule and a viscosity of 5 mPa·s or greater at 25°C. The number of silicon-bonded alkenyl groups per molecule in component (G) is at least two, preferably 2 to 500, more preferably 2 to 100, and even more preferably 2 to 30. If component (G) has fewer than two silicon-bonded alkenyl groups per molecule, crosslinking is not possible, resulting in reduced oil resistance, which is undesirable. Furthermore, if component (G) has more than 500 silicon-bonded alkenyl groups per molecule, curing may require a long time.

[0031] The viscosity of component (G) at 25°C is 5 mPa·s or more, 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 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 alkenyl value bonded to silicon atoms in the total of component (G) is a value exceeding 0.1 mol / 100g, preferably 0.13 mol / 100g or more, more preferably 0.15 mol / 100g or more. If the alkenyl value bonded to silicon atoms in the total of component (G) is 0.1 mol / 100g or less, crosslinkability will be low and oil resistance will be reduced. There is no upper limit for the alkenyl value of component (G), but it can be set to, for example, 0.7 mol / 100g. This alkenyl value is the value of the number of moles of alkenyl groups bonded to silicon atoms contained in a total of 100g of component (G), and 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, then reacted 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 can be any of linear, branched, and cyclic structures, but is preferably a linear structure. 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 be greater than 0.1 mol / 100 g. When two or more components (G) are used in combination, their molecular structures are also 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 at side chains and both ends, and it is more preferable to use in combination organopolysiloxanes each having an alkenyl value of greater than 0.1 mol / 100 g.

[0034] Component (G) is a component that provides the oil resistance and water resistance of the composition, and specific examples thereof include those having a structure represented by average composition formula (1). (In formula (1), R １ are independently an alkenyl-containing organic group having 2 to 10 carbon atoms, and R ２are 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 more that satisfies 0≦a≦3, 1≦b, 2≦ab+c+e, and 5≦b+c+d+e+f+g.

[0035] R １ 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 ２ R is a group selected from unsubstituted or substituted monovalent hydrocarbon groups that do not have a hydroxyl group, an alkoxy group, or an alkenyl group. ２ Examples of the alkoxy group represented by R include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. ２ The unsubstituted or substituted monovalent hydrocarbon group not containing an alkenyl group, represented by formula (1), 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) contains 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 equal to or greater than 0. a is 0≦a≦3, preferably 0 or 1, and more preferably 1. b is a number equal to or greater than 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, i.e., one represented by the following formula (1-1) in which b=2 and e=f=g=0 in formula (1). In formula (1-1), R １ and R ２ are each defined as in formula (1), and a, c, and d are each a number equal to or greater than 0, and are numbers satisfying 0≦a≦3, 2≦2a+c, and 5≦c+d. In formula (1-1), when an alkenyl group is present in the side chain (1≦c), it is more preferable that 2≦c≦500 and 3≦d≦4,000, even more preferable that 5≦c≦100 and 3≦d≦500, and particularly preferable that 10≦c≦50 and 3≦d≦300. In formula (1-1), when an alkenyl group is not present in the side chain (c=0), it is more preferable that 3≦d≦30, and even more preferable that 3≦d≦20.

[0039] Examples of component (G) include, but are not limited to, the following: In the formulas below, 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 formulas below, the total number of siloxane repeating units is an average value. In the formulas below, z1 to z39 are each a number of 0 or greater.

[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, whereas 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 an amount 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 contained in component (H) may be located at either the terminals or the middle of the molecular chain, or may be located at both locations. Component (H) is preferably a linear organohydrogenpolysiloxane represented by the following formula (2): (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; 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 ３ 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. ３The 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 average composition formula (2) include methylhydrogensiloxane-dimethylsiloxane cyclic copolymers, dimethylsiloxane-methylhydrogensiloxane copolymers both ends of which are capped with trimethylsiloxy groups, dimethylpolysiloxanes both ends of which are capped with dimethylhydrogensiloxane groups, dimethylsiloxane-methylhydrogensiloxane copolymers both ends of which are capped with dimethylhydrogensiloxy groups, and methylhydrogensiloxane-diphenylsiloxane copolymers both ends of which are capped with trimethylsiloxy groups. , a methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymer both ends of which are capped with trimethylsiloxy groups, a methylhydrogensiloxane-methylphenylsiloxane-dimethylsiloxane copolymer both ends of which are capped with trimethylsiloxy groups, a methylhydrogensiloxane-dimethylsiloxane-diphenylsiloxane copolymer both ends of which are capped with dimethylhydrogensiloxy groups, a methylhydrogensiloxane-dimethylsiloxane-methylphenylsiloxane copolymer both ends of which are capped with dimethylhydrogensiloxy groups, etc. Component (H) may be used alone, or two or more types may be used 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 order shown below. In each of the following formulas, the total number of siloxane repeating units is an average value. Furthermore, in the following formulas, z42 to z73 are numbers that satisfy the ratio of SiH groups in the organohydrogenpolysiloxane of each formula of 15% to 50%.

[0047] (I) Surfactant The component (I) is a surfactant, and is not particularly limited as long as it can emulsify and disperse the 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, 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, with polyoxyethylene lauryl ether and polyoxyethylene styrenated phenyl ether being more preferred. The nonionic surfactants may be used alone or in combination of two or more. To obtain a stable emulsion composition, it is preferred that the nonionic surfactants, alone or in combination, have an HLB of 10 to 15.

[0048] In addition, anionic surfactants or cationic surfactants can also be used, but from the viewpoint of dispersibility, it is preferable to use them in combination with nonionic surfactants.As anionic surfactants, for example, alkyl sulfate ester salts such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate ester salts, polyoxyethylene alkyl phenyl ether sulfate ester salts, alkyl benzene sulfonates, polyoxyethylene alkyl phenyl ether sulfonates, alkyl diphenyl ether disulfonates, alkanesulfonates, N-acyltaurate salts, dialkyl sulfosuccinate salts, monoalkyl sulfosuccinate salts, polyoxyethylene alkyl ether sulfosuccinate salts, fatty acid salts, polyoxyethylene alkyl ether carboxylate salts, N-acylamino acid salts, monoalkyl phosphate ester salts, dialkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts etc. can be mentioned. 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-based resins, cellulose derivatives, and carboxyvinyl polymers, with PVA-based resins being more preferred. The PVA-based 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-based 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 the 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 that ensures sufficient stability of the silicone emulsion. For example, it is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the 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, while if it 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 Components In the present invention, each of the silicone emulsions (B), (C), and (D) can contain optional components other than those described above. Examples of other optional components include catalyst activity inhibitors (control agents) selected from various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, oxime compounds, organic chloro compounds, and the like, for the purpose of suppressing the catalytic activity of platinum group metal catalysts. Examples of such 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 cure 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 properties will be poor, 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 waterproofing composition of the present invention is preferably within the above-mentioned range per 100 parts by mass of component (A), and the content thereof 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 waterproofing composition is within the above-mentioned range, the composition has good handleability and a good balance between oil resistance and coating weight, which is preferable.

[0053] (F) Platinum group metal catalyst The platinum group metal catalyst of component (F) is a catalyst for promoting the addition reaction between component (G) and component (H), and any catalyst known to those skilled in the art for promoting the so-called hydrosilylation reaction can be used.Such platinum group metal catalysts include, for example, platinum, palladium, rhodium, and ruthenium catalysts, and among these, platinum catalysts are particularly preferred.Such platinum catalysts include, for example, 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 obtaining a good cured coating and being economical, the amount is preferably 1 to 1,000 ppm, more preferably 10 to 500 ppm, and particularly preferably 20 to 200 ppm, calculated as the platinum group metal relative to 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-resistant 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 an aqueous oil-resistant composition comprising the components (A), (B), (E), and (K): (A) 100 parts by mass of 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, (B) 10 to 5,000 parts by mass of an addition-curable silicone emulsion, (E) 1,000 to 50,000 parts by mass of water, and (K) a catalyst composition, wherein the addition-curable silicone emulsion (B) is (G) an alkenyl-containing organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and having a viscosity of 5 mPa·s or more at 25°C, which accounts for 5 to 40 mass% of component (B), and in which the alkenyl value of component (G) in total (the number of moles of silicon-bonded alkenyl groups per 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, which accounts for 1 to 5 times the number of moles of SiH groups in component (H) relative to the number of moles of alkenyl groups in component (G); (I) a surfactant, which accounts for 0.1 to 10 mass% of component (B); and (J) water, which accounts for 10 to 90 mass% of component (B), wherein the (K) catalyst composition is: (F) a platinum group metal catalyst The oil-resistant composition may be a water-based oil-resistant composition containing (I) a surfactant and (J) water.The aqueous oil-resistant composition <2> is an aqueous oil-resistant composition comprising components (A), (C), (D), (E), and (K): (A) 100 parts by mass of a PVA-based 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; (C) 5 to 2,500 parts by mass of a silicone emulsion; (D) the silicone emulsion; (E) 1,000 to 50,000 parts by mass of water; and (K) a catalyst composition, wherein the (C) silicone emulsion 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 more at 25°C: 5 to 60 mass% in component (C), and the alkenyl value of component (G) in total (the number of moles of silicon-bonded alkenyl groups per 100 g of component (G)) exceeds 0.1 mol / 100 g; (I) a surfactant: 0.1 to 10 mass% in component (C); and (J) water: 10 to 90 mass% in component (C), wherein the (D) silicone emulsion comprises: (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule: 5 to 60 mass% in component (D), (I) a surfactant: 0.1 to 10 mass% in component (D), and (J) water: 10 to 90 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) is 1 to 5 times the number of moles of alkenyl groups of component (G) in component (C), and the catalyst composition (K) may be an aqueous oil-resistant composition comprising: (F) a platinum group metal catalyst; (I) a surfactant; and (J) water.

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

[0057] The aqueous oil-proofing composition of the present invention may also contain preservatives, antifoaming agents, fragrances, thickeners, antioxidants, rust inhibitors, pigments, fillers, organic powders, inorganic powders, and the like, as long as the effects of the present invention are not impaired. The amounts of these may be selected from their respective suitable amounts. To further improve oil resistance, the aqueous oil-proofing composition of the present invention may also contain dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, phthalic acid, and terephthalic acid, in an amount of 0.5 to 10% by mass relative to the PVA-based resin. From a safety perspective, it is preferable that the components of the aqueous oil-proofing composition of the present invention consist only of compounds included in the positive list established by the Ministry of Health, Labor, and Welfare and the Japan Paper Association. (Article 18, Paragraph 3 of the Revised Food Sanitation Act and Public Notification No. 370, Positive List of Chemical Substances Related to Paper and Paperboard Intended to Come into Contact with Food)

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

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

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

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

[0062] (Step 1) Preparation of (B) Addition-Curable Silicone Emulsion Component (B) can be produced by known methods. For example, predetermined amounts of components (G), (H), and (I) above and a portion of water (J) are mixed using a stirring device capable of high shear such as a planetary mixer, a combination mixer, or a high-pressure homogenizer, emulsified by phase inversion, and then diluted by adding the remainder of water (J). When preparing the (B) addition-curable silicone emulsion, predetermined amounts of other components such as components (A), (F), the water-soluble resin as the emulsifying aid, and the catalyst activity inhibitor may also be mixed in.

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

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

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

[0066] (Step 2-1) and (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 prepare an aqueous solution of the desired concentration. From the viewpoint of ease of handling, it is preferable that the PVA-based resin (A) is dissolved in water (E) before mixing with the other components, and 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) Preparation of (K) catalyst composition Component (F) may be mixed during the production of addition-curable silicone emulsion (B), but it is preferable to mix component (F), surfactant (I), and water (J) before mixing with the other components, and then mix this with the other components to form the (K) catalyst composition. The (K) catalyst composition may be produced using any device capable of mixing the individual components, but a preferred method is to mix the components using a stirring device capable of high shear such as a planetary mixer, combination mixer, or high-pressure homogenizer, and then emulsify the components by a phase inversion method to form an emulsion.

[0068] (Step 2-3) Mixing the component (B), an aqueous solution of the component (A), and the component (K). (Step 2'-3) Mixing the component (C), the component (D), an aqueous solution of the component (A), and the 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 also 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 improves shelf life, but also makes it possible to easily achieve a wide range of properties by changing the combination of emulsions to be mixed.

[0069] [Oil-proofing treatment method] The aqueous oil-proofing composition of the present invention can be suitably used to impart oil resistance and water resistance to a paper substrate. The method for treating paper with oil resistance 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 a 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 preferred method for applying the aqueous oil-proofing composition is to apply it to the 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, etc. In order to increase the air permeability of the oil-resistant paper, an external addition treatment in which the aqueous oil-proofing composition penetrates into the interior of the paper substrate is preferred, rather than coating the aqueous oil-proofing composition only on the surface of the paper substrate, and impregnation treatment using a pond-type size press is particularly preferred. Furthermore, 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, 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 preferable because it does not deteriorate the flavor or storage stability of food packaged using the grease-resistant paper.

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

[0076] Component (A) (A-1) PVA resin having 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., trade name: 28-98) (A-2) Ethylene-modified PVA resin having 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., trade name: RS-2117) (A-3) PVA resin having 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., trade name: JF-05) Comparative Component (A) (A'-1) PVA resin having 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, trade name: GM-14L)

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

[0078] (G) Component (G-1) (ViMe ２ SiO １／２ ) ２ (Me ２ SiO ２／２ ) １２０ (ViMeSiO ２／２ ) １８ Vinyl value: 0.187 mol / 100 g, viscosity: 300 mPa·s (G-2) (ViMe ２ SiO １／２ ) ２ (Me ２ SiO ２／２ ) １０ Vinyl value: 0.211 mol / 100 g, viscosity: 9.0 mPa·s (G-3) (ViMe ２ SiO １／２ ) ２ (Me ２ SiO ２／２ ) ９５ (ViMeSiO ２／２ ) ３ Vinyl value: 0.070 mol / 100 g, viscosity: 300 mPa·s (G-4) (ViMe ２ SiO １／２ ) ２ (Me ２ SiO ２／２ ) ４３Vinyl value: 0.063 mol / 100 g, viscosity: 60 mPa·s (G-5) (ViMe ２ SiO １／２ ) ２ (Me ２ SiO 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: 7,000 mPa·s, x+y is a value that satisfies the above viscosity, x / y=9. Comparative Example (G) Component (G'-1) (ViMe ２ SiO １／２ ) ２ (Me ２ SiO ２／２ ) １６０ (ViMeSiO ２／２ ) ２ Vinyl value: 0.03 mol / 100 g, viscosity: 400 mPa·s (G′-2) (ViMe ２ SiO １／２ ) ２ (Me ２ SiO ２／２ ) ７４８ Vinyl value: 0.004 mol / 100 g, viscosity: 30,000 mPa·s

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

[0080] (I) Component (I-1) Polyoxyethylene styrenated phenyl ether (trade name: Noigen EA-137, manufactured by Dai-ichi 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 Co., Ltd.) Emulsifying aid (I'-1) PVA resin (manufactured by Mitsubishi Chemical Corporation, trade name: GM-14L) having a viscosity of 18 mPa·s as a 4% aqueous solution at 20°C and a degree of saponification of 88.5 mol%

[0081] A. Preparation of Emulsion Preparation of Addition-Curable Silicone Emulsion (B) [Preparation Example 1] A 5-liter composite emulsifier (TK Combimix M type, product name of Primix Corporation) equipped with an anchor-shaped stirring blade capable of stirring the entire interior of the vessel and a rotatable disk having small tooth-shaped protrusions 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 PVA solution (manufactured by Mitsubishi Chemical Corporation, product name: GM-14L, viscosity of a 4% aqueous solution at 20°C of 18 mPa s, degree of saponification 88.5 mol%) as an emulsification aid, and 0.4 parts by mass of 1-ethynyl-1-cyclohexanol as a catalyst activity inhibitor, and the mixture was stirred and mixed uniformly. Then, 20 parts by mass of phase inversion water was added to cause phase inversion, and the mixture was subsequently stirred for 15 minutes. Next, 56.7 parts by mass of dilution water was added and stirred to obtain an addition-curable emulsion (B-1) with a silicone content of 40%. [Preparation Examples 2 to 16] Addition-curable silicone emulsions (B-2 to 12 and B'-1 to B'-4) were obtained by emulsifying the compositions shown in Tables 1, 2, and 3 below in the same manner as in Preparation Example 1.

[0082] Preparation of Alkenyl Group-Containing Organopolysiloxane-Containing Silicone Emulsion (C) [Preparation Example 17] In a similar manner to Preparation Example 1, 26.7 parts by mass of (G-1), 21.7 parts by mass of (G-2), 0.49 parts by mass of (I-1), 16.2 parts by mass 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 mass of 1-ethynyl-1-cyclohexanol as a catalyst activity inhibitor were charged into a composite emulsifier and mixed uniformly with stirring. After uniform mixing, 14.6 parts by mass of phase inversion water was added to induce phase inversion, and stirring continued for 15 minutes. Next, 41.4 parts by mass of dilution water was added and stirred to obtain an alkenyl group-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 a method similar to that of 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 of 18 mPa s, saponification degree 88.5 mol%) as an emulsification aid were charged into a composite emulsifier and mixed uniformly with stirring, followed by the addition of 5.4 parts by mass of phase inversion water to induce phase inversion, followed by further stirring 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 0.4 mass % and 0.2 mass %, respectively, to obtain a platinum catalyst emulsion composition (K-1).

[0085] B. Preparation of Water-Based Oil-Proofing 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 then filtered using Advantec quantitative filter paper No. 5B (basis weight 108 g / m) as a paper substrate. ２ The filter paper was then wrung out using a wringer and dried in a dryer at 150°C for 3 minutes to obtain oil-resistant 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 component (G), (H-5) as the component H, and (I-2) as the component I, 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-T-2015-532659, (G'-2) was used as the component (G), (H-6) was used as the component (H), and (I'-1) was used as the component I, 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.

[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) from Nisshin Oillio, a drop of oil was placed on greaseproof paper treated with the aqueous oil-resistant composition, and the state of penetration of the oil was visually confirmed 30 minutes after the drop. The criteria were as follows: ◎: (no oil staining or bleed-through after 30 minutes) ◯: (pinhole-shaped oil stains in several places after 30 minutes) △: (oil staining or bleed-through occurs within more than 5 to 15 minutes) ×: (oil staining or bleed-through occurs within 5 minutes)

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

[0092] 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]

[0094]

[0095]

[0096]

[0097] As shown in Tables 1 to 3, paper impregnated with only a PVA-based resin (Comparative Example 1) or paper impregnated with only 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 greaseproof paper impregnated with the aqueous oilproofing composition of the present invention was excellent in oil resistance and water resistance, and had an air permeability of 15 seconds or less, indicating that it had adequate air permeability for greaseproof 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 a decrease in the alkenyl value of all components (G) blended in the composition tended to decrease oil resistance.

[0098] As shown in Table 4 above, compared to the results of Example 1, which is also listed as an example of a composition of the present invention, the composition of Patent Document 1 (Comparative Example 6) did not exhibit oil resistance or water resistance. In the examples of Patent Document 1, it is thought that oil resistance was imparted by coating the composition on the surface of a paper substrate containing a filler and drying it to form a cured film on the surface of the paper substrate. However, when the composition is impregnated into the interior of the paper substrate to exhibit oil resistance, it was suggested that the alkenyl value (vinyl value) of the total of the (G) components in the composition is important. Furthermore, a composition (Comparative Example 7) using a large amount of PVA resin as an emulsifier, such as that disclosed in JP-A-2015-532659, did not exhibit oil resistance, demonstrating the importance of subsequently adding a PVA-based resin with a high degree of saponification to an 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.

[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. A water-based oil-resistant composition comprising the following components (A), (B), (E), and (F): (A) 100 parts by mass of a polyvinyl alcohol (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; (B) 10 to 5,000 parts by mass of an addition-curable silicone emulsion; (E) 1,000 to 50,000 parts by mass of water; and (F) a catalytic amount of a platinum group metal catalyst, wherein the (B) addition-curable silicone emulsion is The aqueous oil-resistant composition comprises: (G) an alkenyl-containing organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and having a viscosity of 5 mPa s or more at 25°C: 5 to 40 mass% in component (B), and having a total alkenyl value of component (G) (the number of moles of silicon-bonded alkenyl groups per 100 g of component (G)) of greater than 0.1 mol / 100 g; (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms (SiH groups) per molecule: 1 to 5 times the number of moles of SiH groups in component (H) relative to the number of moles of alkenyl groups in component (G); (I) a surfactant: 0.1 to 10 mass% in component (B); and (J) water: 10 to 90 mass% in component (B).

2. An aqueous oil resistant composition comprising the following components (A), (C), (D), (E), and (F): (A) 100 parts by mass of a polyvinyl alcohol (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; (C) 5 to 2,500 parts by mass of a silicone emulsion; (D) 1,000 to 50,000 parts by mass of water; and (F) a catalytic amount of a platinum group metal catalyst, wherein the (C) silicone emulsion 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 more at 25°C: 5 to 60 mass% in component (C), and the alkenyl value of component (G) in total (the number of moles of silicon-bonded alkenyl groups per 100 g of component (G)) exceeds 0.1 mol / 100 g; (I) a surfactant: 0.1 to 10 mass% in component (C); and (J) water: 10 to 90 mass% in component (C), wherein the (D) silicone emulsion comprises: (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule: 5 to 60 mass% in component (D), (I) a surfactant: 0.1 to 10 mass% in component (D), and (J) water: 10 to 90 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. The aqueous oil-resistant composition according to claim 1 or 2, wherein the PVA resin (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 claim 1 or 2, wherein the PVA resin (A) is at least one selected from polyvinyl alcohol and modified polyvinyl alcohol resins.

5. A water-based oil-resistant composition according to claim 1 or 2, 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 the side chain and at both ends.

6. The aqueous oil-resistant composition according to claim 1 or 2, wherein component (G) is a linear alkenyl-containing organopolysiloxane represented by the following average composition formula (1-1): (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. The aqueous oil-resistant composition according to claim 1 or 2, 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. The water-based 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. 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. The aqueous oil-resistant composition according to claim 1 or 2, 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) 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 having a viscosity of 5 mPa·s or more at 25°C: 5 to 40 mass% in component (B), and having a total alkenyl valence of components (G) (the number of moles of silicon-bonded alkenyl groups contained in 100 g of components (G)) of more than 0.1 mol / 100 g; and (H) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms (SiH groups) per molecule: 1 to 5 mass% where 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 mass% in component (B); (J) water: 10 to 90 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: (A) 100 parts by mass of 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; (E) water: 1,000 to 50,000 parts by mass; and (F) a catalytic amount of a platinum group metal-based catalyst.

12. A method for producing a water-based oil-resistant composition according to claim 2, comprising: (Step 1') mixing and emulsifying the following components (G), (I), and (J) to prepare (C) a silicone emulsion: (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 more at 25°C: 5 to 60 mass% in component (C), and the alkenyl value of all components (G) (the number of moles of silicon-bonded alkenyl groups contained in 100 g of all components (G)) exceeds 0.1 mol / 100 g; (I) surfactant: 0.1 to 10 mass% in component (C); and (J) water: 10 to 90 mass% in component (C). (Step 1'') 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 mass% in component (D); (I) a surfactant: 0.1 to 10 mass% in component (D); (J) water: 10 to 90 mass% in component (D); and (Step 2') a step of mixing the following components (A), (E), and (F), 5 to 2,500 mass parts of the silicone emulsion (C) prepared in step 1' above, and an amount of the silicone emulsion (D) prepared in step 1'' above, in which the number of moles of SiH groups in component (H) of component (D) corresponds to 1 to 5 times the number of moles of alkenyl groups in component (G) of component (C); (A) 100 parts by mass of a PVA-based resin having a viscosity of 2 to 80 mPa s as a 4% aqueous solution at 20°C and a degree of saponification of 91 mol% or more. (E) water: 1,000 to 50,000 parts by mass; and (F) a platinum group metal catalyst: a catalytic amount.

13. A method for treating oil resistance of paper, which comprises adding the aqueous oil-proofing agent composition according to claim 1 or 2 to a pulp slurry for internal treatment or to a paper substrate for external treatment.

14. Grease-resistant paper treated with the aqueous oil-proofing composition according to claim 1 or 2, which has an air permeability of 1,000 seconds or less according to the Oken air permeability test method measured in accordance with JAPAN TAPPI Paper and Pulp Testing Method No. 5-2:2000.

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