Emulsion composition

Abstract

To provide an emulsion composition for producing a synovial film having high water resistance and a method for producing the same.SOLUTION: An emulsion composition contains a component (A): anion-modified cellulose fiber, a component (B): an organic compound having an ionic group (excluding the component (A)), a component (C): a compound capable of forming a covalent bond with a hydrophilic group in the component (A) (excluding the component (B)), a component (D): an organic compound being liquid at 25°C and 1 atmospheric pressure (excluding the component (B) and component (C)), and a component (E): water.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an emulsion composition containing modified cellulose fibers, and further to a method for producing such an emulsion composition. [Background technology]

[0002] It has been known that cellulose fibers defibrated into fine fibers exhibit excellent emulsifying power. In particular, anion-modified cellulose fibers, in which anionic groups are introduced onto cellulose fibers defibrated into fine fibers, are themselves excellent in dispersion stability and transparency, and emulsion compositions containing these anion-modified cellulose fibers are known to exhibit excellent emulsion stability and a pleasant feel. Furthermore, attempts have been made to provide even better functionality by using hydrophobically modified cellulose fibers obtained by hydrophobically modifying cellulose fibers.

[0003] For example, Patent Document 1 shows that a film exhibiting excellent water resistance and durability and synovial properties can be produced by applying an emulsion composition containing hydrophobically modified cellulose fibers in which a silicone compound or a specific hydrocarbon compound is bonded to cellulose fibers, water, and an organic compound that is liquid at 25°C and 1 atmosphere onto a substrate and drying it (Patent Document 1).

[0004] On the other hand, films with synovial properties are known as surface films that prevent adhesion of fluids such as dirt (Patent Document 2). For example, Patent Document 1 describes the possibility of expanding the application of such films as coating agents for ships, and in this case, such films are expected to be used under conditions of being immersed in water for long periods of time. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] WO2021 / 024933 [Patent Document 2] WO2018 / 164135 Summary of the Invention [Problem to be solved by the invention]

[0006] As mentioned above, there is a demand for a membrane that does not lose its synovial properties even under conditions of prolonged exposure to water. However, it has been newly discovered that under such conditions, the membrane may swell and lose its synovial properties. Therefore, an object of the present invention is to provide an emulsion composition for producing a membrane having excellent water resistance and synovial properties, and a method for producing the same. [Means for solving the problem]

[0007] The present invention relates to the following [1] to [5]. [1] An emulsion composition containing the following components (A), (B), (C), (D), and (E): (A) Anion-modified cellulose fiber (B) An organic compound having an ionic group (excluding the component (A)). (C) A compound capable of forming a covalent bond with the hydrophilic group in the component (A) (excluding the component (B)). (D) Organic compounds that are liquid at 25°C and 1 atmosphere (excluding the above components (B) and (C)). (E) Water [2] A method for producing a membrane containing modified cellulose fibers, comprising a step of drying the emulsion composition described in [1] above. [3] A film obtained by drying the emulsion composition described in [1] above. [4] A biofouling inhibitor comprising the emulsion composition according to [1] or the film according to [3]. [5] A method for producing an emulsion composition, comprising the step of mixing the above-mentioned components (A), (B), (C), (D), and (E). [Effects of the Invention]

[0008] According to the present invention, it is possible to provide an emulsion composition for producing a synovial membrane having excellent water resistance, which can suppress swelling of the membrane even under conditions of long-term exposure to water, and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0009] As a result of intensive research conducted by the present inventors to solve the above problems, they discovered that by incorporating specific compounds capable of covalently bonding with hydrophilic groups in anion-modified cellulose fibers, the water resistance of films formed using emulsion compositions containing these components can be improved, and thus completed the present invention. Although the mechanism by which this effect is exerted is unclear, it is speculated that when a film is formed using the emulsion composition, a three-dimensional crosslinked structure is generated via the specific compound, resulting in improved water resistance of the formed film.

[0010] 1. Emulsified composition The emulsion composition of the present invention contains the following components (A), (B), (C), (D) and (E).

[0011] <Component (A)> Component (A) is an anionically modified cellulose fiber. Examples of the anionic group contained in the anion-modified cellulose fiber include a carboxy group, a sulfonic acid group, and a phosphate group. The anionic group is preferably a carboxy group from the viewpoints of ease of preparation and mild reaction conditions. Examples of the counter ion to 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.

[0012] The anionic group content of the anion-modified cellulose fiber is preferably 0.1 mmol / g or more, more preferably 0.5 mmol / g or more, and even more preferably 0.8 mmol / g or more, from the viewpoint of introducing the modifying group. 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 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] [Method for preparing component (A)] Anion-modified cellulose fibers can be obtained by subjecting raw cellulose fibers to an oxidation treatment or an anionic group addition treatment to introduce at least one anionic group and thereby anion-modifying the fibers.

[0015] 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.

[0016] The average fiber diameter of the raw material cellulose fibers is not particularly limited, but from the viewpoints of handling and cost, it is preferably 1 μm or more, and on the other hand, preferably 300 μm or less.

[0017] The average fiber length of the raw cellulose fibers is not particularly limited, but from the viewpoints of availability and cost, it 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.

[0018] The anionic group to be introduced includes a carboxy group, a sulfonic acid group, or a phosphoric acid group.

[0019] (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 oxidizing them, and a method of reacting the hydroxy groups of cellulose with at least one selected from the group consisting of compounds having carboxy groups, acid anhydrides of compounds having carboxy groups, and derivatives thereof.

[0020] The method for oxidizing the hydroxyl groups of the cellulose is not particularly limited, but for example, a method of oxidizing the cellulose 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 can be applied. For more details, known methods, such as the method described in JP 2011-140632 A, can be referred to.

[0021] 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, such cellulose fibers may be referred to as "oxidized cellulose fibers." Oxidized cellulose fibers are preferred because they are easier to prepare than other anion-modified cellulose fibers.

[0022] 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.

[0023] (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.

[0024] <Ingredient (B)> Component (B) is an organic compound having an ionic group, but does not include organic compounds that fall under component (A). As the ionic group, a cationic group is preferred from the viewpoint of forming an ionic bond with the anion-modified cellulose fiber, and as the organic compound having a cationic group, primary amine, secondary amine, tertiary amine and quaternary ammonium compound are preferred. More preferred examples of component (B) include polymeric compounds having an amino group and hydrocarbon compounds having a cationic group, from the viewpoint of ease of modification.

[0025] [Polymer Compound Having Amino Group] The polymeric compound having an amino group, which is preferred as component (B) in the present invention, is commercially available or can be prepared according to known methods. Only one type of amino-modified polymeric compound may be used, or two or more types may be used.

[0026] Examples of polymeric compounds having an amino group in the present invention include resins such as amino-modified silicones, polyoxyalkyleneamines, amino-modified poly(meth)acrylate polymers, amino-modified vinyl polymers, amino-modified polyesters, amino-modified polycarbonates, polyallylamine, and polyethyleneimine; chain aliphatic polyamines, cyclic aliphatic polyamines, and alicyclic aromatic polyamines; and the reactive group may be located in the main chain, side chain, or terminal of the polymeric compound. Among these, amino-modified silicones are preferred from the viewpoint of ease of modification.

[0027] Amino-modified silicone is a silicone polymer compound with an amino group. The amino-modified silicone has a kinematic 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.

[0028] The kinematic viscosity at 25°C can be determined using an Ostwald viscometer, and from the viewpoint of synovial fluidity, it is more preferably 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.

[0029] 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 synovial fluid properties, 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 weight-average molecular weight is determined by gel permeation chromatography using polystyrene as a standard substance, and the number of nitrogen atoms can be determined by elemental analysis.

[0030] Specific examples of amino-modified silicones include compounds represented by general formula (a1).

[0031] [ka]

[0032] [In the formula, 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 synovial properties. 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 3amay be the same or different, and multiple R 2a may be the same or different.

[0033] 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. The weight-average molecular weight of the compound of general formula (a1) is preferably a number of 2,000 or more and 1,000,000 or less, more preferably a number of 5,000 or more and 100,000 or less, and even more preferably a number of 8,000 or more and 50,000 or less.

[0034] 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.)

[0035] 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)

[0036] Furthermore, from the viewpoint of obtaining a film with high water resistance, 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)].

[0037] 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, Inc., 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: 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 Preferred are 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), 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.

[0038] 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.

[0039] 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.

[0040] The amino-modified silicone may 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 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.

[0041] [Hydrocarbon Compounds Having Cationic Groups] In the present invention, the hydrocarbon-based compound having a cationic group preferred as component (B) is one in which one or more hydrocarbon groups are bonded to one cationic group. Only one type of hydrocarbon-based compound having a cationic group may be used, or two or more types may be used. 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 obtaining a membrane with high water resistance, 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.

[0042] 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.

[0043] (hydrocarbon group) Examples of the hydrocarbon group in the hydrocarbon compound 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 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, and even more preferably 18 or more; from the same viewpoint, it is preferably 40 or less, more preferably 30 or less, even more preferably 24 or less, and even more preferably 22 or less. Unless otherwise specified, the number of carbon atoms in the hydrocarbon group means the number of carbon atoms in one hydrocarbon group.

[0044] The aromatic hydrocarbon group is, for example, selected from the group consisting of an aryl group and an aralkyl group. In the aryl group and the aralkyl group, the aromatic ring itself may be substituted or unsubstituted.

[0045] 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.

[0046] 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 (sometimes abbreviated as "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.

[0047] <Component (C)> Component (C) is a compound capable of forming a covalent bond with the hydrophilic group in component (A), except that compounds corresponding to component (B) are not included in component (C). Examples of the hydrophilic group in component (A) include anionic groups such as a carboxy group, a sulfonic acid group, and a phosphate group, and a hydroxyl group. In the emulsion composition of the present invention, component (C) may or may not be covalently bonded to the hydrophilic group in component (A), or a portion of component (C) may be covalently bonded to the hydrophilic group. Even if a compound can form a covalent bond with component (A), a compound that can form a covalent bond with component (A) as a reaction intermediate (for example, carbodiimide used as a crosslinking agent) does not fall under component (C).

[0048] As the component (C), one or more compounds selected from the group consisting of the following components (a) and (b) are preferred. Component (a): A compound capable of forming a covalent bond with a hydroxy group Component (b): A compound capable of forming a covalent bond with a carboxy group

[0049] [Component (a)] Preferred examples of component (a) include organoalkoxysilane compounds, which are available in a wide variety and are readily available industrially, and organoalkoxysilane compounds having a structure represented by general formula (a) are more preferred. R 1c n Si(OR 2c ) 4-n (a) (In the formula, R 1c , R 2c is a substituent, and n is an integer of 1 to 3. R 1c From the viewpoint of obtaining a film with improved water resistance, is preferably a hydrocarbon group, more preferably an alkyl group, even more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group. R 2c From the viewpoint of obtaining a film with improved water resistance, R is preferably a hydrocarbon group or a hydrogen atom, more preferably an alkyl group, even more preferably an alkyl group having 1 to 6 carbon atoms, even more preferably a methyl group, and even more preferably R 1c It is the same functional group as n is an integer, and is preferably 1 or 2 from the viewpoint of obtaining a film with improved water resistance.

[0050] Specific examples of the organoalkoxysilane compound include trimethoxymethylsilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, i-propyltrimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, i-propyltriethoxysilane, 3-chloropropyltriethoxysilane, vinyltriethoxysilane, and phenyltriethoxysilane. Iethoxysilane, methyltri-i-propoxysilane, ethyltri-i-propoxysilane, n-propyltri-i-propoxysilane, i-propyltri-i-propoxysilane, 3-chloropropyltri-i-propoxysilane, vinyltri-i-propoxysilane, phenyltri-i-propoxysilane, methyltributoxysilane, ethyltributoxysilane, n-propyltributoxysilane, i-propyltributoxysilane, 3-chloropropyltributoxysilane, vinyltributoxysilane, phenyl Tributoxysilane, 3,3,3-trifluorotrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3,4-epoxycyclohexyltrimethoxysilane, 3,3,3-trifluorotriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3,4-epoxycyclohexyl Iethoxysilane, 3,3,3-trifluorotri-i-propoxysilane, 3-methacryloxypropyltri-i-propoxysilane, 3-glycidoxypropyltri-i-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3,4-epoxycyclohexyltri-i-propoxysilane, 3,3,3-trifluorotributoxysilane, 3-methacryloxypropyltributoxysilane, 3-glycidoxypropyltributoxysilane, 3-mercaptopropyltributoxysilane, 3,Examples of suitable silanes include 4-epoxycyclohexyltributoxysilane, dimethoxydimethylsilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane. These silanes can be used alone or in combination of two or more. Furthermore, partial hydrolysis condensates of these silanes can also be used.

[0051] [Component (b)] From the viewpoints of safety and ease of handling, preferred examples of component (b) include crosslinking agents having an oxazoline group or a carbodiimide group. Specific examples of crosslinking agents having an oxazoline group include EPOCROS K-2010E, EPOCROS K-2020E, EPOCROS K-2035E, EPOCROS WS-300, EPOCROS WS-500, and EPOCROS WS-700, all manufactured by Nippon Shokubai Co., Ltd. Specific examples of crosslinking agents having a carbodiimide group include Carbodilite V-02, Carbodilite V-02-L2, Carbodilite SV-02, Carbodilite V-04, and Carbodilite V-10, all manufactured by Nisshinbo Chemical Inc.

[0052] <Ingredient (D)> Component (D) in the present invention is an organic compound that is liquid at 25°C and 1 atmosphere. However, organic compounds corresponding to component (A) or component (B) are not included in component (D). Component (D) may also be a solvent used in producing the emulsion composition.

[0053] The solubility of an organic compound that is liquid at 25°C and 1 atmosphere in water is preferably 10 g or less, more preferably 1 g or less, per 100 g of water at 25°C, from the viewpoint of obtaining an emulsion composition. The molecular weight of component (D) is preferably 100 or more, more preferably 200 or more, from the viewpoint of obtaining a film with improved water resistance, and is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less, from the viewpoint of obtaining a film with improved synovial properties.

[0054] From the viewpoint of obtaining a film with improved water resistance and synovial fluid properties, the compound of component (D) preferably has an SP value of 10 or less, 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.

[0055] 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).

[0056] Component (D) in the present invention is preferably an oil, and examples of the oil include one or more selected from the group consisting of ester oil, silicone oil, and ether oil, from the viewpoint of obtaining a film with improved water resistance and synovial fluid properties, with silicone oil being more preferred.

[0057] 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.

[0058] Examples of silicone oils include dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.

[0059] Examples of ether oils include polyoxypropylene hexyl ether, polyoxypropylene octyl ether, polyoxypropylene decyl ether, polyoxypropylene lauryl ether, dihexyl ether, dioctyl ether, didecyl ether, dilauryl ether, dimyristyl ether, dicetyl ether, distearyl ether, diicosyl ether, and dibehenyl ether, each of which has an average added mole number of oxypropylene groups of 1 to 15.

[0060] <Ingredient (E)> Component (E) in the present invention is water. Component (E) serves as a solvent during the production of anion-modified cellulose fibers or modified cellulose fibers, and as one of the components of the emulsion composition of the present invention. The amount of component (E) includes water, which serves as a medium when various raw materials are used as an aqueous solution or aqueous dispersion.

[0061] <Component (F)> The emulsion composition of the present invention may contain an anionic surfactant as component (F), provided that anionic surfactants corresponding to component (B) or component (D) are not included in component (F).

[0062] From the viewpoint of availability, component (F) may be alkali metal salts such as sodium salts and potassium salts, ammonium salts, or sulfate esters, with sulfonates, sulfate esters, and carboxylates being preferred, and sulfate esters being more preferred.

[0063] Component (F) preferably has a hydrocarbon group such as an alkyl group or an alkenyl group. From the viewpoint of the durability of the film formed, the number of carbon atoms in the hydrocarbon group is preferably 8 or more, more preferably 10 or more, and from the same viewpoint, is preferably 20 or less, more preferably 18 or less.

[0064] <Ingredients (G)> The emulsion composition of the present invention may contain a polyether-modified silicone compound as component (G). By incorporating such component (G) into the emulsion composition, the durability of the resulting film can be improved. From the viewpoint of improving the durability of the film, a trisiloxane-based compound is a preferred example of component (G).

[0065] The HLB value of component (G) is preferably 1 or more and 18 or less, from the viewpoint of the durability of the film obtained by drying the emulsion composition.

[0066] The HLB value of component (G) is an index that represents the balance between hydrophilicity and lipophilicity, and in the present invention refers to the value calculated by the following Griffin formula. HLB value = 20 × total molecular weight of hydrophilic groups / molecular weight

[0067] The kinematic viscosity of component (G) at 25°C is preferably 1 mm from the viewpoint of the durability of the film obtained by drying the emulsion composition. 2 / s or more 1000mm 2 / s or less.

[0068] <Other ingredients> In addition to the above components, the emulsion composition of the present invention may contain polymeric compounds, plasticizers, nucleating agents, fillers (inorganic fillers, organic fillers), hydrolysis inhibitors, flame retardants, antioxidants, lubricants such as hydrocarbon waxes, UV absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, mildew inhibitors, 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, 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.

[0069] <Modified cellulose fiber> During preparation of the emulsion composition of the present invention, some or all of the anion-modified cellulose fiber of component (A) may be bonded to some or all of the organic compound having an ionic group of component (B). The cellulose fiber derivative produced by bonding component (A) and component (B) is called a modified cellulose fiber. The emulsion composition of the present invention may contain such modified cellulose fiber.

[0070] The modifying group in the modified cellulose fiber formed by bonding component (B) to oxidized cellulose fiber is a group derived from component (B), and the structure of the modifying group depends on the structure of component (B) used. The bonding mode of the modifying group to the cellulose fiber is preferably a covalent bond or an ionic bond. From the viewpoint of ease of production, ionic bonds are preferred, and from the viewpoint of the stability of the formed film, covalent bonds are preferred.

[0071] The bonding sites of the modifying groups in the oxidized cellulose fibers are hydroxy groups, aldehyde groups, or carboxy groups that the oxidized cellulose fibers have.

[0072] When the bonding site is a hydroxy group of the oxidized cellulose fiber, the bonding mode is a covalent bond, and examples thereof include an ether bond, an ester bond, and a carbonate bond.

[0073] When the bonding site is a carboxy group of the oxidized cellulose fiber, the bonding mode is an ionic or covalent bond. When the bonding mode is an ionic bond, component (B) is bonded via electrostatic interaction, and when the bonding mode is a covalent bond, it refers to a state where it is bonded via an ester bond, amide bond, etc., and in particular, when it is bonded to a carboxy group of a carboxy group-containing cellulose fiber, it is a state where it is bonded via an ester bond, amide bond, carbonate bond, urethane bond, etc.

[0074] Furthermore, when component (B) is a hydrocarbon compound having a cationic group, the modifying group in the modified cellulose fiber is derived from the hydrocarbon compound having a cationic group. In this case, the bond between the oxidized cellulose fiber and the modifying group is an ionic bond, and the modified cellulose fiber is in a state in which the cationic group of the modifying group is adsorbed to the carboxyl groups on the surface of the cellulose fiber via electrostatic interaction.

[0075] The equivalent weight of the modified group by component (B) in the modified cellulose fiber is determined by the ratio of the modified functional group to the anionic group introduced into the cellulose fiber. The equivalent weight of the modified group can be changed by the type of component (B), reaction temperature, reaction time, solvent, etc. From the viewpoint of obtaining a film with improved water resistance and synovial fluid properties, the modifying group equivalent is preferably 0.1 equivalent or more, more preferably 0.5 equivalent or more, and even more preferably 1 equivalent or more, and 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.

[0076] [Cellulose type I crystal structure and crystallinity] The modified cellulose fiber preferably has a cellulose type I crystal structure due to the use of natural cellulose as its raw material. From the viewpoint of strength development during film formation, the crystallinity of the modified cellulose fiber 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. The cellulose type I crystallinity is measured by the method described in the Examples below.

[0077] [Average fiber diameter of modified cellulose fiber] The average fiber diameter of the 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 modified cellulose fiber is measured by the method described in the Examples below.

[0078] <Properties of emulsion composition> The emulsion composition of the present invention is an emulsified composition containing the aforementioned components (A), (B), (C), (D), and (E) as essential components. The emulsification in the present invention is achieved by mixing water and a liquid organic compound at 25°C and 1 atmosphere, and then applying mechanical force to the mixture to form finely dispersed droplets of one liquid in the other. Either an o / w emulsion or a w / o emulsion may be used, but an o / w emulsion is preferred.

[0079] The content of component (A) in the emulsion composition or at the time of mixing is preferably 0.02% 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 emulsifying power, while from the viewpoint of handleability, it is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less.

[0080] The content of component (B) in the emulsion composition or at the time of mixing 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 obtaining a film with improved water resistance, and is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of film-forming properties.

[0081] The total content of component (A) and component (B) in the emulsion composition or at the time of mixing is preferably 0.02% 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 sufficient emulsification of the composition, and is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of handleability.

[0082] When component (a) and / or component (b) is used as component (C), the amount of component (a) is preferably 25 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 100 parts by mass or more, and even more preferably 200 parts by mass or more per 100 parts by mass of the anion-modified cellulose fiber of component (A), from the viewpoint of obtaining a film with excellent water resistance. On the other hand, the amount of component (a) is preferably 1,000 parts by mass or less, more preferably 500 parts by mass or less, and even more preferably 300 parts by mass or less per 100 parts by mass of the anion-modified cellulose fiber of component (A), from the viewpoint of fully exhibiting the synovial properties of the film.

[0083] When component (a) and / or component (b) is used as component (C), from the viewpoint of obtaining a film with excellent water resistance, the amount of component (b) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 4 parts by mass or more, even more preferably 10 parts by mass or more, and even more preferably 30 parts by mass or more per 100 parts by mass of the anion-modified cellulose fiber of component (A). On the other hand, from the viewpoint of fully exhibiting the synovial properties of the film, the amount of component (b) is preferably 1,000 parts by mass or less, more preferably 500 parts by mass or less, and even more preferably 300 parts by mass or less per 100 parts by mass of the anion-modified cellulose fiber of component (A).

[0084] The content of component (D) in the emulsion composition or at the time of mixing is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of maintaining the emulsion state, while from the viewpoint of solution viscosity and handleability, it is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0085] The mass ratio (A+B / D) of component (A) and component (B) to component (D) in the emulsion composition or when mixed is preferably 0.0001 or more, more preferably 0.001 or more, even more preferably 0.004 or more, even more preferably 0.01 or more, and even more preferably 0.04 or more, from the viewpoint of obtaining a film with improved water resistance and synovial fluid properties, and is preferably 20 or less, more preferably 10 or less, even more preferably 5 or less, even more preferably 3 or less, and even more preferably 2 or less, from the viewpoint of film-forming properties.

[0086] The content of component (E) in the emulsion composition or at the time of mixing is preferably 10% by mass or more, more preferably 50% by mass or more, and even more preferably 75% by mass or more, from the viewpoint of maintaining the emulsion state, while from the viewpoint of the effective amount, it is preferably 98% by mass or less, more preferably 95% by mass or less.

[0087] When component (F) is used, the content of component (F) in the emulsion composition or at the time of mixing is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of emulsion stability, while being preferably 10% by mass or less, more preferably 1% by mass or less, from the viewpoint of the water resistance of the resulting film.

[0088] When component (G) is used, the content of component (G) in the emulsion composition or at the time of mixing is preferably 0.01% by mass or more from the viewpoint of film durability, and is preferably 5% by mass or less from the viewpoint of suppressing an increase in the viscosity of the composition.

[0089] The viscosity of the emulsion composition is not particularly limited, but from the viewpoint of ease of handling, the viscosity at 25° C. is preferably 0.5 mPa s or more and 20 Pa s or less. The viscosity here 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.

[0090] 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), (D), and (E). Mixing the components causes emulsification, resulting in an emulsion composition. For this mixing process, a magnetic stirrer, mechanical stirrer, homomixer, vacuum emulsifier, low-pressure homogenizer, high-pressure homogenizer, grinder, cutter mill, ball mill, jet mill, single-screw extruder, twin-screw extruder, ultrasonic agitator, household juicer mixer, etc. can be used. The mixing process may be performed by combining two or more operations.

[0091] 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.

[0092] 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.

[0093] The order of mixing the components is not particularly limited. For example, in order to suppress aggregation, the method for preparing a mixture containing each component may be as follows: Step 1: mixing component (A) and component (E); and Step 2: mixing the mixture obtained in step 1 with component (B) and component (D); A preparation method having the following formula is preferred. Regarding the mixing order of the other components, from the viewpoint of emulsion stability, when component (b) is added as component (C), it is preferable to add it in step 3 after step 2, and when component (a) is added as component (C), it is preferable to mix it together with components (D) and (B) in step 2. Furthermore, from the viewpoint of suppressing aggregation, component (F) is preferably mixed in step 1.

[0094] By subjecting component (A) to a micronization treatment at any stage in the production process of the emulsion composition, micrometer-scale cellulose fibers can be reduced to nanometer-scale. Reducing the average fiber diameter to the nanometer scale improves the strength of the film when formed, so it is preferable to further carry out a micronization treatment step at any stage in the production process of the emulsion composition.

[0095] A known dispersing machine is preferably used in the micronization process. 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. The solid content of the mixture in the micronization process is preferably 50% by mass or less.

[0096] 3. Method for producing a membrane containing modified cellulose fibers The method of the present invention for producing a membrane containing modified cellulose fibers includes a step of drying the emulsion composition of the present invention or the emulsion composition obtained by the method for producing an emulsion composition of the present invention.

[0097] It is believed that when the water in the emulsion composition is removed by drying, the cellulose fibers that formed the emulsion particles form a networked particulate structure. This is presumably because at least a portion of component (C) crosslinks the particulate structures together as the water dries, improving the durability of the resulting film.

[0098] Specifically, the emulsion composition is applied to a substrate, for example, a solid surface made of glass, resin, metal, ceramics, concrete, wood, stone, fiber, etc., or to skin, hair, etc. Examples of application methods include, but are not limited to, methods using an applicator, bar coder, spin coater, etc., brush coating, hand coating, spraying, dip coating, etc.

[0099] The thickness of the coating film of the emulsion composition on the substrate is preferably 10 μm or more from the viewpoint of film durability, and is preferably 2000 μm or less from the viewpoint of coatability.

[0100] The emulsion composition coating can then be dried to obtain a film. The drying conditions may be under reduced pressure or normal pressure, and the temperature range is preferably 15° C. to 75° C. The drying time is preferably 1 hour to 24 hours.

[0101] 4. Film of emulsion composition The film of the emulsion composition of the present invention obtained by the above-described production method preferably 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 on January 28, 2016).

[0102] The synovial surface property 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 property of the film.

[0103] The thickness of the film of the present invention is not particularly limited, and is preferably 1 μm or more from the viewpoint of film durability, and preferably 2000 μm or less from the viewpoint of economy. The film thickness can be adjusted to a desired value by setting the coating thickness using an application tool such as an applicator or adjusting the proportion of the medium. The film thickness can be measured according to the method described in the Examples below.

[0104] The amount of modified cellulose fiber in the film of the present invention is preferably 1% by mass or more, more preferably 10% by mass or more, from the viewpoint of film durability, and is preferably 65% ​​by mass or less, more preferably 36% by mass or less, and even more preferably 16% by mass or less, from the viewpoint of film synovial properties. The amount of modified cellulose fiber in the film can be determined taking into account the amounts of volatile components (e.g., water and some organic compounds) in the emulsion composition.

[0105] The film of the present invention may contain any optional component that does not impair the effects of the present invention.

[0106] By applying the film of the present invention to a solid surface, the solid surface can be modified into a synovial surface.The film of the present invention not only has excellent synovial properties, but also has excellent durability itself, so that its effect can be maintained for a long period of time.Therefore, it can be suitably used for various applications, for example, as packaging materials for daily necessities, cosmetics, home appliances, etc., interior materials for packaging containers such as blister packs, trays, lunch box lids, etc., food containers, industrial trays and transport pipes used for transporting and protecting industrial parts, and also as covering materials for roofs, building walls, ship bottoms, electric wires, etc.Therefore, it can be suitably used as an anti-fouling film that suppresses the adhesion of dust, etc., an anti-snow film that suppresses the adhesion of snow, ice, etc., and an anti-biofouling film that suppresses the adhesion of aquatic organisms, etc.

[0107] The film of the present invention has excellent synovial properties and is therefore useful as a biofouling inhibitor. Therefore, by applying the emulsion composition of the present invention to the above solid surface as a biofouling inhibitor, a method for inhibiting biofouling can be provided. [Example]

[0108] 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.

[0109] [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.

[0110] [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 (manufactured by Jusco International, product name: IF-3200) 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.

[0111] [Anionic Group Content of Anion-Modified Cellulose Fibers and Modified Cellulose Fibers] A 100 mL beaker is charged 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, product name "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)]

[0112] [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 complete, the fiber was washed with deionized water to obtain cellulose fibers 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 cellulose fiber after oxidation." The aldehyde group content of the oxidized cellulose fiber to be measured was then calculated using Equation 1.

[0113] 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

[0114] [Solid content in dispersion] The measurement is performed using a halogen moisture meter (Shimadzu Corporation; product name "MOC-120H"), with 1 g of sample measured every 30 seconds 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.

[0115] [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.

[0116] <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°).

[0117] 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.

[0118] <Formula B> Cellulose type I crystallinity (%) = [A c / (A c +A a )] × 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.

[0119] [Anion-modified cellulose fiber] Anion-modified cellulose fibers having the physical properties shown in Table 1 were used as raw materials.

[0120] [Table 1]

[0121] [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.

[0122] Next, 0.01 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 filtrate is 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 anionically modified cellulose fibers.

[0123] [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.

[0124] [Table 2]

[0125] Such finely divided anionically modified cellulose fibers can be prepared, for example, by the following fine division treatment and reduction treatment.

[0126] [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).

[0127] [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.

[0128] [Production of modified cellulose fiber and emulsion composition] The modified cellulose fiber and emulsion composition were produced as follows. Here, the numerical values ​​for the composition of each raw material shown in Tables 3 to 5 are in parts by mass, and the total of each raw material including water is 100 parts by mass. Each raw material was used so that the active component of each raw material was the part by mass shown in Tables 3 to 5. The amount of water in component (E) includes the amount of water as a medium when each raw material is used as an aqueous solution, suspension, etc.

[0129] Example 1 The anion-modified cellulose fiber (solid content 21.3%) was weighed into a beaker, and deionized water was added to prepare a suspension. The suspension was stirred at 25°C for 15 hours. A 10% by mass aqueous solution of an anionic surfactant was then added. Silicone oil and amino-modified silicone were then added to the resulting suspension. The solution was stirred with a mechanical stirrer for 1 minute to obtain a mixture. After visually confirming that no coarse aggregates had formed in the mixture, the mixture was subjected to 10 passes at 150 MPa in a high-pressure homogenizer (Yoshida Kikai Co., Ltd., Nanovaita L-ES) to obtain an emulsion containing modified cellulose fiber in which amino-modified silicone was linked to anion-modified cellulose fiber via ionic bonds. The resulting emulsion was a cloudy liquid, and oil droplets dispersed in water were observed under an optical microscope, indicating that it was in an emulsified state. The oxazoline group-containing polymer 1 was added to the emulsion, and the mixture was stirred with a mechanical stirrer for 1 minute to obtain an emulsion composition of the present invention.

[0130] Examples 2 to 12, Comparative Examples 1 to 2 An emulsion composition was obtained in the same manner as in Example 1, except that the blending of each raw material was changed to that shown in Tables 3 and 4.

[0131] Example 13 An emulsion composition was produced by changing the order of blending the raw materials from Example 1, etc. Specifically, the anion-modified cellulose fiber (solid content 21.3%) was weighed into a beaker, and deionized water was added to prepare a suspension. The suspension was then stirred at 25°C for 15 hours. A 10% by mass aqueous solution of anionic surfactant was then added. Silicone oil, amino-modified silicone, and dimethoxydimethylsilane were mixed with the resulting suspension. This solution was stirred with a mechanical stirrer for 1 minute to obtain a mixture. After visually confirming that no coarse aggregates were formed in the mixture, the mixture was subjected to 10 passes at 150 MPa in a high-pressure homogenizer (NanoVita L-ES, manufactured by Yoshida Kikai Co., Ltd.) to obtain an emulsion composition containing modified cellulose fiber in which the amino-modified silicone was ionically bonded to the carboxyl groups of the anion-modified cellulose fiber and the silane coupling agent dimethoxydimethylsilane was covalently bonded to the hydroxyl groups. The resulting composition was a cloudy liquid, and oil droplets dispersed in water were observed under an optical microscope, and therefore it was determined to be an emulsion composition.

[0132] Example 14 An emulsion composition was obtained in the same manner as in Example 13, except that the formulation of the emulsion composition was changed to that shown in Table 3.

[0133] Example 15 To the emulsion composition of Example 14, 0.08 g of a crosslinking agent was added to obtain a mixture.

[0134] Example 16 The reduction-treated, finely divided anion-modified cellulose fiber dispersion (solid content 0.9% by mass), silicone oil, amino-modified silicone, and dimethoxydimethylsilane (Tokyo Chemical Industry Co., Ltd.) were mixed in a beaker, and deionized water was added. The solution was stirred for 5 minutes with a mechanical stirrer and then processed 10 times at 150 MPa with a high-pressure homogenizer (Yoshida Kikai Co., Ltd., Nanovaita L-ES) to obtain an emulsion composition containing modified cellulose fibers in which the amino-modified silicone was ionically bonded to the carboxyl groups of the finely divided anion-modified cellulose fibers and the silane coupling agent dimethoxydimethylsilane was covalently bonded to the hydroxyl groups.

[0135] Examples 17 to 18, Comparative Example 3 An emulsion composition was obtained in the same manner as in Example 16, except that the composition of each raw material was changed to that shown in Table 4.

[0136] Details of the representative components used in the examples are summarized below.

[0137] [Component (B)] Amino-modified silicone: Dow Toray, SS-3551 (kinematic viscosity: 1,000, amino equivalent: 1,700)

[0138] [Component (C)] Oxazoline group-containing polymer 1: Epocross WS300 (active ingredient concentration: 10% by mass), manufactured by Nippon Shokubai Co., Ltd. Oxazoline group-containing polymer 2: Epocross WS700 (active ingredient concentration: 25% by mass), manufactured by Nippon Shokubai Co., Ltd. Oxazoline group-containing polymer 3: Epocross K-2010E (active ingredient concentration 40% by mass), manufactured by Nippon Shokubai Co., Ltd. Oxazoline group-containing polymer 4: Epocross K-2020E (active ingredient concentration: 40% by mass), manufactured by Nippon Shokubai Co., Ltd. Oxazoline group-containing polymer 5: Epocross K-2035E (active ingredient concentration: 40% by mass), manufactured by Nippon Shokubai Co., Ltd. Carbodiimide 1: Carbodilite V-02-L2 (active ingredient concentration: 40% by mass), manufactured by Nisshinbo Chemical Co., Ltd. Carbodiimide 2: Carbodilite SV-02 (active ingredient concentration: 40% by mass), manufactured by Nisshinbo Chemical Co., Ltd. Carbodiimide 3: Carbodilite V-10 (active ingredient concentration: 40% by mass), manufactured by Nisshinbo Chemical Co., Ltd. Carbodiimide 4: Carbodilite E-02 (active ingredient concentration: 40% by mass), manufactured by Nisshinbo Chemical Co., Ltd. Dimethoxydimethylsilane: Tokyo Chemical Industry Co., Ltd. Trimethoxymethylsilane: manufactured by Tokyo Chemical Industry Co., Ltd. Methoxytrimethylsilane: manufactured by Tokyo Chemical Industry Co., Ltd.

[0139] [Component (D)] Silicone oil: Shin-Etsu Chemical Co., Ltd., KF-96-100cs (SP value: 7.3)

[0140] [Component (F)] Anionic surfactant: Fujifilm Wako Pure Chemical Industries, Ltd., sodium dodecyl sulfate

[0141] [Condensing agent] DMTMM: Fujifilm Wako Pure Chemical Industries, Ltd., 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholium chloride

[0142] [Membrane Preparation] 0.5 mL of each of the emulsion compositions prepared in Examples 1 to 18 and Comparative Examples 1 to 3 was applied to separate glass substrates (Micro Slide Glass S2112, manufactured by MATSUNAMI Co., Ltd.) and spread over the entire surface of the glass slide. The composition was then dried at 1 atmosphere, 25°C, and approximately 40% RH for 24 hours to prepare a film.

[0143] [Measurement of membrane water resistance] The membranes of Examples 1 to 15 and Comparative Examples 1 and 2 were prepared as described above. The glass substrate was immersed in a 300 mL beaker filled with water (approximately 23°C), and the swelling ratio of the membrane after 24 hours was calculated using the following formula A. The higher the swelling ratio of the membrane, the lower the water resistance of the membrane. The results are shown in Tables 3 and 4.

[0144] <Formula A> Swelling ratio [%] = [{[Mass after immersion] - [Mass of glass substrate before coating]} ÷ {[Mass before immersion] - [Mass of glass substrate before coating]} - 1] × 100 Mass after immersion: Mass of the glass substrate after the glass substrate and the film formed on the substrate are immersed for a predetermined time. Mass before immersion: Mass of the glass substrate and the film formed on the substrate before immersing the glass substrate in water

[0145] [Slide angle measurement test] The films of Examples 1 to 15 and Comparative Examples 1 and 2 prepared as described above were placed horizontally, and an 8 μL water droplet (23°C) was dropped onto each film at 23°C using a fully automatic contact angle meter (FAMAS, manufactured by Kyowa Interface Science Co., Ltd.) 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 water droplet began to slide was measured. The smaller the water droplet sliding angle, the higher the synovial properties of the film. The composition of each component and the evaluation results are shown in the table below. However, if the water droplet did not slide even when tilted to 80°, the water droplet sliding angle was recorded as "greater than 80."

[0146] [Table 3]

[0147] [Table 4]

[0148] In the above table, molar equivalent *1 refers to the molar equivalent of component (B) relative to the carboxy group in component (A), molar equivalent *2 refers to the molar equivalent of component (C) relative to the carboxy group in component (A), and molar equivalent *3 refers to the molar equivalent of the hydrophilic group in component (F) relative to the amino group in component (B).

[0149] Tables 3 and 4 show that the films obtained by drying the emulsion compositions of the present invention were excellent in synovial properties and water resistance (Examples 1 to 15). On the other hand, the film produced in Comparative Example 1 had excellent synovial properties comparable to those of the Examples, but was significantly inferior in water resistance. This is thought to be due to the absence of component (C) in Comparative Example 1. Furthermore, in Comparative Example 2, a condensing agent was used instead of component (C), and as a result, it was found that not only water resistance but also synovial properties were significantly inferior.

[0150] [Measurement of film durability] The membranes of Examples 16 to 18 and Comparative Example 3 were prepared by the method described above. Using tap water, a constant flow rate (3 L / min) of water (approximately 23°C) was continuously poured onto the substrate from a height of 40 cm for 30 minutes. After 30 minutes of exposure to tap water, the sliding angle of the membrane relative to the water droplet was measured using the same method as in the "Sliding Angle Measurement Test" described above. The smaller the sliding angle after 30 minutes of exposure to flowing water, the higher the durability of the membrane. The composition of each component (parts by mass in the film) and the evaluation results are shown in the table below.

[0151] [Table 5]

[0152] In the above table, the molar equivalent *1 refers to the molar equivalent of component (B) relative to the carboxy group in component (A). Table 5 shows that the films obtained by drying the emulsion compositions of the present invention were excellent in durability (Examples 16 to 18). On the other hand, it was found that the durability of the film in Comparative Example 3, in which component (C) was not blended, was significantly lower than that of Examples 16 to 18. The reason for this is thought to be that component (C) was not blended in Comparative Example 3. [Industrial Applicability]

[0153] The emulsion composition produced by the production method of the present invention can form a film with synovial properties, and can therefore be used as a biofouling inhibitor for various surfaces, such as ships and bridges.

Claims

1. An emulsion composition containing the following components (A), (B), (C), (D) and (E). (A) Anion-modified cellulose fiber (B) Amino-modified silicone (C) One or more compounds selected from the group consisting of a crosslinking agent having an oxazoline group, a crosslinking agent having a carbodiimide group, and an organoalkoxysilane compound. (D) One or more organic compounds that are liquid at 25°C and 1 atmosphere and are selected from the group consisting of ester oils, silicone oils, and ether oils. (E) Water

2. The emulsion composition according to claim 1, further comprising the following component (F): (F) Anionic surfactants (excluding the above-mentioned components (B) and (D)).

3. A method for producing a membrane containing modified cellulose fibers, comprising a step of drying the emulsion composition according to claim 1 or 2.

4. A film obtained by drying the emulsion composition according to claim 1 or 2.

5. A biofouling inhibitor comprising the emulsion composition according to claim 1 or 2 or the film according to claim 4.

6. A method for producing an emulsion composition, comprising the step of mixing the following components (A), (B), (C), (D), and (E): (A) Anion-modified cellulose fiber (B) Amino-modified silicone (C) One or more compounds selected from the group consisting of a crosslinking agent having an oxazoline group, a crosslinking agent having a carbodiimide group, and an organoalkoxysilane compound. (D) One or more organic compounds that are liquid at 25°C and 1 atmosphere and are selected from the group consisting of ester oils, silicone oils, and ether oils. (E) Water

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