Emulsion composition

Abstract

To provide an emulsion composition that can form a film having long-lasting synovial properties, and a coating composition.SOLUTION: An emulsion composition contains a component (A): cellulose fiber having a modifying group, a component (B): water, a component (C): an organic compound being liquid at 25°C and 1 atmospheric pressure, and a component (D): soluble resin. There is also provided a coating composition containing the emulsion composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an emulsion composition. The present invention further relates to a coating composition containing such an emulsion composition. [Background technology]

[0002] Previous attempts have been made to prevent the adhesion of dirt by making objects water-repellent. Recently, slippery liquid-infused porous surfaces (SLIPS) have been reported, in which a liquid lubricant is impregnated into a network structure or a finely textured surface. This allows water and other liquids to slide off at a slight incline, which is more pronounced than with conventional water-repellent technologies. This property is called synovial properties, and it is expected to be applied in a variety of situations. Furthermore, a technology has been disclosed recently in which a film containing specific modified cellulose fibers and an organic medium suppresses the migration of the organic medium, thereby maintaining synovial properties even after repeated use (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-189841 Summary of the Invention [Problem to be solved by the invention]

[0004] The membrane disclosed in Patent Document 1 has a problem in that when it is in contact with running water for a long period of time, the organic medium is gradually lost from the membrane, and the membrane tends to lose its synovial properties. Therefore, the present invention relates to an emulsion composition and a coating composition that can form a film with excellent long-lasting synovial fluid properties. [Means for solving the problem]

[0005] The present invention relates to the following [1] and [2]. [1] An emulsion composition containing the following components (A) to (D): (A) Cellulose fibers with modified groups (B) Water (C) Organic compounds that are liquid at 25°C and 1 atmosphere (D) Melting resin [2] A coating composition comprising the emulsion composition described in [1] above. [Effects of the Invention]

[0006] According to the present invention, it is possible to provide an emulsion composition and a coating composition that can form a film with excellent long-lasting synovial properties. DETAILED DESCRIPTION OF THE INVENTION

[0007] 1. Emulsified composition The emulsion composition of the present invention contains the following components (A) to (D).

[0008] <Component (A)> Component (A) is a cellulose fiber having a modified group. A preferred example of a cellulose fiber having a modifying group is a modified cellulose fiber in which a modifying group is bonded to one or more groups selected from the group consisting of anionic groups and hydroxy groups of an anion-modified cellulose fiber having a type I crystal structure.

[0009] [Anion-modified cellulose fiber] Anion-modified cellulose fibers are cellulose fibers modified to contain anionic groups. Anion-modified cellulose fibers preferably have a cellulose type I crystal structure derived from the raw cellulose fibers. From the viewpoint of improving the durability of the synovial properties of the membrane, the 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 crystallinity is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, and even more preferably 75% or less.

[0010] 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.

[0011] 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 the efficiency of introducing the modifying group into the cellulose fiber, the anionic group is preferably a carboxy group. Examples of the ion (counter ion) that forms a pair with the anionic group in the anion-modified cellulose fiber 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 an acid. As the anion-modified cellulose fiber, a carboxy group-containing cellulose fiber in which the anionic group is a carboxy group is more preferred from the viewpoints of ease of preparation and mild reaction conditions.

[0012] 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, even more preferably 0.6 mmol / g or more, and even more preferably 0.8 mmol / g or more, from the viewpoint of introducing modifying groups. Furthermore, from the viewpoint of improving handleability, it is preferably 3 mmol / g or less, more preferably 2 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.

[0013] 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 strength when formed into a film. The average fiber diameter of the anion-modified cellulose fiber is measured by the method described in the examples below.

[0014] [Modified cellulose fiber] Cellulose fibers having a modifying group are also referred to herein as modified cellulose fibers. From the viewpoint of improving the durability of the synovial fluid properties of the membrane, the modified cellulose fibers are preferably anion-modified cellulose fibers in which a modifying group is bonded to an anionic group or a hydroxy group. The modifying group is introduced by reacting the anion-modified cellulose fiber with a compound for introducing the modifying group (referred to herein as a "modifying compound"). That is, the structure of the modifying group depends on the structure of the modifying compound used.

[0015] When the bonding site of the modifying group is a hydroxy group, the bonding mode between the modifying group and the anion-modified cellulose fiber is a covalent bond, for example, an ether bond, an ester bond, or a carbonate bond.

[0016] When the bonding site of the modifying group is an anionic group, the bonding mode between the modifying group and the anion-modified cellulose fiber is an ionic bond or a covalent bond. Here, when the bonding mode is an ionic bond, the modifying compound having a cationic group bonds to the anionic group via electrostatic interaction. Here, when the bonding mode is a covalent bond, the two are bonded via an ester bond, an amide bond, or the like. In particular, when the anionic group is a carboxy group, the bonding mode is via an ester bond, an amide bond, a carbonate bond, a urethane bond, or the like.

[0017] [Modifying group] The modifying groups include (a) polymer groups and (b) hydrocarbon groups, from the viewpoint of improving the durability of the synovial fluidity of the membrane. These modifying groups may be attached to the anion-modified cellulose fibers either alone or in combination.

[0018] (a) polymer group The polymer group is a functional group containing a polymer structure. From the viewpoint of improving the durability of the synovial fluidity of the membrane, the functional group equivalent of the polymer group is preferably 100 g / mol or more, more preferably 200 g / mol or more, even more preferably 300 g / mol or more, even more preferably 400 g / mol or more, even more preferably 600 g / mol or more, even more preferably 800 g / mol or more, even more preferably 1,500 g / mol or more. From the same viewpoint, it is preferably 20,000 g / mol or less, more preferably 16,000 g / mol or less, even more preferably 14,000 g / mol or less, even more preferably 12,000 g / mol or less, even more preferably 10,000 g / mol or less, even more preferably 7,000 g / mol or less, even more preferably 5,000 g / mol or less, even more preferably 4,000 g / mol or less, even more preferably 3,500 g / mol or less, even more preferably 2,500 g / mol or less. The functional group equivalent is the molecular weight per functional group, and is calculated by functional group equivalent (g / mol) = [weight average molecular weight] / [number of functional groups per molecule].

[0019] From the viewpoint of improving the durability of the synovial properties of the membrane, the weight-average molecular weight of the polymer group 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. The weight average molecular weight in this specification is a value determined by gel permeation chromatography using polystyrene as a standard substance.

[0020] From the viewpoint of improving the durability of the synovial properties of the membrane, the polymer group is preferably a functional group having a repeating structure linked by a structure having an oxygen atom, more preferably a functional group having a repeating structure linked by an oxygen atom, such as a polyoxyalkylene structure or a polysiloxane structure, more preferably a functional group having a polysiloxane structure.

[0021] The polysiloxane structure is a structure having a siloxane bond as the main chain, and may further include an alkylene group. The polysiloxane structure may have a substituent, which will be described later.

[0022] (b) Hydrocarbon group Examples of the hydrocarbon group include monovalent hydrocarbon groups, such as chain saturated hydrocarbon groups, chain unsaturated hydrocarbon groups, cyclic saturated hydrocarbon groups, and (heterocyclic) aromatic hydrocarbon groups.

[0023] From the viewpoint of improving the durability of the synovial properties of the membrane, the number of carbon atoms in the hydrocarbon group is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, even more preferably 4 or more, even more preferably 8 or more, even more preferably 12 or more, even more preferably 16 or more, even more preferably 18 or more, and from the same viewpoint, it is preferably 40 or less, more preferably 30 or less, even more preferably 24 or less, even more preferably 22 or less. The hydrocarbon group may have a substituent as described below, and a part of the hydrocarbon group may be substituted with a hydrogen nitride group.

[0024] (c) Further Substituents The modifying groups such as (a) polymer groups and (b) hydrocarbon groups may further have a substituent. Examples of the substituent include alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, and hexyloxy; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, and sec-butoxycarbonyl; alkoxycarbonyl groups having 1 to 6 carbon atoms, such as 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; dialkylamino groups having an alkyl group with 1 to 6 carbon atoms; and a hydroxy group.

[0025] The bond amount (mmol / g) and introduction rate (mol%) of the modifying group in the modified cellulose fiber refer to the amount and ratio of the modifying group introduced into the modified cellulose fiber. The bond amount and introduction rate of the modifying group can be adjusted by the amount and type of modifying compound added, the reaction temperature, the reaction time, the solvent, etc.

[0026] The amount of the modifying group bonded to the modified cellulose fiber is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, and even more preferably 0.5 mmol / g or more from the viewpoint of improving the durability of the synovial fluidity of the membrane, and is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less, and even more preferably 2 mmol / g or less from the viewpoint of reactivity.

[0027] Furthermore, from the viewpoint of improving the durability of the synovial properties of the membrane, the introduction rate of the modifying group in the modified cellulose fiber is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 40 mol% or more, and even more preferably 50 mol% or more, and from the viewpoint of reactivity, it is preferably 99 mol% or less, more preferably 97 mol% or less, even more preferably 95 mol% or less, and even more preferably 90 mol% or less.

[0028] [Method for producing modified cellulose fibers] The modified cellulose fiber can be produced, for example, by a method comprising the steps of: (1) introducing anionic groups into raw cellulose fiber to obtain anionically modified cellulose fiber; and (2) binding a modifying compound to the anionically modified cellulose fiber obtained by the method comprising step (1) to obtain the modified cellulose fiber.

[0029] (1) A process for obtaining 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 to introduce one or more anionic groups and thereby anionically modifying the fiber.

[0030] Cellulose fibers to be anionically modified, i.e., cellulose fibers used as raw materials for modified cellulose fibers and anionically modified cellulose fibers, are preferably natural cellulose fibers from an environmental perspective, and examples include wood pulp such as softwood pulp and hardwood pulp; cotton pulp such as cotton linter and cotton lint; non-wood pulp such as straw pulp and bagasse pulp; and bacterial cellulose, and these can be used alone or in combination of two or more.

[0031] 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.

[0032] Furthermore, 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. The average fiber diameter and average fiber length of the raw cellulose fibers can be measured according to the method described in the Examples below. 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.

[0033] The anionic group to be introduced includes a carboxy group, a sulfonic acid group, or a phosphoric acid group.

[0034] (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.

[0035] 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.

[0036] By subjecting cellulose fibers to oxidation treatment using TEMPO as a catalyst, the hydroxymethyl group (-CHOH) at the C6 position in 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 fiber derivatives in which the hydroxy groups in the cellulose structural units have been oxidized may be referred to as "oxidized cellulose fibers," and cellulose fiber derivatives in which the C6 position of the cellulose structural units has a carboxy group may be referred to as "TEMPO-oxidized cellulose fibers." Oxidized cellulose fibers are preferred because they are easier to prepare than other anion-modified cellulose fibers. Therefore, one preferred embodiment of the modified cellulose fiber in the present invention is a modified cellulose fiber in which an amino-modified silicone is bonded to an oxidized cellulose fiber, and one more preferred embodiment is a modified cellulose fiber in which an amino-modified silicone is bonded to a TEMPO-oxidized cellulose fiber.

[0037] 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.

[0038] (ii) When sulfonic acid groups or phosphate groups are introduced into cellulose fibers as anionic groups 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.

[0039] (2) A process for obtaining modified cellulose fibers The modified cellulose fiber can be produced by bonding the anion-modified cellulose fiber with one or more compounds selected from the group consisting of a compound having a modifying group, preferably an amino-modified silicone, and a hydrocarbon compound having a cationic group. Such a production method can be a known method, such as the method described in JP 2015-143336 A.

[0040] (Modification compound) From the viewpoint of improving the durability of the synovial properties of the membrane, the modifying compound is a compound that has a modifying group and can bond with anion-modified cellulose fibers, preferably a compound that has a modifying group and can bond with the anionic group or hydroxy group of anion-modified cellulose fibers, more preferably a compound that has a modifying group and a cationic group, even more preferably a compound that has a modifying group and an amino group or a quaternary ammonium group, and even more preferably a primary amine, secondary amine, tertiary amine or quaternary ammonium compound that has a modifying group. Preferred examples of modifying compounds include polymeric compounds having an amino group and hydrocarbon compounds having a cationic group, from the viewpoint of improving the durability of the synovial properties of the membrane.

[0041] (i) Polymer compounds having amino groups Polymer compounds having amino groups that are suitable for use as modifying compounds in the present invention are commercially available or can be prepared according to known methods. Only one type of polymer compound having amino groups may be used, or two or more types may be used.

[0042] The polymer compound having an amino group in the present invention includes resins such as amino-modified silicone, polyoxyalkyleneamine, amino-modified poly(meth)acrylate polymer, amino-modified vinyl polymer, amino-modified polyester, amino-modified polycarbonate, polyallylamine, polyethyleneimine, etc.; chain aliphatic polyamine, cyclic aliphatic polyamine, alicyclic aromatic polyamine, etc., and the position of the reactive group may be any of the main chain, side chain, or terminal of the polymer compound. Among these, amino-modified silicone is preferred from the viewpoint of improving the durability of the synovial property of the film.

[0043] Amino-modified silicone is a silicone compound with an amino group. From the viewpoint of improving the durability of the synovial properties of the membrane, amino-modified silicone has a dynamic viscosity of 10 mm at 25°C. 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.

[0044] The kinematic viscosity at 25°C can be determined using an Ostwald viscometer, and from the viewpoint of improving the durability of the synovial properties of the membrane, 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.

[0045] 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 from the viewpoint of improving the durability of the synovial properties of the membrane, and 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 from the viewpoint of ease of binding to anion-modified cellulose fibers. The amino equivalent is the molecular weight per nitrogen atom and is calculated by the formula: amino equivalent (g / mol) = weight-average molecular weight / number of nitrogen atoms per molecule. Here, the number of nitrogen atoms can be determined by elemental analysis.

[0046] Specific examples of amino-modified silicones include compounds represented by general formula (a1).

[0047] [ka]

[0048] [In formula (a1), R 1a R 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 improving the durability of the synovial properties of the membrane. 2a is a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group, 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 or a hydrogen atom. x and y each represent an average degree of polymerization, 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.

[0049] In the compound of general formula (a1), from the viewpoint of improving the durability of the synovial fluidity of the film, 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 improving the durability of the synovial fluidity of the film, 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.

[0050] 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.)

[0051] 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)

[0052] Furthermore, from the viewpoint of improving the durability of the synovial properties of the membrane, 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)].

[0053] In terms of performance, the amino-modified silicones used in the present invention include TSF4703 (kinematic viscosity: 1000, amino equivalent: 1600) and TSF4708 (kinematic viscosity: 1000, amino equivalent: 2800) manufactured by Momentive Performance Materials, and SS-3551 (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 BY16-892 (kinematic viscosity: 1500, amino equivalent: 1800) manufactured by Dow-Toray. Kinematic viscosity: 2000, 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-80 Preferred are KF-04 (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), and 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.

[0054] 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.

[0055] 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), and SS-3551 (kinematic viscosity: 1000, amino equivalent: 1700) are more preferred.

[0056] The silicone compound may have a substituent. Specific examples of the substituent include those described above under "(c) Further Substituents."

[0057] (ii) Hydrocarbon compounds having cationic groups In the present invention, the hydrocarbon compound having a cationic group is one in which one or more hydrocarbon groups are bonded to one cationic group. The total carbon number of the hydrocarbon compound having a cationic group is preferably 4 or more, more preferably 8 or more, even more preferably 12 or more, even more preferably 16 or more, and even more preferably 18 or more from the viewpoint of improving the durability of the synovial fluidity of the membrane, and is preferably 40 or less, more preferably 30 or less, even more preferably 26 or less, and even more preferably 22 or less from the viewpoint of handleability.

[0058] A hydrocarbon compound having a cationic group is a compound in which the hydrocarbon group is directly bonded to a nitrogen atom or a phosphorus atom via a covalent bond when the cationic group is a primary amine, secondary amine, tertiary amine, quaternary ammonium, phosphonium, etc.; when the cationic group is an amidine, guanidine, etc., the compound is a compound in which the hydrocarbon group is bonded to at least one of the nitrogen atom or carbon atom of the functional group via a covalent bond; when the cationic group is an imidazolium, pyridinium, imidazoline, etc., the compound is a compound in which at least one hydrocarbon group is bonded to any position of the ring structure via a covalent bond. The hydrocarbon compound having a cationic group is more preferably one that does not contain an oxyalkylene group.

[0059] 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.

[0060] The hydrocarbon compound having a cationic 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.

[0061] The hydrocarbon compound having a cationic group may have a substituent. Specific examples of the substituent include those described above in "(c) Further Substituents."

[0062] (Amount of modifying compound used) In the step of obtaining modified cellulose fibers, the equivalent of the functional group reactive with the anionic group of the modifying compound used relative to the anionic group of the anion-modified cellulose fibers is preferably 0.1 equivalents or more, more preferably 0.5 equivalents or more, even more preferably 1 equivalent or more, and even more preferably 1.5 equivalents or more, from the viewpoint of improving the durability of the synovial properties of the film. From the viewpoint of film-forming properties, it is preferably 20 equivalents or less, more preferably 10 equivalents or less, and even more preferably 2 equivalents or less.

[0063] (3) Micro-processing process By micronizing the cellulose at any stage in the manufacturing process of the modified cellulose fiber, it is possible to reduce the micrometer-scale cellulose to the nanometer-scale. By reducing the average fiber diameter to nanometer size, the strength of the film when formed is improved, so it is preferable to carry out an additional micronization treatment step.

[0064] As the apparatus used in the micronization treatment, a known disperser is preferably used. 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 reaction product fiber in the micronization treatment is preferably 50 mass% or less.

[0065] <Ingredient (B)> Component (B) in the present invention is water. Component (B) serves as a solvent when preparing component (A) and as one of the constituents of the emulsion composition of the present invention.

[0066] <Component (C)> Component (C) in the present invention is an organic compound that is liquid at 25° C. and 1 atmosphere. Component (C) may be a solvent used in preparing component (A).

[0067] The solubility of component (C) in water is preferably 10 g or less, and more preferably 1 g or less, per 100 g of water at 25°C. From the viewpoint of improving the durability of the synovial fluidity of the membrane, the 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, and from the same viewpoint, it is preferably 100 or more, more preferably 200 or more.

[0068] 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 improving the durability of the synovial properties of the film, include one or more selected from the group consisting of 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 and / or ester oils.

[0069] 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, glycerol tri-2-ethylhexanoate, and glycerol triisostearate.

[0070] Examples of silicone oils include dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.

[0071] Examples of fats and oils include vegetable oils such as soybean oil, coconut oil, linseed oil, cottonseed oil, rapeseed oil, and castor oil, as well as animal oils.

[0072] From the viewpoint of improving the durability of the synovial properties of the membrane, 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.

[0073] 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).

[0074] 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), and propylene glycol. Fluorine-based inert liquids (e.g., 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-96H-10,000cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), etc.

[0075] <Ingredient (D)> Component (D) in the present invention is a soluble resin. A resin that exhibits solubility under the condition of "contact with running water" is defined as a "soluble resin" in this specification. In the emulsion composition of the present invention, the soluble resin plays a role in improving the durability of the synovial properties of the film and renewing the film surface by dissolving.

[0076] In the present invention, the use of a soluble resin is preferred because it allows stable coating wear resistance to be achieved on ships, underwater structures, and the like.

[0077] The soluble resin is as follows: Metal salt bond-containing copolymer (d1) (hereinafter also referred to as "copolymer (d1)"), Metal salt bond-containing copolymer (d2) (hereinafter also referred to as "copolymer (d2)"), and Silyl ester copolymer (d3) (hereinafter also referred to as "copolymer (d3)") It is preferable that the resin contains one or more soluble resins selected from the group consisting of: The soluble resin may be a copolymer that satisfies the requirements of both copolymers (d1) and (d2), containing both the side chain terminal type metal salt bond structure found in copolymer (d1) and the cross-linked type metal salt bond structure found in copolymer (d2). The soluble resins may be used alone or in combination of two or more.

[0078] [Metal salt bond-containing copolymer (d1)] The metal salt bond-containing copolymer (d1) is an acrylic resin or polyester resin, and is a metal salt bond-containing copolymer having a side chain terminal group represented by general formula (DI). In this specification, the structure may be referred to as a "side chain terminal type metal salt bond." -COO-MO-COR 1 (DI) (In formula (DI), M is zinc or copper, and R 1 is an organic group. When the copolymer (d1) has a plurality of side chain terminal groups represented by formula (DI), each R 1 and M may be the same or different.

[0079] Organic group R in copolymer (d1) 1 (and the organic group R in formula (D-IV) described later) 1 ) is an organic acid residue formed from a monobasic acid, and is preferably a saturated or unsaturated aliphatic hydrocarbon group having from 2 to 30 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having from 3 to 20 carbon atoms, or an aromatic hydrocarbon group having from 6 to 18 carbon atoms, or a substituted product thereof. Examples of the substituted product include a hydroxyl group-substituted product.

[0080] Among the copolymers (d1), acrylic resin-type polymers are preferred. Such acrylic resin-type polymers can be prepared, for example, by a polymerization reaction using a monomer having a metal salt bond represented by general formula (D-IV), i.e., a monobasic acid metal (meth)acrylate (hereinafter also referred to as "monomer (d11)"). CH2=C(R 2 )-COO-MO-COR 1 (D-IV) (In formula (D-IV), M is zinc or copper, and R 1 is an organic group, and R 2 is a hydrogen atom or a methyl group. 1 and preferred types thereof include the organic group R 1 However, in order to distinguish it from the monomer (d21) represented by formula (D-II) which can form a crosslinked metal salt bond described later, R 1 excludes the vinyl group [-CH=CH2] and the isopropenyl group [-C(CH3)=CH2].

[0081] The copolymer (d1) may be a polymer obtained by copolymerization of two or more monomers (d11). Alternatively, the copolymer (d1) may be a polymer obtained by copolymerization of one or more monomers (d11) with one or more other unsaturated monomers copolymerizable with the monomer (d11) (hereinafter also referred to as "monomer (d12)"), i.e., a copolymer having constituent units derived from the monomer (d11) and constituent units derived from the monomer (d12).

[0082] The monomer (d12) can be appropriately selected from various compounds used as polymerizable unsaturated monomers for acrylic resins. For example, monomers that do not contain a metal salt bond, such as alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, and hydroxyalkyl (meth)acrylate, are preferred. Among these, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate are more preferred.

[0083] The acrylic resin type copolymer (d1) can be prepared by, for example, preparing an acrylic resin using (meth)acrylic acid, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, or the like, and then attaching an organic group (R 1 The compound can also be prepared by a method in which a reaction is carried out to introduce a structure having a bonded group (D) to form a side chain terminal group represented by the formula (DI).

[0084] Even when a predetermined side chain terminal group is introduced into the acrylic resin by the above-mentioned preparation method, R 1 In the preparation method, the monobasic acid is converted into an organic group R 1 can be used in a reaction to introduce

[0085] In copolymer (d1), the content of zinc and / or copper resulting from the structure of formula (DI) is preferably 0.5% by mass or more and 20% by mass or less of the copolymer. By using copolymer (d1) that satisfies these conditions, it becomes possible to form an antifouling coating film that is even more excellent in both antifouling properties and wear resistance. Here, the "content of zinc and / or copper" means the total content of zinc and copper when both zinc and copper are contained.

[0086] The content of zinc and / or copper can be adjusted to fall within the above range by adjusting the blending ratio of the monomer (d11) containing these metals and the other monomer (d12) used in preparing the copolymer (d1), or by adjusting the amount of the compound containing zinc and / or copper (e.g., the monobasic acid) added to be subsequently reacted with the acrylic resin.

[0087] [Metal salt bond-containing copolymer (d2)] The metal salt bond-containing copolymer (d2) is a copolymer having a component unit derived from a monomer (d21) represented by general formula (D-II) and a component unit derived from another unsaturated monomer (d22) copolymerizable with the monomer (d21).

[0088] CH2=C(R 2 )-COO-MO-CO-C(R 2 )=CH2(D-II) (In formula (D-II), M is zinc or copper, and R 2 is a hydrogen atom or a methyl group. When the copolymer (d2) contains a plurality of component units derived from the monomer (d21) represented by formula (D-II), each R 2 and M may be the same or different.)

[0089] Examples of the monomer (d21) include zinc diacrylate, zinc dimethacrylate, copper diacrylate, and copper dimethacrylate. The monomer (d21) may be used alone or in combination of two or more.

[0090] Monomer (d21) can be prepared by a known method, for example, by heating and stirring an inorganic metal compound (such as an oxide, hydroxide, or chloride of zinc or copper) and (meth)acrylic acid or an ester compound thereof in the presence of an alcohol-based organic solvent and water at a temperature equal to or lower than the decomposition temperature of the metal salt.

[0091] The component unit derived from the monomer (d21) has a structure represented by the following general formula, which may be referred to herein as a "bridged metal salt bond." 2 represents M and R in formula (D-II). 2 is the same as

[0092] [ka]

[0093] The other unsaturated monomer (d22) copolymerizable with the monomer (d21) can be appropriately selected from various compounds used as polymerizable unsaturated monomers for acrylic resins, similar to the monomer (d12) for the copolymer (d1) described above. That is, as the unsaturated monomer (d22), alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, etc. are preferred, and among these, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, etc. are more preferred.

[0094] The monomer (d11) for the copolymer (d1), i.e., the monobasic metal (meth)acrylate represented by the formula (D-IV), is also a monomer copolymerizable with the monomer (d21), and corresponds to the unsaturated monomer (d22) that can be used to prepare the metal salt bond-containing copolymer (d2). 1 and a preferred embodiment thereof is an organic group R 1 is the same as: The unsaturated monomer (d22) may be used alone or in combination of two or more kinds.

[0095] It is also preferable that the unsaturated monomer (d22) contains a monobasic metal (meth)acrylate represented by the formula (D-IV) and one or more unsaturated monomers selected from the group consisting of alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, and hydroxyalkyl (meth)acrylates.

[0096] Other examples of the unsaturated monomer (d22) include styrene and styrene derivatives; vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylamide and its derivatives; and (meth)acrylonitrile.

[0097] In copolymer (d2), from the same viewpoint as in copolymer (d1), the content of zinc and / or copper resulting from the structure of formula (D-II) is preferably 0.5% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 19% by mass or less, of the copolymer. Here, the "content of zinc and / or copper" means the total content of zinc and copper when both zinc and copper are contained.

[0098] The content of zinc and / or copper can be adjusted by the blending ratio of the monomers used in preparing copolymer (d2). When copolymer (d2) has both a cross-linked metal salt bond structure and a side chain terminal metal salt bond structure, it is preferable that the total content of zinc and / or copper resulting from each structure be within the above range.

[0099] The number-average molecular weight and weight-average molecular weight of copolymer (d1) and copolymer (d2) can be appropriately adjusted taking into consideration the viscosity and storage stability of the antifouling coating composition, the dissolution rate of the antifouling coating film, etc., but the number-average molecular weight is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, and the weight-average molecular weight is preferably from 1,000 to 200,000, more preferably from 1,000 to 100,000. The number average molecular weight in this specification is a value determined by gel permeation chromatography using polystyrene as a standard substance.

[0100] [Silyl ester copolymer (d3)] The silyl ester copolymer (d3) is a copolymer having a component unit (hereinafter also referred to as a "silyl ester component unit") derived from a monomer (d31) represented by general formula (D-III) (hereinafter also referred to as a "silyl ester monomer"), and optionally having a component unit derived from another unsaturated monomer (d32) copolymerizable with the monomer (d31).

[0101] R 7 -CH=C(R 3 )-COO-SiR 4 R 5 R 6 (D-III) (In formula (D-III), R 3 is a hydrogen atom or a methyl group, and R 4 , R 5 and R 6 are each independently a hydrocarbon group, and R 7 is a hydrogen atom or R 8 -O-CO-(However, R 8 is an organic group or SiR 9 R 10 R 11 and R 9 , R 10 and R 11 are each independently a hydrocarbon group.

[0102] Among the silyl ester monomers (d31), R 7 When is a hydrogen atom, the monomer is represented by general formula (D-IIIa). CH2=C(R 3 )-COO-SiR 4 R 5 R 6 (D-IIIa) (In formula (D-IIIa), R 3 , R 4 , R 5 and R 6 are R in formula (D-III), respectively. 3 , R 4 , R 5 and R6 The same as the above R 4 , R 5 and R 6 The hydrocarbon group in is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group such as methyl, ethyl, propyl, or isopropyl.

[0103] Among the silyl ester monomers (d31), R 7 "R 8 When the formula is —O—CO—, the monomer is represented by general formula (D-IIIb). R 8 -O-CO-CH=C(R 3 )-COO-SiR 4 R 5 R 6 (D-IIIb) (In formula (D-IIIb), R 3 , R 4 , R 5 , R 6 and R 8 represents R in formula (D-III) or formula (D-IIIa), respectively. 3 , R 4 , R 5 , R 6 and R 8 The same as the above R 8 The organic group in R is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group such as methyl, ethyl, propyl, or isopropyl. 9 , R 10 and R 11 The hydrocarbon group in is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group such as methyl, ethyl, propyl, or isopropyl.

[0104] Examples of the silyl ester monomer (d34) represented by the formula (D-IIIb) include maleic acid esters (R 3 = hydrogen atoms).

[0105] Examples of the other unsaturated monomer (d32) copolymerizable with the monomer (d31) (or the monomers (d33) and / or (d34)) include the "other unsaturated monomers (d12) and (d22)" exemplified as raw material compounds for the copolymers (d1) and (d2).

[0106] The silyl ester monomer (d31) may be used alone or in combination of two or more kinds, and the other unsaturated monomer (d32) may be used alone or in combination of two or more kinds.

[0107] In the silyl ester copolymer (d3), the component units derived from the silyl ester monomer (d31) are preferably contained in the copolymer (total constituent units 100 mol%) in an amount of 10 mol% to 100 mol%, and the component units derived from other unsaturated monomers (d32) are contained in the remaining amount, i.e., preferably in an amount of 0 mol% to 90 mol%. A content of the component units within the above range is preferred in terms of excellent mechanical strength (e.g., crack resistance) of the resin in the coating film, storage stability of the paint, and elution of the resin in the coating film.

[0108] The number average molecular weight of the silyl ester copolymer (d3) is preferably from 1,000 to 200,000 (two hundred thousand). A number average molecular weight within this range is preferred in that it provides excellent mechanical strength (e.g., crack resistance) of the resin in the coating film, storage stability of the coating material, and elution of the resin in the coating film.

[0109] <Ingredient (E)> The emulsion composition of the present invention may further contain a polyether-modified silicone compound as component (E). By incorporating component (E) into the emulsion composition, the stability of the emulsion composition is improved, and this is also preferable from the viewpoint of improving the durability of the synovial properties of the film. An example of component (E) is a compound having a methyl silicone chain as the main chain and a polyoxyethylene group as the side chain, and specifically, a compound represented by the following general formula:

[0110] [ka]

[0111] In the formula, R 1 is a methylene group, an ethylene group, or a trimethylene group, and R 2 represents an alkyl group having 1 to 4 carbon atoms, m represents an integer of 0 to 50, n represents an integer of 1 to 10, p represents an integer of 1 to 50, and q represents an integer of 0 to 50. 1 (C2H4O) p (C3H6O) q R 2 In the group represented by (C2H4O) p and (C3H6O) q can be random or block.

[0112] The HLB value of component (E) is preferably within a specific range from the viewpoint of the durability of the film obtained by drying the emulsion composition and the stability of the emulsion composition; specifically, it is preferably 1 or more, more preferably 5 or more, and even more preferably 10 or more, and is preferably 18 or less, more preferably 16 or less.

[0113] When two or more polyether-modified silicones with different HLB values ​​are used, the HLB value of component (E) should be such that their weighted average falls within the above range. The HLB value is an index that represents the balance between hydrophilicity and lipophilicity, and in the present invention refers to the value calculated using the following Griffin formula: HLB value = 20 × total molecular weight of hydrophilic groups / molecular weight

[0114] The kinematic viscosity of component (E) at 25°C is preferably within a specific range from the viewpoint of the durability of the film obtained by drying the emulsion composition, and specifically, is preferably within a range of 1 mm 2 / s or more, preferably 5 mm 2 / s or more, preferably 1000 mm 2 / s or less, preferably 500 mm 2 / s or less, more preferably 200 mm 2 / s or less.

[0115] 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 durability of the film obtained by drying the emulsion 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).

[0116] <Component (F)> The emulsion composition of the present invention may further contain a polymer compound as component (F). Component (F) does not include components (A), (D), or (E). By incorporating component (F) into the emulsion composition, the duration of the synovial properties of the membrane can be improved, which is preferable.

[0117] The weight average molecular weight of component (F) is preferably 1,000 or more from the viewpoint of improving the durability of the synovial fluid properties of the membrane, and from the same viewpoint, is preferably 500,000 or less. As the component (F), one or more compounds selected from the group consisting of the following polymer compound (X) and polymer compound (Y) are preferred, with the following polymer compound (Y) being more preferred. Polymer compound (X): a polymer compound having an ester group, an amide group, a urethane group, an amino group, an ether group, or a carbonate group in the main chain Polymer compound (Y): a methacrylic or acrylic polymer having an ester group or an amide group in the side chain (hereinafter also simply referred to as a (meth)acrylic polymer)

[0118] Specific preferred examples of component (F) 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.

[0119] <Other ingredients> In addition to the above components, the emulsion composition of the present invention may contain, within the scope of the present invention, plasticizers, crystal 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, antifungal agents, antibacterial agents, 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, within the scope of the present invention. Similarly, other polymeric materials and other compositions may also be added within the scope of the present invention.

[0120] <Properties of emulsion composition> The emulsion composition of the present invention is an emulsified composition containing the aforementioned components (A), (B), (C), and (D) as essential components. The emulsion composition of the present invention may be either an o / w emulsion or a w / o emulsion, but is preferably an o / w emulsion.

[0121] The content of component (A) in the emulsion composition or during preparation of the emulsion composition is, from the viewpoint of emulsifying power, preferably 0.02% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and even more preferably 1% by mass or more, while, from the viewpoint of handleability, it is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 6% by mass or less.

[0122] The content of component (B) in the emulsion composition or during preparation of the emulsion composition is, from the viewpoint of maintaining the emulsion state, preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and even more preferably 70% by mass or more, and, from the viewpoint of the effective amount, is preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.

[0123] The content of component (C) in the emulsion composition or during preparation of the emulsion composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, from the viewpoint of maintaining the emulsion state, while from the viewpoint of viscosity and handleability, it is preferably 70% by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0124] The content of component (D) in the emulsion composition or during preparation of the emulsion composition is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 4% by mass or more, from the viewpoint of improving the durability of the film, while from the viewpoint of exhibiting synovial properties due to the surface of the film being renewed by running water, it is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 6% by mass or less.

[0125] The content of component (E) in the emulsion composition or during preparation of the emulsion composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the viewpoint of improving the durability of the synovial properties of the membrane, and from the same viewpoint, is preferably 10% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.

[0126] The content of component (F) in the emulsion composition or during preparation of the emulsion composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, from the viewpoint of improving the durability of the synovial properties of the membrane, and from the same viewpoint, is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 7% by mass or less.

[0127] The mass ratio ((D) / (A)) of component (D) to component (A) in the emulsion composition or during preparation of the emulsion composition is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 0.8 or more, from the viewpoint of improving the durability of the synovial properties of the membrane, and from the same viewpoint, is preferably 10 or less, more preferably 5 or less, and even more preferably 2 or less.

[0128] The viscosity of the emulsion composition at 25°C is preferably 0.5 mPa s or more from the viewpoint of ease of handling, and from the same viewpoint, is preferably 30 Pa s or less. Here, the viscosity is measured using a Brookfield viscometer with an appropriate rotor suited to the viscosity range of each sample at 25°C and 60 rpm after stirring for 1 minute.

[0129] 2. Method for producing emulsion composition The method for producing the emulsion composition of the present invention includes a step of mixing the aforementioned components (A), (B), (C), and (D), or a step of mixing anion-modified cellulose fibers, a modifying compound, components (B), (C), and (D), etc.

[0130] Mixing the components causes emulsification, resulting in an emulsion composition. When anion-modified cellulose fiber and a modifying compound are used instead of component (A), component (A) is formed during mixing, resulting in an emulsion composition containing component (A). For such 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.

[0131] The temperature and time for mixing the components are preferably within the range of 5 to 50°C and 1 minute to 3 hours, for example.

[0132] The preferred range of the content of each component when mixed is the same as the preferred range of the content of each component in the emulsion composition of the present invention described above.

[0133] 3.Paint composition The coating composition of the present invention contains the emulsion composition of the present invention. In addition to the emulsion composition, the coating composition may contain known pigments, rust inhibitors, antifouling agents, biocides, etc. Alternatively, the emulsion composition of the present invention can be used as a coating composition as is. When components other than the emulsion composition are included, the amount of such components relative to 100 parts by mass of the emulsion composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, from the viewpoint of improving the durability of the synovial properties of the membrane, and from the same viewpoint, is preferably 100 parts by mass or less, more preferably 50 parts by mass or less. The components other than the emulsion composition may be mixed with the emulsion composition after preparation, or may be mixed together with the other components during preparation of the emulsion composition.

[0134] 4. Membrane The emulsion composition or coating composition of the present invention is applied to a hard surface (e.g., a metal surface, a resin surface, a glass surface, a ceramic surface, or the like) and left at room temperature and pressure, or heated or reduced pressure as necessary, to form a film. The film has synovial properties that are sustained, and therefore the emulsion composition or coating composition of the present invention can be used in applications where synovial properties are desired in water or seawater, such as paints for ship hulls, bridge frameworks, piping, quays, cooling towers, tank interior surfaces, offshore facilities, observation equipment, and fishing nets. [Example]

[0135] The present invention will be specifically described below by showing examples etc. Note that the following examples are merely illustrative of the present invention and are not intended to limit the present invention in any way.

[0136] [Average fiber diameter, average fiber length, and average aspect ratio of anion-modified cellulose fibers and modified cellulose fibers] Water is added to the cellulose fibers to be measured to prepare a dispersion with a cellulose content of 0.0001% by mass. The dispersion is dropped onto mica and dried to form an observation sample. An atomic force microscope (AFM) (Nanoscope II Tapping mode AFM manufactured by Digital Instruments; the probe used is a Point Probe (NCH) manufactured by Nanosensors) is used to measure the fiber height (height difference between where fibers are present and where fibers are not present) of the cellulose fibers in the observation sample. At this time, 100 or more cellulose fibers are extracted from a microscopic image in which the cellulose fibers can be seen, and the average fiber diameter is calculated from their fiber height. The average fiber length is calculated from the distance in the fiber direction. The average aspect ratio is calculated by dividing the average fiber length by the average fiber diameter. The height analyzed in the AFM image can be considered the fiber diameter.

[0137] [Average fiber diameter and average fiber length of raw cellulose fibers] Deionized water is added to the cellulose fibers to be measured to prepare a dispersion containing 0.01% by mass of cellulose. The dispersion is 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%. At least 100 cellulose fibers are measured, and the average ISO fiber diameter and average ISO fiber length are calculated as the average fiber diameter and average fiber length, respectively.

[0138] [Anionic Group Content of Anion-Modified Cellulose Fibers and Modified Cellulose Fibers] 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)]

[0139] [Aldehyde group content of oxidized cellulose fiber] The carboxy group content of the oxidized cellulose fiber to be measured is measured by the above-mentioned method for measuring the anionic group content. Separately, 100 g of the aqueous dispersion of the oxidized cellulose fiber to be measured (solids content: 1.0% by mass), 100 g of acetate buffer (pH 4.8), 0.33 g of 2-methyl-2-butene, and 0.45 g of sodium chlorite were added to a beaker and stirred at 25°C for 16 hours to oxidize any remaining aldehyde groups in the oxidized cellulose fiber. After the reaction was completed, the fiber was washed with deionized water to obtain cellulose fiber with the aldehyde groups oxidized. The reaction solution was freeze-dried, and the carboxyl group content of the resulting dried product was measured using the anionic group content measurement method described above to calculate the "carboxyl group content of the oxidized oxidized cellulose fiber." The aldehyde group content of the oxidized cellulose fiber to be measured was then calculated using Equation 1. Aldehyde group content (mmol / g) = (carboxyl group content of oxidized cellulose fiber after oxidation treatment) - (carboxyl group content of oxidized cellulose fiber to be measured) Equation 1

[0140] [Solid content in dispersion] The measurement is performed using a halogen 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.

[0141] [Confirmation of crystalline structure in modified cellulose fibers] The crystalline structure of the modified cellulose fiber is confirmed by measurement under the following conditions using an X-ray diffractometer (MiniFlexII, manufactured by Rigaku Corporation). The measurement conditions were as follows: X-ray source: Cu / Kα-radiation, tube voltage: 30 kV, tube current: 15 mA, measurement range: diffraction angle 2θ = 5 to 45°, X-ray scan speed: 10° / min. The measurement sample had an area of ​​320 mm 2 The cellulose is compressed into a pellet with a thickness of 1 mm. The degree of crystallinity of the cellulose type I crystal structure is calculated from the obtained X-ray diffraction intensity according to the following formula A.

[0142] <Formula A> Cellulose type I crystallinity (%) = [(I 22.6 -I 18.5 ) / I 22.6 ] x 100 [In the formula, I 22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6°) in X-ray diffraction, I 18.5 indicates the diffraction intensity of the amorphous part (diffraction angle 2θ = 18.5°).

[0143] On the other hand, if the crystallinity obtained by the above formula A is 35% or less, it is preferable to calculate it based on the following formula B in accordance with the description on pages 199-200 of the "Wood Science Experiment Manual" (edited by the Japan Wood Research Society; published in April 2000) in order to improve calculation accuracy. Therefore, when the crystallinity obtained by the above formula A is 35% or less, the value calculated based on the following formula B can be used as the crystallinity.

[0144] <Formula B> Cellulose type I crystallinity (%) = [A c / (A c +A a )] x 100 [In the ceremony, A c is the sum of the peak areas of the lattice planes (002 plane) (diffraction angle 2θ = 22.6°), (011 plane) (diffraction angle 2θ = 15.1°), and (0-11 plane) (diffraction angle 2θ = 16.2°) in X-ray diffraction, A a indicates the peak area of ​​the amorphous portion (diffraction angle 2θ = 18.5°), and each peak area is determined by fitting the obtained X-ray diffraction chart with a Gaussian function.

[0145] [Anion-modified cellulose fiber] Anion-modified cellulose fibers having the physical properties shown in Table 1 were used as raw materials.

[0146] [Table 1]

[0147] Such anionically modified cellulose fibers can be prepared, for example, by the TEMPO oxidation treatment described below.

[0148] [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.

[0149] 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 procedure of dispersing the solids in deionized water and separating the solids by suction filtration is repeated until the conductivity of the filtrate reaches 200 μs / cm or less. The resulting solids are then dehydrated to obtain anionically modified cellulose fibers.

[0150] [Preparation of reduction-treated, finely divided anion-modified cellulose fibers] The anion-modified cellulose fibers were subjected to a micronization treatment and then a reduction treatment to prepare micronized anion-modified cellulose fibers having the physical properties shown in Table 2.

[0151] [Table 2]

[0152] Such finely divided anionically modified cellulose fibers can be prepared, for example, by the following fine division treatment and reduction treatment.

[0153] [Fine processing] Deionized water was added to the anion-modified cellulose fiber to prepare 100 g of a suspension (solid content 2.0% by mass), to which 0.5 M aqueous sodium hydroxide was added to adjust the pH to 8. Deionized water was then added to make a total of 200 g. This suspension was subjected to a micronization treatment three times at 150 MPa using a high-pressure homogenizer to obtain a micronized anion-modified cellulose fiber dispersion (solid content 1.0% by mass).

[0154] [Reduction process] 182 g of a finely divided anion-modified cellulose fiber dispersion (solid content 1.0% by mass) was weighed out and added with deionized water to a total of 400 g. 1.2 mL of 0.1 M aqueous sodium hydroxide and 120 mg of sodium borohydride were added and stirred at 25°C for 4 hours. 9 mL of 1 M hydrochloric acid was then added and stirring continued. After stirring was completed, the solids obtained by suction filtration were dispersed in deionized water, and the solids were separated by suction filtration. This procedure was repeated six times. In this way, a finely divided anion-modified cellulose fiber dispersion (solid content 0.9% by mass) in which the aldehyde groups present in the finely divided anion-modified cellulose fiber had been reduced was obtained.

[0155] [Preparation of soluble resin] The zinc-crosslinked acrylic polymer used as the soluble resin component (D) described in the examples of the present specification can be prepared, for example, by the following method.

[0156] [Preparation of metal-containing monomers] A four-neck flask equipped with a condenser, thermometer, dropping funnel, and stirrer was charged with 85.4 parts by weight of propylene glycol monomethyl ether (PGM) and 40.7 parts by weight of zinc oxide, and the mixture was heated to 75°C with stirring. Subsequently, a mixture of 43.1 parts by weight of methacrylic acid (MAA), 36.1 parts by weight of acrylic acid (AA), and 5 parts by weight of water was added dropwise from the dropping funnel at a constant rate over 3 hours. After stirring for an additional 2 hours, 36 parts by weight of propylene glycol monomethyl ether was added, yielding a reaction solution containing the metal-containing monomer (d21).

[0157] [Preparation of cross-linked copolymers containing metal salt bonds] A four-neck flask equipped with a condenser, thermometer, dropping funnel, and stirrer was charged with 15 parts by weight of propylene glycol monomethyl ether (PGM) and 57 parts by weight of xylene, and the temperature was raised to 100°C while stirring. Subsequently, a transparent mixture consisting of 52 parts by weight of the reaction solution of the metal-containing monomer obtained above, 1 part by weight of methyl methacrylate (MMA), 66.2 parts by weight of ethyl acrylate (EA), 5.4 parts by weight of 2-methoxyethyl acrylate (2-MEA), 2.5 parts by weight of azobisisobutyronitrile (AIBN) (manufactured by Nippon Hydrazine Industrial Co., Ltd.), 7 parts by weight of azobismethylbutyronitrile (AMBN) (manufactured by Nippon Hydrazine Industrial Co., Ltd.), 1 part by weight of the chain transfer agent "Nofumer MSD" (manufactured by Nippon Oil & Fats Corporation), and 10 parts by weight of xylene was added dropwise from the dropping funnel at a constant rate over 6 hours. After the dropwise addition is complete, 0.5 parts by mass of t-butyl peroctoate (TBPO) and 7 parts by mass of xylene are added dropwise over 30 minutes, and the mixture is stirred for another 1 hour and 30 minutes. Then, 4.4 parts by mass of xylene are added, yielding a reaction mixture containing no insoluble matter, a pale yellow, transparent crosslinked metal salt bond-containing copolymer (d2), i.e., a zinc crosslinked acrylic polymer.

[0158] [Preparation of Silyl Ester Copolymer] A reaction vessel equipped with a stirrer, condenser, thermometer, dropping device, nitrogen inlet tube, and heating / cooling jacket is charged with 100 parts by mass of xylene and heated and stirred at 85°C under a nitrogen stream. While maintaining the same temperature, a mixture consisting of 60 parts by mass of triisopropylsilyl acrylate, 40 parts by mass of methyl methacrylate, and 0.3 parts by mass of 2,2'-azobisisobutyronitrile is added dropwise to the reaction vessel over 2 hours using the dropping device. After stirring at the same temperature for 4 hours, 0.4 parts by mass of 2,2'-azobisisobutyronitrile is added, and the mixture is further stirred at the same temperature for 4 hours, yielding a reaction mixture containing a silyl ester copolymer.

[0159] Production Example 1 (Preparation of Emulsion 1) In a beaker, 66.7 g of the reduction-treated, finely divided anion-modified cellulose fiber dispersion (solid content 0.9% by mass), 2.7 g of amino-modified silicone 1 (corresponding to 1.75 equivalents relative to the carboxy groups of the anion-modified cellulose fiber), and 6 g of silicone oil 1 (component (C)) were mixed, and deionized water (component (B)) was added to make a total of 100 g. This solution was processed 10 times in a high-pressure homogenizer (Yoshida Kikai Co., Ltd., Nanovaita L-ES) at 150 MPa, and 0.2 g of polyether-modified silicone 1 (component (E)) was added to obtain emulsion 1 containing cellulose fibers with modified groups, i.e., modified cellulose fibers, in which the amino-modified silicone was linked to the anion-modified cellulose fiber via an ionic bond.

[0160] Production Example 2 (Preparation of Emulsion 2) 2 g of the zinc cross-linked acrylic polymer as component (D) (soluble resin 1) was mixed with 6 g of ethyl acetate and stirred at room temperature for 2 hours to dissolve. This was mixed with 12 g of a 1% aqueous solution of polyether-modified silicone 1 as component (E), and treated with an ultrasonic homogenizer (Nippon Seiki Seisakusho, US-300E, tip diameter Φ7, output 80%) for 5 minutes to obtain emulsion 2 in which the zinc cross-linked acrylic polymer was emulsified in water.

[0161] Production Example 3 (Preparation of Emulsion 3) 2 g of the silyl ester copolymer as component (D) (soluble resin 2) was mixed with 6 g of ethyl acetate and stirred at room temperature for 2 hours to dissolve. This was mixed with 12 g of a 1% aqueous solution of polyether-modified silicone 1 as component (E) and treated with an ultrasonic homogenizer (Nippon Seiki Seisakusho, US-300E, tip diameter Φ7, output 80%) for 5 minutes to obtain emulsion 3 in which the silyl ester copolymer was emulsified in water.

[0162] Production Example 4 (Preparation of Emulsion 4) A hydrolyzable antifouling paint (SEAFLO NEO CF Z Light Red, manufactured by Chugoku Paint Co., Ltd.) serving as component (D) was diluted with ethyl acetate to an active ingredient content of 50% by mass. 10 g of this solution was mixed with 10 g of a 1% aqueous solution of polyether-modified silicone 1 serving as component (E), and the mixture was treated for 5 minutes with an ultrasonic homogenizer (US-300E, manufactured by Nippon Seiki Seisakusho Co., Ltd., tip diameter Φ7, output 80%) to obtain emulsion 4, in which the hydrolyzable antifouling paint was emulsified in water. The solid content in this hydrolyzable antifouling paint was considered to be the active component, and the concentration of the active component in the hydrolyzable antifouling paint was determined using the method described above in "Solid content in dispersion," and was found to be 70.0 mass%.

[0163] Examples 1 to 3 and Comparative Examples 1 to 4 (Production of emulsion composition and film) Emulsions 1 to 4 and styrene acrylic 1 emulsion as component (F) were combined and mixed at room temperature so that the concentrations of active ingredients in the final emulsion compositions would be as shown in Tables 4 and 5. The specific combinations of emulsions in each example are shown in Table 3.

[0164] [Table 3]

[0165] 500 μL of each of the obtained emulsion compositions was spread on a slide glass (PRO-04, manufactured by Matsunami Glass Co., Ltd.) and dried at room temperature for 24 hours to form a film. To evaluate the durability of the synovial properties of this membrane, water at 25°C was dripped onto the membrane from a height of 40 cm at a flow rate of 50 mL / sec, and the sliding angle of a 20 μL water droplet was measured using the following method before dripping, and after 60 and 90 minutes. The results are shown in the table.

[0166] [Slide angle measurement test] The prepared films were placed horizontally, and a 20 μL water droplet (23°C) was dropped onto each film at 23°C using a fully automatic contact angle meter (Kyowa Interface Science Co., Ltd., FAMAS) and allowed to stand for 1 second. The film surface was then tilted to 85° at a rate of 1° / s, and the angle at which the droplet began to slide was measured. The measurement results are shown in the table below. If the droplet did not slide even when tilted to 85°, it was evaluated as "greater than 85". The smaller the water droplet sliding angle, the higher the synovial properties of the film. Films with a sliding angle of "greater than 85" can be evaluated as clearly not having synovial properties.

[0167] [Table 4]

[0168] [Table 5]

[0169] The amount of each component in Tables 4 and 5 is the amount of "active component" excluding the vehicle, etc. The amount of water in component (B) includes the amount of water introduced as a vehicle when each component is used as a solution, suspension, etc.

[0170] The above experiments revealed the following: The films of Examples 1 and 2 maintained their synovial properties even after 90 minutes of exposure to running water. Since a soluble resin is expected to gradually dissolve in running water, it was unexpected that the films formed using the emulsion composition containing a soluble resin maintained their synovial properties for a long time. On the other hand, Comparative Example 1, which did not contain a soluble resin, initially exhibited synovial properties, but lost them after exposure to flowing water. Comparative Examples 2 and 3, which consisted only of a soluble resin, did not exhibit synovial properties at all. Furthermore, the film of Example 3, which used a commercially available hydrolyzable antifouling paint as the soluble resin, maintained synovial properties after 90 minutes of exposure to flowing water. From this, the emulsion composition of the examples containing a pigment or the like can be used as a coating composition.

[0171] Details of the representative components used in the examples are summarized below. Amino-modified silicone 1: Dow-Toray SS-3551 (kinematic viscosity: 1,000, amino equivalent: 1,700) [Component (C)] Silicone oil 1: Shin-Etsu Chemical Co., Ltd., KF-96-100cs (SP value: 7.3) [Component (E)] Polyether-modified silicone 1: Shin-Etsu Chemical Co., Ltd., KF-642, HLB: 14 [Component (F)] Styrene acrylic 1: NeoCryl XK-188 (emulsion, solid content 44.5% by mass) manufactured by DSM [Industrial Applicability]

[0172] The emulsion composition and coating composition of the present invention can form a film with excellent long-lasting synovial properties, and can therefore be used as a paint for ship bottoms, etc.

Claims

1. An emulsion composition containing the following components (A) to (D): (A) Cellulose fibers having modified groups (B) Water (C) An organic compound that is liquid at 25°C and 1 atmosphere. (D) Dissolved resin

2. The emulsion composition according to claim 1 , further comprising the following component (E): (E) Polyether-modified silicone

3. The emulsion composition according to claim 1 , further comprising the following component (F): (F) Polymer compounds (excluding those falling under component (A), component (D), or component (E))

4. 2. The emulsion composition according to claim 1, wherein the mass ratio of component (D) to component (A) ((D) / (A)) is 0.1 or more and 10 or less.

5. The emulsion composition according to claim 1, wherein the content of component (D) is 1% by mass or more and 10% by mass or less.

6. A coating composition comprising the emulsion composition according to any one of claims 1 to 5.