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

Abstract

To provide a non-fluorinated resin-based aqueous oil-resistant agent composition with which oil-resistant paper having high oil resistance and high air permeability can be obtained, the components contained in the composition not including any fluorine-based resin or organic solvent in consideration of health aspects and environment aspects.SOLUTION: An aqueous oil-resistant agent composition contains (A) a cellulose-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) contains (G) an alkenyl group-containing organopolysiloxane, (H) an organohydrogen polysiloxane, (I) a surfactant, and (J) water.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an aqueous oil-resistant agent composition, a method for producing the aqueous oil-resistant agent composition, a method for oil-proof treating paper, and oil-proof paper.

Background Art

[0002] Packaging papers, packaging containers, or paper liners such as food trays used for cooked foods such as fast food, fried foods, and grilled foods that contain a large amount of oil and moisture are imparted with oil resistance and water resistance so that the oil and moisture of the food do not penetrate and stain the surroundings.

[0003] Polyethylene laminated paper obtained by laminating a polyethylene film on one side of a paper substrate has been used for oil-proof paper or oil-proof containers for food. However, polyethylene laminated paper has low air permeability, is likely to cause a decrease in the flavor and storage stability of food, and is difficult to remove the polyethylene film during recycling, resulting in poor recyclability. There is a strong movement towards plastic reduction, and the development of oil-proof paper that does not use polyethylene lamination is desired. Conventionally, fluororesin-based oil-resistant agents have been widely used to impart oil resistance and water resistance to paper. For example, methods such as coating a fluororesin-based oil-resistant agent on the surface of a paper substrate to provide an oil-resistant layer, impregnating a paper substrate with a fluororesin-based oil-resistant agent, or adding a fluororesin-based oil-resistant agent to a pulp slurry have been adopted. However, fluororesin-based oil-resistant agents are not preferable in terms of health and the environment due to their non-degradability and bioaccumulation, and in recent years, oil-resistant agents that do not contain fluorine-based resins (non-fluororesin-based oil-resistant agents) have been demanded.

[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 it is known that excellent oil resistance can be obtained. For example, Patent Document 1 discloses an oil-resistant paper obtained by coating a surface with a composition containing a PVA-based resin and a silicone-based emulsion. Also, acrylic-based and paraffin wax-based emulsions such as those in Patent Documents 2, 3, and 4 are known to have excellent oil resistance. Furthermore, Patent Document 5 describes a water- and oil-repellent composition containing a silicone-based emulsion, a cellulose-based resin, and a carboxylic acid.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, in the case of non-fluorine resin-based oil-resistant agents, in order to exhibit oil resistance while preventing the bleeding of oil and fat components, it is necessary to increase the density of the base material or use a large amount of a blocking agent or an oil-resistant agent. Then, while the oil resistance increases, the air permeability becomes insufficient, easily leading to a decrease in the flavor and storage stability of food. For example, in order to impart oil resistance and water resistance by applying the compositions described in Patent Documents 1 and 5 to a paper base material, not only is the composition for forming a film coated on the surface of the paper base material, but a blocking agent is also required for the paper base material, and there is a concern that the air permeability of the obtained oil-resistant paper will decrease. Although the air permeability has been confirmed in the oil-resistant papers described in Patent Documents 2, 3, and 4, the coating amount of the oil-resistant agent is large, and the air permeability is all 100 seconds or more, which is inferior to that of the fluorine resin-based oil-resistant agent. Thus, an oil-resistant paper that can have both high oil resistance and high air permeability using a non-fluorine resin-based oil-resistant agent has not yet been developed, and there is still room for improvement in this regard. Therefore, the present invention aims to provide an oil-resistant agent composition capable of obtaining an oil-resistant paper having high oil resistance and high air permeability, which does not contain a fluorine-based resin and an organic solvent as components and takes into account both health and environmental aspects, and is a non-fluorine resin-based aqueous oil-resistant agent composition.

Means for Solving the Problems

[0007] As a result of intensive studies to achieve the above object, the present inventors have found that the following aqueous oil-resistant agent composition can achieve the above problems, and have thus arrived at the present invention. That is, the present invention provides the following oil-resistant agent composition and the like.

[0008] [1] The following components (A), (B), (E), and (F): (A) A cellulose-based resin having a viscosity of 2 to 10,000 mPa·s at 20°C in a 2% aqueous solution: 100 parts by mass (B) An addition-curing silicone emulsion: 10 to 10,000 parts by mass (E) Water: 1,000 to 50,000 parts by mass (F) A platinum group metal-based catalyst: a catalytic amount An aqueous oil-resistant agent composition comprising: The above-mentioned (B) addition-curable silicone emulsion is (G) An alkenyl group-containing organopolysiloxane having at least 2 alkenyl groups bonded to silicon atoms in one molecule and having a viscosity of 5 mPa·s or more at 25°C: 5 to 40% by mass in the (B) component, and the alkenyl value of the total (G) component (the number of moles of alkenyl groups bonded to silicon atoms contained in 100 g of the total (G) component) is more than 0.1 mol / 100 g, (H) An organohydrogenpolysiloxane having at least 2 hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule: The mass percentage corresponding to 1 to 5 times the number of moles of SiH groups in the (H) component with respect to the number of moles of alkenyl groups in the (G) component, (I) Surfactant: 0.1 to 10% by mass in the (B) component and (J) Water: 10 to 90% by mass in the (B) component An aqueous oil-resistant agent composition containing the above. [2] The following components (A), (C), (D), (E) and (F): (A) A cellulose resin having a viscosity of 2 to 10,000 mPa·s at 20°C in a 2% aqueous solution: 100 parts by mass (C) Silicone emulsion: 5 to 5,000 parts by mass (D) Silicone emulsion (E) Water: 1,000 to 50,000 parts by mass (F) Platinum group metal-based catalyst: Catalyst amount An aqueous oil-resistant agent composition containing the above, The above-mentioned (C) silicone emulsion is (G) An alkenyl group-containing organopolysiloxane having at least 2 alkenyl groups bonded to silicon atoms in one molecule and having a viscosity of 5 mPa·s or more at 25°C: 5 to 60% by mass in the (C) component, and the alkenyl value of the total (G) component (the number of moles of alkenyl groups bonded to silicon atoms contained in 100 g of the total (G) component) is more than 0.1 mol / 100 g, (I) Surfactant: 0.1 to 10% by mass in the (C) component and (J) Water: 10 to 90% by mass in the (C) component which contains wherein the (D) silicone emulsion contains (H) an organohydrogenpolysiloxane having at least 2 hydrogen atoms bonded to silicon atoms in one molecule: 5 to 60% by mass in the (D) component, (I) a surfactant: 0.1 to 10% by mass in the (D) component, and (J) water: 10 to 90% by mass in the (D) component and the content of the (D) component in the composition is such that the number of moles of the SiH groups of the (H) component in the (D) component corresponds to 1 to 5 times the number of moles of the alkenyl groups of the (G) component in the (C) component, an aqueous oil-resistant agent composition. [3] The aqueous oil-resistant agent composition according to [1] or [2], wherein the (A) component, the cellulose-based resin, is a cellulose ether in which 0.5 to 2.5 hydroxyl groups per glucose ring unit of cellulose are substituted with alkoxy groups. [4] The aqueous oil-resistant agent composition according to any one of [1] to [3], wherein the (G) component contains at least two kinds of a linear organopolysiloxane containing alkenyl groups only at both ends and a linear organopolysiloxane containing alkenyl groups at side chains and both ends. [5] The aqueous oil-resistant agent composition according to any one of [1] to [4], wherein the (G) component is a linear alkenyl group-containing organopolysiloxane represented by the following average composition formula (1-1). [Chemical formula] (In formula (1-1), R 1 is independently an alkenyl group-containing organic group having 2 to 10 carbon atoms, and R 2 is independently one kind of group selected from unsubstituted or substituted monovalent hydrocarbon groups having no hydroxyl group, alkoxy group, and alkenyl group, and a, c, and d are each a number of 0 or more, satisfying 0 ≦ a ≦ 3, 2 ≦ 2a + c, and 5 ≦ c + d.) [6] The aqueous oil-resistant agent composition according to any one of [1] to [5], wherein the ratio of the total number of hydrogen atoms bonded to the silicon atoms of the (H) component to the total number of hydrogen atoms and groups bonded to the silicon atoms is 15 to 50%. [7] The aqueous oil-resistant agent composition according to any one of [1] and [3] to [6], wherein the silicone emulsion of the (B) component further contains 0.5 to 10% by mass of a polyvinyl alcohol (PVA) - based resin in the (B) component. [8] The aqueous oil-resistant agent composition according to any one of [2] to [6], wherein at least one of the silicone emulsion of the (C) component and the silicone emulsion of the (D) component further contains 0.5 to 10% by mass of a polyvinyl alcohol (PVA) - based resin in the (C) component or the (D) component. [9] The aqueous oil-resistant agent composition according to any one of [1] to [8], wherein the total mass of the (G) component and the (H) component is 60 to 2000 parts by mass with respect to 100 parts by mass of the (A) component.

[10] A method for producing the aqueous oil-resistant agent composition according to any one of [1], [3] to [7], and [9], (Step 1) A step of mixing and emulsifying the following (G), (H), (I), and (J) components to prepare an (B) addition-curable silicone emulsion (G) An alkenyl group-containing organopolysiloxane having at least 2 alkenyl groups bonded to silicon atoms in one molecule and having a viscosity of 5 mPa·s or more at 25°C: 5 to 40% by mass in the (B) component, and the alkenyl value of the total (G) component (the number of moles of alkenyl groups bonded to silicon atoms contained in 100 g of the total (G) component) is more than 0.1 mol / 100 g (H) An organohydrogenpolysiloxane having at least 2 hydrogen atoms bonded to silicon atoms (SiH groups) in one molecule: the mass percentage such that the number of moles of SiH groups in the (H) component corresponds to 1 to 5 times the number of moles of alkenyl groups in the (G) component (I) A surfactant: 0.1 to 10% by mass in the (B) component (J) Water: 10 to 90% by mass in the (B) component and (Step 2) A step of mixing the following components (A), (E) and (F) with 10 to 10,000 parts by mass of the (B) addition-curable silicone emulsion prepared in the above Step 1 (A) Cellulose resin having a viscosity at 20 °C of 2 to 10,000 mPa·s in a 2% aqueous solution: 100 parts by mass (E) Water: 1,000 to 50,000 parts by mass (F) Platinum group metal-based catalyst: catalytic amount A method for producing an aqueous oil-resistant agent composition having the above components

[11] A method for producing an aqueous oil-resistant agent composition according to any one of [2] to [6], [8] and [9], wherein (Step 1') A step of mixing and emulsifying the following components (G), (I) and (J) to prepare a (C) silicone emulsion (G) Alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and having a viscosity at 25 °C of 5 mPa·s or more: 5 to 60% by mass in the (C) component, and the alkenyl value of the total (G) component (the number of moles of alkenyl groups bonded to silicon atoms contained in 100 g of the total (G) component) is more than 0.1 mol / 100 g (I) Surfactant: 0.1 to 10% by mass in the (C) component (J) Water: 10 to 90% by mass in the (C) component (Step 1'') A step of mixing and emulsifying the following components (H), (I) and (J) to prepare a (D) silicone emulsion (H) Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule: 5 to 60% by mass in the (D) component (I) Surfactant: 0.1 to 10% by mass in the (D) component (J) Water: 10 to 90% by mass in the (D) component and (Step 2’) Mix the following components (A), (E), and (F) with 5 to 5,000 parts by mass of the (C) silicone emulsion prepared in the above Step 1’ and an amount corresponding to 1 to 5 times the number of moles of the SiH groups of the (H) component in the (D) silicone emulsion (D) component prepared in the above Step 1’’ with respect to the number of moles of the alkenyl groups of the (G) component in the (C) component. (A) A cellulose resin with a viscosity of 2 to 10,000 mPa·s at 20°C in a 2% aqueous solution: 100 parts by mass (E) Water: 1,000 to 50,000 parts by mass (F) A platinum group metal-based catalyst: a catalytic amount A method for producing an aqueous oil-resistant agent composition having the above.

[12] A method for oil-proofing paper, wherein the aqueous oil-resistant agent composition according to any one of [1] to [9] is internally added to a pulp slurry or externally added to a paper base material.

[13] An oil-proof paper treated with the aqueous oil-resistant agent composition according to any one of [1] to [9], having an air permeability of 1,000 seconds or less as measured according to JAPAN TAPPI Paper Pulp Test Method No. 5-2:2000. [Advantages of the Invention]

[0009] The present invention combines a cellulose resin having excellent affinity with paper and a silicone having good water resistance and air permeability, taking advantage of both materials. By treating a paper base material with a composition obtained by combining materials having a specific structure of the present invention under specific conditions and curing it, an oil-proof paper having excellent oil resistance and water resistance and high air permeability can be obtained. And, due to the high air permeability of the oil-proof paper of the present invention, when packaging food, it can prevent oil stains without impairing the flavor of the food. Furthermore, both the cellulose-based resin and silicone contained in the aqueous oil-resistant agent composition of the present invention are materials with high environmental safety and harmlessness, and can be suitably used as alternatives to organic fluorine compounds. In addition, since the aqueous oil-resistant agent composition of the present invention does not contain an organic solvent, it is possible to avoid disadvantages such as environmental problems and biological risks caused by the use of organic solvents. The paper substrate treated with the composition of the present invention is easy to recycle and has a small environmental load, and can solve the harmfulness and environmental problems derived from fluorine compounds.

Embodiments for Carrying Out the Invention

[0010] [Aqueous Oil-Resistant Agent Composition] Hereinafter, the aqueous oil-resistant agent composition of the present invention will be described in more detail. In this specification, unless otherwise specified, “%” indicates a ratio based on mass.

[0011] (A) Cellulose-Based Resin The cellulose-based resin of component (A) is a compound in which different substituents are introduced by chemical modification into the hydroxyl groups contained in cellulose molecules. The cellulose-based resin has a viscosity of 2 to 10,000 mPa·s at 20°C in a 2% aqueous solution, preferably 10 to 8,000 mPa·s, more preferably 20 to 4,000 mPa·s. If the viscosity of the 2% aqueous solution at 20°C is less than 2 mPa·s, the oil resistance will be insufficient, and if it exceeds 10,000 mPa·s, the coatability of the composition will deteriorate. The viscosity at 20°C is a value measured by a BM type viscometer (for example, manufactured by Tokyo Keiki Co., Ltd.) at 20°C. In addition, the rotor, rotation speed, and rotation time are appropriately selected based on conventional methods according to the viscosity (the same applies hereinafter).

[0012] The cellulose-based resin preferably used in the present invention is cellulose ethers obtained by substituting the hydroxyl groups of cellulose with an etherifying agent; esterified cellulose esters, with cellulose ethers being particularly preferred. Many of these cellulose ethers are approved as food additives, pharmaceuticals, and cosmetic raw materials. They are not only harmless to the human body but also have slow biodegradability and are known as extremely environmentally friendly materials.

[0013] Examples of cellulose ethers include alkyl celluloses (such as methyl cellulose and ethyl cellulose) in which the hydroxyl groups of cellulose are substituted with alkoxy groups; hydroxyalkyl celluloses (such as hydroxyethyl cellulose and hydroxypropyl cellulose) in which the hydroxyl groups of cellulose are substituted with hydroxyalkoxy groups; hydroxyalkylalkyl celluloses (such as hydroxypropylmethyl cellulose) in which the hydroxyl groups of cellulose are substituted with alkoxy groups and hydroxyalkoxy groups; carboxyalkyl celluloses (such as carboxymethyl cellulose) in which the hydroxyl groups of cellulose are substituted with carboxyalkoxy groups, etc. Preferred are methyl cellulose, ethyl cellulose, and hydroxypropylmethyl cellulose, and more preferred is methyl cellulose. Examples of cellulose esters include cellulose acetate, cellulose acetate phthalate, etc.

[0014] The degree of substitution of cellulose ethers or cellulose esters is the number of hydroxyl groups substituted by an etherifying agent or an esterifying agent per glucose ring unit of cellulose. This degree of substitution is preferably 0.5 to 2.5, more preferably 0.8 to 2.2, and even more preferably 1.0 to 2.0. If the degree of substitution is less than 0.5, the solubility in water may be low and the workability of manufacturing the composition may deteriorate. If the degree of substitution exceeds 2.5, sufficient oil resistance may not be imparted. In addition, when the hydroxyl groups in one molecule of cellulose ether or cellulose ester are substituted with two or more types of substituents, the total value of the substitution degrees of each of the two or more types of substituents is preferably from 0.5 to 2.5, more preferably from 0.8 to 2.2, and still more preferably from 1.0 to 2.0.

[0015] In the present invention, commercially available cellulose ethers can generally be used. Specifically, METHOCEL, ETHOCEL (manufactured by Dow Chemical), NATROSOL (manufactured by Hercules), HEC Daicel, CMC Daicel (manufactured by Daicel Chemical Industries), Fujichem HEC (manufactured by Sumitomo Seika), Serogen (manufactured by Daiichi Kogyo Seiyaku), Metrose (manufactured by Shin-Etsu Chemical), etc. can be mentioned. The cellulose-based resin as the component (A) may be used alone or in combination of two or more.

[0016] The content of the component (A) in the composition of the present invention is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the total amount of the components excluding water. Note that the total amount of the components excluding water is the total amount of the components other than (E) water and (J) water in the following (B) addition-curable silicone emulsion, (C) silicone emulsion, (D) silicone emulsion, and (K) catalyst composition in the composition.

[0017] The aqueous oil-resistant agent composition of the present invention contains, as a silicone emulsion, 〈1〉(B) Addition-curable silicone emulsion or 〈2〉(C) Silicone emulsion and (D) silicone emulsion and contains. The (B) addition-curable silicone emulsion contains (G) alkenyl group-containing organopolysiloxane, (H) organohydrogenpolysiloxane, (I) surfactant, and (J) water. The (C) silicone emulsion contains (G) alkenyl group-containing organopolysiloxane, (I) surfactant, and (J) water. (D) The silicone emulsion contains (H) organohydrogensiloxane, (I) surfactant, and (J) water. Each of the components (G) to (J) will be described later. In this specification, an aqueous oil-resistant agent composition containing (B) an addition-curable silicone emulsion may be described as "aqueous oil-resistant agent composition <1>", and an aqueous oil-resistant agent composition containing (C) a silicone emulsion and (D) a silicone emulsion may be described as "aqueous oil-resistant agent composition <2>". Emulsification for obtaining the components (B) to (D) may be carried out using a general emulsifying and dispersing machine. Examples of the emulsifying and dispersing machine include high-speed rotation centrifugal spraying type stirrers such as homodispersers, high-speed rotation shearing type stirrers such as homomixers, high-pressure injection type emulsifying and dispersing machines such as pressure type homogenizers, colloid mills, ultrasonic emulsifiers, and the like. The volume average particle diameter measured by a laser diffraction / scattering type particle size distribution measuring device of each emulsion of the obtained components (B) to (D) is preferably 50 to 10,000 nm, and more preferably 100 to 1,500 nm.

[0018] (B) Addition-curable silicone emulsion The blending amount of the component (B) is 10 to 10,000 parts by mass, preferably 100 to 4,000 parts by mass, and more preferably 250 to 2,000 parts by mass with respect to 100 parts by mass of the component (A). When the blending amount of the component (B) is less than 10 parts by mass with respect to 100 parts by mass of the component (A), the water resistance is insufficient, and when it is more than 10,000 parts by mass, the oil resistance is insufficient.

[0019] The content ratio of the component (G) in the component (B) is 5 to 40% by mass, preferably 10 to 35% by mass, and more preferably 15 to 30% by mass. When the content ratio of the component (G) in the component (B) is outside the above range, the oil resistance and water resistance become low.

[0020] The content ratio of component (H) in component (B) is a mass percentage corresponding to 1 to 5 times the molar number of SiH groups in component (H) relative to the molar number of alkenyl groups in component (G), preferably a mass percentage corresponding to 1.1 to 3 times, and more preferably a mass percentage corresponding to 1.2 to 2.5 times. When the content ratio of component (H) in component (B) is outside the above range, the oil resistance and water resistance will decrease.

[0021] The content ratio of component (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. When the content ratio of component (I) in component (B) is less than the above lower limit, emulsification becomes difficult, and when it is more than the above upper limit, the oil resistance and water resistance will decrease.

[0022] The content ratio of component (J) in component (B) is 10 to 90% by mass, preferably 20 to 80% by mass, and more preferably 30 to 70% by mass. When the content ratio of component (J) in component (B) is less than the above lower limit, dispersion becomes difficult, and when it is more than the above upper limit, the stability of the emulsion over time will decrease.

[0023] In the aqueous oil-resistant agent composition <1>, the total mass of component (G) and component (H) is preferably 60 to 2000 parts by mass, more preferably 150 to 1000 parts by mass, and even more preferably 200 to 500 parts by mass with respect to 100 parts by mass of component (A).

[0024] (C) Organopolysiloxane-containing silicone emulsion having an alkenyl group The compounding amount of component (C) is 5 to 5000 parts by mass with respect to 100 parts by mass of component (A), preferably 50 to 2000 parts by mass, and more preferably 125 to 1000 parts by mass. When the compounding amount of component (C) is less than 5 parts by mass with respect to 100 parts by mass of component (A), the water resistance is insufficient, and when it is more than 5000 parts by mass, the oil resistance is insufficient.

[0025] The content ratio of component (G) in component (C) is 5 to 60% by mass, preferably 10 to 50% by mass, and more preferably 15 to 40% by mass. When the content ratio of component (G) in component (C) is outside the above range, the oil resistance and water resistance decrease.

[0026] The content ratio of component (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. When the content ratio of component (I) in component (C) is less than the above lower limit, emulsification becomes difficult, and when it is more than the above upper limit, the oil resistance and water resistance decrease.

[0027] The content ratio of component (J) in component (C) is 10 to 90% by mass, preferably 20 to 80% by mass, and more preferably 30 to 70% by mass. When the content ratio of component (J) in component (C) is less than the above lower limit, dispersion becomes difficult, and when it is more than the above upper limit, the stability of the emulsion over time decreases.

[0028] (D) Organohydrogenpolysiloxane-containing silicone emulsion The compounding amount of component (D) is the mass % corresponding to 1 to 5 times, preferably 1.1 to 3.0 times, and more preferably 1.2 to 2.5 times the number of moles of SiH groups in component (D) relative to the number of moles of alkenyl groups in component (C). When the compounding amount of component (D) is outside the above range, the oil resistance and water resistance decrease.

[0029] The content ratio 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. When the content ratio of component (H) in component (D) is outside the above range, the oil resistance and water resistance decrease.

[0030] The content ratio 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. When the content ratio of component (I) in component (D) is less than the above lower limit, emulsification becomes difficult, and when it is more than the above upper limit, the oil resistance and water resistance decrease.

[0031] (D) component, the content ratio of (J) component is 10 to 90% by mass, preferably 20 to 80% by mass, more preferably 30 to 70% by mass. When the content ratio of (J) component in (D) component is less than the above lower limit value, dispersion becomes difficult, and when it is more than the above upper limit value, the stability of the emulsion over time becomes low.

[0032] In the aqueous oil-resistant agent composition <2>, the total mass of (G) component and (H) component is preferably 60 to 2000 parts by mass, more preferably 150 to 1000 parts by mass, still more preferably 200 to 500 parts by mass with respect to 100 parts by mass of (A) component.

[0033] · (G) alkenyl group-containing organopolysiloxane (G) component is an organopolysiloxane having at least 2 alkenyl groups bonded to silicon atoms in one molecule and having a viscosity at 25 ° C of 5 mPa·s or more. The number of alkenyl groups bonded to silicon atoms in (G) component is at least 2 in one molecule, preferably 2 to 500, more preferably 2 to 100, still more preferably 2 to 30. When the number of alkenyl groups bonded to silicon atoms in (G) component is less than 2 in one molecule, there is no crosslinkability, so the oil resistance becomes low, which is not preferable. Also, when the number of alkenyl groups bonded to silicon atoms in (G) component is more than 500 in one molecule, it may take time for curing.

[0034] (G) component has a viscosity at 25 ° C of 5 mPa·s or more, preferably 10 to 10,000 mPa·s, more preferably 20 to 5,000 mPa·s, still more preferably 50 to 1,000 mPa·s. When the viscosity of (G) component at 25 ° C is lower than 5 mPa·s, it becomes difficult to prepare the emulsion, and the oil resistance and stability may decrease. Note that there is no upper limit to the viscosity of (G) component at 25 ° C, but it can be, for example, 100,000 mPa·s. In addition, when using multiple types of component (G), it is also possible to mix a low-viscosity organopolysiloxane corresponding to component (G) and a high-viscosity or raw rubber-like organopolysiloxane corresponding to component (G) and adjust to the above viscosity range.

[0035] The alkenyl value bonded to silicon atoms in the total of component (G) is a value exceeding 0.1 mol / 100 g, preferably 0.13 mol / 100 g or more, and more preferably 0.15 mol / 100 g or more. When the alkenyl value bonded to silicon atoms in the total of component (G) is 0.1 mol / 100 g or less, the crosslinkability decreases and the oil resistance deteriorates. Although there is no limitation on the upper limit of the alkenyl value of component (G), for example, it can be 0.7 mol / 100 g. This alkenyl value is the value of the number of moles of alkenyl groups bonded to silicon atoms contained in 100 g of the total of component (G), and usually, it can be calculated from the iodine value determined by the Hanus method (a method in which a compound is allowed to act on a Hanus reagent, then reacted with an aqueous potassium iodide solution, and the generated iodine is titrated with sodium thiosulfate, in accordance with JIS K 0070) (the same applies hereinafter).

[0036] The molecular structure of component (G) is not particularly limited and can be any of linear, branched, and cyclic structures, but preferably, it is a linear structure. Component (G) may be used alone or in combination of two or more. When using two or more of component (G) in combination, it is sufficient that the average alkenyl value calculated from the total of component (G) exceeds 0.1 mol / 100 g. In addition, when using two or more of component (G) 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 side chains and at both ends, and it is more preferable to use in combination those in which the alkenyl value of each organopolysiloxane exceeds 0.1 mol / 100 g.

[0037] (G) component is a component for expressing oil resistance and water resistance of the composition, and specifically, those having a structure represented by the average composition formula (1) are exemplified.

Chemical formula

[0038] R 1 is an alkenyl group-containing organic group having 2 to 10 carbon atoms, preferably having 2 to 8 carbon atoms, and more preferably having 2 to 6 carbon atoms. As R 1 , for example, alkenyl groups such as vinyl group, allyl group, hexenyl group, etc. can be mentioned.

[0039] R 2 is a group selected from unsubstituted or substituted monovalent hydrocarbon groups having no hydroxyl group, alkoxy group, and alkenyl group. R 2 Examples of the alkoxy group represented by include methoxy group, ethoxy group, propoxy group, isopropoxy group, etc. R 2 The unsubstituted or substituted monovalent hydrocarbon group having no alkenyl group 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 having preferably 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, etc.; cycloalkyl groups having preferably 5 to 8 carbon atoms such as cyclohexyl group, etc.; aryl groups having preferably 6 to 10 carbon atoms such as phenyl group, tolyl group, etc.; aralkyl groups having preferably 7 to 10 carbon atoms such as benzyl group, etc. Among them, as the unsubstituted or substituted monovalent hydrocarbon group, a methyl group or a phenyl group is preferable, and a methyl group is particularly preferable. The alkenyl group-containing organopolysiloxane represented by the formula (1) is R 2 It is preferable that the ratio of the number of methyl groups to the total number is 70% or more, more preferably 80% or more, and still more preferably 90% or more.

[0040] In the formula (1), a, b, c, d, e, f, and g are each independently a number of 0 or more. a satisfies 0 ≦ a ≦ 3, preferably 0 or 1, and more preferably 1. b is a number of 1 or more, and satisfies 2 ≦ ab + c + e and 5 ≦ b + c + d + e + f + g.

[0041] The alkenyl group-containing organopolysiloxane represented by the formula (1) is particularly preferably a linear one, that is, in the formula (1), b = 2 and e = f = g = 0, and is represented by the following formula (1-1).

Chemical formula

[0042] (G) components include, for example, the following, but are not limited thereto. In the following formulas, 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 as follows. In the following formulas, the total value of the number of repeating units of siloxane is an average value. Also, in the following formula, z1 to z39 are each a number of 0 or more. [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula]

[0043] · (H) Organohydrogenpolysiloxane The (H) component is an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms (hereinafter referred to as SiH groups) in one molecule. The ratio of the total number of SiH groups to the total number of SiH groups and groups bonded to silicon atoms in the (H) component is preferably 15 to 50%, more preferably 20 to 45%, and still more preferably 30 to 40%. When the ratio of the SiH groups in the (H) component is less than 15%, the crosslinking density may be low and the oil resistance may decrease. When it is more than 50%, the reactivity may decrease and it may take time for curing.

[0044] (G) The alkenyl groups contained in the component react with the SiH groups in the (H) component to form a crosslinked structure. That is, the (H) component functions as a crosslinking agent. From the perspective of crosslinking balance, the blending amount of the (H) component is such that the ratio of the number of SiH groups in the (H) component to the number of all alkenyl groups in the (G) component 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 the (H) component does not satisfy the above range, the crosslinking balance becomes inappropriate, and the oil resistance and water resistance decrease.

[0045] (H) The molecular structure of the component may be any of linear, branched, cyclic, and three-dimensional network structures, or a mixture thereof. Also, the SiH groups possessed by the (H) component may be located at either the molecular chain ends or in the middle of the molecular chain, or at both. The (H) component is preferably a linear organohydrogenpolysiloxane represented by the following formula (2).

Chemical formula

[0046] In the above formula (2), R 3 are each independently a hydroxyl group or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms and no aliphatic unsaturated bond. As the monovalent hydrocarbon group having no aliphatic unsaturated bond of R 3 , an alkyl group and an aryl group are preferable, and a methyl group, an ethyl group, a propyl group, and a phenyl group are more preferable, and a methyl group is particularly preferable.

[0047] i is a number from 0 to 200, preferably from 3 to 150, more preferably from 5 to 100. j is a number from 0 to 200, preferably from 0 to 100, 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, still more preferably from 10 to 80. i + j + 2 is a number from 3 to 400, preferably from 5 to 200, more preferably from 10 to 100.

[0048] Examples of the organohydrogenpolysiloxane represented by the above average composition formula (2) include, for example, methylhydrogen siloxane - dimethylsiloxane cyclic copolymer, dimethylsiloxane - methylhydrogen siloxane copolymer blocked at both ends with trimethylsiloxy groups, dimethylpolysiloxane blocked at both ends with dimethylhydrogen siloxy groups, dimethylsiloxane - methylhydrogen siloxane copolymer blocked at both ends with dimethylhydrogen siloxy groups, methylhydrogen siloxane - diphenylsiloxane copolymer blocked at both ends with trimethylsiloxy groups, methylhydrogen siloxane - diphenylsiloxane - dimethylsiloxane copolymer blocked at both ends with trimethylsiloxy groups, methylhydrogen siloxane - methylphenylsiloxane - dimethylsiloxane copolymer blocked at both ends with trimethylsiloxy groups, methylhydrogen siloxane - dimethylsiloxane - diphenylsiloxane copolymer blocked at both ends with dimethylhydrogen siloxy groups, methylhydrogen siloxane - dimethylsiloxane - methylphenylsiloxane copolymer blocked at both ends with dimethylhydrogen siloxy groups, etc. Component (H) may be used alone or in combination of two or more.

[0049] Examples of component (H) include, but are not limited to, linear or branched siloxanes represented by the following formula. In the following formula, Me and Ph represent a methyl group and a phenyl group, respectively. The bonding order of each siloxane unit shown in parentheses is not limited as follows. In the following formulas, the total value of the number of repeating units of the siloxane is an average value. In the following formulae, z42 to z73 are each a number that satisfies 15% to 50% of the proportion of SiH groups in the organohydrogenpolysiloxane of each formula. [Chemical formula] [Chemical formula] [Chemical formula]

[0050] · (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 it is preferably one containing a nonionic surfactant. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, polyoxyethylene modified organopolysiloxane, polyoxyethylene polyoxypropylene modified organopolysiloxane, etc. Among them, polyoxyethylene lauryl ether, polyoxyethylene oxypropylene lauryl ether, polyoxyethylene acetylene glycol ether, polyoxyethylene sorbitan monolaurate, and polyoxyethylene styrenated phenyl ether are preferable, and polyoxyethylene lauryl ether and polyoxyethylene styrenated phenyl ether are more preferable. The nonionic surfactant may be used alone or in combination of two or more. To obtain a stable emulsion composition, it is preferable that the HLB is 10 to 15 as a whole for the nonionic surfactant used alone or in combination of two or more.

[0051] In addition, anionic surfactants and cationic surfactants can also be used, but it is preferable to use them in combination with the nonionic surfactant from the viewpoint of dispersibility. Examples of the anionic surfactant include alkyl sulfate esters such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate esters, polyoxyethylene alkyl phenyl ether sulfate esters, alkylbenzene sulfonates, polyoxyethylene alkyl phenyl ether sulfonates, alkyl diphenyl ether disulfonates, alkane sulfonates, N-acyl taurates, dialkyl sulfosuccinates, monoalkyl sulfosuccinates, polyoxyethylene alkyl ether sulfosuccinates, fatty acid salts, polyoxyethylene alkyl ether carboxylates, N-acyl amino acid salts, monoalkyl phosphate esters, dialkyl phosphate esters, polyoxyethylene alkyl ether phosphate esters, and the like. Examples of the cationic surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts, polyoxyethylene alkyldimethylammonium salts, dipolyoxyethylene alkylmethylammonium salts, tripolyoxyethylene alkylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts, monoalkylamine salts, monoalkylamideamine salts, and the like.

[0052] In each of the silicone emulsions of component (B), component (C), and component (D), in order to assist the emulsification of component (G) and component (H) and improve the stability, a water-soluble resin can be used in combination with a surfactant as an emulsification aid. Examples of the water-soluble resin include PVA-based resins, cellulose derivatives, carboxyvinyl polymers, etc., with PVA-based resins being more preferred. The PVA-based resin preferably has a viscosity of 10 to 50 mPa·s at 20°C in a 4% aqueous solution and a saponification degree of 85 to 95 mol%, and more preferably has a viscosity of 15 to 30 mPa·s and a saponification degree of 87.5 to 92 mol%. This water-soluble resin may 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 on the platinum group metal-based catalyst of component (F) described below as possible. The amount of the water-soluble resin is preferably the minimum amount that can sufficiently obtain the stability of the silicone emulsion, similar to the surfactant described above. For example, it is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, based on 100 parts by mass in total of component (G) and component (H). If the amount of the water-soluble resin is more than the above upper limit, it may inhibit the addition reaction and reduce the oil resistance and water resistance. If it is less than the lower limit, it is difficult to obtain the stabilization effect.

[0053] ·(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.

[0054] · Other components In the present invention, each of the silicone emulsions of component (B), component (C), and component (D) can contain optional components other than the above-described components. Examples of other optional components include catalyst activity inhibitors (controllers) selected from various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, oxime compounds, organic chloro compounds, etc. for the purpose of suppressing the catalytic activity of platinum group metal-based catalysts. For example, acetylene 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, 1-ethynyl-1-cyclohexanol, etc., acetylene compounds such as 3-methyl-3-1-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, etc., reaction products of these acetylene compounds with alkoxysilane or siloxane or hydrogen silane, vinyl siloxanes such as tetramethylvinylsiloxane cyclic body, organic nitrogen compounds such as benzotriazole and other organic phosphorus compounds, oxime compounds, and organic chloro compounds, etc. can be mentioned. The degree of the curing suppression effect by the addition reaction controller varies depending on its chemical structure. Therefore, for each of the addition reaction controllers to be used, the addition amount can be appropriately adjusted according to a conventionally known method. By adding an appropriate amount of the addition reaction controller, the oil-resistant agent composition becomes excellent in long-term storage stability at room temperature and heat curability.

[0055] (E) Water (E) component is water, and the same one as the above-mentioned (J) component can be used. The content of the (E) component in the aqueous oil-resistant agent 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 with respect to 100 parts by mass of the (A) component. If the content of the (E) component is less than 1,000 parts by mass with respect to 100 parts by mass of the (A) component, the handleability deteriorates, and if it is more than 50,000, the coating amount decreases, resulting in insufficient oil resistance. Further, in the aqueous oil-resistant agent composition of the present invention, the content of component (E) is within the above range with respect to 100 parts by mass of component (A), and the content with respect to a total of 100 parts of components (A), (G), and (H) 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. When the content of component (E) in the aqueous oil-resistant agent composition is within the above range, it is preferable because the handleability is good and the balance between oil resistance and coating amount is also good.

[0056] (F) Platinum group metal-based catalyst (F) The platinum group metal-based catalyst of the component is a catalyst for promoting the addition reaction between component (G) and component (H), and any of those known to those skilled in the art as those for promoting the so-called hydrosilylation reaction can be used. Examples of such platinum group metal-based catalysts include catalysts such as platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts. Among these, platinum-based catalysts are particularly preferably used. Examples of this platinum-based catalyst include chloroplatinic acid, an alcohol solution or an aldehyde solution of chloroplatinic acid, various complexes of chloroplatinic acid with olefins or vinylsiloxanes, and various complexes of platinum with olefins or vinylsiloxanes.

[0057] The addition amount of the platinum group metal-based catalyst may be a catalytic amount. For example, from the viewpoint of obtaining a good cured film and economy, it is preferably in the range of 1 to 1,000 ppm in terms of platinum group metal with respect to the total mass of components (G) and (H), more preferably 10 to 500 ppm, and particularly preferably 20 to 200 ppm. If the blending amount of component (F) is less than the above lower limit value, there is a possibility of insufficient curing, and if it is more than the upper limit value, the cost may increase.

[0058] The aqueous oil-resistant agent composition of the present invention may contain component (F) as a mixture with (I) a surfactant and (E) water. That is, the aqueous oil-resistant agent composition <1> is (A), (B), (E), and (K) components: (A) A cellulose resin with a viscosity of 2 to 10,000 mPa·s at 20°C in a 2% aqueous solution: 100 parts by mass (B) An addition-curing silicone emulsion: 10 to 10,000 parts by mass (E) Water: 1,000 to 50,000 parts by mass (K) A catalyst composition An aqueous oil-resistant agent composition containing wherein the above (B) addition-curing silicone emulsion is (G) An alkenyl group-containing organopolysiloxane having at least 2 alkenyl groups bonded to silicon atoms in one molecule and a viscosity of 5 mPa·s or more at 25°C: 5 to 40% by mass in component (B), and the total alkenyl value of component (G) (the number of moles of alkenyl groups bonded to silicon atoms contained in 100 g of the total component (G)) is more than 0.1 mol / 100 g (H) An organohydrogenpolysiloxane having at least 2 hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule: a mass percentage corresponding 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% by mass in component (B) and (J) Water: 10 to 90% by mass in component (B) containing wherein the above (K) catalyst composition is (F) A platinum group metal-based catalyst (I) A surfactant and (J) Water It may be an aqueous oil-resistant agent composition containing Also, the aqueous oil-resistant agent composition <2> is (A), (C), (D), (E) and (K) components: (A) A cellulose resin with a viscosity of 2 to 10,000 mPa·s at 20°C in a 2% aqueous solution: 100 parts by mass (C) A silicone emulsion: 5 to 5,000 parts by mass (D) A silicone emulsion (E) Water: 1,000 to 50,000 parts by mass (K) A catalyst composition An aqueous oil-resistant agent composition comprising: The above (C) silicone emulsion is (G) An alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and having a viscosity of 5 mPa·s or more at 25°C: 5 to 60% by mass in the (C) component, and the total alkenyl value of the (G) component (the number of moles of alkenyl groups bonded to silicon atoms contained in 100 g of the total (G) component) is more than 0.1 mol / 100 g. (I) Surfactant: 0.1 to 10% by mass in the (C) component and (J) Water: 10 to 90% by mass in the (C) component and contains: The above (D) silicone emulsion is (H) An organohydropolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule: 5 to 60% by mass in the (D) component, (I) Surfactant: 0.1 to 10% by mass in the (D) component and (J) Water: 10 to 90% by mass in the (D) component and contains, and the content of the (D) component in the composition is such that the number of moles of the SiH groups of the (H) component in the (D) component corresponds to 1 to 5 times the number of moles of the alkenyl groups of the (G) component in the (C) component. The above (K) catalyst composition is (F) A platinum group metal-based catalyst (I) Surfactant and (J) Water and may be an aqueous oil-resistant agent composition containing.

[0059] (K) The catalyst composition is particularly preferably an aqueous emulsion mixture of the (F) component, the (I) component and the (J) component, that is, an emulsion having water as the continuous phase. The content ratio of the (F) component in the (K) catalyst composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and still more preferably 0.3 to 3% by mass. (K) As for the surfactant (I) used in the catalyst composition, those similar to the above can be exemplified. The surfactant (I) used in the (K) catalyst composition preferably contains a nonionic surfactant, similar to the surfactant used for emulsifying the (G) component and the (H) component. The content ratio of the (I) component in the (K) catalyst composition is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and still more preferably 0.3 to 2% by mass. When the content ratio of the (I) component in the (K) catalyst composition is more than 5% by mass, the addition reaction may be inhibited and the oil resistance and water resistance may decrease. When it is less than 0.1% by mass, the stability may deteriorate. The content ratio of the (J) component in the (K) catalyst composition is preferably 10 to 90% by mass, more preferably 20 to 85% by mass, and still more preferably 30 to 80% by mass. When the content ratio of the (J) component in the (K) catalyst composition is less than 10% by mass, the (F) component may be difficult to disperse. When it is more than 90% by mass, the stability of the emulsion over time may be low. In order to obtain a stable emulsion, the (K) catalyst composition may contain, in addition to the above (F), (I) components and (J) component, components that can be contained in each silicone emulsion of the above (B), (C) and (D) components.

[0060] Moreover, the aqueous oil-resistant agent composition of the present invention may be blended with a preservative, an antifoaming agent, a fragrance, a thickener, an antioxidant, a rust preventive, a pigment, a filler, an organic powder, an inorganic powder, etc. within a range that does not impair the effects of the present invention. These amounts are selected from their respective suitable amounts. In addition, each component in the aqueous oil-resistant agent composition of the present invention is preferably composed only of compounds listed in the Positive List specified by the Ministry of Health, Labour and Welfare and the Japan Paper Federation from the viewpoint of safety. (Article 18, Paragraph 3 of the Amended Food Sanitation Law and Notification No. 370, Positive List of Chemical Substances for Paper and Paperboard Intended to Come into Contact with Food)

[0061] [Method for Producing Aqueous Oil-Resistant Agent Composition] The water-based oil-resistant agent composition <1> of the present invention can be produced by mixing (A) a cellulose resin, (B) an addition-curing silicone emulsion, (E) water, and (F) a platinum group metal-based catalyst. The order of addition of each component is not particularly limited. However, as a preferred production method of the water-based oil-resistant agent composition <1>, (Step 1) A step of mixing, emulsifying the components (G), (H), (I), and (J) to prepare the (B) addition-curing silicone emulsion and (Step 2) A step of mixing the components (A), (E), and (F) with the (B) addition-curing silicone emulsion prepared in the above Step 1 A method having these steps can be mentioned.

[0062] As a more preferred production method of the water-based oil-resistant agent composition <1>, (Step 1) A step of mixing, emulsifying the components (G), (H), (I), and (J) to prepare the (B) addition-curing 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 (B) addition-curing silicone emulsion prepared in the above Step 1, the aqueous solution of the component (A) prepared in the above (Step 2-1), and the (K) catalyst composition prepared in the above (Step 2-2) A method having these steps can be mentioned.

[0063] The water-based oil-resistant agent composition <2> of the present invention can be produced by mixing (A) a cellulose resin, (C) a silicone emulsion, (D) a silicone emulsion, (E) water, and (F) a platinum group metal-based catalyst. The order of addition of each component is not particularly limited. However, as a preferred production method of the water-based oil-resistant agent composition <2>, (Step 1') A step of mixing, emulsifying the components (G), (I), and (J) to prepare the (C) silicone emulsion Step (H) of mixing and emulsifying components (H), (I) and (J) to prepare silicone emulsion (D). and Step (2') of mixing components (A), (E) and (F), silicone emulsion (C) prepared in step (1') and silicone emulsion (D) prepared in step (1''). There is provided a method having the above steps.

[0064] As a more preferred method for producing the aqueous oil-resistant agent composition <2>, Step (1') of mixing and emulsifying components (G), (I) and (J) to prepare silicone emulsion (C). Step (1'') of mixing and emulsifying components (H), (I) and (J) to prepare silicone emulsion (D). Step (2'-1) of mixing components (A) and (E) to prepare an aqueous solution of component (A). Step (2'-2) of mixing components (F), (I) and (J) to prepare catalyst composition (K). and Step (2'-3) of mixing silicone emulsion (C) prepared in step (1'), silicone emulsion (D) prepared in step (1''), the aqueous solution of component (A) prepared in step (2'-1) and catalyst composition (K) prepared in step (2'-2). There is provided a method having the above steps.

[0065] Step (1) of preparing addition-curable silicone emulsion (B). Component (B) can be produced by a known method. For example, a method of mixing a predetermined amount of components (G), (H) and (I) and a part of (J) water using a high-shear stirring device such as a planetary mixer, a combination mixer or a high-pressure homogenizer, emulsifying by the phase inversion method, and adding the remaining part of (J) water for dilution can be mentioned. When preparing addition-curable silicone emulsion (B), other components such as component (A), component (F), the water-soluble resin as the above-mentioned emulsifying aid and the catalyst activity inhibitor may be mixed in predetermined amounts respectively.

[0066] (Step 1’)(C) Preparation of silicone emulsion (C) component can be manufactured by known methods. For example, a predetermined amount of the above (G) component and (I) component, and a part of (J) water are mixed using a high-shear stirring device such as a planetary mixer, a combination mixer, a high-pressure homogenizer, etc., emulsified by the phase inversion method, and the remaining part of (J) water is added for dilution. The method may be mentioned. When preparing the (C) silicone emulsion, the (A) component, the (F) component, other components such as the water-soluble resin as the above-mentioned emulsification aid and the catalyst activity inhibitor may be mixed in predetermined amounts respectively.

[0067] (Step 1’’)(D) Preparation of silicone emulsion (D) component can be manufactured by known methods. For example, a predetermined amount of the above (H) component and (I) component, and a part of (J) water are mixed using a high-shear stirring device such as a planetary mixer, a combination mixer, a high-pressure homogenizer, etc., emulsified by the phase inversion method, and the remaining part of (J) water is added for dilution. The method may be mentioned. When preparing the (D) silicone emulsion, the (A) component, the (F) component, other components such as the water-soluble resin as the above-mentioned emulsification aid and the catalyst activity inhibitor may be mixed in predetermined amounts respectively.

[0068] (Step 2) Mixing of (A), (E) and (F) components with (B) component (Step 2’)(A), (E) and (F) components, (C) component and (D) component are mixed In Step 2 and Step 2’, each component may be uniformly mixed, and each component may be mixed using a known mixing device. From the stability of the emulsion, the mixing is preferably carried out at 10 to 30 °C.

[0069] (Step 2-1), (Step 2’-1) Preparation of aqueous solution of (A) component (Step 2-1) and (Step 2'-1) are steps of dissolving component (A) in (E) water to form an aqueous solution with a desired concentration. From the perspective of ease of handling, the cellulose-based resin of component (A) is preferably dissolved in (E) water in advance before mixing with other components and mixed with other components as a mixture of component (A) and component (E). The concentration of component (A) in the aqueous solution of component (A) obtained in this step is preferably 0.5 to 10% by mass.

[0070] (Step 2-2), (Step 2'-2) Preparation of (K) catalyst composition Component (F) may be mixed during the production of the (B) addition-curing silicone emulsion. However, before mixing with other components, it is preferable to mix component (F), (I) surfactant, and (J) water and mix with other components as the (K) catalyst composition. The (K) catalyst composition may be produced using an apparatus capable of mixing each component. However, a method of mixing using a high-shear stirring device such as a planetary mixer, a combi mixer, or a high-pressure homogenizer and emulsifying by the phase inversion method to form an emulsion is preferable.

[0071] (Step 2-3) Mixing of component (B), the aqueous solution of component (A), and component (K) (Step 2'-3) Mixing of component (C), component (D), the aqueous solution of component (A), and component (K) Step 2-3 is preferably carried out immediately before using the aqueous oil-resistant agent composition <1> (for example, immediately before coating on a paper substrate). Also, Step 2'-3 is preferably carried out immediately before using the aqueous oil-resistant agent composition <2> (for example, immediately before coating on a paper substrate). This suppresses the dehydrogenation of organohydrogensiloxane, not only has excellent shelf life, but also can easily achieve a wide range of properties by changing the combination of emulsions to be mixed.

[0072] [Oil-resistant treatment method] The aqueous oil-resistant agent composition of the present invention can be suitably used to impart oil resistance and water resistance to a paper substrate. As a method for oil-proof treating paper, an internal addition treatment method of adding the aqueous oil-proof agent composition of the present invention to a pulp slurry may be used, or the aqueous oil-proof agent composition of the present invention may be applied to a paper base material after papermaking, or the paper base material after papermaking may be impregnated with the aqueous oil-proof agent composition of the present invention and dried, which may be an external addition treatment method.

[0073] [Oil-proof paper] The oil-proof paper of the present invention can be manufactured by applying the above oil-proof treatment method to a paper base material, and preferably can be obtained by coating or impregnating the paper base material with the aqueous oil-proof agent composition of the present invention.

[0074] Examples of the paper base material include those made by papermaking using various papermaking machines using chemical pulps such as hardwood pulp and softwood pulp, mechanical pulps such as groundwood pulp and thermomechanical pulp, waste paper pulp, etc. Specifically, sun-dried kraft paper, non-sun-dried kraft paper, fine paper, medium paper, lightly coated paper, coated paper, one-sided coated paper, base paper for processing, paperboard, white board paper, liner, semi-glassine paper, glassine paper, parchment paper, etc. can be mentioned. Further, as the pulp, those containing a pH adjuster, a sizing agent, a paper strength enhancer, a wet paper strength agent, a yield improver, a drainage improver, a dye, an antifoaming agent, a filler, etc. may be used.

[0075] As a method for applying the aqueous oil-proof agent composition, a method of applying it to a paper base material by external addition is preferable. For example, methods of applying using a bar coater, a knife coater, a size press coater, a roll coater, a reverse roll coater, an air knife coater, a calender, a gate roll coater, a blade coater, a curtain coater, a gravure coater, rod metering, a two-roll size press, etc. can be mentioned. In order to increase the air permeability of the oil-proof paper, an external addition treatment of infiltrating the aqueous oil-proof agent composition into the paper base material is more preferable than coating only the surface of the paper base material with the aqueous oil-proof agent composition, and it is particularly preferable to perform an impregnation treatment with a pond type size press. Also, the amount (solid content after drying) of the aqueous oil-proof agent composition is not particularly limited, but 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.

[0076] 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. The drying conditions are, for example, a temperature of preferably 80 to 180° C., more preferably 100 to 150° C., and even more preferably 120 to 150° C. From the viewpoint 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.

[0077] 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 since it depends on the paper base material and the 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, for example, 5 seconds. If the air permeability of the grease-resistant paper is 1000 seconds or less, it is preferable because the flavor and storage stability of the food packaged using the grease-resistant paper are not deteriorated. EXAMPLES

[0078] 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 component (A) and PVA emulsification aid given below are all values ​​measured using a BM type viscometer at 20° C. The viscosities of component (G) given below are all values ​​measured using a B type rotational viscometer at 25° C. The vinyl value is a value calculated from the iodine value obtained by measurement using the Hanus method according to JIS K 0070. In the following, Me and Vi represent a methyl group and a vinyl group, respectively.

[0079] Component (A) Methyl cellulose with a viscosity of 25 mPa·s at 20 °C in a 2% aqueous solution and a methoxy group substitution degree of 1.8 Methyl cellulose with a viscosity of 4 mPa·s at 20 °C in a 2% aqueous solution and a methoxy group substitution degree of 1.8 Methyl cellulose with a viscosity of 100 mPa·s at 20 °C in a 2% aqueous solution and a methoxy group substitution degree of 1.8 Methyl cellulose with a viscosity of 8,000 mPa·s at 20 °C in a 2% aqueous solution and a methoxy group substitution degree of 1.8 Hydroxypropylmethylcellulose with a viscosity of 50 mPa·s at 20 °C in a 2% aqueous solution, a methoxy group substitution degree of 1.8, and a hydroxypropyl group substitution degree of 0.15

[0080] Component (F) Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex

[0081] Component (G) (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, rubbery at 25°C, viscosity of solution dissolved in toluene to a concentration of 30 mass% is 7,000 mPa·s, x + y is a value satisfying the above viscosity, x / y = 9 (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

[0082] (Component (H)) (H-1) (Me3SiO 1 / 2 )2(MeHSiO 2 / 2 ) 70 (Me2SiO 2 / 2 ) 28 SiH group content: 1.08 mol / 100 g, viscosity: 122 mPa·s (H-2) (Me3SiO 1 / 2 )2(MeHSiO 2 / 2 ) 45 (Me2SiO 2 / 2 ) 17 SiH group content: 1.10 mol / 100 g, viscosity: 44 mPa·s (H-3) (Me3SiO 1 / 2 )2(MeHSiO 2 / 2 ) 50 (Me2SiO 2 / 2 ) 48 SiH group content: 0.75 mol / 100 g, viscosity: 117 mPa·s (H-4) (Trimethylsilyloxy 1 / 2 )2(Methylhydrogensilyloxy 2 / 2 ) 80 (Dimethylsilyloxy 2 / 2 ) 100 SiH group content: 0.65 mol / 100 g, viscosity: 370 mPa·s (H-5) (Trimethylsilyloxy 1 / 2 )2(Methylhydrogensilyloxy 2 / 2 ) 38 SiH group content: 1.60 mol / 100 g, viscosity: 20 mPa·s

[0083] (I) component (I-1) Polyoxyethylene styrenated phenyl ether (trade name: Neugen 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 Corporation)

[0084] A. Preparation of emulsion Preparation of addition-curing silicone emulsion (B) [Preparation Example 1] A 5-liter composite emulsifying device (TK Combimix M type, product name of Primix Corporation) having an anchor-type stirring blade capable of stirring the entire inside of the container and a rotatable disk provided with small tooth-shaped protrusions alternately up and down on the periphery was charged with 93.3 parts by mass of the above (G-1), 75.8 parts by mass of the above (G-2), 64.2 parts by mass of the above (H-1), 2.3 parts by mass of the above (I-1) as a surfactant, 77.8 parts by mass of a 15% aqueous PVA solution (manufactured by Mitsubishi Chemical Corporation, product name: GM-14L, viscosity at 20 °C of a 4% aqueous solution is 18 mPa·s, saponification degree 88.5 mol%) as an emulsification aid, and 1.4 parts by mass of 1-ethynyl-1-cyclohexanol as a catalyst activity inhibitor, and after uniformly stirring and mixing, 70 parts by mass of phase-inverted water was added to cause phase inversion, and stirring was continued for 15 minutes. Then, 198.5 parts by mass of dilution water was added and stirred to obtain an addition-curing type emulsion (B-1) containing 40% silicone.

[0085] [Preparation Examples 2 to 14] In the same manner as in Preparation Example 1, emulsification was carried out with the compositions shown in Tables 1, 2, and 3 below to obtain addition-curing type silicone emulsions (B-2 to 12, B'-1, 2).

[0086] Preparation of organopolysiloxane-containing silicone emulsion (C) having an alkenyl group [Preparation Example 15] In the same manner as in Preparation Example 1, 93.3 parts by mass of (G-1), 75.8 parts by mass of (G-2), 1.7 parts by mass of (I-1), 56.8 parts by mass of a 15% aqueous PVA solution (manufactured by Mitsubishi Chemical Corporation, product name: GM-14L, viscosity at 20 °C of a 4% aqueous solution is 18 mPa·s, saponification degree 88.5 mol%) as an emulsification aid, and 1.4 parts by mass of 1-ethynyl-1-cyclohexanol as a catalyst activity inhibitor were charged into a composite emulsifying device, and after uniformly stirring and mixing, 51.1 parts by mass of phase-inverted water was added to cause phase inversion, and stirring was continued for 15 minutes. Then, 144.9 parts by mass of dilution water was added and stirred to obtain an organopolysiloxane-containing silicone emulsion (C-1) having an alkenyl group and containing 40% silicone.

[0087] Preparation of organohydrogenpolysiloxane-containing silicone emulsion (D) [Preparation Example 16] In the same manner as in Preparation Example 1, 64.2 parts by mass of (H-1), 0.6 part by mass of (I-1), and 21 parts by mass of a 15% aqueous PVA solution (manufactured by Mitsubishi Chemical Corporation, trade name: GM-14L, viscosity at 20 °C of 4% aqueous solution is 18 mPa·s, saponification degree 88.5 mol%) as an emulsification aid were charged into a compound emulsifying device, uniformly stirred and mixed, then 18.9 parts by mass of phase-inverted water was added to cause phase inversion, and stirring was continued for 15 minutes. Subsequently, 53.6 parts by mass of dilution water was added and stirred to obtain a silicone emulsion (D-1) containing organohydrogenpolysiloxane with 40% silicone content.

[0088] Preparation of Catalyst Composition (K) [Preparation Example 17] In the catalyst composition, it was mixed and emulsified with water so that (F-1) was 0.4% by mass and (I-2) was 0.2% by mass to obtain a platinum catalyst emulsion composition (K-1).

[0089] B. Preparation of Aqueous Oil-Resistant Agent Composition and Oil-Resistant Paper [Example 1] 2,000 parts by mass of an aqueous solution of 5% cellulose resin (A-1) previously dissolved in water, 583.3 parts by mass of an addition-curing type silicone emulsion (B-1) with 40% silicone content, 5,983 parts by mass of water (E), and 16.7 parts by mass of a platinum catalyst emulsion (K-1) (platinum weight relative to silicone content is 85 ppm) were added and well mixed to obtain an aqueous oil-resistant agent composition. The prepared aqueous oil-resistant agent composition was impregnated with Advantec quantitative filter paper No. 5B (basis weight 108 g / m 2 , air permeability 3.6 s) as a paper substrate, the filter paper was squeezed with a squeezing machine, and then heat-dried at 150 °C for 3 minutes with a dryer to obtain oil-resistant paper.

[0090] [Examples 2 to 19, Comparative Examples 1 to 4] In the same manner as in Example 1, an aqueous oil-resistant agent composition was prepared with the formulations shown in Tables 1 to 3 below, and oil-resistant paper was obtained by treating a paper substrate.

[0091] [Example 20] In the same manner as in Example 1, 2,000 parts by mass of an aqueous solution of 5% cellulose resin (A-1), 425.8 parts by mass of an organopolysiloxane-containing silicone emulsion (C-1) having an alkenyl group with 40% silicone content, 157.5 parts by mass of an organohydrogenpolysiloxane-containing silicone emulsion (D-1) with 40% silicone content, and 16.7 parts by mass of a platinum catalyst emulsion (K-1) (platinum weight relative to silicone content is 85 ppm) were added and thoroughly mixed to obtain an aqueous oil-resistant agent composition. Using the prepared aqueous oil-resistant agent composition, an oil-resistant paper was obtained by treating a paper substrate in the same manner as in Example 1.

[0092] [Comparative Example 5] With reference to Example 4 of Patent Document 5 (Japanese Patent Application Laid-Open No. 2006-257159), (A-3) was used as the component (A), (G’-1) as the component (G), (H-5) as the component (H), (I-2) as the component (I), and succinic acid was used as the additive. An emulsion was prepared and formulated in the same manner as in Preparation Example 1 with the composition shown in Table 4 to obtain a composition. Using the prepared composition, an oil-resistant paper was obtained by treating a paper substrate in the same manner as in Example 1.

[0093] C. Evaluation Items and Methods For each of the obtained oil-resistant papers, evaluations of each physical property were carried out according to the methods shown below. The evaluation results are shown in Tables 1 to 4.

[0094] Oil Resistance Using rapeseed oil from Nisshin Oillio Group Co., Ltd. (product name: Nisshin Canola Oil), one drop of oil was placed on the oil-resistant paper treated with the aqueous oil-resistant agent composition, and the penetration state of the oil was visually confirmed 30 minutes after the drop. The criteria are as follows. ◎: (After 30 minutes, there is no oil stain and no seepage through the back.) 〇: (After 30 minutes, there are several pinhole-like oil stains.) △: (Oil stain and seepage through the back occur after more than 5 minutes and within 15 minutes.) ×: (Oil stain and seepage through the back occur within 5 minutes.)

[0095] Water Resistance One drop of water was placed on the oil-resistant paper treated with the aqueous oil-resistant agent composition, and the penetration state of the water was visually confirmed 30 minutes after the dropping. The criteria are as follows. 〇: (Water does not penetrate at all after 30 minutes) △: (Water penetrates in more than 5 minutes and within 15 minutes) ×: (Water penetrates within 5 minutes)

[0096] Air permeability The air permeability was measured in accordance with JAPAN TAPPI Paper Pulp Test Method No. 5-2:2000. The Wang Research Type Air Permeability Tester (Model: 2040-C) of Kumagai Riki Kogyo Co., Ltd. was used for the tester, and the air permeability was calculated as the average value of three different points.

[0097]

Table 1

[0098]

Table 2

[0099]

Table 3

[0100]

Table 4

[0101] As shown in Tables 1 to 3 above, the paper obtained by impregnating only the cellulose-based resin (Comparative Example 1) or the paper obtained by impregnating only the silicone emulsion (Comparative Example 2) was inferior in either oil resistance or water resistance. Further, the papers obtained by impregnating the composition in which the total alkenyl value in the (G) component was 0.1 mol / 100 g or less (Comparative Examples 3 to 4) were inferior in oil resistance. On the one hand, the oil-resistant paper obtained by impregnating with the aqueous oil-resistant agent composition of the present invention has the advantages of both cellulose-based resin and silicone emulsion, is excellent in oil resistance and water resistance, has an air permeability of 30 seconds or less, and has appropriate air permeability as food oil-resistant paper. In addition, it was found that the silicone emulsion has no significant difference in the performance of the obtained oil-resistant paper whether the components (G) and (H) are contained in the same emulsion (Examples 1 to 19) or in different emulsions (Example 20). In the present invention, the alkenyl value of the component (G) is important, and when the total alkenyl value of the component (G) blended in the composition decreases, the oil resistance tends to decrease.

[0102] As shown in Table 4 above, compared with the result of Example 7 listed as an example of the composition of the present invention, in the case of the composition of Patent Document 5 (Comparative Example 5), oil resistance was not exhibited. In the examples of Patent Document 5, it is considered that the composition was applied to the surface of the paper substrate containing a blocking agent, dried, and a cured film was formed on the surface of the paper substrate to impart oil resistance. However, when the composition is impregnated into the paper substrate to exhibit oil resistance, it is suggested that the total alkenyl value (vinyl value) of the component (G) in the composition is important.

[0103] It was found that the oil-resistant paper of the present invention satisfies all of high oil resistance, water resistance, and air permeability by the cellulose-based resin having affinity for paper and the organopolysiloxane having water resistance and air permeability being dispersed and physically entangled with each other inside the paper. In order to promote the physical entanglement of the cellulose-based resin and the organopolysiloxane, the crosslinking density of the organopolysiloxane is important, and it is necessary to use an alkenyl group-containing organopolysiloxane having a high alkenyl value.

Industrial Applicability

[0104] The oil-resistant paper treated with the aqueous oil-resistant agent composition of the present invention can achieve both oil resistance, water resistance, and air permeability. Therefore, the oil-resistant paper of the present invention can be suitably used for wrapping papers, packaging containers, or food trays for cooked foods such as fast foods, fried foods, and grilled foods that contain a large amount of oil and moisture.

Claims

1. The following components (A), (B), (E) and (F): (A) A cellulose resin having a viscosity of 2 to 10,000 mPa·s at 20 °C in a 2% aqueous solution: 100 parts by mass (B) An addition-curing silicone emulsion: 10 to 10,000 parts by mass (E) Water: 1,000 to 50,000 parts by mass (F) A platinum group metal-based catalyst: a catalytic amount A water-based oil-resistant agent composition containing the above, wherein the above (B) addition-curing silicone emulsion is (G) An alkenyl group-containing organopolysiloxane having at least 2 alkenyl groups bonded to silicon atoms in one molecule and having a viscosity of 5 mPa·s or more at 25 °C: 5 to 40% by mass in component (B), and the total alkenyl value of component (G) (the number of moles of alkenyl groups bonded to silicon atoms contained in 100 g of the total component (G)) is more than 0.1 mol / 100 g, (H) An organohydrogenpolysiloxane having at least 2 hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule: a mass percentage corresponding to 1 to 5 times the number of moles of SiH groups in component (H) with respect to the number of moles of alkenyl groups in component (G), (I) A surfactant: 0.1 to 10% by mass in component (B) and (J) Water: 10 to 90% by mass in component (B) A water-based oil-resistant agent composition containing the above.

2. The following components (A), (C), (D), (E) and (F): (A) A cellulose resin having a viscosity of 2 to 10,000 mPa·s at 20 °C in a 2% aqueous solution: 100 parts by mass (C) A silicone emulsion: 5 to 5,000 parts by mass (D) A silicone emulsion (E) Water: 1,000 to 50,000 parts by mass (F) A platinum group metal-based catalyst: a catalytic amount A water-based oil-resistant agent composition containing the above, wherein the above (C) silicone emulsion is (G) An alkenyl group-containing organopolysiloxane having at least 2 alkenyl groups bonded to silicon atoms in one molecule and having a viscosity of 5 mPa·s or more at 25 °C: 5 to 60% by mass in component (C), and the total alkenyl value of component (G) (the number of moles of alkenyl groups bonded to silicon atoms contained in 100 g of the total component (G)) is more than 0.1 mol / 100 g, (I) A surfactant: 0.1 to 10% by mass in component (C) and (J) Water: 10 to 90% by mass in component (C) containing the above, wherein the above (D) silicone emulsion is (H) An organohydrogenpolysiloxane having at least 2 hydrogen atoms bonded to silicon atoms in one molecule: 5 to 60% by mass in component (D), (I) Surfactant: 0.1 to 10% by mass in component (D) and (J) Water: 10 to 90% by mass in component (D) Aqueous oil-resistant agent composition, which contains the above components, and the content of component (D) in the composition is an amount corresponding to 1 to 5 times the number of moles of the SiH groups of component (H) in component (D) with respect to the number of moles of the alkenyl groups of component (G) in component (C).

3. The aqueous oil-resistant agent composition according to claim 1 or 2, wherein the cellulose-based resin as component (A) is a cellulose ether in which 0.5 to 2.5 hydroxyl groups per glucose ring unit of cellulose are substituted with alkoxy groups.

4. The aqueous oil-resistant agent composition according to claim 1 or 2, wherein component (G) contains at least two of a linear organopolysiloxane containing alkenyl groups only at both ends and a linear organopolysiloxane containing alkenyl groups at both side chains and both ends.

5. The aqueous oil-resistant agent composition according to claim 1 or 2, wherein component (G) is a linear alkenyl group-containing organopolysiloxane represented by the following average composition formula (1-1). 【Chemical 1】 (In formula (1-1), R 1 is independently an alkenyl group-containing organic group having 2 to 10 carbon atoms, and R 2 is independently one kind of group selected from unsubstituted or substituted monovalent hydrocarbon groups having no hydroxyl group, alkoxy group, and alkenyl group, and a, c, and d are each a number of 0 or more, satisfying 0 ≦ a ≦ 3, 2 ≦ 2a + c, and 5 ≦ c + d.)

6. The aqueous oil-resistant agent composition according to claim 1 or 2, wherein the ratio of the total number of hydrogen atoms bonded to silicon atoms in component (H) to the total number of hydrogen atoms bonded to silicon atoms and the groups bonded to silicon atoms is 15 to 50%.

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

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

9. The aqueous oil-resistant agent composition according to claim 1 or 2, wherein the total mass of components (G) and (H) is 60 to 2000 parts by mass with respect to 100 parts by mass of component (A).

10. A method for producing the aqueous oil-resistant agent composition according to claim 1, comprising: (Step 1) A step of mixing and emulsifying the following components (G), (H), (I) and (J) to prepare an addition-curable silicone emulsion as component (B). (G) An alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and having a viscosity at 25 °C of 5 mPa·s or more: 5 to 40% by mass in the (B) component, and the total alkenyl value of the (G) component (the number of moles of alkenyl groups bonded to silicon atoms contained in 100 g of the total (G) component) is more than 0.1 mol / 100 g (H) An organohydrogenpolysiloxane having at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule: a mass percentage corresponding to 1 to 5 times the number of moles of SiH groups in the (H) component relative to the number of moles of alkenyl groups in the (G) component (I) Surfactant: 0.1 to 10% by mass in the (B) component (J) Water: 10 to 90% by mass in the (B) component And (Step 2) A step of mixing the following (A), (E), and (F) components with 10 to 10,000 parts by mass of the (B) addition-curable silicone emulsion prepared in the above Step 1 (A) A cellulose resin having a viscosity of 2 to 10,000 mPa·s at 20 °C in a 2% aqueous solution: 100 parts by mass (E) Water: 1,000 to 50,000 parts by mass (F) A platinum group metal-based catalyst: a catalytic amount A method for producing an aqueous oil-resistant agent composition.

11. The method for producing an aqueous oil-resistant agent composition according to claim 2, comprising: (Step 1') A step of mixing and emulsifying the following (G), (I), and (J) components to prepare a (C) silicone emulsion (G) An alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and having a viscosity at 25 °C of 5 mPa·s or more: 5 to 60% by mass in the (C) component, and the total alkenyl value of the (G) component (the number of moles of alkenyl groups bonded to silicon atoms contained in 100 g of the total (G) component) is more than 0.1 mol / 100 g (I) Surfactant: 0.1 to 10% by mass in the (C) component (J) Water: 10 to 90% by mass in the (C) component (Step 1'') A step of mixing and emulsifying the following (H), (I), and (J) components to prepare a (D) silicone emulsion (H) An organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule: 5 to 60% by mass in the (D) component (I) Surfactant: 0.1 to 10% by mass in the (D) component (J) Water: 10 to 90% by mass in the (D) component And Step (Process 2'): Mix the following components (A), (E), and (F) with 5 to 5,000 parts by mass of the (C) silicone emulsion prepared in the above Step 1' and an amount corresponding to 1 to 5 times the number of moles of the SiH groups of the (H) component in the (D) component of the (D) silicone emulsion prepared in the above Step 1'' Component (A): 100 parts by mass of a cellulose-based resin having a viscosity of 2 to 10,000 mPa·s at 20°C in a 2% aqueous solution Component (E): 1,000 to 50,000 parts by mass of water Component (F): A platinum group metal-based catalyst in a catalytic amount A method for producing an aqueous oil-resistant agent composition having the above components

12. A method for treating paper to be oil-resistant, wherein the aqueous oil-resistant agent composition according to Claim 1 or 2 is added internally to a pulp slurry or externally to a paper base material

13. An oil-resistant paper treated with the aqueous oil-resistant agent composition according to Claim 1 or 2, having an air permeability of 1,000 seconds or less as measured according to JAPAN TAPPI Paper Pulp Test Method No. 5-2:2000