WO2025142817A1 - Aqueous oil-resistant agent composition, method for producing aqueous oil-resistant agent composition, method for oil resistance treatment for paper, and oil-resistant paper - Google Patents

Abstract

[Problem] To provide a non-fluorinated resin-based aqueous oil-resistant agent composition with which an 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 resins or an organic solvents in consideration of health aspects and environment aspects. [Solution] An aqueous oil-resistant agent composition containing (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.

Description

Water-based oil-resistant composition, method for producing water-based oil-resistant composition, method for oil-resistant treatment of paper, and oil-resistant paper

The present invention relates to an aqueous oil-resistant composition, a method for producing an aqueous oil-resistant composition, an oil-resistant treatment method for paper, and oil-resistant paper.

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

For grease-resistant paper or grease-resistant containers for food, polyethylene-laminated paper, which has a polyethylene film laminated on one side of a paper base material, has been used, but polyethylene-laminated paper has problems such as low air permeability, which can lead to a deterioration in the flavor and storage stability of food, and poor recyclability because the polyethylene film is difficult to remove when recycling. There is also a strong movement away from plastics, and there is a demand for the development of grease-resistant paper that does not use polyethylene lamination.
Conventionally, fluororesin-based oil-proofing agents have been widely used to impart oil resistance and water resistance to paper, and examples of such methods include a method of coating the surface of a paper base material with a fluororesin-based oil-proofing agent to provide an oil-resistant layer, a method of impregnating a paper base material with a fluororesin-based oil-proofing agent, or a method of adding a fluororesin-based oil-proofing agent to a pulp slurry, etc. However, fluororesin-based oil-proofing agents are undesirable from the standpoint of health and the environment due to their difficulty in decomposing and bioaccumulating, and in recent years, there has been a demand for oil-proofing agents that do not contain fluororesin (non-fluororesin-based oil-proofing agents).

Therefore, hydrophilic resins that form films, such as polyvinyl alcohol (PVA) resins and polysaccharides, are widely used as non-fluorine resin-based oil-resistant agents, and are known to provide excellent oil resistance. For example, Patent Document 1 discloses oil-resistant paper whose surface is coated with a composition containing a PVA resin and a silicone emulsion. In addition, acrylic and paraffin wax emulsions such as those in Patent Documents 2, 3, and 4 are also known to have excellent oil resistance. Furthermore, Patent Document 5 describes a water- and oil-repellent composition that contains a silicone emulsion, a cellulose resin, and a carboxylic acid.

JP 2005-139418 A JP 2013-237941 A JP 2020-122250 A JP 2022-188338 A JP 2006-257159 A

However, in the case of non-fluororesin-based oil-resistant agents, in order to develop oil resistance while preventing the seepage of oil and fat components, it is necessary to make the substrate dense or to use a large amount of a filler or oil-resistant agent. In this case, while the oil resistance is increased, the air permeability becomes insufficient, which is likely to lead 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 substrate, not only is a film-forming composition coated on the surface of the paper substrate, but a filler is also required for the paper substrate, and there is a concern that the air permeability of the resulting grease-resistant paper will decrease. Although the grease-resistant papers described in Patent Documents 2, 3, and 4 have confirmed air permeability, the amount of oil-resistant agent applied is large, and the air permeability is 100 seconds or more in all cases, which is not as good as that of a fluororesin-based oil-resistant agent.
As described above, no greaseproof paper that uses a non-fluororesin-based greaseproofing agent and has both high oil resistance and high air permeability has yet been developed, and there is still room for improvement in this regard.
Therefore, an object of the present invention is to provide an oil-resistant composition capable of producing oil-resistant paper having high oil resistance and high air permeability, which is a non-fluorine resin-based water-based oil-resistant composition containing components that do not contain fluorine resins or organic solvents and that takes into consideration health and environmental aspects.

Means of the Invention The present inventors have conducted extensive research to achieve the above object and have found that the following aqueous oil-resistant agent composition can achieve the above object, thereby completing the present invention.
That is, the present invention provides the following oil-resistant agent composition, etc.

（式（１－１）中、Ｒ¹は独立に、炭素数２～１０のアルケニル基含有有機基であり、Ｒ²は独立に、水酸基、アルコキシ基及びアルケニル基を有さない非置換または置換の１価炭化水素基から選択される１種の基であり、ａ、ｃ、ｄはそれぞれ０以上の数であり、０≦ａ≦３、２≦２ａ＋ｃ、かつ、５≦ｃ＋ｄを満たす数である。）
［６］
　（Ｈ）成分のケイ素原子に結合する水素原子及びケイ素原子に結合する基の合計個数に対するケイ素原子に結合する水素原子の合計個数の割合が１５～５０％である［１］～［５］のいずれか１項に記載の水系耐油剤組成物。
［７］
　（Ｂ）成分のシリコーンエマルジョンが、さらにポリビニルアルコール（ＰＶＡ）系樹脂を、（Ｂ）成分中０．５～１０質量％含むものである［１］及び［３］～［６］のいずれか１項に水系耐油剤組成物。
［８］
　（Ｃ）成分のシリコーンエマルジョン及び（Ｄ）成分のシリコーンエマルジョンの少なくとも一方が、さらにポリビニルアルコール（ＰＶＡ）系樹脂を、（Ｃ）成分中又は（Ｄ）成分中０．５～１０質量％含むものである［２］～［６］のいずれか１項に記載の水系耐油剤組成物。
［９］
　（Ｇ）成分及び（Ｈ）成分の合計質量が、（Ａ）成分１００質量部に対し、６０～２０００質量部である［１］～［８］のいずれか１項に記載の水系耐油剤組成物。
［１０］
　［１］、［３］～［７］及び［９］のいずれか１項に記載の水系耐油剤組成物の製造方法であって、
（工程１）下記（Ｇ）、（Ｈ）、（Ｉ）及び（Ｊ）成分を混合、乳化し、（Ｂ）付加硬化型シリコーンエマルジョンを調製する工程
（Ｇ）ケイ素原子に結合したアルケニル基を１分子中に少なくとも２個有し、２５℃における粘度が５ｍＰａ・ｓ以上のアルケニル基含有オルガノポリシロキサン：（Ｂ）成分中５～４０質量％であり、（Ｇ）成分合計のアルケニル価（（Ｇ）成分合計１００ｇ中に含まれるケイ素原子に結合したアルケニル基のモル数）が０．１ｍｏｌ／１００ｇ超である
（Ｈ）ケイ素原子に結合した水素原子（ＳｉＨ基）を１分子中に少なくとも２個有するオルガノハイドロジェンポリシロキサン：（Ｇ）成分中のアルケニル基のモル数に対して（Ｈ）成分中のＳｉＨ基のモル数が１～５倍に相当する質量％
（Ｉ）界面活性剤：（Ｂ）成分中０．１～１０質量％
（Ｊ）水：（Ｂ）成分中１０～９０質量％
並びに
（工程２）下記（Ａ）、（Ｅ）及び（Ｆ）成分と、上記（工程１）で調製した（Ｂ）付加硬化型シリコーンエマルジョン１０～１０,０００質量部とを混合する工程
（Ａ）２％水溶液の２０℃での粘度が２～１０,０００ｍＰａ・ｓのセルロース系樹脂：１００質量部
（Ｅ）水：１，０００～５０,０００質量部
（Ｆ）白金族金属系触媒：触媒量
を有する、水系耐油剤組成物の製造方法。
［１１］
　［２］～［６］、［８］及び［９］のいずれか１項に記載の水系耐油剤組成物の製造方法であって、
（工程１’）下記（Ｇ）、（Ｉ）及び（Ｊ）成分を混合、乳化し、（Ｃ）シリコーンエマルジョンを調製する工程
（Ｇ）ケイ素原子に結合したアルケニル基を１分子中に少なくとも２個有し、２５℃における粘度が５ｍＰａ・ｓ以上のアルケニル基含有オルガノポリシロキサン：（Ｃ）成分中５～６０質量％であり、（Ｇ）成分合計のアルケニル価（（Ｇ）成分合計１００ｇ中に含まれるケイ素原子に結合したアルケニル基のモル数）が０．１ｍｏｌ／１００ｇ超である
（Ｉ）界面活性剤：（Ｃ）成分中０．１～１０質量％
（Ｊ）水：（Ｃ）成分中１０～９０質量％
（工程１’’）下記（Ｈ）、（Ｉ）及び（Ｊ）成分を混合、乳化し、（Ｄ）シリコーンエマルジョンを調製する工程
（Ｈ）ケイ素原子に結合した水素原子を１分子中に少なくとも２個有するオルガノハイドロジェンポリシロキサン：（Ｄ）成分中５～６０質量％
（Ｉ）界面活性剤：（Ｄ）成分中０．１～１０質量％
（Ｊ）水：（Ｄ）成分中１０～９０質量％
並びに
（工程２’）下記（Ａ）、（Ｅ）及び（Ｆ）成分と、上記（工程１’）で調製した（Ｃ）シリコーンエマルジョン５～５,０００質量部と、上記（工程１’’）で調製した（Ｄ）シリコーンエマルジョン（Ｄ）成分中の（Ｈ）成分のＳｉＨ基のモル数が、（Ｃ）成分中の（Ｇ）成分のアルケニル基のモル数の１～５倍に相当する量とを混合する工程
（Ａ）２％水溶液の２０℃での粘度が２～１０,０００ｍＰａ・ｓのセルロース系樹脂：１００質量部
（Ｅ）水：１，０００～５０,０００質量部
（Ｆ）白金族金属系触媒：触媒量
を有する、水系耐油剤組成物の製造方法。
［１２］
　［１］～［９］のいずれか１項に記載の水系耐油剤組成物を、パルプスラリーに内添処理又は紙基材に外添処理する、紙の耐油処理方法。
［１３］
　ＪＡＰＡＮ　ＴＡＰＰＩ　紙パルプ試験方法　Ｎｏ．５－２：２０００に準じて測定した王研式透気度による透気度が１，０００秒以下である、［１］～［９］のいずれか１項に記載の水系耐油剤組成物により処理された耐油紙。 [1]
The following components (A), (B), (E) and (F):
(A) 100 parts by mass of a cellulose-based resin having a viscosity of 2 to 10,000 mPa·s in a 2% aqueous solution at 20°C; (B) 10 to 10,000 parts by mass of an addition-curing silicone emulsion; (E) 1,000 to 50,000 parts by mass of water; and (F) a catalytic amount of a platinum group metal catalyst,
The addition curing silicone emulsion (B) is
(G) an alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms per molecule and having a viscosity of 5 mPa·s or more at 25° C., which accounts for 5 to 40 mass% of component (B), and the total alkenyl value of component (G) (the number of moles of alkenyl groups bonded to silicon atoms contained in a total of 100 g of component (G)) exceeds 0.1 mol/100 g;
(H) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms (SiH groups) per molecule: mass% 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) Surfactant: 0.1 to 10% by mass in component (B) and (J) Water: 10 to 90% by mass in component (B)
The water-based oil-resistant composition comprises:
[2]
The following components (A), (C), (D), (E) and (F):
(A) 100 parts by mass of a cellulose-based resin having a viscosity of 2 to 10,000 mPa·s in a 2% aqueous solution at 20°C; (C) 5 to 5,000 parts by mass of a silicone emulsion; (D) 1,000 to 50,000 parts by mass of a silicone emulsion; (E) 1,000 to 50,000 parts by mass of water; and (F) a catalytic amount of a platinum group metal catalyst,
The silicone emulsion (C) is
(G) an alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms per molecule and having a viscosity of 5 mPa·s or more at 25° C., which accounts for 5 to 60 mass% of component (C), and the total alkenyl value of component (G) (the number of moles of alkenyl groups bonded to silicon atoms contained in a total of 100 g of component (G)) exceeds 0.1 mol/100 g;
(I) Surfactant: 0.1 to 10% by mass in component (C) and (J) Water: 10 to 90% by mass in component (C)
and
The silicone emulsion (D) is
(H) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms per molecule: 5 to 60 mass% of component (D);
(I) Surfactant: 0.1 to 10% by mass in component (D) and (J) Water: 10 to 90% by mass in component (D)
wherein the content of component (D) in the composition is an amount 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).
[3]
The aqueous oil-resistant composition according to [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 composition according to any one of [1] to [3], wherein the component (G) contains at least two types of linear organopolysiloxanes: a linear organopolysiloxane containing alkenyl groups only at both ends; and a linear organopolysiloxane containing alkenyl groups in a side chain and at both ends.
[5]
The aqueous oil-resistant composition according to any one of [1] to [4], wherein the component (G) is a linear alkenyl-containing organopolysiloxane represented by the following average composition formula (1-1):

(In formula (1-1), R ¹ is independently an alkenyl-containing organic group having 2 to 10 carbon atoms, R ² is independently a group selected from unsubstituted or substituted monovalent hydrocarbon groups having no hydroxyl group, alkoxy group, or alkenyl group, and a, c, and d are each a number of 0 or more that satisfies 0≦a≦3, 2≦2a+c, and 5≦c+d.)
[6]
The aqueous oil-resistant composition according to any one of [1] to [5], 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 groups bonded to silicon atoms is 15 to 50%.
[7]
The aqueous oil-resistant composition according to any one of [1] and [3] to [6], wherein the silicone emulsion of the component (B) further contains a polyvinyl alcohol (PVA)-based resin in an amount of 0.5 to 10 mass% in the component (B).
[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 component (C) and the silicone emulsion of the component (D) further contains a polyvinyl alcohol (PVA)-based resin in an amount of 0.5 to 10 mass% in the component (C) or the component (D).
[9]
The aqueous oil resistant composition according to any one of [1] to [8], wherein the total mass of the component (G) and the component (H) is 60 to 2000 parts by mass per 100 parts by mass of the component (A).
[10]
A method for producing the aqueous oil-resistant composition according to any one of [1], [3] to [7], and [9], comprising the steps of:
(Step 1) A step of preparing an addition-curable silicone emulsion (B) by mixing and emulsifying the following components (G), (H), (I), and (J): (G) an alkenyl-group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms per molecule and having a viscosity of 5 mPa·s or more at 25°C: (H) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms (SiH groups) per molecule, which accounts for 5 to 40% by mass of component (B) and has an alkenyl value of component (G) in total (the number of moles of alkenyl groups bonded to silicon atoms contained in a total of 100 g of component (G)) of greater than 0.1 mol/100 g: (H) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms (SiH groups) per molecule, which corresponds 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) Surfactant: 0.1 to 10% by mass in component (B)
(J) Water: 10 to 90% by mass in component (B)
and (Step 2) mixing the following components (A), (E), and (F) with 10 to 10,000 parts by mass of the addition-curable silicone emulsion (B) prepared in (Step 1) above, comprising: (A) 100 parts by mass of a cellulose-based resin having a viscosity of 2 to 10,000 mPa·s as a 2% aqueous solution at 20°C; (E) 1,000 to 50,000 parts by mass of water; and (F) a catalytic amount of a platinum group metal catalyst.
[11]
A method for producing the aqueous oil-resistant composition according to any one of [2] to [6], [8] and [9], comprising the steps of:
(Step 1') A step of preparing a silicone emulsion (C) by mixing and emulsifying the following components (G), (I), and (J): (G) an alkenyl-group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms per molecule and having a viscosity of 5 mPa·s or more at 25° C.: 5 to 60 mass% of component (C), and (I) a surfactant in which the alkenyl value of component (G) in total (the number of moles of alkenyl groups bonded to silicon atoms contained in a total of 100 g of component (G)) exceeds 0.1 mol/100 g: 0.1 to 10 mass% of component (C).
(J) Water: 10 to 90% by mass in component (C)
(Step 1″) A step of preparing a silicone emulsion (D) by mixing and emulsifying the following components (H), (I), and (J): (H) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms per molecule: 5 to 60% by mass of component (D);
(I) Surfactant: 0.1 to 10% by weight of component (D)
(J) Water: 10 to 90% by mass in component (D)
and (Step 2') a process for producing an aqueous oil resistant composition comprising the following components (A), (E) and (F): (A) 100 parts by mass of a cellulose-based resin having a viscosity of 2 to 10,000 mPa s as a 2% aqueous solution at 20°C; (E) 1,000 to 50,000 parts by mass of water; and (F) a catalytic amount of a platinum group metal catalyst.
[12]
A method for treating oil resistance of paper, comprising adding the aqueous oil-proofing agent composition according to any one of [1] to [9] to a pulp slurry for internal treatment or to a paper substrate for external treatment.
[13]
[1]-[9], wherein the air permeability according to Oken air permeability measured in accordance with JAPAN TAPPI Paper and Pulp Testing Method No. 5-2:2000 is 1,000 seconds or less.

The present invention combines a cellulose-based resin, which has excellent affinity with paper, with a silicone, which has good water resistance and air permeability, thereby achieving the advantages of both materials. By treating a paper base material with a composition that combines materials having a specific structure of the present invention under specific conditions and then curing it, it is possible to obtain grease-resistant paper that has excellent oil and water resistance and high air permeability.
Furthermore, the greaseproof paper of the present invention has high air permeability, so when food is wrapped in it, it can prevent oil stains without impairing the flavor of the food.
Furthermore, the cellulose resin and silicone contained in the aqueous oil-resistant agent composition of the present invention are both environmentally safe and harmless materials, and can be suitably used as substitutes for 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 hazards caused by the use of organic solvents. Paper substrates treated with the composition of the present invention are easily recycled and become products with low environmental impact, and can solve the harmfulness and environmental problems caused by fluorine compounds.

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

(A) Cellulosic Resin The cellulose resin of component (A) is a compound in which different substituents are introduced into the hydroxyl groups contained in the cellulose molecule by chemical modification.
The viscosity of the cellulose resin in a 2% aqueous solution at 20°C is 2 to 10,000 mPa·s, 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 is insufficient, and if it exceeds 10,000 mPa·s, the coatability of the composition is poor. The viscosity at 20°C is a value measured with a BM type viscometer (for example, manufactured by Tokyo Keiki Co., Ltd.) at 20°C. The rotor, rotation speed, and rotation time are appropriately selected according to the viscosity based on the usual method (same below).

Cellulose-based resins suitable for use in the present invention are cellulose ethers in which the hydroxyl groups of cellulose are substituted by reacting with an etherifying agent; esterified cellulose esters are preferred, with cellulose ethers being particularly preferred. Many of these cellulose ethers are approved as food additives, pharmaceuticals, and cosmetic ingredients, and are not only harmless to the human body, but are also known to be extremely environmentally friendly materials that are slowly biodegradable.

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

The degree of substitution of cellulose ethers or cellulose esters is the number of hydroxyl groups substituted by an 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, the solubility in water may be low, and the workability of producing the composition may be deteriorated, while 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 kinds of substituents, the total value of the degrees of substitution of the two or more kinds of substituents is preferably 0.5 to 2.5, more preferably 0.8 to 2.2, and even more preferably 1.0 to 2.0.

In the present invention, commercially available cellulose ethers can be used. Specific examples of such cellulose ethers include METHOCEL, ETHOCEL (manufactured by Dow Chemical), NATROSOL (manufactured by Hercules), HEC Daicel, CMC Daicel (manufactured by Daicel Chemical Industries, Ltd.), Fujichemi HEC (manufactured by Sumitomo Seikagaku Co., Ltd.), Cellogen (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and Metrose (manufactured by Shin-Etsu Chemical Co., Ltd.).
The cellulose-based resin of the component (A) may use one type alone, or two or more types in combination.

The content of component (A) in the composition of the present invention is preferably from 3 to 50 mass %, and more preferably from 5 to 40 mass %, based on the total amount of components excluding water.
The total amount of components excluding water is the combined amount of (E) water in the composition, as well as (B) addition curable silicone emulsion, (C) silicone emulsion, (D) silicone emulsion, and (K) catalyst composition other than (J) water, which will be described below.

The aqueous oil-resistant composition of the present invention comprises, as the silicone emulsion,
Contains <1> (B) an addition curing type silicone emulsion or <2> (C) a silicone emulsion and (D) a silicone emulsion.
(B) The addition-curable silicone emulsion contains (G) an alkenyl-containing organopolysiloxane, (H) an organohydrogenpolysiloxane, (I) a surfactant, and (J) water.
The (C) silicone emulsion contains (G) an alkenyl group-containing organopolysiloxane, (I) a surfactant, and (J) water.
The (D) silicone emulsion contains (H) an organohydrogenpolysiloxane, (I) a surfactant, and (J) water.
Components (G) to (J) will be described later.
In this specification, an aqueous oil-resistant composition containing the (B) addition curing type silicone emulsion may be referred to as an "aqueous oil-resistant composition <1>", and an aqueous oil-resistant composition containing the (C) silicone emulsion and the (D) silicone emulsion may be referred to as an "aqueous oil-resistant composition <2>".

The emulsification for obtaining the components (B) to (D) may be carried out using a general emulsifying disperser. Examples of the emulsifying disperser include a high-speed rotating centrifugal radiation type agitator such as a homodisper, a high-speed rotating shear type agitator such as a homomixer, a high-pressure jet type emulsifying disperser such as a pressure homogenizer, a colloid mill, and an ultrasonic emulsifying machine. The volume average particle size of each of the obtained emulsions of the components (B) to (D) measured by a laser diffraction/scattering type particle size distribution measuring device is preferably 50 to 10,000 nm, and more preferably 100 to 1,500 nm.

(B) Addition-curable silicone emulsion The amount of 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, per 100 parts by mass of component (A). If the amount of component (B) is less than 10 parts by mass per 100 parts by mass of component (A), water resistance will be insufficient, and if it exceeds 10,000 parts by mass, oil resistance will be insufficient.

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.

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

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 above, emulsification becomes difficult, and if it is more than the upper limit above, oil resistance and water resistance become poor.

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 above, dispersion becomes difficult, and if it is more than the upper limit above, the stability of the emulsion over time decreases.

In the aqueous oil-resistant composition <1>, the total mass of the (G) and (H) components is preferably 60 to 2,000 parts by mass, more preferably 150 to 1,000 parts by mass, and even more preferably 200 to 500 parts by mass, per 100 parts by mass of the (A) component.

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

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.

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 above, emulsification becomes difficult, and if it is more than the upper limit above, oil resistance and water resistance become poor.

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 above, dispersion becomes difficult, and if it is more than the upper limit above, the stability of the emulsion over time decreases.

(D) Organohydrogenpolysiloxane-Containing Silicone Emulsion The amount of component (D) blended is a mass % equivalent 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). If the amount of component (D) blended is outside the above range, the oil resistance and water resistance will be reduced.

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.

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 above, emulsification becomes difficult, and if it is more than the upper limit above, oil resistance and water resistance become poor.

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 above, dispersion becomes difficult, and if it is more than the upper limit above, the stability of the emulsion over time decreases.

In the aqueous oil-resistant composition <2>, the total mass of the (G) and (H) components is preferably 60 to 2,000 parts by mass, more preferably 150 to 1,000 parts by mass, and even more preferably 200 to 500 parts by mass, per 100 parts by mass of the (A) component.

(G) Alkenyl Group-Containing Organopolysiloxane Component (G) is an organopolysiloxane that has at least two alkenyl groups bonded to silicon atoms in each molecule and has a viscosity of 5 mPa·s or greater 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, and oil resistance is reduced, which is not preferred. 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.

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

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

There are no particular limitations on the molecular structure of component (G) and it may be any of a straight-chain, branched, or cyclic structure, although a straight-chain structure is preferred.
The component (G) may be used alone or in combination of two or more. When two or more components (G) are used in combination, the average alkenyl value calculated from the total of the components (G) should exceed 0.1 mol/100 g.
In addition, when two or more types of component (G) are used in combination, their molecular structures are not particularly limited, but it is preferable to use in combination a linear organopolysiloxane containing alkenyl groups only at both ends and a linear organopolysiloxane containing alkenyl groups at a side chain and both ends, and it is more preferable to use in combination organopolysiloxanes in which the alkenyl value of each exceeds 0.1 mol/100 g.

（式（１）中、Ｒ¹は独立に、炭素数２～１０のアルケニル基含有有機基であり、Ｒ²は独立に、水酸基、アルコキシ基及びアルケニル基を有さない非置換または置換の１価炭化水素基から選択される１種の基であり、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇは互いに独立に、０以上の数であり、０≦ａ≦３、１≦ｂ、２≦ａｂ＋ｃ＋ｅ、かつ、５≦ｂ＋ｃ＋ｄ＋ｅ＋ｆ＋ｇを満たす数である。） Component (G) is a component for imparting oil resistance and water resistance to the composition, and specific examples thereof include those having a structure represented by average composition formula (1).

(In formula (1), R ¹ is independently an alkenyl-containing organic group having 2 to 10 carbon atoms, R ² is independently a group selected from unsubstituted or substituted monovalent hydrocarbon groups having no hydroxyl group, alkoxy group, or alkenyl group, and a, b, c, d, e, f, and g are independently numbers of 0 or more that satisfy 0≦a≦3, 1≦b, 2≦ab+c+e, and 5≦b+c+d+e+f+g.)

^R1 is an alkenyl-containing organic group having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 6 carbon atoms. Examples of ^R1 include alkenyl groups such as vinyl, allyl, and hexenyl.

^R2 is a group selected from unsubstituted or substituted monovalent hydrocarbon groups that do not contain a hydroxyl group, an alkoxy group, or an alkenyl group.
Examples of the alkoxy group represented by ^R2 include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group.
The unsubstituted or substituted monovalent hydrocarbon group having no alkenyl group represented by ^R2 preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms. Examples of the unsubstituted or substituted monovalent hydrocarbon group include alkyl groups preferably having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, and butyl groups; cycloalkyl groups preferably having 5 to 8 carbon atoms, such as cyclohexyl groups; aryl groups preferably having 6 to 10 carbon atoms, such as phenyl and tolyl groups; and aralkyl groups preferably having 7 to 10 carbon atoms, such as benzyl groups. Among these, the unsubstituted or substituted monovalent hydrocarbon group is preferably a methyl group or a phenyl group, and particularly preferably a methyl group.
In the alkenyl-containing organopolysiloxane represented by formula (1), the ratio of the number of methyl groups to the total number of ^R2's is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.

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

　式（１－１）中、Ｒ¹及びＲ²は、それぞれ、式（１）と同義であり、ａ、ｃ、ｄはそれぞれ０以上の数であり、０≦ａ≦３、２≦２ａ＋ｃかつ５≦ｃ＋ｄを満たす数である。
　また、式（１－１）中、側鎖にアルケニル基を有する場合（１≦ｃ）は、２≦ｃ≦５００、３≦ｄ≦４，０００であることがより好ましく、５≦ｃ≦１００、３≦ｄ≦５００であることが更に好ましく、１０≦ｃ≦５０、３≦ｄ≦３００であることが特に好ましい。
　また、式（１－１）中、側鎖にアルケニル基を有さない場合（ｃ＝０）は、３≦ｄ≦３０であることがより好ましく、３≦ｄ≦２０であることが更に好ましい。 The alkenyl-containing organopolysiloxane represented by formula (1) is particularly preferably linear, that is, one represented by the following formula (1-1) in which b=2 and e=f=g=0 in formula (1).

In formula (1-1), R ¹ and R ² are defined as in formula (1), and a, c, and d are each a number of 0 or more that satisfies 0≦a≦3, 2≦2a+c, and 5≦c+d.
In addition, in formula (1-1), when an alkenyl group is present in a side chain (1≦c), it is more preferable that 2≦c≦500, 3≦d≦4,000, further preferably that 5≦c≦100, 3≦d≦500, and particularly preferably that 10≦c≦50, 3≦d≦300.
In addition, in formula (1-1), when there is no alkenyl group in the side chain (c=0), it is more preferable that 3≦d≦30, and further more preferable that 3≦d≦20.

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

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

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

（式（２）中、Ｒ³は互いに独立に、水酸基又は脂肪族不飽和結合を有さない置換もしくは非置換の炭素原子数１～１０の１価炭化水素基である。ｈは０または１であり、ｉ及びｊは、０≦ｉ≦２００、０≦ｊ≦２００の数であり、２≦２ｈ＋ｉ≦２００及び３≦ｉ＋ｊ＋２≦４００を満たす数である。） The molecular structure of component (H) may be linear, branched, cyclic, or three-dimensional network structure, or may be a mixture of these. The SiH groups of component (H) may be located at either the terminal or middle of the molecular chain, or may be located at both. Component (H) is preferably a linear organohydrogenpolysiloxane represented by the following formula (2).

(In formula (2), ^R3 's are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms that does not have a hydroxyl group or an aliphatic unsaturated bond. h is 0 or 1, and i and j are numbers that satisfy 0≦i≦200, 0≦j≦200, and 2≦2h+i≦200 and 3≦i+j+2≦400.)

In the above formula (2), ^R3 's are each independently a hydroxyl group or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms that does not have an aliphatic unsaturated bond. The monovalent hydrocarbon group having no aliphatic unsaturated bond of ^R3 is preferably an alkyl group or an aryl group, more preferably a methyl group, an ethyl group, a propyl group, or a phenyl group, and particularly preferably a methyl group.

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

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

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

(I) Surfactant The (I) component is a surfactant, and is not particularly limited as long as it can emulsify and disperse the (G) component and the (H) component in water, but it is preferable that it contains a nonionic surfactant. Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl 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 these, polyoxyethylene lauryl ether, polyoxyethylene oxypropylene lauryl ether, polyoxyethylene acetylene glycol ether, polyoxyethylene sorbitan monolaurate and polyoxyethylene styrenated phenyl ether are preferred, and polyoxyethylene lauryl ether and polyoxyethylene styrenated phenyl ether are more preferred.
The nonionic surfactant may be used alone or in combination of two or more. In order to obtain a stable emulsion composition, it is preferable that the nonionic surfactants used alone or in combination as a whole have an HLB of 10 to 15.

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

In each silicone emulsion of the (B), (C) and (D) components, a water-soluble resin may be used as an emulsification aid together with a surfactant in order to aid in the emulsification of the (G) and (H) components and improve stability. Examples of the water-soluble resin include PVA-based resins, cellulose derivatives and carboxyvinyl polymers, with PVA-based resins being more preferred. The PVA-based resin is preferably one having a viscosity of 10 to 50 mPa·s in a 4% aqueous solution at 20°C and a saponification degree of 85 to 95 mol%, more preferably one having 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 for the emulsification aid that has as little catalytic poisoning as possible against the platinum group metal catalyst of the (F) component described below.
The amount of the water-soluble resin is preferably the minimum amount that provides sufficient stability for the silicone emulsion, similar to the above-mentioned surfactant. For example, it is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the total of the (G) and (H) components. If the amount of the water-soluble resin is more than the upper limit, the addition reaction may be inhibited, resulting in a decrease in oil resistance and water resistance, whereas if it is less than the lower limit, it is difficult to obtain a stabilizing effect.

(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.

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

(E) Water Component (E) is water, and the same as component (J) described above can be used. The content of component (E) in the aqueous oil-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, per 100 parts by mass of component (A). If the content of component (E) is less than 1,000 parts by mass per 100 parts by mass of component (A), handling properties will deteriorate, and if it is more than 50,000 parts by mass, the coating amount will decrease, resulting in insufficient oil resistance.
The content of component (E) in the aqueous oil-resistant composition of the present invention is preferably within the above range per 100 parts by mass of component (A), and is preferably 400 to 5,000 parts by mass, more preferably 1,000 to 3,000 parts by mass, and particularly preferably 1,500 to 2,000 parts by mass per 100 parts by mass of components (A), (G), and (H). When the content of component (E) in the aqueous oil-resistant composition is within the above range, the composition has good handleability and a good balance between oil resistance and coating amount, which is preferable.

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

The amount of platinum group metal catalyst added may be any catalytic amount. For example, in order to obtain a good cured coating and from an economical standpoint, the amount is preferably in the range of 1 to 1,000 ppm, more preferably 10 to 500 ppm, and particularly preferably 20 to 200 ppm, of platinum group metal relative to the total mass of components (G) and (H). If the amount of component (F) is less than the lower limit above, curing may be insufficient, and if it is more than the upper limit above, costs may increase.

The aqueous oil-resistant composition of the present invention may contain the component (F) as a mixture with the surfactant (I) and water (E).
That is, the aqueous oil-resistant composition <1> is
Components (A), (B), (E) and (K):
(A) 100 parts by mass of a cellulose-based resin having a viscosity of 2 to 10,000 mPa·s in a 2% aqueous solution at 20°C; (B) 10 to 10,000 parts by mass of an addition-curing silicone emulsion; (E) 1,000 to 50,000 parts by mass of water; (K) a water-based oil-resistant composition containing a catalyst composition,
The addition curing silicone emulsion (B) is
(G) an alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms per molecule and having a viscosity of 5 mPa·s or more at 25° C., which accounts for 5 to 40 mass% of component (B), and the total alkenyl value of component (G) (the number of moles of alkenyl groups bonded to silicon atoms contained in a total of 100 g of component (G)) exceeds 0.1 mol/100 g;
(H) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms (SiH groups) per molecule: mass% 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) Surfactant: 0.1 to 10% by mass in component (B) and (J) Water: 10 to 90% by mass in component (B)
and
The catalyst composition (K) is
The oil-resistant composition may be a water-based oil-resistant composition comprising (F) a platinum group metal catalyst, (I) a surfactant, and (J) water.

The aqueous oil-resistant composition <2> is
Components (A), (C), (D), (E) and (K):
(A) a cellulose resin having a viscosity of 2 to 10,000 mPa·s in a 2% aqueous solution at 20°C: 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 water-based oil-resistant composition comprising a catalyst composition,
The silicone emulsion (C) is
(G) an alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms per molecule and having a viscosity of 5 mPa·s or more at 25° C., which accounts for 5 to 60 mass% of component (C), and the total alkenyl value of component (G) (the number of moles of alkenyl groups bonded to silicon atoms contained in a total of 100 g of component (G)) exceeds 0.1 mol/100 g;
(I) Surfactant: 0.1 to 10% by mass in component (C) and (J) Water: 10 to 90% by mass in component (C)
and
The silicone emulsion (D) is
(H) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms per molecule: 5 to 60 mass% of component (D);
(I) Surfactant: 0.1 to 10% by mass in component (D) and (J) Water: 10 to 90% by mass in component (D)
the content of component (D) in the composition is an amount 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);
The catalyst composition (K) is
The oil-resistant composition may be a water-based oil-resistant composition comprising (F) a platinum group metal catalyst, (I) a surfactant, and (J) water.

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

The aqueous oil-resistant composition of the present invention may further contain preservatives, defoamers, fragrances, thickeners, antioxidants, rust inhibitors, pigments, fillers, organic powders, inorganic powders, etc., within the range not impairing the effects of the present invention. The amounts of these substances are selected from the appropriate amounts for each.
From the viewpoint of safety, each component of the aqueous oil-proofing composition of the present invention is preferably composed only of compounds included in the positive list prescribed by the Ministry of Health, Labor and Welfare and the Japan Paper Association (Article 18, paragraph 3 of the revised Food Sanitation Act and Notification No. 370, the positive list of chemical substances related to paper and paperboard intended to come into contact with food).

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

A more preferable method for producing the aqueous oil-resistant composition <1> is as follows:
Examples of the method include a method having the steps of: (Step 1) mixing and emulsifying components (G), (H), (I), and (J) to prepare an addition curing type silicone emulsion (B); (Step 2-1) mixing components (A) and (E) to prepare an aqueous solution of component (A); (Step 2-2) mixing components (F), (I), and (J) to prepare a catalyst composition (K); and (Step 2-3) mixing the addition curing type silicone emulsion (B) prepared in (Step 1) above, the aqueous solution of component (A) prepared in (Step 2-1) above, and the catalyst composition (K) prepared in (Step 2-2) above.

The aqueous oil-resistant composition <2> of the present invention can be produced by mixing (A) a cellulose-based resin, (C) a silicone emulsion, (D) a silicone emulsion, (E) water, and (F) a platinum group metal catalyst.
The order of adding each component is not particularly limited, but a preferred method for producing the aqueous oil-resistant composition <2> is as follows:
Examples of the method include a method having a step of (Step 1') mixing and emulsifying components (G), (I), and (J) to prepare a silicone emulsion (C); (Step 1'') mixing and emulsifying components (H), (I), and (J) to prepare a silicone emulsion (D); and (Step 2') 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.

A more preferable method for producing the aqueous oil-resistant composition <2> is as follows:
Examples of the method include a method having a step of: (Step 1') mixing and emulsifying components (G), (I), and (J) to prepare a silicone emulsion (C); (Step 1''); mixing and emulsifying components (H), (I), and (J) to prepare a silicone emulsion (D); (Step 2'-1) mixing components (A) and (E) to prepare an aqueous solution of component (A); (Step 2'-2) mixing components (F), (I), and (J) to prepare a catalyst composition (K); and (Step 2'-3) mixing the silicone emulsion (C) prepared in (Step 1'), the silicone emulsion (D) prepared in (Step 1''), the aqueous solution of component (A) prepared in (Step 2'-1), and the catalyst composition (K) prepared in (Step 2'-2).

(Step 1) Preparation of (B) Addition-Cure Silicone Emulsion Component (B) can be produced by a known method, for example by mixing predetermined amounts of components (G), (H), and (I) with a portion of water (J) using a stirring device capable of high shear such as a planetary mixer, a combination mixer, or a high-pressure homogenizer, emulsifying by a phase inversion method, and diluting by adding the remainder of water (J).
When preparing the (B) addition-curable silicone emulsion, the (A) component, the (F) component, the water-soluble resin acting as the emulsifying aid described above, and other components such as a catalyst activity inhibitor may each be mixed in a predetermined amount.

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

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

(Step 2) Mixing components (A), (E), and (F) with component (B) (Step 2') Mixing components (A), (E), and (F) with component (C) and component (D) In (Step 2) and (Step 2'), each component only needs to be mixed uniformly, and each component may be mixed using a known mixing device. From the viewpoint of emulsion stability, mixing is preferably performed at 10 to 30°C.

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

(Step 2-2), (Step 2'-2) Preparation of (K) Catalyst Composition Although the component (F) may be mixed during the production of the addition-curable silicone emulsion (B), it is preferable to mix the component (F), the surfactant (I) and water (J) prior to mixing with the other components, and then mix this mixture with the other components to form the (K) catalyst composition.
The catalyst composition (K) may be produced using an apparatus capable of mixing the components. A method in which the components are mixed using an agitation apparatus capable of high shear, such as a planetary mixer, a combination mixer, or a high-pressure homogenizer, and then emulsified by a phase inversion method to form an emulsion is preferred.

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

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

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

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

[0043] The method for applying the aqueous oil-resistant agent composition is preferably a method of applying the composition to a paper substrate by external addition. Examples of the method include a method of applying the composition using a bar coater, a knife coater, a size press coater, a roll coater, a reverse roll coater, an air knife coater, a calendar, a gate roll coater, a blade coater, a curtain coater, a gravure coater, a rod metering coater, a two-roll size press, or the like.
In order to increase the air permeability of grease-resistant paper, it is preferable to use an external addition treatment in which the aqueous oil-resistant composition penetrates into the interior of the paper base material, rather than coating the aqueous oil-resistant composition only on the surface of the paper base material, and it is particularly preferable to use a pond-type size press for impregnation treatment.
The amount of the aqueous oil-resistant composition (solid content after drying) is not particularly limited, but is preferably about 0.1 to 10 g/m ² , more preferably about 0.5 to 3 g/m ² , and even more preferably about 0.5 to 2 g/m ^2. If the amount of the aqueous oil-resistant composition is within the above range, excellent oil resistance and air permeability are obtained, which is preferable.

After the coating process, the paper substrate is heat-treated to dry the water-based oil-resistant composition. Examples of heat sources include hot air dryers, infrared heaters, and rotary dryers. Drying conditions include a temperature of preferably 80 to 180°C, more preferably 100 to 150°C, and even more preferably 120 to 150°C. From the viewpoints of productivity and the addition reaction of the 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.

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 Test Method No. 5-2:2000. The air permeability of the grease-resistant paper is not particularly limited as it depends on the paper base material and coating method, but is preferably 1000 seconds or less, more preferably 500 seconds or less, and even more preferably 5 to 300 seconds. There is no lower limit to the air permeability of the grease-resistant paper, but it can be set to, for example, 5 seconds. It is preferable for the air permeability of the grease-resistant paper to be 1000 seconds or less, since this does not reduce the flavor or storage stability of food packaged using the grease-resistant paper.

The present invention will be specifically described below using examples and comparative examples, but the present invention is not limited to these.
The viscosities of the component (A) and the PVA emulsification aid given below are all values measured using a BM type viscometer at 20° C. The viscosities of the 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 in accordance with JIS K 0070.
In the following, Me and Vi represent a methyl group and a vinyl group, respectively.

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

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

(G) Component (G-1)
(ViMe ₂ SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₁₂₀ (ViMeSiO _2/2 ) ₁₈
Vinyl value: 0.187 mol/100 g, viscosity: 300 mPa·s
(G-2)
(ViMe ₂ SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₁₀
Vinyl value: 0.211 mol/100 g, viscosity: 9.0 mPa·s
(G-3)
(ViMe ₂ SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₉₅ (ViMeSiO _2/2 ) ₃
Vinyl value: 0.070 mol/100 g, viscosity: 300 mPa·s
(G-4)
(ViMe ₂ SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₄₃
Vinyl value: 0.063 mol/100 g, viscosity: 60 mPa·s
(G-5)
(ViMe ₂ SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) _x (ViMeSiO _2/2 ) _y
Vinyl value: 0.13 mol/100 g, rubber-like at 25° C., viscosity of a solution dissolved in toluene to give a concentration of 30% by mass is 7,000 mPa·s, x+y is a value that satisfies the above viscosity, x/y=9
(G′-1)
(ViMe ₂ SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₁₆₀ (ViMeSiO _2/2 ) ₂
Vinyl value: 0.03 mol/100 g, viscosity: 400 mPa·s

(H) Component (H-1)
(Me ₃ SiO _1/2 ) ₂ (MeHSiO _2/2 ) ₇₀ (Me ₂ SiO _2/2 ) ₂₈
SiH group content: 1.08 mol/100 g, viscosity: 122 mPa・s
(H-2)
(Me ₃ SiO _1/2 ) ₂ (MeHSiO _2/2 ) ₄₅ (Me ₂ SiO _2/2 ) ₁₇
SiH group content: 1.10 mol/100 g, viscosity: 44 mPa・s
(H-3)
(Me ₃ SiO _1/2 ) ₂ (MeHSiO _2/2 ) ₅₀ (Me ₂ SiO _2/2 ) ₄₈
SiH group content: 0.75 mol/100 g, viscosity: 117 mPa・s
(H-4)
(Me ₃ SiO _1/2 ) ₂ (MeHSiO _2/2 ) ₈₀ (Me ₂ SiO _2/2 ) ₁₀₀
SiH group content: 0.65 mol/100 g, viscosity: 370 mPa・s
(H-5)
(Me ₃ SiO _1/2 ) ₂ (MeHSiO _2/2 ) ₃₈
SiH group content: 1.60 mol/100 g, viscosity: 20 mPa・s

(I) Component (I-1) Polyoxyethylene styrenated phenyl ether (trade name: Noigen EA-137, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) HLB: 13.0
(I-2) Polyoxyethylene lauryl ether (product 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 (product name: Surfynol PSA-336, manufactured by Evonik Co., Ltd.)

A. Preparation of Emulsion Preparation of Addition-Cure Silicone Emulsion (B) [Preparation Example 1]
A 5-liter composite emulsifier (TK Combimix M type, product name of Primix Corporation) having an anchor-shaped stirring blade capable of stirring the entire inside of the vessel and a rotatable disk having small tooth-shaped protrusions alternately provided 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 solution of PVA (manufactured by Mitsubishi Chemical Corporation, product name: GM-14L, 4% aqueous solution has a viscosity of 18 mPa·s at 20°C, and a saponification degree of 88.5 mol%) as an emulsification aid, and 1.4 parts by mass of 1-ethynyl-1-cyclohexanol as a catalyst activity inhibitor, and the mixture was stirred and mixed uniformly, and then 70 parts by mass of phase inversion water was added to cause phase inversion, followed by stirring for 15 minutes. Next, 198.5 parts by weight of dilution water was added and stirred to obtain an addition curing type emulsion (B-1) with a silicone content of 40%.

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

Preparation of silicone emulsion (C) containing organopolysiloxane having alkenyl groups [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 15% aqueous PVA solution (manufactured by Mitsubishi Chemical Corporation, trade name: GM-14L, 4% aqueous solution has a viscosity of 18 mPa·s at 20°C, saponification degree of 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 emulsifier, and after uniform stirring and mixing, 51.1 parts by mass of phase inversion water was added to cause phase inversion, 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 an alkenyl group with a silicone content of 40%.

Preparation of organohydrogenpolysiloxane-containing silicone emulsion (D) [Preparation Example 16]
Using the same method 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% aqueous PVA solution (manufactured by Mitsubishi Chemical Corporation, product name: GM-14L, 4% aqueous solution has a viscosity of 18 mPa·s at 20°C, and a saponification degree of 88.5 mol%) as an emulsification aid were charged into a composite emulsifier, and after uniform mixing and stirring, 18.9 parts by mass of phase inversion water was added to cause phase inversion, followed by stirring 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%.

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

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

[Examples 2 to 19, Comparative Examples 1 to 4]
In the same manner as in Example 1, aqueous oil-resistant compositions were prepared according to the formulations shown in Tables 1 to 3 below, and paper substrates were treated with the compositions to obtain oil-resistant papers.

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

[Comparative Example 5]
With reference to Example 4 of Patent Document 5 (JP 2006-257159 A), (A-3) as component (A), (G'-1) as component (G), (H-5) as component (H), (I-2) as component (I) and succinic acid as an additive were used, and emulsified and blended in the same manner as in Preparation Example 1 in the composition shown in Table 4 to obtain a composition. A paper substrate was treated with the prepared composition in the same manner as in Example 1 to obtain grease-resistant paper.

C. Evaluation Items and Methods The physical properties of each of the obtained greaseproof papers were evaluated according to the methods shown below. The evaluation results are shown in Tables 1 to 4.

Oil resistance Using rapeseed oil (product name: Nisshin Canola Oil) manufactured by Nisshin Oillio Co., Ltd., a drop of oil was placed on greaseproof paper treated with the aqueous oil-resistant composition, and the state of penetration of the oil was visually confirmed 30 minutes after the drop. The criteria were as follows.
◎: (After 30 minutes, there is no oil staining or bleed-through at all)
○: (After 30 minutes, there are several pinhole-shaped oil stains)
△: (Oil stains and bleed-through occur within 5 to 15 minutes)
×: (Oil stains and bleed-through occur within 5 minutes)

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

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

As shown in Tables 1 to 3, the paper obtained by impregnation with only a cellulose resin (Comparative Example 1) or the paper obtained by impregnation with only a silicone emulsion (Comparative Example 2) was poor in either oil resistance or water resistance. Furthermore, the paper obtained by impregnation with a composition in which the total alkenyl value in component (G) was 0.1 mol/100 g or less (Comparative Examples 3 and 4) was poor in oil resistance.
On the other hand, the grease-resistant paper obtained by impregnation with the aqueous grease-resistant composition of the present invention possesses the respective advantages of the cellulose-based resin and the silicone emulsion, and has excellent oil resistance and water resistance, an air permeability of 30 seconds or less, and thus has appropriate air permeability for grease-resistant paper for food use.
It was also found that there was no significant difference in the performance of the resulting grease-resistant paper whether the silicone emulsion contained the (G) and (H) components in the same emulsion (Examples 1 to 19) or in different emulsions (Example 20).
In the present invention, the alkenyl value of component (G) is important, and it has been observed that as the alkenyl value of the entire component (G) contained in the composition decreases, the oil resistance tends to decrease.

As shown in Table 4 above, compared to the results of Example 7, which is also shown 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 believed that the composition was applied to the surface of a paper substrate containing a filler, and then dried to form a hardened film on the surface of the paper substrate, thereby imparting oil resistance, but it was suggested that when the composition is impregnated into the interior of the paper substrate to exhibit oil resistance, the alkenyl value (vinyl value) of the total of the (G) components in the composition is important.

It has been found that the grease-resistant paper of the present invention has high oil resistance, water resistance, and air permeability because the cellulose resin, which has an affinity with paper, and the water-resistant, air-permeable organopolysiloxane are dispersed and physically entangled inside the paper. In order to promote the physical entanglement of the cellulose resin and the organopolysiloxane, the crosslink density of the organopolysiloxane is important, and it is necessary to use an alkenyl-group-containing organopolysiloxane with a high alkenyl value.

Oil-resistant paper treated with the aqueous oil-resistant composition of the present invention is able to achieve both oil resistance, water resistance, and air permeability. Therefore, the grease-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 baked foods that contain a lot of oil and water.

Claims (13)

The following components (A), (B), (E) and (F):
(A) 100 parts by mass of a cellulose-based resin having a viscosity of 2 to 10,000 mPa·s in a 2% aqueous solution at 20°C; (B) 10 to 10,000 parts by mass of an addition-curing silicone emulsion; (E) 1,000 to 50,000 parts by mass of water; and (F) a catalytic amount of a platinum group metal catalyst,
The addition curing silicone emulsion (B) is
(G) an alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms per molecule and having a viscosity of 5 mPa·s or more at 25° C., which accounts for 5 to 40 mass% of component (B), and the total alkenyl value of component (G) (the number of moles of alkenyl groups bonded to silicon atoms contained in a total of 100 g of component (G)) exceeds 0.1 mol/100 g;
(H) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms (SiH groups) per molecule: mass% 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) Surfactant: 0.1 to 10% by mass in component (B) and (J) Water: 10 to 90% by mass in component (B)
The water-based oil-resistant composition comprises: The following components (A), (C), (D), (E) and (F):
(A) 100 parts by mass of a cellulose-based resin having a viscosity of 2 to 10,000 mPa·s in a 2% aqueous solution at 20°C; (C) 5 to 5,000 parts by mass of a silicone emulsion; (D) 1,000 to 50,000 parts by mass of a silicone emulsion; (E) 1,000 to 50,000 parts by mass of water; and (F) a catalytic amount of a platinum group metal catalyst,
The silicone emulsion (C) is
(G) an alkenyl group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms per molecule and having a viscosity of 5 mPa·s or more at 25° C., which accounts for 5 to 60 mass% of component (C), and the total alkenyl value of component (G) (the number of moles of alkenyl groups bonded to silicon atoms contained in a total of 100 g of component (G)) exceeds 0.1 mol/100 g;
(I) Surfactant: 0.1 to 10% by mass in component (C) and (J) Water: 10 to 90% by mass in component (C)
and
The silicone emulsion (D) is
(H) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms per molecule: 5 to 60 mass% of component (D);
(I) Surfactant: 0.1 to 10% by mass in component (D) and (J) Water: 10 to 90% by mass in component (D)
wherein the content of component (D) in the composition is an amount 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). The aqueous oil-resistant composition according to claim 1 or 2, in which the cellulose-based resin (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. The aqueous oil-resistant composition according to claim 1 or 2, wherein component (G) contains at least two types of linear organopolysiloxanes: a linear organopolysiloxane containing alkenyl groups only at both ends; and a linear organopolysiloxane containing alkenyl groups at the side chain and both ends. 3. The aqueous oil-resistant composition according to claim 1, wherein component (G) is a linear, alkenyl-containing organopolysiloxane represented by the following average composition formula (1-1):

(In formula (1-1), R ¹ is independently an alkenyl-containing organic group having 2 to 10 carbon atoms, R ² is independently a group selected from unsubstituted or substituted monovalent hydrocarbon groups having no hydroxyl group, alkoxy group, or alkenyl group, and a, c, and d are each a number of 0 or more that satisfies 0≦a≦3, 2≦2a+c, and 5≦c+d.) 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%. The water-based oil-resistant composition according to claim 1, wherein the silicone emulsion of component (B) further contains 0.5 to 10 mass % of a polyvinyl alcohol (PVA)-based resin in component (B). The aqueous oil-resistant composition according to claim 2, wherein at least one of the silicone emulsion of component (C) and the silicone emulsion of component (D) further contains 0.5 to 10 mass % of a polyvinyl alcohol (PVA)-based resin in component (C) or component (D). The aqueous oil-resistant composition according to claim 1 or 2, wherein the total mass of components (G) and (H) is 60 to 2000 parts by mass per 100 parts by mass of component (A). A method for producing the aqueous oil-resistant composition according to claim 1, comprising the steps of:
(Step 1) A step of preparing an addition-curable silicone emulsion (B) by mixing and emulsifying the following components (G), (H), (I), and (J): (G) an alkenyl-group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms per molecule and having a viscosity of 5 mPa·s or more at 25°C: (H) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms (SiH groups) per molecule, which accounts for 5 to 40% by mass of component (B) and has an alkenyl value of component (G) in total (the number of moles of alkenyl groups bonded to silicon atoms contained in a total of 100 g of component (G)) of greater than 0.1 mol/100 g: (H) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms (SiH groups) per molecule, which corresponds 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) Surfactant: 0.1 to 10% by mass in component (B)
(J) Water: 10 to 90% by mass in component (B)
and (Step 2) mixing the following components (A), (E), and (F) with 10 to 10,000 parts by mass of the addition-curable silicone emulsion (B) prepared in (Step 1) above, comprising: (A) 100 parts by mass of a cellulose-based resin having a viscosity of 2 to 10,000 mPa·s as a 2% aqueous solution at 20°C; (E) 1,000 to 50,000 parts by mass of water; and (F) a catalytic amount of a platinum group metal catalyst. A method for producing the aqueous oil-resistant composition according to claim 2, comprising the steps of:
(Step 1') A step of preparing a silicone emulsion (C) by mixing and emulsifying the following components (G), (I), and (J): (G) an alkenyl-group-containing organopolysiloxane having at least two alkenyl groups bonded to silicon atoms per molecule and having a viscosity of 5 mPa·s or more at 25° C.: 5 to 60 mass% of component (C), and (I) a surfactant in which the alkenyl value of component (G) in total (the number of moles of alkenyl groups bonded to silicon atoms contained in a total of 100 g of component (G)) exceeds 0.1 mol/100 g: 0.1 to 10 mass% of component (C).
(J) Water: 10 to 90% by mass in component (C)
(Step 1″) A step of preparing a silicone emulsion (D) by mixing and emulsifying the following components (H), (I), and (J): (H) an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms per molecule: 5 to 60% by mass of component (D);
(I) Surfactant: 0.1 to 10% by weight of component (D)
(J) Water: 10 to 90% by mass in component (D)
and (Step 2') a process for producing an aqueous oil resistant composition comprising the following components (A), (E) and (F): (A) 100 parts by mass of a cellulose-based resin having a viscosity of 2 to 10,000 mPa s as a 2% aqueous solution at 20°C; (E) 1,000 to 50,000 parts by mass of water; and (F) a catalytic amount of a platinum group metal catalyst. A method for treating paper to be oil-resistant, comprising adding the aqueous oil-resistant composition according to claim 1 or 2 to a pulp slurry for internal treatment or to a paper substrate for external treatment. Oil-resistant paper treated with the aqueous oil-resistant composition according to claim 1 or 2, which has an air permeability of 1,000 seconds or less according to the Oken air permeability measured in accordance with JAPAN TAPPI Paper and Pulp Test Method No. 5-2:2000.