Composition

Abstract

To provide a composition for forming a film excellent in sustainability of synovial fluid properties when exposed outdoors.SOLUTION: The composition comprises the following component (A), component (B), component (C) and component (D): (A) an anion-modified cellulose fiber; (B) a hydrophobic compound having a cationic functional group; and (C) an organic compound that is liquid at 25 °C and 1 atm (excluding those corresponding to the component (B)). (D) Inorganic fine particles having a hydrophobic group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition, more particularly to a composition containing inorganic fine particles. [Background technology]

[0002] Surface films and coating films have been developed to prevent the adhesion of dirt, snow and ice, marine organisms, etc. Recently, a film having synovial properties containing hydrophobically modified cellulose fibers and oil has become known as such a surface film. Patent Document 1 discloses that a film having synovial properties can be obtained by applying an emulsion composition containing anion-modified cellulose fibers, amino-modified silicone, and an organic compound that is liquid at 25°C and 1 atmosphere to a solid surface.

[0003] Such a membrane with synovial properties can also be used outdoors. Forming the membrane on outdoor structures, such as traffic lights, can prevent dirt and snow from adhering to them, and is expected to reduce maintenance costs.

[0004] However, there are unique circumstances when using the membrane outdoors, such as the presence of external factors that can damage the membrane itself, such as rainwater and sunlight, and a membrane that can maintain its synovial properties even when exposed to these external factors is required.

[0005] In an attempt to deal with such external factors, inorganic fine particles have been incorporated into the film. For example, Patent Document 2 discloses a resin composition containing inorganic fine particles such as titanium oxide (titanium dioxide), and attempts to provide a coating film that combines hardness and abrasion resistance. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent Publication No. 2021-095557 [Patent Document 2] Patent Publication No. 2021-154632 Summary of the Invention [Problem to be solved by the invention]

[0007] However, no technology has been known to improve the durability of a membrane having synovial properties.

[0008] Therefore, the present invention relates to providing a composition for forming a film that has excellent synovial fluid durability when exposed to the outdoors. [Means for solving the problem]

[0009] The present invention relates to the following [1] to

[12] . [1] A composition containing the following components (A), (B), (C), and (D): (A) Anion-modified cellulose fiber (B) Hydrophobic compound having a cationic functional group (C) Organic compounds that are liquid at 25°C and 1 atmosphere (excluding those that fall under component (B) above). (D) Inorganic fine particles having hydrophobic groups [2] The composition according to [1] above, further comprising component (E). (E) Wetting agent (excluding those corresponding to component (C) above) [3] The composition according to [1] or [2] above, further comprising a component (F). (F) Aggregation inhibitor (excluding those corresponding to the above component (E)) [4] The composition according to any one of the above [1] to [3], wherein the content of component (A) is 0.1 parts by mass or more and 50 parts by mass or less per 100 parts by mass of component (C). [5] The composition according to any one of the above [1] to [4], wherein the content of component (D) is 1 part by mass or more and 100 parts by mass or less per 100 parts by mass of component (C). [6] The composition according to any one of the above [1] to [5], wherein the content of component (D) is 20 parts by mass or more and 2,000 parts by mass or less per 100 parts by mass of component (A). [7] The composition according to any one of the above [1] to [6], wherein the content of component (D) is 0.1% by mass or more and 15% by mass or less. [8] The composition according to any one of the above [1] to [7], wherein the hydrophobic group in component (D) is a silyl group and / or a dimethylsilicone modification. [9] A composition comprising the following components (A), (B), (C), and (D): (A) Anion-modified cellulose fiber (B) Hydrophobic compound having a cationic functional group (C) Organic compounds that are liquid at 25°C and 1 atmosphere (excluding those that fall under component (B) above). (D) Inorganic fine particles having hydrophobic groups

[10] An inorganic fine particle-containing emulsion composition containing the following components (A), (B), (C), and (D): (A) Anion-modified cellulose fiber (B) Hydrophobic compound having a cationic functional group (C) Organic compounds that are liquid at 25°C and 1 atmosphere (excluding those that fall under component (B) above). (D) Inorganic fine particles having hydrophobic groups

[11] A coating agent containing the composition according to any one of [1] to [9] above or the inorganic fine particle-containing emulsion composition according to

[10] above.

[12] A film obtained by drying the composition according to any one of the above [1] to [9] or the inorganic fine particle-containing emulsion composition according to the above

[10] . [Effects of the Invention]

[0010] According to the present invention, a composition for forming a film that has excellent synovial fluid properties when exposed to the outdoors can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0011] As a result of the inventors' investigations, they discovered that by adding a specific inorganic microparticle component, i.e., inorganic microparticles having hydrophobic groups as component (D), to a composition containing anion-modified cellulose fibers, a composition can be obtained that can form a film that can exhibit excellent and sustained synovial fluid properties, and thus completed the present invention.

[0012] The estimated mechanism by which the effects of the present invention are achieved is that, since "inorganic fine particles having hydrophobic groups" do not have hydrophilic functional groups, even if the proportion of component (C) decreases due to rainfall, for example, the presence of component (D) causes the surface of the film to always be composed of hydrophobic functional groups. Furthermore, unlike inorganic fine particles having hydrophilic groups, component (C), which is a hydrophobic inorganic fine particle, has high compatibility with the similarly hydrophobic components (B) and (C), and is uniformly dispersed within the film without agglomeration, which is thought to suppress film cracks and the absorption of moisture into the film, which cause peeling.

[0013] The composition of the present invention contains the following components (A), (B), (C) and (D).

[0014] <Component (A)> Component (A) is an anionically modified cellulose fiber. Anionically modified cellulose fibers are cellulose fibers that have been anionically modified so as to contain anionic groups.

[0015] Anion-modified cellulose fibers have a cellulose type I crystal structure derived from the raw cellulose fibers. From the viewpoint of composition stability, the degree of crystallinity of the anion-modified cellulose fibers is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more. From the viewpoint of raw material availability, the degree of crystallinity is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, and even more preferably 75% or less.

[0016] In this specification, the crystallinity of various cellulose fibers refers to the cellulose type I crystallinity calculated from the diffraction intensity value obtained by X-ray diffraction, and can be measured according to the method described in the Examples below. Cellulose type I refers to the crystalline form of natural cellulose, and cellulose type I crystallinity refers to the proportion of crystalline regions in the entire cellulose fiber. The presence or absence of a cellulose type I crystalline structure can be determined by the presence of a peak at 2θ = 22.6° in X-ray diffraction measurement.

[0017] Examples of the anionic group contained in the anion-modified cellulose fiber include a carboxy group, a sulfonic acid group, and a phosphate group. From the viewpoint of bonding with component (B), the anionic group is preferably a carboxy group. As the anion-modified cellulose fiber, a carboxy group-containing cellulose fiber in which the anionic group is a carboxy group is preferred from the viewpoints of ease of preparation and mild reaction conditions.

[0018] Examples of counter ions to the anionic groups in anion-modified cellulose fibers include metal ions such as sodium ions, potassium ions, calcium ions, and aluminum ions that are generated in the presence of alkali during production, and protons that are generated by substituting these metal ions with acid.

[0019] The anionic group content in the anion-modified cellulose fiber is preferably 0.1 mmol / g or more, more preferably 0.4 mmol / g or more, and even more preferably 1.0 mmol / g or more, from the viewpoint of bonding strength with component (B). Furthermore, from the viewpoint of improving handleability, it is preferably 3.0 mmol / g or less, more preferably 2.0 mmol / g or less, and even more preferably 1.8 mmol / g or less. The "anionic group content" refers to the total amount of anionic groups in the cellulose constituting the cellulose fiber, and is specifically measured by the method described in the Examples below.

[0020] The average fiber diameter of the anion-modified cellulose fiber is preferably 0.1 nm or more, more preferably 1.0 nm or more, and even more preferably 2.0 nm or more from the viewpoint of handleability, and is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less from the viewpoint of film strength. In this specification, anion-modified cellulose fiber having an average fiber diameter on the nm scale may be referred to as "micronized anion-modified cellulose fiber." The average fiber diameter of the anion-modified cellulose fiber is measured by the method described in the Examples below.

[0021] [Method for producing anion-modified cellulose fibers] The anionically modified cellulose fiber used in the present invention can be obtained by subjecting raw cellulose fiber to an oxidation treatment or an anionic group addition treatment, thereby introducing one or more anionic groups per glucose residue and anionically modifying the fiber.

[0022] The cellulose fibers to be anionically modified, i.e., the cellulose fibers used as the raw material for anionically modified cellulose fibers, are preferably natural cellulose fibers from an environmental perspective, and examples thereof include wood pulps such as softwood pulp and hardwood pulp; cotton pulps such as cotton linter and cotton lint; non-wood pulps such as straw pulp and bagasse pulp; and bacterial cellulose, and these can be used alone or in combination of two or more.

[0023] The average fiber diameter of the raw material cellulose fibers is preferably 1 μm or more, and preferably 300 μm or less, from the viewpoints of handling and cost. Moreover, from the viewpoints of availability and cost, the average fiber length of the raw cellulose fibers is preferably 100 μm or more and preferably 5,000 μm or less. From the viewpoint of dispersibility, it is preferable to use cellulose fibers that have been subjected to a fiber shortening treatment such as alkaline hydrolysis or acid hydrolysis, and have an average fiber length of 1 μm or more and 1,000 μm or less.

[0024] The anionic group to be introduced includes a carboxy group, a sulfonic acid group, or a phosphoric acid group.

[0025] (i) When carboxyl groups are introduced as anionic groups into cellulose fibers Methods for introducing carboxy groups into cellulose fibers include, for example, a method of converting hydroxy groups of cellulose into carboxy groups by oxidation, and a method of reacting the hydroxy groups of cellulose with one or more compounds selected from the group consisting of compounds having carboxy groups, acid anhydrides of compounds having carboxy groups, and derivatives thereof.

[0026] The hydroxyl groups of the cellulose can be oxidized, for example, by reacting an oxidizing agent such as sodium hypochlorite with a bromide such as sodium bromide using 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) as a catalyst. For more details, known methods, such as those described in JP 2011-140632 A, can be used.

[0027] By subjecting cellulose fibers to oxidation treatment using TEMPO as a catalyst, the hydroxymethyl group (-CHOH) at the C6 position of the cellulose structural unit is selectively converted to a carboxy group. This method is particularly advantageous in that it has excellent selectivity for the hydroxy group at the C6 position, which is the target of oxidation on the surface of the raw cellulose fiber, and the reaction conditions are mild. Therefore, a preferred embodiment of the anion-modified cellulose fiber of the present invention is a cellulose fiber in which the C6 position of the cellulose structural unit is a carboxy group. In this specification, cellulose fibers obtained by oxidizing hydroxy groups in cellulose structural units are sometimes referred to as "oxidized cellulose fibers," and cellulose fibers obtained by oxidizing cellulose fibers using TEMPO as a catalyst and having a carboxy group at the C6 position of the cellulose structural units are sometimes referred to as "TEMPO-oxidized cellulose fibers." Oxidized cellulose fibers, particularly TEMPO-oxidized cellulose fibers, are preferred because they are easier to prepare than other anion-modified cellulose fibers.

[0028] By further subjecting the oxidized cellulose fibers to a further oxidation treatment or reduction treatment, it is possible to prepare oxidized cellulose fibers from which the remaining aldehyde groups have been removed.

[0029] (ii) When sulfonic acid groups or phosphate groups are introduced as anionic groups into cellulose fibers As a method for introducing sulfonic acid groups as anionic groups into cellulose fibers, a method of adding sulfuric acid to cellulose fibers and heating the fibers can be given. Methods for introducing phosphate groups as anionic groups into cellulose fibers include mixing a powder or aqueous solution of phosphoric acid or a phosphoric acid derivative with dry or wet cellulose fibers, adding an aqueous solution of phosphoric acid or a phosphoric acid derivative to a dispersion of cellulose fibers, etc. When these methods are employed, dehydration treatment, heat treatment, etc. are generally carried out after mixing or adding a powder or aqueous solution of phosphoric acid or a phosphoric acid derivative.

[0030] <Ingredient (B)> Component (B) is a hydrophobic compound having a cationic functional group. Component (B) may be used alone or in combination of two or more. From the viewpoint of synovial properties, component (B) is preferably one or more compounds selected from the group consisting of polymeric compounds having cationic functional groups and hydrocarbon compounds having cationic functional groups. Furthermore, from the viewpoint of compatibility with component (C) and of hydrophobizing component (A), amino-modified silicone is more preferred as component (B).

[0031] Examples of the cationic functional group in component (B) include an amino group, an ammonium group, and an imidazolium group, and from the viewpoint of availability, an amino group is preferred. In this specification, the term "amino group" refers to a monovalent functional group obtained by removing one hydrogen atom from ammonia, a primary amine, or a secondary amine.

[0032] (i) Polymer compounds having cationic functional groups The weight-average molecular weight of the polymer compound having a cationic functional group is preferably 2,000 or more, more preferably 5,000 or more, and even more preferably 8,000 or more, from the viewpoint of strength during film formation, and from the same viewpoint, is preferably 1,000,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0033] From the viewpoint of ease of modification, examples of polymer compounds include silicones having cationic functional groups, polyoxyalkylene oxides, poly(meth)acrylates, polyvinyls, polyesters, polyamides, and polycarbonates, and amino-modified silicones are more preferred.

[0034] The silicone has a polysiloxane structure with a siloxane bond as the main chain, which may further include an alkylene group. The polysiloxane structure may have a substituent, which will be described later.

[0035] [Substituent] Examples of the substituent include alkoxy groups having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, an isopentyloxy group, and a hexyloxy group; a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, and the like. alkoxycarbonyl groups having 1 to 6 carbon atoms in the alkoxy group, such as a carboxyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, or an isopentyloxycarbonyl group; halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; acyl groups having 1 to 6 carbon atoms, such as an acetyl group or a propionyl group; aralkyl groups; aralkyloxy groups; alkylamino groups having 1 to 6 carbon atoms; and dialkylamino groups having an alkyl group with 1 to 6 carbon atoms.

[0036] [Amino-modified silicone] From the viewpoint of the stability of the composition, component (B) is more preferably a silicone having an amino group (referred to herein as an "amino-modified silicone").

[0037] As an amino-modified silicone, the kinematic viscosity at 25°C is 10mm 2 / s or more 20,000mm 2 Further, amino-modified silicones having an amino equivalent of 400 g / mol or more and 16,000 g / mol or less are preferred.

[0038] The kinematic viscosity at 25°C can be determined using an Ostwald viscometer. From the viewpoint of film strength, it is more preferable to use a viscosity of 20 mm. 2 / s or more, more preferably 50 mm 2 / s or more, and from the viewpoint of handling, 10,000 mm 2 / s or less, more preferably 5,000 mm 2 / s or less.

[0039] From the viewpoint of strength during film formation, the amino equivalent is preferably 400 g / mol or more, more preferably 600 g / mol or more, and even more preferably 800 g / mol or more, and from the viewpoint of ease of bonding to anion-modified cellulose fibers, it is preferably 16,000 g / mol or less, more preferably 14,000 g / mol or less, and even more preferably 12,000 g / mol or less. The amino equivalent is the molecular weight per nitrogen atom and can be determined by quantifying the amount of nitrogen atoms in a sample by elemental analysis and calculating the mass of the sample containing 1 mole of nitrogen atoms.

[0040] Specific examples of amino-modified silicones include compounds represented by general formula (a1).

[0041] [ka]

[0042] [In the formula, R 1aR represents a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom, and is preferably a methyl group or a hydroxy group from the viewpoint of synovial properties. 2a is a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom, and from the same viewpoint, is preferably a methyl group or a hydroxy group. B represents a side chain having at least one amino group, and R 3a represents an alkyl group having 1 to 3 carbon atoms, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom. x and y each represent an average degree of polymerization, with x being an integer of 0 or more and y being an integer of 1 or more, and are selected so that the kinematic viscosity at 25°C and amino equivalent of the compound fall within the above-mentioned ranges. 1a , R 2a , R 3a may be the same or different, and multiple R 2a may be the same or different.

[0043] In the compound of general formula (a1), from the viewpoint of synovial properties, x is preferably a number of 10 or more and 10,000 or less, more preferably a number of 20 or more and 5,000 or less, and even more preferably a number of 30 or more and 3,000 or less. y is preferably a number of 1 or more and 1,000 or less, more preferably a number of 1 or more and 500 or less, and even more preferably a number of 1 or more and 200 or less. From the viewpoint of strength during film formation, the weight-average molecular weight of the compound of general formula (a1) is preferably 2,000 or more, more preferably 5,000 or more, and even more preferably 8,000 or more, and from the same viewpoint, it is preferably 1,000,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0044] In the general formula (a1), examples of the side chain B having an amino group include the following. -C3H6-NH2 -C3H6-NH-C2H4-NH2 -C3H6-NH-[C2H4-NH] e -C2H4-NH2 -C3H6-NH(CH3) -C3H6-NH-C2H4-NH(CH3) -C3H6-NH-[C2H4-NH] f -C2H4-NH(CH3) -C3H6-N(CH3)2 -C3H6-N(CH3)-C2H4-N(CH3)2 -C3H6-N(CH3)-[C2H4-N(CH3)] g -C2H4-N(CH3)2 -C3H6-NH-cyclo-C5H 11 (where e, f, and g are numbers from 1 to 30.)

[0045] The amino-modified silicone used in the present invention can be produced, for example, by hydrolyzing an organoalkoxysilane represented by general formula (a2) with excess water to obtain a hydrolyzate, and then heating the resulting hydrolyzate with dimethylcyclopolysiloxane in the presence of a basic catalyst such as sodium hydroxide to 80 to 110°C to cause an equilibrium reaction, and then neutralizing the basic catalyst with an acid when the reaction mixture reaches the desired viscosity (see JP 53-98499 A). H2N(CH2)2NH(CH2)3Si(CH3)(OCH3)2(a2)

[0046] Furthermore, from the viewpoint of strength during film formation, the amino-modified silicone is preferably at least one selected from the group consisting of monoamino-modified silicones having one amino group in one of the side chains B and diamino-modified silicones having two amino groups in one of the side chains B, and more preferably at least one selected from the group consisting of compounds in which the side chain B having an amino group is represented by -C3H6-NH2 [hereinafter referred to as component (a1-1)] and compounds in which the side chain B having an amino group is represented by -C3H6-NH-C2H4-NH2 [hereinafter referred to as component (a1-2)].

[0047] The amino-modified silicones used in the present invention may be selected from the following in terms of performance: TSF4703 (kinematic viscosity: 1000, amino equivalent: 1600) and TSF4708 (kinematic viscosity: 1000, amino equivalent: 2800) manufactured by Momentive Performance Materials; SS-3551 (kinematic viscosity: 1000, amino equivalent: 1700), FZ-3710 (kinematic viscosity: 1000, amino equivalent: 1700), SF8457C (kinematic viscosity: 1200, amino equivalent: 1800), SF8417 (kinematic viscosity: 1200, amino equivalent: 1700), SF8452C (kinematic viscosity: 600, amino equivalent: 6400), BY16-209 (kinematic viscosity: 500, amino equivalent: 1800), and BY16-209 (kinematic viscosity: 500, amino equivalent: 1800) manufactured by Dow-Toray Industries, Inc. -892 (kinematic viscosity: 1500, amino equivalent: 2000), BY16-898 (kinematic viscosity: 2000, amino equivalent: 2900), FZ-3760 (kinematic viscosity: 220, amino equivalent: 1600), BY16-213 (kinematic viscosity: 55, amino equivalent: 2700), Shin-Etsu Chemical Co., Ltd.'s KF-8002 (kinematic viscosity: 1100, amino equivalent: 1700 ), KF-8004 (kinematic viscosity: 800, amino equivalent: 1500), KF-8005 (kinematic viscosity: 1200, amino equivalent: 11000), KF-867 (kinematic viscosity: 1300, amino equivalent: 1700), KF-864 (kinematic viscosity: 1700, amino equivalent: 3800), KF-859 (kinematic viscosity: 60, amino equivalent: 6000). In parentheses, kinematic viscosity is measured at 25°C (unit: mm 2 / s), and the unit of amino equivalent is g / mol.

[0048] As the component (a1-1), BY16-213 (kinematic viscosity: 55, amino equivalent: 2700) and BY16-853U (kinematic viscosity: 14, amino equivalent: 450) are more preferred.

[0049] As the (a1-2) component, SF8417 (kinematic viscosity: 1200, amino equivalent: 1700), BY16-209 (kinematic viscosity: 500, amino equivalent: 1800), FZ-3760 (kinematic viscosity: 220, amino equivalent: 1600), SF8452C (kinematic viscosity: 600, amino equivalent: 6400), KF-8002 (kinematic viscosity: 1100, amino equivalent: 1700), SS-3551 (kinematic viscosity: 1000, amino equivalent: 1700), and FZ-3710 (kinematic viscosity: 1000, amino equivalent: 1700) are more preferred.

[0050] (ii) Hydrocarbon compounds having cationic functional groups A hydrocarbon compound having a cationic functional group is one in which one or more hydrocarbon groups are bonded to one cationic functional group. The total carbon number of the hydrocarbon compound having a cationic functional group is preferably 16 or more, more preferably 18 or more, from the viewpoint of synovial fluid properties, and is preferably 40 or less, more preferably 30 or less, and even more preferably 26 or less, from the viewpoint of handleability. When the cationic functional group is a primary amine, secondary amine, tertiary amine, or quaternary ammonium, the hydrocarbon compound having a cationic functional group is a compound in which the hydrocarbon group is directly bonded to a nitrogen atom via a covalent bond. When the cationic functional group is imidazolium, pyridinium, imidazoline, or the like, the hydrocarbon compound is a compound in which at least one hydrocarbon group is bonded to any position of the ring structure via a covalent bond.

[0051] [Hydrocarbon group] Examples of the hydrocarbon group in the hydrocarbon compound having a cationic functional group include a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, a cyclic saturated hydrocarbon group, and an aromatic hydrocarbon group. From the viewpoint of availability, the number of carbon atoms in the hydrocarbon group is preferably 16 or more, more preferably 18 or more, and from the same viewpoint, is preferably 40 or less, more preferably 30 or less, and even more preferably 24 or less.

[0052] Unless otherwise specified, the number of carbon atoms in a hydrocarbon group means the number of carbon atoms in one hydrocarbon group. Specific examples of the chain saturated hydrocarbon group include a hexadecyl group, an octadecyl group, a docosyl group, and an octacosanyl group. Specific examples of the chain unsaturated hydrocarbon group include a hexadecenyl group and an octadecenyl group. Specific examples of the cyclic saturated hydrocarbon group include a cyclohexadecyl group and a cyclooctadecyl group.

[0053] [Examples of hydrocarbon compounds] The hydrocarbon compound having a cationic functional group is preferably a hydrocarbon compound having an amino group, such as a primary amine, a secondary amine, a tertiary amine, or a quaternary ammonium (referred to as a "hydrocarbon amine" in this specification.) Specific examples of such hydrocarbon amines include hexadecylamine, stearylamine, oleylamine, dioctylamine, didecylamine, didodecylamine, trihexylamine, trioctylamine, tetrabutylammonium salt, tetrahexylammonium salt, dimethyldioctylammonium salt, dimethyldidecylammonium salt, and trimethylhexadecylammonium salt.

[0054] The hydrocarbon compounds may further have some hydrogen atoms substituted with, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxy group, a methoxy group, an ethoxy group, a carboxy group, an aldehyde group, a ketone group, or a thiol group.

[0055] <Ingredient (C)> Component (C) in the present invention is an organic compound that is liquid at 25°C and 1 atmosphere, except for those that fall under the category of component (B).

[0056] The solubility of component (C) in water is preferably 1 g or less, more preferably 0.1 g or less, and even more preferably 0.01 g or less per 100 g of water at 25° C., from the viewpoint of synovial fluid properties. The weight average molecular weight of component (C) is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less from the viewpoint of synovial properties, and is preferably 100 or more, more preferably 200 or more from the same viewpoint.

[0057] Specific examples of component (C) in the present invention include oils, organic solvents, polymerizable monomers, prepolymers, etc. Component (C) in the present invention is preferably an oil, and examples of the oil, from the viewpoint of exhibiting high lubricity, include one or more selected from the group consisting of higher alcohols, ester oils, hydrocarbon oils, silicone oils, ether oils, fats and oils, fluorine-based inert liquids, and fatty acids, preferably one or more selected from the group consisting of ester oils, silicone oils, ether oils, fats and oils, and fluorine-based inert liquids, more preferably one or more selected from the group consisting of silicone oils, ester oils, and ether oils, and even more preferably silicone oils.

[0058] Examples of higher alcohols include alcohols having a saturated or unsaturated, linear or branched alkyl chain having 8 to 22 carbon atoms, such as 1-octanol, 2-octanol, 1-decanol, 2-decanol, oleyl alcohol, isostearyl alcohol, and behenyl alcohol.

[0059] Examples of ester oils include monoester oils, diester oils, and triester oils, and specific examples include aliphatic or aromatic monocarboxylic or dicarboxylic acid esters having 2 to 18 carbon atoms, such as isopropyl myristate, octyldodecyl myristate, myristyl myristate, 2-hexyldecyl myristate, isopropyl palmitate, glycerin tri-2-ethylhexanoate, and glycerin triisostearate.

[0060] Examples of silicone oils include siloxane compounds such as dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane; and modified silicones such as phenyl-modified silicone, alkyl-modified silicone, polyether-modified silicone, and fluorine-modified silicone.

[0061] From the viewpoint of the stability of the composition, component (C) preferably has an SP value of 10 or less, more preferably 9.5 or less, even more preferably 9.0 or less, and even more preferably 8.5 or less, and from the same viewpoint, preferably 6.0 or more, more preferably 6.5 or more. For example, an oil agent having an SP value of 10 or less, as described below, can be exemplified as a preferred example.

[0062] The SP value in this specification refers to the solubility parameter calculated by the Fedors method (unit: (cal / cm 3 ) 1 / 2 ) and are described in, for example, references such as "SP Value Basics, Applications and Calculation Methods" (Johokikansha, 2005) and Polymer Handbook Third Edition (A Wiley-Interscience publication, 1989).

[0063] Examples of oils having an SP value of 10 or less that can be suitably used in the present invention include oleic acid (SP value: 9.2), D-limonene (SP value: 9.4), PEG400 (SP value: 9.4), dimethyl succinate (SP value: 9.9), neopentyl glycol dicaprate (SP value: 8.9), hexyl laurate (SP value: 8.6), isopropyl laurate (SP value: 8.5), isopropyl myristate (SP value: 8.5), isopropyl palmitate (SP value: 8.5), isopropyl oleate (SP value: 8.6), hexadecane (SP value: 8.0), olive oil (SP value: 9.3), jojoba oil (SP value: 8.6), squalane (SP value: 7.9), liquid paraffin (SP value: 7.9), fluorine-based inert liquids (e.g., fluorine-based inert liquids), and the like. Fluorinert FC-40 (manufactured by 3M, SP value: 6.1), Fluorinert FC-43 (manufactured by 3M, SP value: 6.1), Fluorinert FC-72 (manufactured by 3M, SP value: 6.1), Fluorinert FC-770 (manufactured by 3M, SP value: 6.1)), silicone oil (e.g., KF96-1cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-10cs (manufactured by Shin-Etsu Chemical Co., Ltd.), , SP value: 7.3), KF-96-50cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-100cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-1000cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-3000cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96H-10,000cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), etc. All of these oils are liquid at 25°C and 1 atmosphere.

[0064] <Ingredient (D)> Component (D) in the present invention is inorganic fine particles having a hydrophobic group. Examples of materials for inorganic fine particles include silicon dioxide, zinc oxide, and titanium oxide, with silicon dioxide being preferred from the viewpoint of sustainability in synovial fluid.

[0065] The hydrophobic group is a functional group that imparts hydrophobicity to inorganic particles by bonding with them. Specific examples of such hydrophobic groups include silyl groups, hydrocarbon groups, and dimethylsilicone modifications. From the viewpoint of synovial fluid sustainability, silyl groups and / or dimethylsilicone modifications are preferred, and monomethylsilyl groups, trimethylsilyl groups, and dimethylsilyl groups are more preferred. Furthermore, the hydrocarbon group preferably has 1 to 40 carbon atoms, and specific examples thereof include methyl groups, ethyl groups, propyl groups, phenyl groups, octyl groups, dodecanyl groups, octadecyl groups, and octadecenyl groups.

[0066] Methods for bonding hydrophobic groups to inorganic fine particles include known methods, such as hydrophobizing inorganic fine particles using a treating agent for hydrophobizing treatment. Commercially available inorganic fine particles having hydrophobic groups can be used.

[0067] Specific examples of inorganic fine particles having hydrophobic groups include trimethylsiloxysilicate (MQ resin), polymethylsilsesquioxane, and hydrophobic fumed silica, with MQ resin and hydrophobic fumed silica being more preferred from the viewpoint of synovial fluid sustainability.

[0068] The "fine particles" in component (D) specifically refer to particles having an average primary particle diameter of 3 nm or more and 20 μm or less. From the viewpoint of synovial fluid sustainability, the average primary particle size of component (D) is preferably 5 nm or more, while from the same viewpoint, the average primary particle size of component (D) is preferably 20 μm or less, more preferably 15 μm or less. Specifically, the average primary particle diameter of component (D) is a value obtained by observing particles of component (D) using a transmission electron microscope, a scanning electron microscope, or the like, selecting a predetermined number of 200 particles of component (D), measuring the longest linear portion (maximum major axis) of each of these particles of component (D), and calculating the weighted average of these measured values.

[0069] <Ingredient (E)> The composition of the present invention may further contain a wetting agent as component (E), except for those corresponding to component (C) above. Wetting agents that can be used in the present invention include those used in water-containing products such as water-based paints, water-based inks, daily necessities, and cosmetics, and preferred examples thereof include polyether-modified silicones, water-miscible organic solvents such as ethanol and isopropanol, alkyl glyceryl ethers such as 2-ethylhexyl glyceryl ether, nonionic surfactants such as Surfynol, and anionic surfactants such as sodium dodecyl sulfate. Component (E) may be used alone or in combination of two or more.

[0070] Polyether-modified silicone compounds that can be preferably used as component (E) are commercially available, and examples of commercially available products include KF-615A, KF-640, KF-642, KF-643, KF-644, KF-351A, KF-354L, KF-355A, KF-6011, KF-6012, KF-6015, KF-6016, KF-6017, KF-6020, and KF-6043 manufactured by Shin-Etsu Chemical Co., Ltd., and from the viewpoint of the synovial fluid retention of the film obtained by drying the composition, KF-640, KF-642, KF-643, KF-351A, KF-354L, and KF-355A can be preferably used. Commercially available products having a structure that does not fall within the general formula above (for example, KF-6028 and KF-6038 manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as component (E).

[0071] <Component (F)> The composition of the present invention may further contain a coagulation inhibitor as component (F). However, those corresponding to the above-mentioned component (E) are excluded. Since the coagulation inhibitor has the effect of inhibiting the coagulation of hydrophobic components in water, it is preferable to contain or incorporate such a component. Component (F) may be used alone or in combination of two or more types.

[0072] The aggregation inhibitor may be one or more selected from the group consisting of anionic surfactants and anionic polymer dispersants. From the viewpoint of the water resistance of the formed film, anionic polymer dispersants are more preferred.

[0073] (1) Anionic surfactants The anionic surfactant is preferably one having a hydrocarbon group such as an alkyl group or an alkenyl group, and in this case, the number of carbon atoms in the hydrocarbon group is preferably 8 or more, more preferably 10 or more, and preferably 18 or less, more preferably 16 or less. Specific examples of such anionic surfactants include higher fatty acid salts such as sodium laurate and potassium palmitate; alkyl sulfate ester salts such as sodium lauryl sulfate and potassium lauryl sulfate; alkyl ether sulfate ester salts such as polyoxyethylene triethanolamine lauryl sulfate; N-acyl sarcosinate salts such as sodium lauroyl sarcosinate; higher fatty acid amide sulfonates such as sodium N-myristoyl-N-methyl taurate; alkyl phosphates such as sodium monostearyl phosphate; polyoxyethylene sodium oleyl ether phosphate, polyoxyethylene Examples include polyoxyethylene alkyl ether phosphates such as sodium stearyl ether phosphate; long-chain alkyl sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate; alkyl benzene sulfonates such as sodium linear dodecyl benzene sulfonate and triethanolamine linear dodecyl benzene sulfonate; and long-chain N-acyl glutamates such as monosodium N-lauroyl glutamate, monosodium N-stearoyl-L-glutamate, disodium N-stearoyl glutamate, and monosodium N-myristoyl-L-glutamate. As the salt of the anionic surfactant, alkali metal salts such as sodium and potassium, and ammonium salts are preferred. Among these, sulfonates, sulfates, and carboxylates are preferred from the viewpoint of availability.

[0074] (2) Anionic polymer dispersants The anionic polymer dispersant includes "a polymer compound having an anionic group and having one or more counter cations selected from the group consisting of ammonium ions and organic ammonium ions." Such a "polymeric compound having an anionic group and having one or more counter cations selected from the group consisting of ammonium ions and organic ammonium ions" may be blended in the form of a salt of a "polymeric compound having an anionic functional group" and "one or more compounds selected from the group consisting of ammonia and organic amines", or the "polymeric compound having an anionic functional group" and "one or more compounds selected from the group consisting of ammonia and organic amines" may be blended separately. Examples of the anionic functional group in the polymer compound having such anionic functional groups include a carboxy group, a sulfonic acid group, a sulfate group, a phosphorous acid group, and a phosphate group. Among these, a carboxy group is preferred from the viewpoint of easy availability. The functional group equivalent weight of the polymer compound having such anionic functional groups is preferably 50 g / mol or more, more preferably 60 g / mol or more, from the viewpoint of the water resistance of the resulting membrane, and is preferably 300 g / mol or less, more preferably 200 g / mol or less, from the viewpoint of the aggregation suppression effect. Here, "functional group equivalent weight" refers to the molecular weight per anionic functional group (i.e., the molecular weight of the polymer compound having such anionic functional groups / the number of anionic functional groups), and is determined by quantifying the amount of anionic functional groups in a sample by neutralization titration and calculating the mass of the sample containing 1 mole of anionic functional groups. Examples of polymer compounds having such an anionic functional group include polyacrylic acid, polymethacrylic acid, polymaleic acid copolymers, polyallylsulfonic acid, and copolymers containing these constituent monomers. Among these, polyacrylic acid is preferred from the viewpoint of easy availability. The weight-average molecular weight of the polymer compound having an anionic functional group is preferably 500 or more, more preferably 1,000 or more, from the viewpoint of the aggregation-inhibiting effect, and from the same viewpoint, is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0075] The counter cation here is preferably one or more selected from the group consisting of ammonium ions and organic ammonium ions. The organic ammonium ions may be any of primary ammonium cations, secondary ammonium cations, tertiary ammonium cations, and quaternary ammonium cations, all of which have an organic group. From the viewpoint of the water resistance of the resulting membrane, the number of carbon atoms in the organic group of the organic ammonium ion is preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less. The organic ammonium ion is generated by protonation of an organic amine. Specific examples of the organic amine that provides the organic ammonium ion include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, ethylenediamine, triethanolamine, dimethylaminoethanol, aniline, pyrrolidine, and piperidine.

[0076] From the viewpoint of improving the water resistance of the synovial fluid surface film, the counter cation component is preferably one that volatilizes from the composition when the composition is dried to form the synovial fluid surface film. From this viewpoint, the compounds providing the counter cation are more preferably ammonia (boiling point: -33°C), triethylamine (boiling point: 89°C), and dimethylaminoethanol (boiling point: 133°C).

[0077] <Water> The composition of the present invention may further comprise water, which serves as a solvent and as one of the components of the composition of the present invention.

[0078] <Ingredients (G)> The composition of the present invention may further contain component (G), which is a polymer compound that does not fall under the category of component (A), component (B), or component (C). Specifically, from the viewpoint of improving durability, component (G) is preferably one or more compounds selected from the group consisting of components (X) and (Y) below. The composition of the present invention may contain both component (X) and component (Y). Component (X): A polymer compound having, in the main chain, one or more groups selected from the group consisting of an ester group, an amide group, a urethane group, an amino group, an ether group, a carbonate group, and a siloxane group. Component (Y): A methacrylic or acrylic polymer compound having an ester group or an amide group in the side chain. The weight average molecular weight of component (G) is preferably 1,000 or more from the viewpoint of improving the durability of the film, and from the same viewpoint, is preferably 500,000 or less.

[0079] [Component (X)] Examples of the component (X) having an ester group in the main chain include condensates of dicarboxylic acids such as adipic acid, sebacic acid, dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and alkenylsuccinic acid with diols such as ethylene glycol, propylene glycol, and butanediol, as well as condensates of compounds having both a hydroxy group and a carboxyl group in one molecule, such as glycolic acid and lactic acid. Examples of the component (X) having an amide group in the main chain include condensates of dicarboxylic acids such as adipic acid, sebacic acid, dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and alkenylsuccinic acid with diamines such as aliphatic diamines such as ethylenediamine, hexamethylenediamine, and propylenediamine. Examples of the component (X) having a urethane group in the main chain include polymers of diisocyanates such as tolysine diisocyanate, diphenyl isocyanate, xylylene diisocyanate, and hexamethylene diisocyanate with diols such as ethylene glycol, propylene glycol, and butanediol. Examples of the component (X) having an amino group in the main chain include polymers of alkylimines such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, and hexyleneimine. Examples of the component (X) having an ether group in the main chain include polymers of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, and polymers of formaldehyde. Examples of the component (X) having a carbonate group in the main chain include condensation products of phosgene with polyols such as 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, and 1,1-bis(4-hydroxyphenyl)cyclohexane. Examples of the component (X) having a siloxane group in the main chain include silicone elastomers and silicone acrylates.

[0080] [Component (Y)] Examples of methacrylic or acrylic polymers having an ester group or an amide group in a side chain (also simply referred to as a (meth)acrylic polymer in this specification) include polyalkyl(meth)acrylates such as polymethyl(meth)acrylate, polyethyl(meth)acrylate, and polybutyl(meth)acrylate; copolymers with acrylic such as styrene acrylic and urethane acrylic; and poly(meth)acrylamides such as poly(meth)acrylamide, poly-N-methyl(meth)acrylamide, poly-N,N-dimethyl(meth)acrylamide, and poly-N-phenyl(meth)acrylamide.

[0081] In the present invention, from the viewpoint of improving the durability of the film, (X) a polymer compound having a urethane group in the main chain and / or (Y) a methacrylic or acrylic polymer compound having an ester group or an amide group in the side chain is preferred. In addition, a styrene polymer may also be used.

[0082] Component (G) is preferably incorporated in the form of an emulsion or dispersion. When component (G) is added, it is preferable to prepare a mixture containing components (A) to (C) and then mix the mixture with component (G).

[0083] By incorporating component (G), when the composition of the present invention is applied to a target substrate to form a dry film on the substrate, it is possible to improve the adhesion between the dry film and the target substrate.In particular, when applied to the surface of metals such as stainless steel, aluminum, copper, etc., or the surface of plastics such as polyethylene, polypropylene, polycarbonate, acrylic, etc., or the dried coating film of acrylic, epoxy, silyl, or urethane paints, such as architectural paints, antifouling paints, anticorrosion paints, marine paints, automotive paints, industrial paints, anti-snow paints, and household paints, the adhesion after drying is significantly improved. The viscosity of the composition can be increased by blending a polymer emulsion into the composition, which can prevent dripping even when the composition is applied thickly to a vertical surface. From the viewpoint of durability, the amount of component (G) to be blended is preferably 10 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 100 parts by mass or more, calculated as net component (G), per 100 parts by mass of anion-modified cellulose fiber; on the other hand, from the viewpoint of the synovial properties of the film, it is preferably 5,000 parts by mass or less, more preferably 3,000 parts by mass or less, and even more preferably 2,000 parts by mass or less.

[0084] The breaking elongation of the film (dry film) obtained by drying the composition obtained by blending component (G) is preferably 50% or more, more preferably 100% or more, and even more preferably 200% or more, from the viewpoint of improving the adhesion between the dry film and the target substrate. The elastic modulus of the dry film is preferably 3 GPa or less, more preferably 1 GPa or less, and even more preferably 0.5 GPa or less, from the viewpoint of improving the adhesion between the dry film and the target substrate.

[0085] <Other ingredients> In addition to the above components, the composition of the present invention may contain antifouling agents, antibacterial compounds (e.g., organic synthetic antibacterial agents, natural antibacterial agents, and inorganic antibacterial agents), plasticizers, nucleating agents, fillers (inorganic fillers, organic fillers), hydrolysis inhibitors, flame retardants, antioxidants, lubricants such as hydrocarbon waxes and anionic surfactants, UV absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, foaming agents, surfactants; polysaccharides such as starches and alginic acid; natural proteins such as gelatin, glue, and casein; inorganic compounds such as tannins, zeolites, ceramics, and metal powders; fragrances; flow control agents; leveling agents; conductive agents; UV dispersants; and deodorizers, as long as the effects of the present invention are not impaired. Similarly, other polymeric materials and other compositions may also be added as long as the effects of the present invention are not impaired.

[0086] The composition of the present invention is a composition obtained by blending the above-mentioned components (A), (B), (C), and (D), and it is preferable to further blend water, component (E), and / or component (F) as necessary.

[0087] <Properties of the composition> The composition of the present invention contains the above-mentioned components (A), (B), (C) and (D) as essential components.

[0088] The content of component (A) in the composition or during the preparation of the composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more, from the viewpoint of stability of the composition, while from the viewpoint of handleability it is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1.5% by mass or less, and even more preferably 1.2% by mass or less.

[0089] Regarding the ratio of component (C) to component (A), from the viewpoint of the stability of the composition, the content of component (A) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, even more preferably 3 parts by mass or more, and even more preferably 8 parts by mass or more, per 100 parts by mass of component (C); on the other hand, from the viewpoint of handleability, the content is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.

[0090] The content of component (B) in the composition of the present invention or during preparation of the composition of the present invention is, from the viewpoint of the strength of the film to be formed and the stability of the composition, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 40 parts by mass or more, and even more preferably 50 parts by mass or more, per 100 parts by mass of component (C); on the other hand, from the viewpoint of film-forming properties, it is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 80 parts by mass or less.

[0091] Furthermore, the ratio of component (A) to component (B), calculated as [[number of moles of cationic functional groups in component (B)] / [number of moles of anionic groups in component (A)]] × 100 (%), is preferably 50% or more, more preferably 100% or more, and even more preferably 125% or more, from the viewpoint of increasing the amount of component (C) retained in the formed film, while from the viewpoint of the stability of the composition of the present invention, it is preferably 500% or less, more preferably 300% or less.

[0092] The content of component (D) in the composition of the present invention or during the preparation of the composition of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, from the viewpoint of synovial fluid durability and sand and dust resistance, while from the viewpoint of handleability during blending, it is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0093] The content of component (D) in the composition of the present invention or when preparing the composition of the present invention is, from the viewpoint of synovial fluid durability and sand and dust resistance, preferably 20 parts by mass or more, more preferably 50 parts by mass or more, when component (A) is taken as 100 parts by mass. On the other hand, from the viewpoint of handleability during blending, the content of component (D) is preferably 2,000 parts by mass or less, more preferably 1,000 parts by mass or less, even more preferably 700 parts by mass or less, and even more preferably 500 parts by mass or less, when component (A) is taken as 100 parts by mass.

[0094] Furthermore, with regard to the ratio of component (C) to component (D), from the viewpoints of synovial fluid durability and sand and dust resistance, the content of component (D) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more, per 100 parts by mass of component (C); on the other hand, from the viewpoint of handleability during blending, the content is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 75 parts by mass or less, and even more preferably 70 parts by mass or less.

[0095] In the present invention, when a wetting agent of component (E) is contained or blended, the content or blending amount of component (E) in the composition of the present invention or during preparation of the composition of the present invention is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.1 mass% or more, and on the other hand, is preferably 5 mass% or less, more preferably 2 mass% or less, even more preferably 1 mass% or less.

[0096] In the present invention, it is preferable to contain or incorporate component (F) from the viewpoint of suppressing aggregation of hydrophobic components in water. The content or blending amount of component (F) in the composition of the present invention or when preparing the composition of the present invention is, from the viewpoint of exerting the above-mentioned effects, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of aggregation suppression, when an anionic surfactant is used as component (F), and preferably 1% by mass or less, more preferably 0.5% by mass or less, from the viewpoint of water resistance of the film. When an anionic polymer dispersant is used as component (F), the content is preferably 0.01% by mass or more, more preferably 0.04% by mass or more, from the viewpoint of aggregation suppression, and preferably 0.5% by mass or less, more preferably 0.2% by mass or less, even more preferably 0.15% by mass or less, from the viewpoint of aggregation suppression and synovial properties. When an anionic polymer dispersant is used as component (F), and a counter cation component is used or is blended as a salt, the content of component (F) does not include the content of the counter cation component.

[0097] The water content in the composition of the present invention or during preparation of the composition of the present invention is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 80% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less.

[0098] The composition of the present invention may be an emulsion composition. In this case, the emulsion composition of the present invention is an inorganic fine particle-containing emulsion composition containing component (A), component (B), component (C), and component (D). The emulsion state is determined by visually observing the composition, and if it is cloudy, it is considered to be in an emulsion state. The emulsion composition of the present invention may be either an O / W type emulsion or a W / O type emulsion, but is preferably an O / W type emulsion.

[0099] Applications of the composition or inorganic fine particle-containing emulsion composition of the present invention include, for example, coating agents that impart antifouling properties, waterproofing properties, and properties that prevent the adhesion of snow, bacteria, and the like to various surfaces placed outdoors, such as coating agents for road facilities such as signs, road signs, traffic lights, and electronic bulletin boards; bodies and glass surfaces and headlights of automobiles, airplanes, trains, ships, agricultural and industrial heavy machinery, motorcycles, and the like; sensors; roofs, exterior walls, windows, storage tanks, cooling towers, piping, outdoor units, carports, tents, offshore facilities, quays, bridges, power plant facilities, electric wires, and solar panels.

[0100] The composition of the present invention or the inorganic fine particle-containing emulsion composition can be produced by mixing the above-mentioned components. For the mixing treatment, a magnetic stirrer, a mechanical stirrer, a homomixer, a vacuum emulsifier, a low-pressure homogenizer, a high-pressure homogenizer, a grinder, a cutter mill, a ball mill, a jet mill, a single-screw extruder, a twin-screw extruder, an ultrasonic agitator, a household juicer mixer, etc. The mixing treatment may be carried out by combining two or more types of operations.

[0101] The temperature and time when mixing the components are not particularly limited, but are preferably within the temperature range of 5 to 50° C. and the time range of 1 minute to 3 hours, for example.

[0102] The preferred ranges of the content of each component, the ratio between components, etc. are the same as those preferred ranges for the composition of the present invention described above.

[0103] At any stage in the production process of the composition, components or compositions containing anionically modified cellulose fibers can be subjected to a micronization treatment to reduce the micrometer-scale cellulose fibers to the nanometer scale. Reducing the average fiber diameter of the anionically modified cellulose fibers to the nanometer scale improves the stability of the composition and the strength of the film when formed, so it is preferable to carry out such a micronization treatment step.

[0104] A known dispersing machine is preferably used as the apparatus used in the micronization treatment. For example, a disintegrator, a beater, a low-pressure homogenizer, a high-pressure homogenizer, a grinder, a cutter mill, a ball mill, a jet mill, a single-screw extruder, a twin-screw extruder, an ultrasonic agitator, a household juicer mixer, etc. can be used. In addition, the solid content of the target material in the micronization treatment is preferably 50% by mass or less. The operating conditions of the apparatus during the micronization treatment can be appropriately set by a person skilled in the art based on known operating conditions or the operating conditions described in the instruction manual for each apparatus.

[0105] The film of the present invention can be produced by drying the composition of the present invention or the inorganic fine particle-containing emulsion composition to form a film. For example, the composition of the present invention is applied to a hard surface (e.g., a metal surface, a resin surface, a glass surface, a porcelain surface, a ceramic surface) and the like, and the composition is dried at room temperature and normal pressure, or if necessary, by heating or reducing the pressure, to form a film. In the membrane, the anion-modified cellulose fiber of component (A) and the hydrophobic compound having a cationic functional group of component (B) form a salt.

[0106] The film exhibits the synovial surface properties shown in the literature (Technology of Super Water-Repellent, Super Oil-Repellent, and Synovial Surfaces / Publisher: Hiroshi Motoki / Publisher: Science & Technology Co., Ltd. / Published January 28, 2016). In this specification, a film that exhibits such synovial surface properties (or simply "synovial properties") is also referred to as a "synovial surface film." The synovial surface properties can be measured, for example, by the method described in the "Sliding Angle Measurement Test" in the Examples below. The smaller the sliding angle value, the higher the synovial properties of the film. [Example]

[0107] The present invention will be specifically described below with reference to examples. Note that the following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention. Note that "normal pressure" refers to 101.3 kPa, and "normal temperature" refers to 25°C.

[0108] [Confirmation of crystalline structure in various cellulose fibers] The crystal structure of various celluloses such as cellulose raw materials, anion-modified cellulose fibers, and modified cellulose fibers is confirmed by measurement using a diffractometer (MiniFlex II, manufactured by Rigaku Corporation) under the following conditions. Measurement pellet preparation conditions: A pressure of 10 to 20 MPa was applied to the target cellulose using a tablet press to form pellets with an area of ​​320 mm 2 Prepare a smooth pellet with a thickness of 1 mm. X-ray diffraction analysis conditions: step angle 0.01°, scan speed 10° / min, measurement range: diffraction angle 2θ = 5 to 40° X-ray source: Cu / Kα-radiation, tube voltage: 15kv, tube current: 30mA Peak splitting conditions: After removing background noise, the peak is fitted with a Gaussian function so that the error between 2θ = 13-23° is within 5%. The crystalline structure of each type of cellulose is confirmed by measurement using the above-mentioned diffractometer under the above-mentioned conditions. The crystallinity of the cellulose type I crystal structure is calculated based on the following formula (A) using the area of ​​the X-ray diffraction peak obtained by the above-mentioned peak division. Cellulose type I crystallinity (%) = [I cr / (I cr +I am )]×100 (A) [In the formula, I cr is the area of ​​the diffraction peak of the lattice plane (002 plane) (diffraction angle 2θ = 22-23°) in X-ray diffraction, I am indicates the area of ​​the diffraction peak of the amorphous part (diffraction angle 2θ = 18.5°).

[0109] [Average fiber diameter and average fiber length of various cellulose fibers] Depending on the size of the cellulose fibers to be measured, one of the following two measurement methods was selected for measurement. (1) Deionized water or N,N-dimethylformamide (DMF) was added to the cellulose fibers to be measured to prepare a dispersion with a DMF content of 0.0001% by mass. The dispersion was dropped onto mica and dried to prepare an observation sample. The fiber height (height difference between the presence and absence of fibers) of the cellulose fibers in the observation sample was measured using an atomic force microscope (AFM) (Digital Instruments, Nanoscope II Tapping mode AFM; Nanosensors, Point Probe (NCH) probe). One hundred cellulose fibers were extracted from the microscope image in which the cellulose fibers were visible, and the average fiber diameter was calculated from their fiber height. The average fiber length was calculated from the distance in the fiber direction. (2) Deionized water was added to the cellulose fibers to be measured to prepare a dispersion with a cellulose content of 0.01% by mass. This dispersion was measured using a wet dispersion image analysis particle size distribution analyzer (IF-3200, manufactured by Jusco International) under the following conditions: front lens: 2x, telecentric zoom lens: 1x, image resolution: 0.835 μm / pixel, syringe inner diameter: 6515 μm, spacer thickness: 500 μm, image recognition mode: ghost, threshold: 8, analysis sample volume: 1 mL, and sampling: 15%. The cellulose fibers were then approximated as a rectangle, with the length of the minor axis being the fiber diameter and the length of the major axis being the fiber length. Each value was measured for 100 cellulose fibers, and the average was calculated.

[0110] [Anionic Group Content of Anion-Modified Cellulose Fiber] A 100 mL beaker is filled with 0.5 g of dry cellulose fiber to be measured, and deionized water or a 2:1 methanol / water mixture is added to make a total volume of 55 mL. 5 mL of 0.01 M sodium chloride aqueous solution is then added to prepare a dispersion. The dispersion is stirred until the cellulose fiber to be measured is fully dispersed. 0.1 M hydrochloric acid is added to the dispersion to adjust the pH to 2.5-3. Using an automatic titrator (DKK-TOA Corporation, AUT-701), 0.05 M sodium hydroxide aqueous solution is added dropwise to the dispersion with a waiting time of 60 seconds, and the conductivity and pH values ​​are measured every minute. Measurements are continued until the pH reaches approximately 11, and a conductivity curve is obtained. The sodium hydroxide titration amount is determined from this conductivity curve, and the anionic group content of the cellulose fiber to be measured is calculated using the following formula: Anionic group content (mmol / g) = [sodium hydroxide titration amount × sodium hydroxide aqueous solution concentration (0.05 M)] / [mass of cellulose fiber to be measured (0.5 g)]

[0111] [Solid content in dispersion] The measurement is performed using an infrared moisture meter (Shimadzu Corporation, MOC-120H). Measurements are performed every 30 seconds on 1 g of sample at a constant temperature of 150°C, and the value when the mass loss is 0.1% or less of the initial amount of the sample is taken as the solid content.

[0112] [Measurement of emulsion droplet size by laser diffraction method] The particle size of the emulsified droplets is measured by laser diffraction using an LA-960 manufactured by Horiba Ltd. Measurement conditions: Add water to the measurement cell, and measure the volume particle size distribution and volume median particle size (D 50 ) is measured. D 50 The value is the particle size of the emulsion droplets. The relative refractive index is 1.40, the temperature is 25°C, the circulation pump is ON, the circulation speed is 5, and the stirring speed is 5.

[0113] [Glucose moiety in anion-modified cellulose fiber] With regard to the mass of the glucose portion in anion-modified cellulose fibers and micronized anion-modified cellulose fibers, the "mass of the glucose portion" refers to the entire glucose unit including the anionic group bonded to the glucose unit, i.e., the glucose unit in which the hydroxymethyl group has been converted to a carboxy group.

[0114] [Anion-modified cellulose fiber] As the anion-modified cellulose fiber, one having the physical properties shown in Table 1, that is, anion-modified cellulose fiber 1, was used.

[0115] [Table 1]

[0116] Such anionically modified cellulose fibers can be prepared, for example, by the method described in the TEMPO oxidation treatment below.

[0117] [TEMPO oxidation treatment] 10 g of bleached softwood kraft pulp fiber (natural cellulose fiber) and 990 g of deionized water were weighed into a 2-liter polypropylene beaker equipped with a mechanical stirrer and impeller and stirred at 25°C and 100 rpm for 30 minutes. Next, 0.13 g of TEMPO, 1.3 g of sodium bromide, and 35.5 g of a 10.5% by weight sodium hypochlorite solution were added to the 10 g of pulp fiber in this order. Next, pH stat titration was performed using an automatic titrator, and the pH was maintained at 10.5 by dropwise addition of 0.5 M sodium hydroxide solution. The reaction was carried out at 25°C for 120 minutes with stirring at 100 rpm.

[0118] Next, 1 M hydrochloric acid is added to the suspension while stirring to adjust the pH of the suspension to 2. The solids are then separated by suction filtration. The solids are dispersed in deionized water and the solids are separated by suction filtration. This procedure is repeated until the conductivity of the filtrate reaches 200 μs / cm or less. The resulting solids are then dehydrated to obtain anion-modified cellulose fibers.

[0119] Next, 1 M hydrochloric acid is added to the suspension while stirring to adjust the pH of the suspension to 2. The solids are then separated by suction filtration. The solids are dispersed in deionized water and the solids are separated by suction filtration. This procedure is repeated until the conductivity of the filtrate reaches 200 μS / cm or less. The resulting solids are then dehydrated to obtain the anion-modified cellulose fibers listed in Table 1.

[0120] [Preparation of dispersion of finely divided anion-modified cellulose fibers (component (A))] [Dispersion of fine anion-modified cellulose fiber 1] 949.2 g of deionized water and 30.8 g of 1 mol / L ammonia water were added to the anion-modified cellulose fiber 1 to prepare 1,020 g of a suspension (solid content: 1.0% by mass). This suspension was subjected to a single micronization treatment at 150 MPa using a high-pressure homogenizer (NanoVeita L-ES, manufactured by Yoshida Kikai Co., Ltd.) to obtain a dispersion of micronized anion-modified cellulose fiber 1 (solid content: 1.0% by mass). The obtained micronized anion-modified cellulose fiber had a carboxy group content of 1.40 mmol / g, an average fiber diameter of 3.3 nm, an average fiber length of 600 nm, and a crystallinity of 60%.

[0121] [Preparation of inorganic fine particle-containing emulsion composition] Examples 1 to 11 [Mixture 1] Mixture 1 was obtained by mixing 30 g of the dispersion of the above-mentioned finely divided anion-modified cellulose fiber 1 (solid content 1.0 mass%), 15 g of deionized water, and 0.20 g of a 10 mass% aqueous polyacrylic acid solution prepared by adding polyacrylic acid (component (F)) to deionized water.

[0122] [Mixture 2] A mixture of 2.4 g of silicone oil (component (C)), 1.79 g of amino-modified silicone (component (B)), and component (D) listed in Tables 2 and 3 was stirred and mixed at 2000 rpm for 20 minutes using a planetary centrifugal mixer (Thinky Corporation, Awatori Rentaro ARE-310) to obtain mixture 2. The ratio of component (A) to component (B) was calculated using the formula [[number of moles of cationic functional groups in component (B)] / [number of moles of anionic groups in component (A)]] × 100 (%) and is shown in Tables 2 and 3. The amount of component (D) used was the amount listed in Tables 2 and 3.

[0123] [Emulsified composition containing inorganic fine particles] The entire amount of Mixture 1 obtained by the above operation was transferred to a beaker, and then the entire amount of Mixture 2 was added and stirred for 1 minute at room temperature using a mechanical stirrer. The obtained mixture was processed six times at 150 MPa using a high-pressure homogenizer (NanoVeita L-ES, manufactured by Yoshida Kikai Co., Ltd.) to obtain Mixture 3. All Mixtures 3 were cloudy liquids, and oil droplets dispersed in water were observed using an optical microscope, and therefore were determined to be inorganic fine particle-containing emulsion compositions. The volume median particle diameter (D 50 ) are listed in Tables 2 and 3. Polyether-modified silicone (component (E)) was added to mixture 3 so as to obtain the composition shown in Tables 2 and 3, and mixed to prepare the inorganic fine particle-containing emulsion compositions shown in Tables 2 and 3.

[0124] [Preparation of inorganic fine particle-containing emulsion composition] Comparative Example 1 [Mixture A] Mixture A was obtained by mixing 70 g of the dispersion of the above-mentioned finely divided anion-modified cellulose fiber 1 (solid content 1.0 mass%), 25.7 g of deionized water, and 0.42 g of a 10 mass% aqueous polyacrylic acid solution prepared by adding polyacrylic acid (component (F)) to deionized water.

[0125] [Mixture B] A mixture of 4.2 g of silicone oil (component (C)) and 4.17 g of amino-modified silicone (component (B)) was stirred and mixed at 2000 rpm for 20 minutes using a planetary centrifugal mixer (Thinky Corporation, Awatori Rentaro ARE-310) to obtain mixture B. The ratio of component (A) to component (B) was calculated using the formula [[number of moles of cationic functional groups in component (B)] / [number of moles of anionic groups in component (A)]] × 100 (%) and is shown in Table 3.

[0126] [Emulsifying composition] The entire amount of mixture A obtained by the above operation was transferred to a beaker, and then the entire amount of mixture B was added and stirred for 1 minute at room temperature using a mechanical stirrer. The obtained mixture was processed six times at 150 MPa using a high-pressure homogenizer (Yoshida Kikai Co., Ltd., Nanovaita L-ES) to obtain mixture C. The obtained mixture was a cloudy liquid, and since it was observed under an optical microscope that oil droplets were dispersed in water, it was determined to be an emulsion composition. The volume median particle diameter (D 50 ) were as listed in Table 3. Titanium dioxide (component (D')) prepared as a 30 mass% aqueous dispersion and polyether-modified silicone (component (E)) were added to mixture C in this order and mixed so as to obtain the composition shown in Table 3, thereby preparing the emulsion composition of Comparative Example 1.

[0127] Test Example [Preparation of dry film] Each of the inorganic microparticle-containing emulsion compositions of the examples and comparative examples obtained above was applied to a glass slide (26 mm x 76 mm) using a pipette so that the film thickness after drying would be 80 μm, and the film was dried for 24 hours under conditions of an air temperature of 25°C and a relative humidity of 40% to obtain a dried film.

[0128] [Measurement of dry film thickness] A portion of the dried film prepared as described above was scraped off with a metal spatula to expose the surface of the glass slide. Images of the dried film surface and the glass slide surface were taken with a laser microscope (Lasertec Corporation, OPTELICS HYBRID+, light source: xenon lamp, objective lens: Nikon TU Plan Fluor 10x, NA: 0.30). The heights of the glass slide surface and the dried film surface were calculated using the built-in image software, and the difference between them was taken as the thickness of the dried film.

[0129] [Measurement of Martens hardness] The Martens hardness of each of the prepared dried films was measured using a dynamic ultra-microhardness tester (DUH-211, manufactured by Shimadzu Corporation) under the following measurement conditions. Each sample was measured five times in total, and the average value was used as the measured value. Test mode: Indenter push-in test Test force: 1.5 mN Load speed: 0.15mN / sec Load holding time: 5 seconds Indenter type: Triangular 115 Indenter elastic modulus: 1.14 x 10 6 N / mm 2

[0130] [Oil Bleed Rate Measurement] For each dried film, a PP porous film (GATSBY oil blotting film manufactured by Mandom Corporation) was pressed against the entire surface to remove the component (C) that had bled onto the film surface. This operation was repeated twice, and the weight of the absorbed component (C) was quantified from the change in weight of the dried film before and after removal. The oil-bleed rate of component (C) was then measured using the following formula. formula: (Oil bleeding rate) [wt%] = (weight of component (C) absorbed by the PP porous film) / (weight of dry film before oil removal) × 100

[0131] [Measurement of dust adhesion amount] As the sand dust, JIS Z 8901 test powder 1 type 8 (Kanto loam baked product) was passed through a sieve with a mesh size of 160 μm and sprinkled over the entire surface of each dried film integrated with the glass slide substrate. The glass slide was then inverted to remove excess sand dust from the film. The weight of the sand dust adhering to the dried film was then taken as the amount of sand dust adhesion. Note that any sand dust that had fallen on the glass slide other than the film was removed with a Kimwipe before measuring the amount of sand dust adhesion.

[0132] [Slide angle measurement test] The dried film immediately after preparation and the dried film after the durability acceleration test described below were placed horizontally, and 20 μL of deionized water (23 ° C) was dropped onto each film using a fully automatic contact angle meter (DropMaster DMo-702, manufactured by Kyowa Interface Science Co., Ltd.) at an air temperature of 23 ° C and a relative humidity of 40%, and the film was left to stand for 10 seconds. Next, the film surface was tilted to 85 ° at a speed of 1 ° / s, and the angle at which the droplet began to slide was measured. The smaller the droplet sliding angle, the higher the synovial property of the film. A sliding angle of 75 ° or less can be evaluated as having a certain degree of synovial property. For Comparative Example 1, measurement was not possible because the dried film peeled off.

[0133] [Accelerated durability test] The above-mentioned dried film was fixed together with the glass slide substrate in an accelerated weathering tester (Super Xenon Weather Meter SX75, manufactured by Suga Test Instruments Co., Ltd.) with the surface oriented vertically, and the above-mentioned dried film was exposed for 144 hours under the following conditions: Condition 1, followed by Condition 2, which were repeated. This accelerated durability test evaluated whether the film could maintain its synovial properties when exposed to rainwater and sunlight. The "unmeasurable" mark in the table indicates that the film peeled off during the accelerated durability test, making it impossible to perform the measurement. The synovial fluid retention rate (%) in the table is a value defined as "[sliding angle before accelerated durability test] / [sliding angle after accelerated durability test]×100".

[0134] Condition 1 Xenon lamp radiant intensity: 180W / m 2 Tank temperature: 28℃ Humidity inside the tank: 98%RH Deionized water spray pressure: 0.1 MPa (0.48 L / min) Duration: 18 minutes Condition 2 Xenon lamp radiant intensity: 180W / m 2 Black panel temperature: 63℃ Humidity inside the tank: 50%RH Duration: 1 hour 42 minutes

[0135] The compositions and evaluation results in the above examples are shown in Tables 2 and 3. The details of the reagents used in the above examples are as follows: [Component (B)] Amino-modified silicone: Dow Toray, DOWSIL™ FZ-3710, viscosity: 800-1,000 mm 2 / s (Dow Corning Corporate Test CTM0004), Amino equivalent: 1,660-1,900g / mol [Component (C)] Silicone oil: KF-96-100CS manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3. This component (C) had no cationic functional groups and was liquid at 25° C. and 1 atmosphere. [Component (D)] Trimethylsiloxysilicate: Wacker Asahi Kasei Silicone Co., Ltd., BEISIL TMS 803, median particle size: 10 μm, surface functional group: trimethylsilyl Polymethylsilsesquioxane 1: Shin-Etsu Chemical Co., Ltd., KMP-590, average particle size: 2 μm, surface functional group: monomethylsilyl Polymethylsilsesquioxane 2: Shin-Etsu Chemical Co., Ltd., KMP-591, average particle size: 5 μm, surface functional group: monomethylsilyl Polymethylsilsesquioxane 3: Shin-Etsu Chemical Co., Ltd., X-52-854, average particle size: 0.7 μm, surface functional group: monomethylsilyl Fumed silica 1: AEROSIL NAX50, manufactured by Nippon Aerosil Co., Ltd., primary particle size: 30 nm, surface functional group: trimethylsilyl Fumed silica 2: AEROSIL RX300, manufactured by Nippon Aerosil Co., Ltd., primary particle size: 7 nm, surface functional group: trimethylsilyl Fumed silica 3: AEROSIL RY200, manufactured by Nippon Aerosil Co., Ltd., primary particle size: 12 nm, surface functional groups: dimethylsilyl, trimethylsilyl (silicone oil modified) Fumed silica 4: AEROSIL R974, manufactured by Nippon Aerosil Co., Ltd., primary particle size: 12 nm, surface functional group: dimethylsilyl Fumed silica 5: AEROSIL R976S, manufactured by Nippon Aerosil Co., Ltd., primary particle size: 7 nm, surface functional group: dimethylsilyl

[0136] [Component (D')] Titanium dioxide: Sakai Chemical Industry Co., Ltd., STR-100N, primary particle size: 15 nm [Component (E)] Polyether modified silicone: Shin-Etsu Chemical Co., Ltd., KF-642, HLB: 12, dynamic viscosity Degrees (25℃): 50mm 2 / s [Component (F)] Polyacrylic acid: Nippon Shokubai Co., Ltd., Aqualic HL-415, solid content: 45% by mass, weight average molecular weight: 10,000 Ammonia (as a counter cation component): Kanto Chemical Co., Ltd., 1 mol / L ammonia water (1N) Deionized water

[0137] [Table 2]

[0138] [Table 3]

[0139] From the above evaluation results, it was found that the dry films formed using the compositions of the present invention maintained a considerable degree of synovial fluid resistance, as they had a sliding angle of 75° or less even after the accelerated durability test. Furthermore, the dry films formed using the compositions of the present invention all had a small amount of sand and dust adhesion, indicating that they had strong resistance to sand and dust. Thus, it was found that the films of the present invention can achieve both resistance to sand and dust and durability of synovial fluid performance against long-term exposure. The improved sand and dust resistance is thought to be due to the fact that the surface hardness of the film can be improved by incorporating hard inorganic fine particles into component (C), the main component of the film, and as a result, the amount of sand and dust adhesion to the film itself can be reduced. In contrast, in Comparative Example 1, in which titanium dioxide, i.e., inorganic fine particles without hydrophobic groups, was used instead of the inorganic fine particles with hydrophobic groups of component (D), the obtained dried film had sand and dust resistance, but the film peeled off during the accelerated durability test, making it impossible to evaluate after the accelerated durability test, and it was therefore found to have significantly inferior durability. [Industrial Applicability]

[0140] The composition of the present invention can form a synovial film with excellent synovial fluid durability when used outdoors, and can therefore be used as a paint or coating agent for outdoor structures.

Claims

1. A composition containing the following components (A), (B), (C) and (D): (A) Anion-modified cellulose fiber (B) Hydrophobic compound having a cationic functional group (C) Organic compounds that are liquid at 25°C and 1 atmosphere (excluding those that fall under the category of component (B) above). (D) Inorganic fine particles having hydrophobic groups

2. The composition of claim 1 further comprising component (E). (E) Wetting agent (excluding those corresponding to the above-mentioned component (C))

3. The composition of claim 1 further comprising component (F). (F) Aggregation inhibitor (excluding those corresponding to the above-mentioned component (E))

4. The composition according to claim 1, wherein the content of component (A) is 0.1 parts by mass or more and 50 parts by mass or less per 100 parts by mass of component (C).

5. The composition according to claim 1, wherein the content of component (D) is 1 part by mass or more and 100 parts by mass or less per 100 parts by mass of component (C).

6. The composition according to claim 1, wherein the content of component (D) is 20 parts by mass or more and 2,000 parts by mass or less per 100 parts by mass of component (A).

7. The composition according to claim 1, wherein the content of component (D) is 0.1% by mass or more and 15% by mass or less.

8. The composition of claim 1, wherein the hydrophobic group in component (D) is a silyl group and / or a dimethylsilicone modification.

9. A composition comprising the following components (A), (B), (C) and (D): (A) Anion-modified cellulose fiber (B) Hydrophobic compound having a cationic functional group (C) Organic compounds that are liquid at 25°C and 1 atmosphere (excluding those that fall under the category of component (B) above). (D) Inorganic fine particles having hydrophobic groups

10. An inorganic fine particle-containing emulsion composition comprising the following components (A), (B), (C) and (D): (A) Anion-modified cellulose fiber (B) Hydrophobic compound having a cationic functional group (C) Organic compounds that are liquid at 25°C and 1 atmosphere (excluding those that fall under the category of component (B) above). (D) Inorganic fine particles having hydrophobic groups

11. A coating agent comprising the composition according to any one of claims 1 to 9 or the inorganic fine particle-containing emulsion composition according to claim 10.

12. A film obtained by drying the composition according to any one of claims 1 to 9 or the inorganic fine particle-containing emulsion composition according to claim 10.

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