Water-based oil-resistant agent composition, method for producing a water-based oil-resistant agent composition, method for treating paper to be oil-resistant, 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 a water-based oil-resistant composition, a method for producing a water-based oil-resistant composition, a method for treating paper to make it oil-resistant, and oil-resistant paper. [Background technology]

[0002] Paper packaging, packaging containers, and food trays used for cooked foods such as fast food, fried foods, and grilled foods that contain a lot of oil and moisture are treated to be oil-resistant and water-resistant to prevent the oil and moisture from the food from seeping in and staining the surrounding area.

[0003] For food-grade oil-resistant paper or containers, polyethylene laminated paper, which consists of a paper base laminated with polyethylene film on one side, has been used. However, polyethylene laminated paper has problems such as low air permeability, which can easily lead to a decrease in food flavor and storage stability, and difficulty in removing the polyethylene film during recycling, resulting in poor recyclability. With the growing movement towards reducing plastic use, there is a demand for the development of oil-resistant paper that does not use polyethylene lamination. Furthermore, conventionally, fluororesin-based oil repellents have been widely used to impart oil and water resistance to paper. For example, methods include coating the surface of the paper substrate with a fluororesin-based oil repellent to create an oil-resistant layer, impregnating the paper substrate with a fluororesin-based oil repellent, or adding a fluororesin-based oil repellent to the pulp slurry. However, fluororesin-based oil repellents are undesirable from a health and environmental perspective due to their poor biodegradability and bioaccumulation potential, and in recent years, there has been a demand for oil repellents that do not contain fluororesins (non-fluororesin-based oil repellents).

[0004] Accordingly, as non-fluororesin-based oil resistance agents, 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 having a surface coated with a composition containing a PVA-based resin and a silicone-based emulsion. It is also known that acrylic and paraffin wax-based emulsions such as those described in Patent Documents 2, 3, and 4 also 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] Japanese Unexamined Patent Application Publication No. 2005-139418 [Patent Document 2] Japanese Unexamined Patent Application Publication No. 2013-237941 [Patent Document 3] Japanese Unexamined Patent Application Publication No. 2020-122250 [Patent Document 4] Japanese Unexamined Patent Application Publication No. 2022-188338 [Patent Document 5] Japanese Unexamined Patent Application Publication No. 2006-257159 [Summary of the Invention] [Problem to be Solved by the Invention]

[0006] However, in the case of non-fluoropolymer oil resistant agents, in order to exhibit oil resistance while preventing the seepage of oil components, it is necessary to either increase the density of the substrate or use a large amount of sealant and oil resistant agent. As a result, while oil resistance is increased, air permeability becomes insufficient, which can easily lead to a decrease in the flavor and storage stability of food. For example, in order to impart oil and water resistance by applying the compositions described in Patent Documents 1 and 5 to a paper substrate, not only is the film-forming composition coated onto the surface of the paper substrate, but a sealant is also required on the paper substrate, raising concerns that the air permeability of the resulting oil-resistant paper will decrease. Although air permeability has been confirmed in the oil-resistant papers described in Patent Documents 2, 3, and 4, the amount of oil resistant agent applied was large, and the air permeability in all cases was 100 seconds or more, which is inferior to that of fluoropolymer oil resistant agents. Thus, oil-resistant paper that combines high oil resistance and high air permeability using non-fluoropolymer oil-resistant agents has yet to be developed, and there is still room for improvement in this regard. Accordingly, the present invention aims to provide an oil-resistant composition that can produce oil-resistant paper having high oil resistance and high air permeability, and which does not contain fluororesins or organic solvents, and is a non-fluororesin-based water-based oil-resistant composition that takes into consideration health and environmental aspects. [Means for solving the problem]

[0007] As a result of diligent research to achieve the above objectives, the inventors of this invention have discovered that the following water-based oil-resistant composition can accomplish the above problems, and have thus come to fruition. In other words, the present invention provides the following oil-resistant compositions, etc.

[0008] [1] The following components (A), (B), (E), and (F): (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) Addition-curing silicone emulsion: 10 to 10,000 parts by mass (E) Water: 1,000~50,000 parts by mass (F) Platinum group metal catalyst: Catalyst amount A water-based oil-resistant composition containing, The above (B) addition-curing silicone emulsion is (G) Alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and a viscosity of 5 mPa·s or more at 25°C: (B) 5 to 40% by mass, 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 greater than 0.1 mol / 100 g. (H) Organohydrogenpolysiloxane having at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule: (G) The number of moles of SiH groups in component (H) corresponds to 1 to 5 times the number of moles of alkenyl groups in component (G) by mass, (I) Surfactants: 0.1 to 10% by mass of component (B) and (J) Water: 10-90% by mass in (B) component A water-based oil-resistant composition containing the following: [2] The following components (A), (C), (D), (E), and (F): (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) Silicone emulsion: 5 to 5,000 parts by mass (D) Silicone emulsion (E) Water: 1,000~50,000 parts by mass (F) Platinum group metal catalyst: Catalyst amount A water-based oil-resistant composition containing, The above (C) silicone emulsion, (G) Alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and a viscosity of 5 mPa·s or more at 25°C: (C) component makes up 5-60% by mass, and the total alkenyl value of component (G) (the number of moles of alkenyl groups bonded to silicon atoms contained in 100g of total component (G)) is greater than 0.1 mol / 100g. (I) Surfactants: 0.1 to 10% by mass of component (C) and (J) Water: 10~90% by mass in (C) component It includes, The above (D) silicone emulsion, (H) Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule: (D) 5-60% by mass of component (I) Surfactants: 0.1 to 10% by mass of component (D) and (J) Water: 10-90% by mass in (D) component A water-based oil-resistant composition comprising the above, wherein the amount 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] (A) The water-based oil-resistant composition according to [1] or [2], wherein the cellulose resin component is a cellulose ether obtained by substituting 0.5 to 2.5 hydroxyl groups per glucose ring unit of cellulose with alkoxy groups. [4] A water-based oil-resistant composition according to any one of [1] to [3], wherein component (G) comprises at least two linear organopolysiloxanes containing alkenyl groups only at both ends, and linear organopolysiloxanes containing alkenyl groups in the side chain and at both ends. [5] A water-based oil-resistant composition according to any one of the following [1] to [4], wherein component (G) is a linear alkenyl group-containing organopolysiloxane represented by the following average composition formula (1-1). [ka] (In formula (1-1), R 1 R is an organic group containing an alkenyl group with 2 to 10 carbon atoms, 2 (i) is independently selected from unsubstituted or substituted monovalent hydrocarbon groups that do not have a hydroxyl group, alkoxy group, or alkenyl group, and a, c, and d are each numbers greater than or equal to 0, satisfying 0 ≤ a ≤ 3, 2 ≤ 2a + c, and 5 ≤ c + d.) [6] A water-based oil-resistant composition according to any one of the following [1] to [5], wherein the ratio of the total number of hydrogen atoms bonded to silicon atoms to the total number of hydrogen atoms bonded to silicon atoms and groups bonded to silicon atoms in component (H) is 15 to 50%. [7] A water-based oil-resistant composition according to any one of the following [1] and [3] to [6], wherein the silicone emulsion of component (B) further contains 0.5 to 10% by mass of polyvinyl alcohol (PVA) resin in component (B). [8] A water-based oil-resistant composition according to any one of the following [2] to [6], wherein at least one of the silicone emulsion of component (C) and the silicone emulsion of component (D) further contains a polyvinyl alcohol (PVA) resin in an amount of 0.5 to 10% by mass in component (C) or component (D). [9] The water-based oil-resistant composition according to any one of the claims [1] to [8], wherein the total mass of component (G) and component (H) is 60 to 2000 parts by mass per 100 parts by mass of component (A).

[10] A method for producing an aqueous oil-resistant composition according to any one of items [1], [3] to [7] and [9], (Step 1) A step to prepare an addition-curing silicone emulsion (B) by mixing and emulsifying the components (G), (H), (I), and (J) below. (G) Alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and a viscosity of 5 mPa·s or higher at 25°C: (B) component makes up 5 to 40% by mass, and the total alkenyl value of component (G) (the number of moles of alkenyl groups bonded to silicon atoms contained in 100 g of total component (G)) is greater than 0.1 mol / 100 g. (H) Organohydrogenpolysiloxane having at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule: (G) The number of moles of SiH groups in component (H) corresponds to 1 to 5 times the number of moles of alkenyl groups in component (G) by mass % (I) Surfactants: 0.1 to 10% by mass of component (B) (J) Water: 10-90% by mass in (B) component and (Step 2) A step of mixing components (A), (E), and (F) below with 10 to 10,000 parts by mass of the addition-curing silicone emulsion (B) prepared in Step 1 above. (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: 1,000~50,000 parts by mass (F) Platinum group metal catalyst: Catalyst amount A method for producing a water-based oil-resistant composition having the following characteristics.

[11] A method for producing an aqueous oil-resistant composition according to any one of items [2] to [6], [8] and [9], (Step 1') A step in which components (G), (I), and (J) below are mixed and emulsified to prepare (C) a silicone emulsion. (G) Alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and a viscosity of 5 mPa·s or more at 25°C: (C) component makes up 5-60% by mass, and the total alkenyl value of component (G) (the number of moles of alkenyl groups bonded to silicon atoms contained in 100g of total component (G)) is greater than 0.1 mol / 100g (I) Surfactants: 0.1 to 10% by mass of component (C) (J) Water: 10~90% by mass in (C) component (Step 1'') A step in which components (H), (I), and (J) below are mixed and emulsified to prepare (D) a silicone emulsion. (H) Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule: (D) 5-60% by mass of component (I) Surfactants: 0.1 to 10% by mass of component (D) (J) Water: 10-90% by mass in (D) component and (Step 2') A step of mixing components (A), (E), and (F) below with 5 to 5,000 parts by mass of the (C) silicone emulsion prepared in Step 1' above and an amount of the (D) silicone emulsion prepared in Step 1'' above in which the number of moles of SiH groups of component (H) in component (D) corresponds to 1 to 5 times the number of moles of alkenyl groups of component (G) in component (C). (A) 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: 1,000~50,000 parts by mass (F) Platinum group metal catalyst: Catalyst amount A method for producing a water-based oil-resistant composition having the following characteristics.

[12] A method for treating paper to be oil-resistant, comprising adding a water-based oil-resistant agent composition described in any one of items [1] to [9] to a pulp slurry internally or externally to a paper substrate.

[13] Oil-resistant paper treated with any one of the water-based oil-resistant agent compositions described in [1] to [9], wherein the air permeability measured according to the Oken method, as measured in accordance with JAPAN TAPPI Paper Pulp Test Method No. 5-2:2000, is 1,000 seconds or less. [Effects of the Invention]

[0009] This invention combines a cellulose-based resin, which has excellent affinity with paper, with silicone, which has good water resistance and breathability, thereby achieving the advantages of both materials. By treating a paper substrate with a composition of materials having a specific structure according to this invention, combined under specific conditions, and curing it, an oil-resistant paper with excellent oil and water resistance and high breathability can be obtained. Furthermore, because the oil-resistant paper of the present invention has high breathability, it can prevent oil stains without impairing the flavor of food when packaging it. Furthermore, the cellulose resin and silicone contained in the water-based oil-resistant composition of the present invention are both highly environmentally safe and harmless materials, and can be suitably used as substitutes for organofluorine compounds. In addition, since the water-based oil-resistant composition of the present invention does not contain organic solvents, it can avoid the disadvantages of environmental problems and biological hazards caused by the use of organic solvents. Paper substrates treated with the composition of the present invention are easily recyclable, resulting in products with a low environmental impact, and solving the harmful and environmental problems associated with fluorine compounds. [Modes for carrying out the invention]

[0010] [Water-based oil-resistant agent composition] The aqueous oil-resistant composition of the present invention will be described in more detail below. In this specification, unless otherwise specified, "%" indicates a percentage by mass.

[0011] (A) Cellulose resin The cellulose-based resin of component (A) is a compound in which different substituents are introduced to the hydroxyl groups contained in cellulose molecules through chemical modification. The cellulose 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, and 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 coating properties of the composition will be poor. The viscosity at 20°C is the value measured using a BM type viscometer (for example, manufactured by Tokyo Keiki Co., Ltd.) at 20°C. The rotor, rotation speed, and rotation time should be appropriately selected according to the viscosity based on conventional methods (the same applies hereinafter).

[0012] The cellulose resins suitably used in the present invention are preferably cellulose ethers, which are obtained by substituting the hydroxyl groups of cellulose with an etherifying agent; esterified cellulose esters are preferred, and cellulose ethers are particularly preferred. Many of these cellulose ethers are approved as food additives, pharmaceuticals, and cosmetic ingredients, and are known not only to be harmless to the human body but also to be extremely environmentally friendly materials due to their slow biodegradability.

[0013] Examples of cellulose ethers include alkylcellulose (methylcellulose, ethylcellulose, etc.) in which the hydroxyl groups of cellulose are substituted with alkoxy groups; hydroxyalkylcellulose (hydroxyethylcellulose, hydroxypropylcellulose, etc.) in which the hydroxyl groups of cellulose are substituted with hydroxyalkoxy groups; hydroxyalkylalkylcellulose (hydroxypropylmethylcellulose, etc.) in which the hydroxyl groups of cellulose are substituted with alkoxy and hydroxyalkoxy groups; and carboxyalkylcellulose (carboxymethylcellulose, etc.) in which the hydroxyl groups of cellulose are substituted with carboxyalkoxy groups. Preferably, methylcellulose, ethylcellulose, and hydroxypropylmethylcellulose are used, and more preferably, methylcellulose. Examples of cellulose esters include cellulose acetate and cellulose phthalate acetate.

[0014] The degree of substitution of cellulose ethers or cellulose esters refers to the number of hydroxyl groups substituted by the etherifying agent or 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, solubility in water is low, which may impair the workability of the composition during manufacturing. If the degree of substitution exceeds 2.5, sufficient oil resistance may not be imparted. Furthermore, when a hydroxyl group in one molecule of cellulose ether or cellulose ester is substituted with two or more substituents, the sum of the degree of substitution of each of the two or more substituents is preferably 0.5 to 2.5, more preferably 0.8 to 2.2, and even more preferably 1.0 to 2.0.

[0015] The present invention can use commercially available cellulose ethers, specifically including METHOCEL, ETHOCEL (manufactured by Dow Chemical), NATROSOL (manufactured by Hercules), HEC Daicel, CMC Daicel (manufactured by Daicel Chemical Industries, Ltd.), Fuji Chemi HEC (manufactured by Sumitomo Seika Co., Ltd.), Selogen (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and Metrose (manufactured by Shin-Etsu Chemical Co., Ltd.). The cellulose resin of component (A) may be used alone or in combination of two or more types.

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

[0017] The present invention provides an aqueous oil-resistant composition as a silicone emulsion, <1> (B) Addition-curing silicone emulsion or <2> (C) Silicone emulsion and (D) Silicone emulsion It contains. (B) Addition-curing silicone emulsion contains (G) an alkenyl group-containing organopolysiloxane, (H) an organohydrogenpolysiloxane, (I) a surfactant, and (J) water. (C) The silicone emulsion contains (G) an alkenyl group-containing organopolysiloxane, (I) a surfactant, and (J) water. (D) The silicone emulsion contains (H) organohydrogensiloxane, (I) surfactant, and (J) water. Components (G) through (J) will be described later. In this specification, a water-based oil-resistant composition containing (B) an addition-curing silicone emulsion may be described as "water-based oil-resistant composition <1>", and a water-based oil-resistant composition containing (C) a silicone emulsion and (D) a silicone emulsion may be described as "water-based oil-resistant composition <2>". Emulsification to obtain components (B) to (D) can be carried out using a general emulsifying and dispersing machine. Examples of emulsifying and dispersing machines include high-speed rotating centrifugal radiation stirrers such as homodispersers, high-speed rotating shear stirrers such as homomixers, high-pressure jet emulsifying and dispersing machines such as pressure homogenizers, colloid mills, ultrasonic emulsifiers, etc. The volume-average particle size of each emulsion of components (B) to (D) obtained, measured by a laser diffraction / scattering particle size distribution analyzer, is preferably 50 to 10,000 nm, and more preferably 100 to 1,500 nm.

[0018] (B) Addition-curing silicone emulsion The amount of component (B) is 10 to 10,000 parts by mass per 100 parts by mass of component (A), preferably 100 to 4,000 parts by mass, and more preferably 250 to 2,000 parts by mass. If the amount of component (B) is less than 10 parts by mass per 100 parts by mass of component (A), the water resistance will be insufficient, and if it is more than 10,000 parts by mass, the oil resistance will be insufficient.

[0019] The content of component (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 the content of component (G) in component (B) is outside the above range, the oil resistance and water resistance will be reduced.

[0020] The content ratio of component (H) in component (B) is such that 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) by mass%, preferably 1.1 to 3 times, and more preferably 1.2 to 2.5 times. If the content ratio of component (H) in component (B) is outside the above range, the oil resistance and water resistance will be reduced.

[0021] The content 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. If the content of component (I) in component (B) is less than the lower limit, emulsification becomes difficult, and if it is more than the upper limit, oil resistance and water resistance become low.

[0022] The content 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. If the content of component (J) in component (B) is less than the lower limit, dispersion becomes difficult, and if it is more than the upper limit, the long-term stability of the emulsion decreases.

[0023] In the water-based oil-resistant 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, based on 100 parts by mass of component (A).

[0024] (C) Silicone emulsion containing organopolysiloxane having alkenyl groups The amount of component (C) is 5 to 5,000 parts by mass per 100 parts by mass of component (A), preferably 50 to 2,000 parts by mass, and more preferably 125 to 1,000 parts by mass. If the amount of component (C) is less than 5 parts by mass per 100 parts by mass of component (A), the water resistance will be insufficient, and if it is more than 5,000 parts by mass, the oil resistance will be insufficient.

[0025] The content 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. If the content of component (G) in component (C) is outside the above range, the oil resistance and water resistance will be reduced.

[0026] The content 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. If the content of component (I) in component (C) is less than the lower limit, emulsification becomes difficult, and if it is more than the upper limit, oil resistance and water resistance become low.

[0027] The content 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. If the content of component (J) in component (C) is less than the lower limit, dispersion becomes difficult, and if it is more than the upper limit, the long-term stability of the emulsion decreases.

[0028] (D) Organohydrogen polysiloxane-containing silicone emulsion The amount of component (D) is such that the number of moles of SiH groups in component (D) is 1 to 5 times the number of moles of alkenyl groups in component (C) by mass%, preferably 1.1 to 3.0 times, and more preferably 1.2 to 2.5 times. If the amount of component (D) is outside the above range, the oil resistance and water resistance will be reduced.

[0029] 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.

[0030] 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 lower limit, emulsification becomes difficult, and if it is more than the upper limit, oil resistance and water resistance become low.

[0031] 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 lower limit, dispersion becomes difficult, and if it is more than the upper limit, the long-term stability of the emulsion decreases.

[0032] In the water-based oil-resistant composition <2>, 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, based on 100 parts by mass of component (A).

[0033] (G) Alkenyl group-containing organopolysiloxane Component (G) is an organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and a viscosity of 5 mPa·s or higher at 25°C. The number of alkenyl groups bonded to silicon atoms in component (G) is at least 2 per molecule, preferably 2 to 500, more preferably 2 to 100, and even more preferably 2 to 30. If the number of alkenyl groups bonded to silicon atoms in component (G) is less than 2 per molecule, there is no crosslinking property, resulting in low oil resistance, which is undesirable. Also, if the number of alkenyl groups bonded to silicon atoms in component (G) is more than 500 per molecule, curing may take a long time.

[0034] The viscosity of component (G) at 25°C is 5 mPa·s or higher, 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 decrease. There is no upper limit to the viscosity of component (G) at 25°C, but it can be, for example, 100,000 mPa·s. Furthermore, when using multiple types of component (G), the viscosity can be adjusted to the above viscosity range by mixing a low-viscosity organopolysiloxane corresponding to component (G) with a high-viscosity or natural rubber-like organopolysiloxane corresponding to component (G).

[0035] (G) The alkenyl value of the silicon atoms bonded to the total silicon atoms in the component is greater than 0.1 mol / 100 g, preferably 0.13 mol / 100 g or more, and more preferably 0.15 mol / 100 g or more. If the alkenyl value of the silicon atoms bonded to the total silicon atoms in the component is 0.1 mol / 100 g or less, the crosslinking ability will be low and the oil resistance will decrease. There is no upper limit to the alkenyl value of the component (G), but it can be, for example, 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 silicon atoms in the component (G), and can usually be calculated from the iodine value obtained by the Hanus method (a method in which the compound is reacted with the Hanus reagent, then reacted with an aqueous potassium iodide solution, and the iodine produced 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 linear, branched, or cyclic, but a linear structure is preferred. Component (G) may be used alone or in combination of two or more. When using two or more components (G) in combination, the average alkenyl number calculated from the total of the components (G) must exceed 0.1 mol / 100g. Furthermore, when two or more components (G) are used in combination, their molecular structures are not particularly limited, but it is preferable to use a combination of a linear organopolysiloxane containing alkenyl groups only at both ends and a linear organopolysiloxane containing alkenyl groups in the side chain and at both ends, and it is even more preferable to use a combination of organopolysiloxanes whose alkenyl value exceeds 0.1 mol / 100 g.

[0037] Component (G) is a component for developing oil resistance and water resistance of the composition, and specifically, those having a structure represented by 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 has 2 to 8 carbon atoms, and more preferably 2 to 6 carbon atoms. Examples of R 1 include alkenyl groups such as a vinyl group, an allyl group, and a hexenyl group.

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

[0040] In equation (1), a, b, c, d, e, f, and g are mutually independent numbers that are greater than or equal to 0. a is such that 0 ≤ a ≤ 3, preferably 0 or 1, and more preferably 1. b is a number greater than or equal to 1, such that 2 ≤ ab + c + e and 5 ≤ b + c + d + e + f + g.

[0041] The alkenyl group-containing organopolysiloxane represented by formula (1) is preferably linear, i.e., in formula (1), b=2 and e=f=g=0, as shown in the following formula (1-1). [ka] In formula (1-1), R 1 and R 2 These are equivalent to equation (1), where a, c, and d are all non-negative numbers satisfying 0 ≤ a ≤ 3, 2 ≤ 2a + c, and 5 ≤ c + d. Furthermore, in formula (1-1), when the side chain has an alkenyl group (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. Furthermore, in formula (1-1), when the side chain does not have an alkenyl group (c=0), it is more preferable that 3≦d≦30, and even more preferable that 3≦d≦20.

[0042] (G) Examples of components include, but are not limited to, the following. 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 to the following. In each of the following formulas, the total number of repeating siloxane units is the average value. Furthermore, in the following formula, z1 to z39 are all numbers greater than or equal to 0. [ka] [ka] [ka] [ka]

[0043] (H) Organohydrogenpolysiloxane Component (H) 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 component (H) is preferably 15 to 50%, more preferably 20 to 45%, and even more preferably 30 to 40%. If the proportion of SiH groups in component (H) is less than 15%, the crosslinking density will be low, and oil resistance may decrease. If it is more than 50%, reactivity will decrease, and curing may take longer.

[0044] The alkenyl groups in component (G) and the SiH groups in component (H) undergo an addition reaction to form a crosslinked structure. In other words, component (H) functions as a crosslinking agent. From the viewpoint of crosslinking balance, the amount of component (H) is such that the ratio 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 meet the above range, the crosslinking balance will be inappropriate, and the oil resistance and water resistance will decrease.

[0045] The molecular structure of component (H) may be linear, branched, cyclic, or a three-dimensional network structure, or a mixture thereof. Furthermore, the SiH group of component (H) may be located at the end of the molecular chain, in the middle of the molecular chain, or both. Component (H) is preferably a linear organohydrogenpolysiloxane represented by the following formula (2). [ka] (In formula (2), R 3 These are, independently of each other, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, without hydroxyl groups or aliphatic unsaturated bonds. h is 0 or 1, and i and j are numbers satisfying 0 ≤ i ≤ 200 and 0 ≤ j ≤ 200, and 2 ≤ 2h + i ≤ 200 and 3 ≤ i + j + 2 ≤ 400.

[0046] In equation (2) above, R 3 These are, independently of each other, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms that do not have a hydroxyl group or an aliphatic unsaturated bond. 3 The monovalent hydrocarbon group that does not have an 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 most preferably a methyl group.

[0047] i is a number between 0 and 200, preferably between 3 and 150, and more preferably between 5 and 100. j is a number between 0 and 200, preferably between 0 and 100, and more preferably between 5 and 50. 2h+i is a number between 2 and 200, preferably between 4 and 150, more preferably between 5 and 100, and even more preferably between 10 and 80. i+j+2 is a number between 3 and 400, preferably between 5 and 200, and more preferably between 10 and 100.

[0048] Examples of organohydrogenpolysiloxanes represented by the above average composition formula (2) include methylhydrogensiloxane-dimethylsiloxane cyclic copolymer, dimethylsiloxane-methylhydrogensiloxane copolymer with trimethylsiloxy groups sealed at both ends, dimethylpolysiloxane with dimethylhydrogensiloxy groups sealed at both ends, dimethylsiloxane-methylhydrogensiloxane copolymer with dimethylhydrogensiloxy groups sealed at both ends, and methylhydrogensiloxane-diphenylsiloxane copolymer with trimethylsiloxy groups sealed at both ends. Examples include methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymers with trimethylsiloxy groups sealed at both ends, methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymers, methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymers with dimethylhydrogensiloxy groups sealed at both ends, methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymers, and methylhydrogensiloxane / dimethylsiloxane / methylphenylsiloxane copolymers with dimethylhydrogensiloxy groups sealed at both ends. Component (H) may be used alone or in combination of two or more types.

[0049] The (H) component may include, but is not limited to, linear or branched siloxanes represented by the following formulas. In the following formulas, 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 to the following. In each of the following formulas, the total number of repeating siloxane units is the average value. Furthermore, in the following formulas, z42 to z73 are the numbers that satisfy the proportion of SiH groups in the organohydrogenpolysiloxane of each formula to be between 15% and 50%. [ka] [ka] [ka]

[0050] (I) Surfactants Component (I) is a surfactant, and there are no particular restrictions as long as it can emulsify and disperse components (G) and (H) in water, but it is preferable that it 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 and polyoxyethylene Poly Oxypropylene lauryl ether, polyoxyethylene acetylene glycol ether, polyoxyethylene sorbitan monolaurate, and polyoxyethylene styrene-phenyl ether are preferred, with polyoxyethylene lauryl ether and polyoxyethylene styrene-phenyl ether being more preferred. 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 nonionic surfactant, either alone or as a whole of two or more, have an HLB of 10 to 15.

[0051] Anionic and cationic surfactants can also be used, but their use in combination with nonionic surfactants is preferable from the standpoint of dispersibility. Examples of anionic surfactants include alkyl sulfate esters such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, alkylbenzene sulfonate, polyoxyethylene alkylphenyl ether sulfonate, alkyl diphenyl ether disulfonate, alkanesulfonate, N-acyl taurate, dialkyl sulfosuccinate, monoalkyl sulfosuccinate, polyoxyethylene alkyl ether sulfosuccinate, fatty acid salts, polyoxyethylene alkyl ether carboxylate, N-acyl amino acid salt, monoalkyl phosphate salt, dialkyl phosphate salt, and polyoxyethylene alkyl ether phosphate salt. Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, polyoxyethylenealkyldimethylammonium salts, dipolyoxyethylenealkylmethylammonium salts, tripolyoxyethylenealkylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts, monoalkylamine salts, and monoalkylamidoamine salts.

[0052] In the silicone emulsions of components (B), (C), and (D), a water-soluble resin may be used in combination with a surfactant as an emulsifying agent to aid in the emulsification of components (G) and (H) and to improve stability. Examples of water-soluble resins include PVA-based resins, cellulose derivatives, and carboxyvinyl polymers, but PVA-based resins are more preferred. The PVA-based resin is preferably one whose viscosity at 20°C in a 4% aqueous solution is 10 to 50 mPa·s and whose degree of saponification is 85 to 95 mol%, and more preferably one whose viscosity is 15 to 30 mPa·s and whose degree of saponification is 87.5 to 92 mol%. This water-soluble resin may also function as a thickener. In particular, it is preferable to select a water-soluble resin as an emulsifying agent that has as little catalytic poisoning effect as possible on the platinum group metal catalyst of component (F), which will be described later. The amount of water-soluble resin is preferably the minimum amount necessary to ensure sufficient stability of the silicone emulsion, similar to the surfactant described above. 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, it may inhibit the addition reaction and reduce oil and water resistance, and if it is less than the lower limit, it will be difficult to obtain the stabilizing effect.

[0053] ·(J)Water Component (J) is water, which forms the continuous phase of the emulsion, and various types of water can be used, such as deionized water or purified water.

[0054] Other ingredients In the present invention, each silicone emulsion of component (B), component (C), and component (D) may contain optional components other than those described above. Other optional components include, for example, catalyst activity inhibitors (controllers) selected from various organic nitrogen compounds, organophosphorus compounds, acetylene compounds, oxime compounds, and organochloro compounds, for the purpose of suppressing the catalytic activity of platinum group metal catalysts. Examples include acetylene alcohols such as 3-methyl-1-butyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 3-methyl-1-pentin-3-ol, 2-phenyl-3-butyne-2-ol, and 1-ethynyl-1-cyclohexanol; acetylene compounds such as 3-methyl-3-1-penten-1-yine and 3,5-dimethyl-3-hexen-1-yine; reaction products of these acetylene compounds with alkoxysilanes, siloxanes, or hydrogensilanes; vinylsiloxanes such as tetramethylvinylsiloxane cyclic compounds; organic nitrogen compounds such as benzotriazole; and other organophosphorus compounds, oxime compounds, and organic chloro compounds. The degree of curing inhibition effect by the addition reaction control agent varies depending on its chemical structure. Therefore, the amount of each addition reaction control agent used can be appropriately adjusted according to conventionally known methods. By adding an appropriate amount of addition reaction control agent, the oil-resistant composition exhibits superior long-term storage stability at room temperature and excellent heat-curing properties.

[0055] Component (E) is water, and the same as component (J) described above can be used. The content of component (E) in the water-based oil-resistant composition of the present invention is 1,000 to 50,000 parts by mass per 100 parts by mass of component (A), preferably 2,000 to 30,000 parts by mass, and more preferably 3,000 to 10,000 parts by mass. If the content of component (E) is less than 1,000 parts by mass per 100 parts by mass of component (A), handling performance will be poor, and 50,000 Mass part If the amount is too high, the coating amount decreases, resulting in insufficient oil resistance. Furthermore, in the water-based oil-resistant composition of the present invention, the content of component (E) is preferably within the above range relative to 100 parts by mass of component (A), and the content of components (A), (G), and (H) relative to 100 parts in total 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. The above range for the content of component (E) in the water-based oil-resistant composition is preferable because it provides good handling properties and a good balance between oil resistance and coating amount.

[0056] (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 so-called hydrosilylation reactions can be used. Examples of such platinum group metal catalysts include platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts, among which platinum-based catalysts are particularly preferred. Examples of such platinum-based catalysts include chloroplatinic acid, an alcohol solution or aldehyde solution of chloroplatinic acid, complexes of chloroplatinic acid with various olefins or vinylsiloxanes, and complexes of platinum with various olefins or vinylsiloxanes.

[0057] The amount of platinum group metal catalyst added should be in catalytic amounts. For example, from an economic standpoint, while obtaining a good cured film, it is preferable that the amount of platinum group metal equivalent be in the range of 1 to 1,000 ppm relative to the total mass of components (G) and (H), more preferably 10 to 500 ppm, and particularly preferably 20 to 200 ppm. If the amount of component (F) is less than the lower limit, curing may be insufficient, and if it is more than the upper limit, the cost may increase.

[0058] The water-based oil-resistant composition of the present invention comprises (F) component, (I) surfactant and ( J ) It may be included as a mixture with water. In other words, the water-based oil-resistant agent composition <1> is Components (A), (B), (E), and (K): (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) Addition-curing silicone emulsion: 10 to 10,000 parts by mass (E) Water: 1,000~50,000 parts by mass (K) Catalyst composition A water-based oil-resistant composition containing, The above (B) addition-curing silicone emulsion is (G) Alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and a viscosity of 5 mPa·s or more at 25°C: (B) 5 to 40% by mass, 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 greater than 0.1 mol / 100 g. (H) Organohydrogenpolysiloxane having at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule: (G) The number of moles of SiH groups in component (H) corresponds to 1 to 5 times the number of moles of alkenyl groups in component (G) by mass, (I) Surfactants: 0.1 to 10% by mass of component (B) and (J) Water: 10-90% by mass in (B) component It includes, The above (K) catalyst composition is (F)Platinum group metal catalyst (I) Surfactants and (J)Water It may also be a water-based oil-resistant composition containing [the specified ingredient]. Furthermore, the water-based oil-resistant agent composition <2> is Components (A), (C), (D), (E), and (K): (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) Silicone emulsion: 5 to 5,000 parts by mass (D) Silicone emulsion (E) Water: 1,000~50,000 parts by mass (K) Catalyst composition A water-based oil-resistant composition containing, The above (C) silicone emulsion, (G) Alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and a viscosity of 5 mPa·s or more at 25°C: (C) component makes up 5-60% by mass, and the total alkenyl value of component (G) (the number of moles of alkenyl groups bonded to silicon atoms contained in 100g of total component (G)) is greater than 0.1 mol / 100g. (I) Surfactants: 0.1 to 10% by mass of component (C) and (J) Water: 10-90% by mass in (C) component It includes, The above (D) silicone emulsion, (H) Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule: (D) 5-60% by mass of component (I) Surfactants: 0.1 to 10% by mass of component (D) and (J) Water: 10-90% by mass in (D) component The composition contains such that the amount of component (D) in the composition is such that the number of moles of SiH groups of component (H) in component (D) is equivalent to 1 to 5 times the number of moles of alkenyl groups of component (G) in component (C). The above (K) catalyst composition is (F)Platinum group metal catalyst (I) Surfactants and (J)Water It may also be a water-based oil-resistant composition containing [the specified ingredient].

[0059] (K) The catalyst composition is preferably an aqueous emulsion mixture of components (F), (I), and (J), i.e., an emulsion with water as the continuous phase. (K) The content of component (F) in the catalyst composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and even more preferably 0.3 to 3% by mass. Examples of surfactants used in the catalyst composition (K) are the same as those described above. The surfactant used in the catalyst composition (K) preferably includes a nonionic surfactant, similar to the surfactants used for emulsifying components (G) and (H). (K) The content of component (I) in the catalyst composition is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and even more preferably 0.3 to 2% by mass. If the content of component (I) in the catalyst composition is greater than 5% by mass, the addition reaction may be inhibited and the oil resistance and water resistance may decrease, and if it is less than 0.1% by mass, the stability may deteriorate. (K) The content of component (J) in the 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 catalyst composition is less than 10% by mass, component (F) may not disperse well, and if it is more than 90% by mass, the long-term stability of the emulsion may be low. (K) In order to make the catalyst composition a stable emulsion, in addition to components (F), (I), and (J) above, the catalyst composition may also contain components that can be contained in the silicone emulsions of components (B), (C), and (D) above.

[0060] Furthermore, the water-based oil-resistant composition of the present invention may contain preservatives, defoamers, fragrances, thickeners, antioxidants, rust inhibitors, pigments, fillers, organic powders, inorganic powders, etc., to the extent that they do not impair the effects of the present invention. The amounts of these ingredients are selected from suitable amounts for each. Furthermore, from a safety standpoint, it is preferable that each component of the water-based oil-resistant composition of the present invention consists only of compounds listed in the positive list prescribed by the Ministry of Health, Labour and Welfare and the Japan Paper Association. (Article 18, Paragraph 3 of the revised Food Sanitation Act and Notification No. 370, Positive list of chemical substances related to paper and cardboard intended to come into contact with food)

[0061] [Method for producing a water-based oil-resistant composition] The water-based oil-resistant 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 catalyst. The order in which each component is added is not particularly limited, but a preferred method for producing the water-based oil-resistant agent composition <1> is as follows: (Step 1) A step in which components (G), (H), (I), and (J) are mixed and emulsified to prepare (B) an addition-curing silicone emulsion. and (Step 2) A step of mixing components (A), (E), and (F) with the addition-curing silicone emulsion (B) prepared in Step 1 above. One example is a method having the following characteristics.

[0062] A more preferred method for producing the water-based oil-resistant composition <1> is as follows: (Step 1) A step in which components (G), (H), (I), and (J) are mixed and emulsified to prepare (B) an addition-curing silicone emulsion. (Step 2-1) A step to mix components (A) and (E) to prepare an aqueous solution of component (A). (Step 2-2) A step in which components (F), (I), and (J) are mixed to prepare the catalyst composition (K). and (Step 2-3) A step of mixing the addition-curing silicone emulsion (B) prepared in Step 1 above, an aqueous solution of component (A) prepared in Step 2-1 above, and the catalyst composition (K) prepared in Step 2-2 above. One example is a method having the following characteristics.

[0063] The water-based oil-resistant 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 catalyst. The order in which each component is added is not particularly limited, but a preferred method for producing the water-based oil-resistant agent composition <2> is as follows: (Step 1') A step in which components (G), (I), and (J) are mixed and emulsified to prepare (C) a silicone emulsion. (Step 1'') A step in which components (H), (I), and (J) are mixed and emulsified to prepare (D) a silicone emulsion. and (Step 2') A step of mixing components (A), (E), and (F) with the silicone emulsion (C) prepared in Step 1' above and the silicone emulsion (D) prepared in Step 1'' above. One example is a method having the following characteristics.

[0064] A more preferred method for producing the water-based oil-resistant composition <2> is as follows: (Step 1') A step in which components (G), (I), and (J) are mixed and emulsified to prepare (C) a silicone emulsion. (Step 1'') A step in which components (H), (I), and (J) are mixed and emulsified to prepare (D) a silicone emulsion. (Step 2'-1) A step of mixing components (A) and (E) to prepare an aqueous solution of component (A). (Step 2'-2) A step in which components (F), (I), and (J) are mixed to prepare the catalyst composition (K). and (Step 2'-3) A step of mixing the (C) silicone emulsion prepared in Step 1' above, the (D) silicone emulsion prepared in Step 1'' above, an aqueous solution of component (A) prepared in Step 2'-1 above, and the (K) catalyst composition prepared in Step 2'-2 above. One example is a method having the following characteristics.

[0065] (Step 1) (B) Preparation of addition-curing silicone emulsion Component (B) can be produced by known methods. For example, predetermined amounts of components (G), (H), and (I) and a portion of water (J) are mixed using a high-shear stirring device such as a planetary mixer, combi-mixer, or high-pressure homogenizer, emulsified by phase inversion, and diluted by adding the remainder of water (J). (B) When preparing the addition-curing silicone emulsion, components (A), (F), the water-soluble resin as an emulsifying aid as described above, and other components such as catalyst activity inhibitors may be mixed in predetermined amounts.

[0066] (Step 1')(C) Preparation of silicone emulsion Component (C) can be produced by known methods. For example, a method may be used in which predetermined amounts of components (G) and (I) and a portion of water (J) are mixed using a high-shear stirring device such as a planetary mixer, combi-mixer, or high-pressure homogenizer, emulsified by phase inversion, and then diluted by adding the remainder of water (J). (C) When preparing the silicone emulsion, components (A), (F), the water-soluble resin as an emulsifying aid as described above, and other components such as catalyst activity inhibitors may be mixed in predetermined amounts.

[0067] (Step 1'')(D) Preparation of silicone emulsion Component (D) can be produced by known methods. For example, a method may be used in which predetermined amounts of components (H) and (I) and a portion of water (J) are mixed using a high-shear stirring device such as a planetary mixer, combi-mixer, or high-pressure homogenizer, emulsified by phase inversion, and then diluted by adding the remainder of water (J). (D) When preparing the silicone emulsion, components (A), (F), the water-soluble resin as an emulsifying aid as described above, and other components such as catalyst activity inhibitors may be mixed in predetermined amounts.

[0068] (Step 2) Mixing of components (A), (E), and (F) with component (B) (Step 2') Mixing of components (A), (E), and (F) with component (C) and component (D) In steps 2 and 2', it is sufficient for each component to be uniformly mixed, and this can be done using a known mixing apparatus. For the stability of the emulsion, mixing is preferably carried out at 10 to 30°C.

[0069] (Step 2-1), (Step 2'-1) Preparation of aqueous solution of component (A) Steps 2-1 and 2'-1 are steps to dissolve component (A) in water (E) to obtain an aqueous solution of a desired concentration. From the viewpoint of ease of handling, it is preferable to dissolve the cellulose resin (A) in water (E) beforehand and mix it with the 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)(K) Preparation of catalyst composition Component (F) may be mixed during the production of the addition-curing silicone emulsion (B), but it is preferable to mix component (F), (I) surfactant and (J) water before mixing with other components, and then mix the resulting (K) catalyst composition with the other components. (K) The catalyst composition may be manufactured using an apparatus capable of mixing each component, but a preferred method is to mix the components using a high-shear stirring device such as a planetary mixer, combi-mixer, or high-pressure homogenizer, and then emulsify it by a phase inversion method to form an emulsion.

[0071] (Step 2-3) Mixing of component (B), aqueous solution of component (A), and component (K) (Step 2'-3) Mixing of component (C), component (D), aqueous solution of component (A), and component (K) Steps 2-3 are preferably performed immediately before using the water-based oil-resistant composition <1> (for example, immediately before applying it to the paper substrate). Furthermore, steps 2'-3 are preferably performed immediately before using the water-based oil-resistant composition <2> (for example, immediately before applying it to the paper substrate). This suppresses the dehydrogenation of organohydrogensiloxanes, resulting in excellent shelf life, and allows for easy achievement of a wide range of properties by changing the combination of emulsions mixed.

[0072] [Oil-resistant treatment method] The water-based oil-resistant composition of the present invention can be suitably used to impart oil resistance and water resistance to paper substrates. As a method for oil-resistant treatment of paper, it may be an internal treatment method in which the aqueous oil-resistant agent composition of the present invention is added to the pulp slurry, or it may be an external treatment method in which the aqueous oil-resistant agent composition of the present invention is coated onto the paper substrate after papermaking, or the paper substrate after papermaking is impregnated with the aqueous oil-resistant agent composition of the present invention and dried.

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

[0074] Examples of paper substrates include those produced by papermaking using various paper machines with chemical pulps such as hardwood pulp and softwood pulp, mechanical pulps such as wood pulp and thermomechanical pulp, and recycled paper pulp. Specifically, examples include bleached kraft paper, unbleached kraft paper, fine paper, medium paper, lightly coated paper, coated paper, glossy paper, processed paper, cardboard, white cardboard, liner, semi-glassine paper, glassine paper, and parchment paper. Furthermore, the pulp may contain pH adjusters, sizing agents, paper strength enhancers, wet paper strength enhancers, yield enhancers, water drainage enhancers, dyes, defoamers, fillers, etc.

[0075] As a coating method for water-based oil-resistant compositions, a method of external application to a paper substrate is preferred. Examples of such methods include application using a bar coater, knife coater, size press coater, roll coater, reverse roll coater, air knife coater, calender, gate roll coater, blade coater, curtain coater, gravure coater, rod metering, or a two-roll size press. To improve the air permeability of oil-resistant paper, external application of the water-based oil-resistant agent composition to the interior of the paper substrate is preferred over coating only the surface of the paper substrate with the water-based oil-resistant agent composition, and impregnation using a pound-type size press is particularly preferred. Furthermore, the amount of the water-based oil-resistant agent composition (solid content after drying) is not particularly limited, but preferably 0.1 to 10 g / m². 2 , more preferably 0.5~3g / m 2More preferably 0.5 to 2 g / m 2 This is the extent to which it is preferable that the amount of the water-based oil-resistant agent composition is within the above range, as this provides excellent oil resistance and air permeability.

[0076] After coating, the paper substrate is dried to remove the water-based oil-resistant composition by heat treatment. Examples of heat sources include hot air dryers, infrared heaters, and rotary dryers. As for drying conditions, for example, the temperature is 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 water-based oil-resistant 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 oil-resistant paper of the present invention is the Oken-type air permeability measured in accordance with JAPAN TAPPI Paper Pulp Test Method No. 5-2:2000. The air permeability of oil-resistant paper is not particularly limited as it depends on the paper substrate and coating method, but it 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 oil-resistant paper, but it can be, for example, 5 seconds. An air permeability of oil-resistant paper of 1000 seconds or less is preferable because it does not reduce the flavor or storage stability of food packaged using the oil-resistant paper. [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 viscosity of component (A) and the emulsifying agent PVA listed below was measured at 20°C using a BM-type viscometer. The viscosity of component (G) listed below was measured at 25°C using a B-type rotational viscometer. The vinyl number was measured using the Hanus method in accordance with JIS K 0070, and the value was calculated from the obtained iodine number. In the following, Me and Vi represent a methyl group and a vinyl group, respectively.

[0079] (A) component (A-1) Methylcellulose with a viscosity of 25 mPa·s at 20°C in a 2% aqueous solution and a degree of methoxy group substitution of 1.8. (A-2) Methylcellulose with a viscosity of 4 mPa·s at 20°C in a 2% aqueous solution and a degree of methoxy group substitution of 1.8. (A-3) Methylcellulose with a viscosity of 100 mPa·s at 20°C in a 2% aqueous solution and a degree of methoxy group substitution of 1.8. (A-4) Methylcellulose with a viscosity of 8,000 mPa·s at 20°C in a 2% aqueous solution and a degree of methoxy group substitution of 1.8. (A-5) Hydroxypropyl methylcellulose with a viscosity of 50 mPa·s at 20°C in a 2% aqueous solution, a degree of substitution of methoxy groups of 1.8, and a degree of substitution of hydroxypropyl groups of 0.15.

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

[0081] (G) Component (G-1) (ViMe2SiO 1 / 2 )2(Me2SiO 2 / 2 ) 120 (ViMeSiO 2 / 2 ) 18 Vinyl value: 0.187 mol / 100g, Viscosity: 300 mPa·s (G-2) (ViMe2SiO 1 / 2 )2(Me2SiO 2 / 2 ) 10 Vinyl value: 0.211 mol / 100g, Viscosity: 9.0 mPa·s (G-3) (ViMe2SiO 1 / 2 )2(Me2SiO 2 / 2 ) 95 (ViMeSiO 2 / 2 )3 Vinyl value: 0.070 mol / 100g, Viscosity: 300 mPa·s (G-4) (ViMe2SiO 1 / 2 )2(Me2SiO 2 / 2) 43 Vinyl value: 0.063 mol / 100g, Viscosity: 60 mPa·s (G-5) (ViMe2SiO 1 / 2 )2(Me2SiO 2 / 2 ) x (ViMeSiO 2 / 2 ) y Vinyl value: 0.13 mol / 100g, in a natural rubber-like state at 25°C, the viscosity of the solution dissolved in toluene to a concentration of 30% by mass is 7,000 mPa·s, x+y is the 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 / 100g, Viscosity: 400 mPa·s

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

[0083] (I) component (I-1) Polyoxyethylene styrene-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) A mixture of ethoxylated 2,4,7,9-tetramethyl-5-decine-4,7-diol and sodium di-2-ethylhexyl sulfosuccinate (product name: Surfinol PSA-336, manufactured by Evonik)

[0084] A. Preparation of emulsion Preparation of addition-curing silicone emulsion (B) [Preparation Example 1] In a 5-liter composite emulsifier (TK Combimix M type, product name: Primix Co., Ltd.) having an anchor-shaped stirring blade capable of stirring the entire contents of the container and a rotatable disc with small tooth-shaped protrusions alternately arranged on the upper and lower edges, 93.3 parts by mass of (G-1), 75.8 parts by mass of (G-2), 64.2 parts by mass of (H-1), 2.3 parts by mass of (I-1) as a surfactant, 77.8 parts by mass of a 15% PVA aqueous solution (manufactured by Mitsubishi Chemical Corporation, product name: GM-14L, viscosity of a 4% aqueous solution at 20°C is 18 mPa·s, degree of saponification 88.5 mol%) as an emulsifying aid, and 1.4 parts by mass of 1-ethynyl-1-cyclohexanol as a catalyst activity inhibitor, the mixture was uniformly stirred and mixed, then 70 parts by mass of phase inversion water was added to invert the phase, and the mixture was continued to stir for 15 minutes. Next, 198.5 parts by mass of dilution water were added and stirred to obtain an addition-curing emulsion (B-1) with a silicone content of 40%.

[0085] [Preparation Examples 2-14] Using the same method as in Preparation Example 1, the compositions shown in Tables 1, 2, and 3 below were emulsified to obtain addition-curing silicone emulsions (B-2 to 12, B'-1, 2).

[0086] Preparation of an 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% PVA aqueous solution (manufactured by Mitsubishi Chemical Corporation, product name: GM-14L, viscosity of a 4% aqueous solution at 20°C is 18 mPa·s, degree of saponification 88.5 mol%) as an emulsifying aid, and 1.4 parts by mass of 1-ethynyl-1-cyclohexanol as a catalyst activity inhibitor were charged into a composite emulsifier, uniformly stirred and mixed, then 51.1 parts by mass of phase inversion water was added to invert the phase, and the mixture was stirred for 15 minutes. Next, 144.9 parts by mass of dilution water was added and stirred to obtain an organopolysiloxane-containing silicone emulsion (C-1) having alkenyl groups with a silicone content of 40%.

[0087] Preparation of an 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 parts by mass of (I-1), and 21 parts by mass of a 15% PVA aqueous solution (manufactured by Mitsubishi Chemical Corporation, product name: GM-14L, viscosity of a 4% aqueous solution at 20°C is 18 mPa·s, degree of saponification 88.5 mol%) as an emulsifying aid were charged into a composite emulsifier and uniformly stirred and mixed. Then, 18.9 parts by mass of phase inversion water was added to invert the phase, and the mixture was stirred for 15 minutes. Next, 53.6 parts by mass of dilution water was added and stirred to obtain an organohydrogenpolysiloxane-containing silicone emulsion (D-1) with a silicone content of 40%.

[0088] Preparation of catalyst composition (K) [Preparation Example 17] The catalyst composition was mixed with water and emulsified to obtain a platinum catalyst emulsion composition (K-1) at a concentration of 0.4% by mass and 0.2% by mass of (F-1).

[0089] B. Preparation of water-based oil-resistant compositions and oil-resistant paper [Example 1] A aqueous solution of 5% cellulose resin (A-1) pre-dissolved in water was added to 2,000 parts by mass, an addition-curing silicone emulsion (B-1) with 40% silicone content was added to 583.3 parts by mass, water (E) was added to 16.7 parts by mass of platinum catalyst emulsion (K-1) (platinum weight relative to silicone content was 85 ppm), and the mixture was thoroughly combined to obtain a water-based oil-resistant agent composition. To the prepared water-based oil-resistant agent composition, Advantec's quantitative filter paper No. 5B (basis weight 108 g / m²) was used as a paper substrate. 2 The filter paper was impregnated with a material with an air permeability of 3.6s, squeezed in a squeezing machine, and then heated and dried in a dryer at 150°C for 3 minutes to obtain oil-resistant paper.

[0090] [Examples 2-19, Comparative Examples 1-4] Using the same method as in Example 1, water-based oil-resistant compositions were prepared with the formulations shown in Tables 1 to 3 below, and oil-resistant paper was obtained by treating the paper substrate with these compositions.

[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 a silicone emulsion containing an organopolysiloxane with 40% silicone content and alkenyl groups (C-1), 157.5 parts by mass of a silicone emulsion containing an organohydrogenpolysiloxane with 40% silicone content (D-1), and 16.7 parts by mass of a platinum catalyst emulsion (K-1) (platinum weight relative to silicone content: 85 ppm) were added and thoroughly mixed to obtain a water-based oil-resistant agent composition. Oil-resistant paper was obtained by treating a paper substrate with the prepared water-based oil-resistant agent composition in the same manner as in Example 1.

[0092] [Comparative Example 5] Based on Example 4 of Patent Document 5 (Japanese Patent Publication No. 2006-257159), (A-3) was used as component (A), (G'-1) as component (G), (H-5) as component (H), (I-2) as component (I), and succinic acid as an additive. A composition was obtained by emulsifying and blending the components in the same manner as in Preparation Example 1, with the composition shown in Table 4. Oil-resistant paper was obtained by treating a paper substrate with the prepared composition in the same manner as in Example 1.

[0093] C. Evaluation items and methods Each of the obtained oil-resistant papers was evaluated for its physical properties according to the method described below. The evaluation results are shown in Tables 1 to 4.

[0094] Oil resistance Using rapeseed oil from Nisshin Oillio Co., Ltd. (product name: Nisshin Canola Oil), one drop of oil was placed on oil-resistant paper treated with a water-based oil-resistant agent composition, and the degree of oil penetration was visually checked for 30 minutes after dropping. The criteria are as follows: ◎: (No oil stains or bleed-through after 30 minutes) 〇: (After 30 minutes, there are several pinhole-like oil stains.) △: (Oil stains and bleed-through occur between 5 and 15 minutes) ×: (Oil stains and bleed-through occur within 5 minutes)

[0095] water resistance One drop of water was placed on oil-resistant paper treated with a water-based oil-repellent composition, and the degree of water penetration was visually observed for 30 minutes after the drop. The criteria were as follows: ○: (No water penetrates at all after 30 minutes) △: (Water penetrates within 5 to 15 minutes) ×: (Water penetrates within 5 minutes)

[0096] Air permeability Air permeability was measured in accordance with JAPAN TAPPI Paper and Pulp Testing Method No. 5-2:2000. A Kumagai Riki Kogyo Co., Ltd. Ouken-type air permeability tester (model: 2040-C) was used, 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 1-3 above, paper obtained by impregnating only with cellulose resin (Comparative Example 1) or paper obtained by impregnating only with silicone emulsion (Comparative Example 2) exhibited inferior oil resistance and water resistance. Furthermore, paper obtained by impregnating with compositions in which the total alkenyl number in component (G) was 0.1 mol / 100g or less (Comparative Examples 3-4) exhibited inferior oil resistance. On the other hand, the oil-resistant paper obtained by impregnating it with the water-based oil-resistant composition of the present invention possesses the advantages of both cellulose resin and silicone emulsion, exhibits excellent oil and water resistance, has an air permeability of 30 seconds or less, and has appropriate air permeability for food-grade oil-resistant paper. Furthermore, it was found that there was no significant difference in the performance of the resulting oil-resistant paper whether the silicone emulsion contained components (G) and (H) in the same emulsion (Examples 1-19) or in different emulsions (Example 20). In this invention, the alkenyl value of component (G) is important, and a decrease in the overall alkenyl value of component (G) incorporated into the composition tended to lead to a decrease in oil resistance.

[0102] As shown in Table 4 above, compared to the results of Example 7, which is listed as an example of the composition of the present invention, the composition of Patent Document 5 (Comparative Example 5) did not exhibit oil resistance. In the example of Patent Document 5, it is thought that the composition was applied to the surface of a paper substrate containing a sealant, dried, and a hardened film was formed on the surface of the paper substrate to impart oil resistance. However, when impregnating the paper substrate with the composition to exhibit oil resistance, it was suggested that the total alkenyl value (vinyl value) of component (G) in the composition is important.

[0103] The oil-resistant paper of the present invention has been found to satisfy high oil resistance, water resistance, and air permeability all at once because a cellulosic resin, which is compatible with paper, and an organopolysiloxane, which is water-resistant and air-permeable, are dispersed and physically intertwined within the paper. In order to promote the physical intertwining of the cellulosic resin and the organopolysiloxane, the crosslinking density of the organopolysiloxane is important, and it is necessary to use an organopolysiloxane containing alkenyl groups with a high alkenyl value. [Industrial applicability]

[0104] Oil-resistant paper treated with the water-based oil-resistant composition of the present invention can achieve a combination of oil resistance, water resistance, and breathability. Therefore, the oil-resistant paper of the present invention can be suitably used as packaging paper, packaging containers, or food trays for cooked foods such as fast food, fried foods, and grilled foods that contain a lot of oil and moisture.

Claims

1. The following components (A), (B), (E), and (F): (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) Addition-curing silicone emulsion: 10 to 10,000 parts by mass (E) Water: 1,000 to 50,000 parts by mass (F) Platinum group metal catalyst: catalyst amount A water-based oil-resistant composition containing, The above (B) addition-curing silicone emulsion is (G) Alkenyl group-containing organopolysiloxane having at least two 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 of 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 greater than 0.1 mol / 100 g. (H) Organohydrogenpolysiloxane having at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule: (G) The number of moles of SiH groups in component (H) corresponds to 1 to 5 times the number of moles of alkenyl groups in component (G) by mass, (I) Surfactants: 0.1 to 10% by mass of component (B) and (J) Water: 10 to 90% by mass in component (B) A water-based oil-resistant composition containing the following:

2. The following components (A), (C), (D), (E), and (F): (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 catalyst: catalyst amount A water-based oil-resistant composition containing, The above (C) silicone emulsion, (G) Alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and a viscosity of 5 mPa·s or more at 25°C: 5 to 60% by mass of 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 greater than 0.1 mol / 100 g. (I) Surfactants: 0.1 to 10% by mass of component (C) and (J) Water: 10 to 90% by mass in component (C) It includes, The above (D) silicone emulsion, (H) Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule: (D) 5 to 60% by mass of component (I) Surfactants: 0.1 to 10% by mass of component (D) and (J) Water: 10 to 90% by mass in component (D) A water-based oil-resistant composition comprising the above, wherein the amount 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 cellulose resin component (A) is a cellulose ether obtained by substituting 0.5 to 2.5 hydroxyl groups per glucose ring unit of cellulose with alkoxy groups.

4. The water-based oil-resistant composition according to claim 1 or 2, wherein component (G) comprises at least two types: 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.

5. The water-based oil-resistant 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). 【Chemistry 1】 (In formula (1-1), R 1 R is an organic group containing an alkenyl group having 2 to 10 carbon atoms, 2 (i) is independently 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 numbers greater than or equal to 0, satisfying 0 ≤ a ≤ 3, 2 ≤ 2a + c, and 5 ≤ c + d.)

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

7. 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 polyvinyl alcohol (PVA) resin in component (B).

8. The water-based 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% by mass in component (C) or component (D).

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

10. A method for producing the aqueous oil-resistant composition described in claim 1, (Step 1) A step of mixing and emulsifying the following components (G), (H), (I), and (J) to prepare (B) an addition-curing silicone emulsion. (G) Alkenyl group-containing organopolysiloxane having at least two 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 of 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 greater than 0.1 mol / 100 g. (H) Organohydrogenpolysiloxane having at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule: (G) 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) Surfactants: 0.1 to 10% by mass of component (B) (J) Water: 10 to 90% by mass in component (B) and (Step 2) A step of mixing components (A), (E), and (F) below with 10 to 10,000 parts by mass of the addition-curing silicone emulsion (B) prepared in Step 1 above. (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) Platinum group metal catalyst: catalyst amount A method for producing a water-based oil-resistant composition having the following characteristics.

11. A method for producing the aqueous oil-resistant composition described in claim 2, (Step 1') A step of mixing and emulsifying the components (G), (I), and (J) below to prepare (C) a silicone emulsion. (G) Alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and a viscosity of 5 mPa·s or more at 25°C: 5 to 60% by mass of 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 greater than 0.1 mol / 100 g. (I) Surfactants: 0.1 to 10% by mass of component (C) (J) Water: 10 to 90% by mass in component (C) (Step 1'') A step of mixing and emulsifying the following components (H), (I), and (J) to prepare (D) a silicone emulsion. (H) Organohydrogenpolysiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule: (D) 5 to 60% by mass of component (I) Surfactants: 0.1 to 10% by mass of component (D) (J) Water: 10 to 90% by mass in component (D) and (Step 2') A step of mixing components (A), (E), and (F) below with 5 to 5,000 parts by mass of the (C) silicone emulsion prepared in Step 1' above and an amount of the (D) silicone emulsion prepared in Step 1'' above in which the number of moles of SiH groups of component (H) in component (D) corresponds to 1 to 5 times the number of moles of alkenyl groups of component (G) in component (C). (A) 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) Platinum group metal catalyst: catalyst amount A method for producing a water-based oil-resistant composition having the following characteristics.

12. A method for treating paper to be oil-resistant, comprising adding the aqueous oil-resistant composition described in claim 1 or 2 to a pulp slurry internally or to a paper substrate externally.

13. Oil-resistant paper treated with the water-based oil-resistant agent composition according to claim 1 or 2, wherein the air permeability measured according to the Oken method, measured in accordance with JAPAN TAPPI Paper and Pulp Test Method No. 5-2:2000, is 1,000 seconds or less.

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