Emulsion composition

Abstract

To provide a film having excellent antibacterial properties, and a composition that can form the film.SOLUTION: An emulsion composition includes (A) cellulose fibers having a modifying group, (B) water, (C) an organic compound being liquid at 25°C and 1 atmospheric pressure and (D) a compound having antibacterial property, with the mass ratio of component (D) and component (A) ((D) / (A)) of 0.0001 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to an emulsified composition. [Background technology]

[0002] In recent years, there has been a growing demand for antimicrobial compositions or surface treatments that can prevent various problems caused by microorganisms, such as infections and biofilm adhesion. Ideally, these should be easily applied to the target surface and provide sustained effectiveness. For example, existing technologies include the following Non-Patent Documents 1-3. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Coatings 2020,10,1239 [Non-Patent Document 2] Biomaterials 2007, 28, 4192-4199 [Non-Patent Document 3] Biointerfaces 2014, 113, 115-124 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, existing technologies have drawbacks, such as insufficient microbial adhesion suppression (Non-Patent Documents 1 and 2) and unconvenient treatment conditions (Non-Patent Document 3). Therefore, the object of the present invention is to provide a film with excellent antibacterial properties and a composition capable of forming such a film. [Means for solving the problem]

[0005] The present invention relates to the following [1] to [4]. 〔1〕An emulsified composition containing the following components (A) to (D), wherein the mass ratio of component (D) to component (A) ((D) / (A)) is 0.0001 or more. (A) Cellulose fiber having a modifying group (B) Water (C) An organic compound that is liquid at 25°C and 1 atm (D) A compound having antibacterial properties 〔2〕A biofouling inhibitor, antifouling agent or antibacterial agent containing the emulsified composition according to 〔1〕 above. 〔3〕A film obtained by applying the emulsified composition according to 〔1〕 above or the biofouling inhibitor, antifouling agent or antibacterial agent according to 〔2〕 above. 〔4〕A method for producing an emulsified composition, which includes a step of mixing the following components (A) to (D), wherein the mass ratio of component (D) to component (A) ((D) / (A)) is 0.0001 or more. (A) Cellulose fiber having a modifying group (B) Water (C) An organic compound that is liquid at 25°C and 1 atm (D) A compound having antibacterial properties

Effects of the Invention

[0006] According to the present invention, it is possible to provide a film excellent in antibacterial properties and an emulsified composition for forming the film.

Modes for Carrying Out the Invention

[0007] As a result of investigations by the present inventors, an emulsified composition containing modified cellulose fibers having a specific structure, an organic medium, water, and a compound having specific antibacterial properties was found. Such an emulsified composition can form a strong film by a simple treatment method of spraying it on the surface of an object, and it was further found that the microbial adhesion inhibitory effect exhibited by such a film is sufficiently high, thereby completing the present invention.

[0008] 1. Emulsified composition The emulsified composition of the present invention contains the following components (A) to (D).

[0009] <Component (A)> Component (A) is a cellulose fiber having a modifying 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 hydroxyl groups of an anionic modified cellulose fiber having a type I crystal structure.

[0010] [Anionic modified cellulose fiber] Anionically modified cellulose fibers are cellulose fibers that have been anionically modified to contain anionic groups. Anionically modified cellulose fibers have a cellulose type I crystalline structure derived from the raw cellulose fibers. From the viewpoint of improving the antibacterial properties of the film, the degree of crystallinity of the anionically modified cellulose fibers is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more. Also, from the viewpoint of raw material availability, it is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, and even more preferably 75% or less.

[0011] In this specification, the degree of crystallinity of various cellulose fibers is the degree of cellulose type I crystallinity calculated from the diffraction intensity value 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 the degree of cellulose type I crystallinity means the proportion of the crystalline region in the total 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.

[0012] Anionic groups contained in anionic-modified cellulose fibers include, for example, carboxyl groups, sulfonic acid groups, and phosphate groups. From the viewpoint of the efficiency of introducing modifying groups into cellulose fibers, carboxyl groups are preferred. Examples of counterions to the anionic groups in anionic-modified cellulose fibers include metal ions such as sodium ions, potassium ions, calcium ions, and aluminum ions that are generated in the presence of alkali during production, and protons that are generated by substituting these metal ions with acid. As anionically modified cellulose fibers, carboxyl-containing cellulose fibers, in which the anionic group is a carboxyl group, are more preferred from the viewpoint of ease of preparation and mild reaction conditions.

[0013] The anionic group content in anionically modified cellulose fibers 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 handling properties, 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. Note that "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.

[0014] The average fiber diameter of the anion-modified cellulose fibers 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 handling ease, and preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less, from the viewpoint of film strength. The average fiber diameter of the anion-modified cellulose fibers is measured by the method described in the examples below.

[0015] [Modified cellulose fiber] Cellulose fibers having a modifying group are also referred to as modified cellulose fibers in this specification. From the viewpoint of improving the antibacterial properties of the membrane, modified cellulose fibers are preferably those in which a modifying group is bonded to the anionic group or hydroxyl group of anionically modified cellulose fiber. The modifying group is introduced by a reaction between a compound for introducing the modifying group (referred to as a "modifying compound" in this specification) and the anionically modified cellulose fiber. That is, the structure of the modifying group depends on the structure of the modifying compound used.

[0016] When the modifying group is bonded to a hydroxyl group, the bonding mode between the modifying group and the anionically modified cellulose fiber is a covalent bond, such as an ether bond, ester bond, or carbonate bond.

[0017] When the modifying group is bonded to an anionic group, the bond between the modifying group and the anionically modified cellulose fiber is either ionic or covalent. In the case of an ionic bond, the modifying compound having a cationic group bonds to the anionic group via electrostatic interaction. In the case of a covalent bond, the two are bonded via ester bonds, amide bonds, etc. In particular, when the anionic group is a carboxyl group, the bond is formed via ester bonds, amide bonds, carbonate bonds, urethane bonds, etc.

[0018] [Modifying group] Examples of modifying groups, from the viewpoint of improving the antibacterial properties of the membrane, include (a) polymer groups and (b) hydrocarbon groups. These modifying groups may be attached to the anionic modified cellulose fibers individually or in combination of two or more types.

[0019] (a) Polymer group A polymer group is a functional group containing a polymer structure. From the viewpoint of improving the antibacterial properties of the film, 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, and even more preferably 1,500 g / mol or more. From a similar 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, and even more preferably 2,500 g / mol or less. Functional group equivalent is the molecular weight per functional group, and can be calculated using the formula: Functional group equivalent (g / mol) = [weight-average molecular weight] / [number of functional groups per molecule].

[0020] 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, from the viewpoint of improving the antibacterial properties of the film, and similarly, preferably 1,000,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0021] From the viewpoint of improving the antibacterial properties of the film, the polymer group is preferably a functional group having a repeating structure linked by 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, and more preferably a functional group having a polysiloxane structure.

[0022] A polysiloxane structure is a structure in which siloxane bonds form the main chain, and which may also contain alkylene groups. The polysiloxane structure may also have substituents as described later.

[0023] (b) hydrocarbon group Examples of hydrocarbon groups include monovalent hydrocarbon groups, such as chain-type saturated hydrocarbon groups, chain-type unsaturated hydrocarbon groups, cyclic saturated hydrocarbon groups, and (heterocyclic) aromatic hydrocarbon groups.

[0024] From the viewpoint of improving the antibacterial properties of the film, 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, preferably 40 or less, more preferably 30 or less, even more preferably 24 or less, and even more preferably 22 or less. The hydrocarbon group may have substituents described later, and a portion of the hydrocarbon group may be substituted with a hydrogen nitride group.

[0025] (c) Further substituents The above-mentioned polymer groups (a) and hydrocarbon groups (b) may have further substituents. Examples of substituents 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 groups; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, and sec-butoxycarbonyl groups. Examples include alkoxy-carbonyl groups with 1 to 6 carbon atoms, such as tert-butoxycarbonyl, pentyloxycarbonyl, and isopentyloxycarbonyl groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; acyl groups with 1 to 6 carbon atoms, such as acetyl and propionyl groups; aralkyl groups; aralkyloxy groups; alkylamino groups with 1 to 6 carbon atoms; dialkylamino groups with 1 to 6 carbon atoms in the alkyl group; and hydroxyl groups.

[0026] The amount of modifying groups (mmol / g) and the introduction rate (mol%) in modified cellulose fibers refer to the amount and proportion of modifying groups introduced into the modified cellulose fibers. The amount of modifying groups and the introduction rate can be adjusted by the amount and type of modifying compound added, the reaction temperature, the reaction time, the solvent, etc.

[0027] From the viewpoint of improving the antibacterial properties of the membrane, the amount of modifying groups bound to the modified cellulose fibers 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. Furthermore, from the viewpoint of reactivity, it is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less, and even more preferably 2 mmol / g or less.

[0028] Furthermore, from the viewpoint of improving the antibacterial properties of the membrane, the rate of introduction of modifying groups in the modified cellulose fibers 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. 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.

[0029] [Method for producing modified cellulose fibers] Modified cellulose fibers can be produced, for example, by a method comprising: (1) a step of introducing anionic groups into raw cellulose fibers to obtain anionically modified cellulose fibers; and (2) a step of bonding a modifying compound to the anionically modified cellulose fibers obtained by a method including step (1) to obtain modified cellulose fibers.

[0030] (1) Process for obtaining anionic modified cellulose fibers The anionically modified cellulose fibers used in the present invention can be obtained by subjecting raw material cellulose fibers to an oxidation treatment or an anionic group addition treatment to introduce one or more anionic groups and thereby anionically modify them.

[0031] The cellulose fibers to be anionically modified, i.e., the cellulose fibers used as raw materials for modified cellulose fibers and anionically modified cellulose fibers, are preferably natural cellulose fibers from an environmental standpoint. Examples include wood pulp such as coniferous pulp and hardwood pulp; cotton pulp such as cotton linters and cotton lint; non-wood pulp such as straw pulp and bagasse pulp; and bacterial cellulose. One of these can be used alone or in combination of two or more.

[0032] The average fiber diameter of the cellulose fibers used as raw materials is preferably 1 μm or more, and preferably 300 μm or less, from the viewpoint of handling ease and cost.

[0033] Furthermore, from the viewpoint 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 in which the average fiber length is 1 μm or more and 1,000 μm or less, obtained by shortening the raw cellulose fibers through alkaline hydrolysis treatment, acid hydrolysis treatment, etc.

[0034] Examples of anionic groups that can be introduced include carboxyl groups, sulfonic acid groups, or phosphate groups.

[0035] (i) When introducing a carboxyl group as an anionic group into cellulose fibers Methods for introducing carboxyl groups into cellulose fibers include, for example, oxidizing the hydroxyl groups of cellulose to convert them into carboxyl groups, or reacting the hydroxyl groups of cellulose with one or more compounds selected from the group consisting of compounds having carboxyl groups, acid anhydrides of compounds having carboxyl groups, and derivatives thereof.

[0036] As a method for oxidizing the hydroxyl groups of the cellulose, for example, a method can be applied in which 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) is used as a catalyst to react with an oxidizing agent such as sodium hypochlorite and a bromide such as sodium bromide to perform the oxidation treatment. More specifically, known methods, such as the method described in Japanese Patent Application Publication No. 2011-140632, can be referred to.

[0037] By oxidizing cellulose fibers using TEMPO as a catalyst, the hydroxymethyl group (-CH2OH) at the C6 position of the cellulose constituent unit is selectively converted to a carboxyl group. This method is particularly advantageous because it exhibits excellent selectivity for the hydroxyl group at the C6 position on the surface of the raw material cellulose fibers, and the reaction conditions are mild. Therefore, a preferred embodiment of the anionically modified cellulose fiber in the present invention is a cellulose fiber in which the C6 position of the cellulose constituent unit is a carboxyl group. In this specification, cellulose fibers obtained by oxidation of hydroxyl groups in cellulose constituent units may be referred to as "oxidized cellulose fibers," and cellulose fibers in which the C6 position of the cellulose constituent unit is a carboxyl group may be referred to as "TEMPO-oxidized cellulose fibers." Oxidized cellulose fibers are preferred because they are easier to prepare than other anionically modified cellulose fibers. Therefore, one preferred embodiment of the modified cellulose fibers 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.

[0038] By further oxidation or reduction treatment of oxidized cellulose fibers, oxidized cellulose fibers from which the remaining aldehyde groups have been removed can be prepared.

[0039] (ii) When introducing a sulfonic acid group or a phosphate group as an anionic group into cellulose fibers Methods for introducing sulfonic acid groups as anionic groups into cellulose fibers include adding sulfuric acid to the cellulose fibers and heating them. Methods for introducing phosphate groups as anionic groups into cellulose fibers include mixing cellulose fibers in a dry or wet state with powder or aqueous solution of phosphate or a phosphate derivative, or adding an aqueous solution of phosphate or a phosphate derivative to a dispersion of cellulose fibers. When these methods are employed, generally, after mixing or adding powder or aqueous solution of phosphate or a phosphate derivative, dehydration and heat treatment are performed.

[0040] (2) Process for obtaining modified cellulose fibers Modified cellulose fibers can be produced by bonding the anionically modified cellulose fibers with one or more compounds selected from the group consisting of compounds having a modifying group, preferably amino-modified silicones, and hydrocarbon compounds having a cationic group. Known methods, such as those described in Japanese Patent Application Publication No. 2015-143336, can be used for this production method.

[0041] (3) Compound for modification The modifying compound is, from the viewpoint of improving the antibacterial properties of the membrane, a compound having a modifying group and capable of binding to anionic modified cellulose fibers, preferably a compound having a modifying group and capable of binding to anionic or hydroxyl groups of anionic modified cellulose fibers, more preferably a compound having a modifying group and a cationic group, even more preferably a compound having a modifying group and an amino group or a quaternary ammonium group, and even more preferably a primary amine, secondary amine, tertiary amine, and quaternary ammonium compound having a modifying group. Preferred examples of modifying compounds include polymer compounds having amino groups and hydrocarbon compounds having cationic groups, from the viewpoint of improving the antibacterial properties of the membrane.

[0042] (i) Polymer compounds having an amino group For use as a modification compound in this invention, a polymer compound having a preferred amino group can be commercially available or prepared according to known methods. One or more polymer compounds having an amino group may be used.

[0043] Examples of polymer compounds having amino groups 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, polyallylamines, and polyethyleneimines; and chain-like aliphatic polyamines, cyclic aliphatic polyamines, aromatic polyamines, etc. The position of the reactive group may be in the main chain, side chains, or terminals of the polymer compound. Among these, amino-modified silicones are preferred from the viewpoint of improving the antibacterial properties of the film. By using amino-modified silicones as the modifying compound, the modifying group having the polysiloxane structure described above can be provided to the modified cellulose fibers.

[0044] Amino-modified silicones are silicone compounds that contain amino groups. For example, an amino-modified silicone has a kinematic viscosity of 10 mmHg at 25°C. 2 / s or more 20,000mm 2 A concentration of less than or equal to / s is preferred. Furthermore, amino-modified silicones with an amino equivalent of 400 g / mol to 16,000 g / mol are preferred.

[0045] The kinematic viscosity at 25°C can be determined using an Ostwald viscometer, and from the viewpoint of improving the antibacterial properties of the film, 20 mm is more preferable. 2 / s or more, more preferably 50mm 2 It is 10,000 mm or more, and more preferably from the standpoint of handling performance. 2 / s or less, more preferably 5,000 mm 2 It is less than or equal to / s.

[0046] Also, from the viewpoint of improving the antibacterial property of the film, the amino equivalent is preferably 400 g / mol or more, more preferably 600 g / mol or more, and still more preferably 800 g / mol or more. From the viewpoint of ease of bonding to the anionic modified cellulose fiber, it is preferably 16,000 g / mol or less, more preferably 14,000 g / mol or less, and still more preferably 12,000 g / mol or less. The amino equivalent is the molecular weight per nitrogen atom, and the amino equivalent (g / mol) = weight average molecular weight / number of nitrogen atoms per molecule, and is determined. Here, the weight average molecular weight is a value determined by gel permeation chromatography using polystyrene as a standard substance, and the number of nitrogen atoms can be determined by an elemental analysis method.

[0047] Specific examples of the amino-modified silicone include compounds represented by the general formula (a1).

[0048] [Chemical formula]

[0049] [In the formula, R 1a 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 viewpoints of lubricity and improvement of the antibacterial property of the film. R 2a represents a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group, or a hydrogen atom, and is preferably a methyl group or a hydroxy group from the same viewpoints. 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 the average degree of polymerization, and are selected so that the kinematic viscosity and amino equivalent of the compound at 25 °C are within the above ranges. Incidentally, R 1a , R 2a , R 3a may be the same or different from each other, and a plurality of R 2a may be the same or different from each other. ]

[0050] In the compound of general formula (a1), from the viewpoint of improving synovial properties and antibacterial properties of the membrane, x is preferably a number between 10 and 10,000, more preferably a number between 20 and 5,000, and even more preferably a number between 30 and 3,000. Y is preferably a number between 1 and 1,000, more preferably a number between 1 and 500, and even more preferably a number between 1 and 200. 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 viewpoint of improving antibacterial properties of the membrane, preferably 1,000,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0051] In general formula (a1), the following can be considered as side chain B having an amino group. -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 (Here, e, f, and g are numbers from 1 to 30.)

[0052] 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 hydrolysate, and then heating the hydrolysate obtained from this hydrolysate with dimethylcyclopolysiloxane using a basic catalyst such as sodium hydroxide to 80-110°C to allow an equilibrium reaction to occur, and then neutralizing the basic catalyst with an acid when the reaction mixture reaches a desired viscosity (see Japanese Patent Publication No. 53-98499). H2N(CH2)2NH(CH2)3Si(CH3)(OCH3)2(a2)

[0053] Furthermore, the amino-modified silicone is preferably one or more selected from the group consisting of monoamino-modified silicone having one amino group in one of the side chains B and diamino-modified silicone having two amino groups in one of the side chains B, from the viewpoint of improving the antibacterial properties of the film, and more preferably one or more selected from the group consisting of compounds in which the amino-group-containing side chain B is represented by -C3H6-NH2 [hereinafter referred to as component (a1-1)] and compounds in which the amino-group-containing side chain B is represented by -C3H6-NH-C2H4-NH2 [hereinafter referred to as component (a1-2)].

[0054] In this invention, the amino-modified silicones are, in terms of performance, TSF4703 (kinematic viscosity: 1000, amino equivalent: 1600) and TSF4708 (kinematic viscosity: 1000, amino equivalent: 2800) from 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: 2800) from Dow Toray. (Mino 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), KF-8002 (kinematic viscosity: 1100, amino equivalent: 1700) manufactured by Shin-Etsu Chemical Co., Ltd., KF-80 Preferred are KF-8005 (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 The value is expressed as ( / s), and the unit of amino equivalent is g / mol.

[0055] (a1-1) BY16-213 (kinematic viscosity: 55, amino equivalent: 2700) and BY16-853U (kinematic viscosity: 14, amino equivalent: 450) are more preferred as component (a1-1).

[0056] (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.

[0057] Furthermore, polymer compounds having an amino group may also have substituents. Specific examples of substituents include those described in "(c) Further substituents" above.

[0058] (ii) hydrocarbon compounds having cationic groups In the present invention, a hydrocarbon compound having a cationic group is one in which one or more hydrocarbon groups are bonded to one cationic group. From the viewpoint of improving the antibacterial properties of the film, the total number of carbon atoms in 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 handling, it is preferably 40 or less, more preferably 30 or less, even more preferably 26 or less, and even more preferably 22 or less.

[0059] Hydrocarbon compounds containing a cationic group are compounds in which the hydrocarbon group is directly bonded to a nitrogen atom or 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., it is a compound in which the hydrocarbon group is covalently bonded to at least one of the nitrogen atoms or carbon atoms of the functional group. When the cationic group is an imidazolium, pyridinium, imidazoline, etc., it is a compound in which at least one hydrocarbon group is covalently bonded to any position in the ring structure. Hydrocarbon compounds having cationic groups are more preferably those that do not contain oxyalkylene groups.

[0060] The above hydrocarbon compounds may have some hydrogen atoms further substituted. Examples of substituents include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, hydroxyl groups, methoxy groups, ethoxy groups, carboxyl groups, aldehyde groups, ketone groups, and thiol groups.

[0061] The hydrocarbon compounds having the cationic group described above are preferably hydrocarbon compounds having an amino group, such as primary amines, secondary amines, tertiary amines, and quaternary ammonium compounds (hereinafter referred to as "hydrocarbon amines"). Specific examples of such hydrocarbon amines include hexadecylamine, stearylamine, oleylamine, dioctylamine, didecylamine, didodecylamine, trihexylamine, trioctylamine, tetrabutylammonium salt, tetrahexylammonium salt, dimethyldioctylammonium salt, dimethylddecylammonium salt, and trimethylhexadecylammonium salt.

[0062] Furthermore, hydrocarbon compounds having cationic groups may also have substituents. Specific examples of substituents include those described in "(c) Further substituents" above.

[0063] (iii) Amount of modifying compound used In the process of obtaining modified cellulose fibers, the equivalent amount of functional groups of the modifying compound used that can react with the anionic groups of the anionic groups of the anionic-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 antibacterial properties of the film. Furthermore, from the viewpoint of film formation, it is preferably 20 equivalents or less, more preferably 10 equivalents or less, and even more preferably 2 equivalents or less.

[0064] (4) Miniaturization process By refining the cellulose at any stage in the manufacturing process of modified cellulose fibers, micrometer-scale cellulose can be refined to a nanometer scale. Since reducing the average fiber diameter to nanometer size improves the strength during film formation, it is preferable to further perform the refinement process.

[0065] For the micronization process, known dispersers are preferably used. For example, disintegrators, beaters, low-pressure homogenizers, high-pressure homogenizers, grinders, cutter mills, ball mills, jet mills, short-screw extruders, twin-screw extruders, ultrasonic stirrers, household juicer mixers, etc., can be used. Furthermore, the solid content of the reactant fibers in the micronization process is preferably 50% by mass or less.

[0066] <Ingredient (B)> In this invention, component (B) is water. Component (B) serves as a solvent in the preparation of component (A) and as one of the constituent components of the emulsified composition of this invention.

[0067] <Ingredient (C)> In this invention, component (C) is an organic compound that is liquid at 25°C and 1 atm. Component (C) may also be the solvent used in the preparation of component (A).

[0068] 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. The weight-average molecular weight of component (C) is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less, from the viewpoint of improving the antibacterial properties of the membrane, and preferably 100 or more, and more preferably 200 or more, from the same viewpoint.

[0069] Component (C) in the present invention specifically includes oils, organic solvents, polymerizable monomers, prepolymers, etc. Component (C) in the present invention is preferably an oil, and from the viewpoint of improving the antibacterial properties of the film, examples of oils include one or more selected from the group consisting of alcohols, ester oils, hydrocarbon oils, silicone oils, ether oils, fats and oils, fluorinated inert liquids, and fatty acids. One or more selected from the group consisting of ester oils, silicone oils, ether oils, fats and oils, and fluorinated inert liquids are preferred, one or more selected from the group consisting of silicone oils, ester oils, and ether oils are more preferred, and silicone oil and / or ester oil are even more preferred.

[0070] Examples of ester oils include monoester oils, diester oils, and triester oils. 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, glyceryl tri-2-ethylhexanoate, and glyceryl triisostearate.

[0071] Examples of silicone oils include dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.

[0072] Examples of oils and fats include vegetable oils such as soybean oil, coconut oil, linseed oil, cottonseed oil, rapeseed oil, and castor oil, as well as animal oils.

[0073] From the viewpoint of improving the antibacterial properties of the film, 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 with an SP value of 10 or less, as described later, can be cited as a preferred example.

[0074] In this specification, SP value refers to the solubility parameter calculated by the Fedors method (unit: (cal / cm³) 3 ) 1 / 2 This is shown in references such as "SP Value Basics, Applications, and Calculation Methods" (Information Organization Co., Ltd., 2005) and "Polymer Handbook Third Edition" (A Wiley-Interscience publication, 1989).

[0075] Examples of oils with an SP value of 10 or less that are preferably 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 f 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 oils (e.g., KF96-1cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: Examples include 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. All of these oils are liquid at 25°C and 1 atm.

[0076] <Ingredient (D)> In this invention, component (D) is an antibacterial compound. Antibacterial action includes all effects such as sterilization, germicidal action, disinfection, bacteriostatic action, antimicrobial action, antiseptic action, antifungal action, and antifungal action. Examples of compounds with antibacterial properties include organically synthesized antibacterial agents, natural product antibacterial agents, and inorganic antibacterial agents.

[0077] Examples of organic synthetic antimicrobial agents include isothiazolinate antimicrobial agents, biguanide antimicrobial agents, surfactant antimicrobial agents (amphoteric surfactant antimicrobial agents, quaternary ammonium salt antimicrobial agents), phenol antimicrobial agents, pyridine antimicrobial agents, carbanilide antimicrobial agents, amino acid antimicrobial agents, sulfide antimicrobial agents, nitrile antimicrobial agents, polymer antimicrobial agents, carboxylic acid antimicrobial agents, alcohol antimicrobial agents, medetomidine, and tralopyril (4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile).

[0078] Examples of isothiazolin-based antibacterial agents include 1,2-benzoisothiazole-3(2H)-one (BIT), 2-n-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, or 2-methyl-4,5-trimethylene-4-isothiazolin-3-one.

[0079] Examples of biguanide antibacterial agents include chlorhexidine digluconate (CHG), chlorhexidine diacetate, chlorhexidine dihydrochloride, chlorhexidine diphosphanylate, poly(hexamethylene biguanide) hydrochloride (PHMB), and chlorhexidine-2-acrylamido-2-methylpropanesulfonic acid copolymer.

[0080] As quaternary ammonium salt-based antibacterial agents, preferred quaternary ammonium salts have a linear or branched C1-C16 alkyl group, a linear or branched C1-C16 alkenyl group, a C1-C16 hydroxyalkyl group, or a C1-C16 phenylalkyl group as substituents on the quaternary nitrogen atom. Examples include benzalkonium chloride; benzethonium chloride; cetylpyridinium chloride; organosilicon quaternary ammonium salts (e.g., 3-(methoxysilyl)propyloctadecyldimethylammonium chloride); N-polyoxyalkylene-N,N,N-trialkylammonium salts; N-alkylammonium salts, N,N-dialkylammonium salts, N,N,N-trialkylammonium salts, N,N,N-tetraalkylammonium salts. Examples include quaternary ammonium salts (e.g., cetyltrimethylammonium chloride, didecyldimethylammonium chloride, toridodecylmethylammonium chloride, octadecyldimethylammonium chloride, dioctyldimethylammonium chloride); chloroallylhexaminonium chloride; quaternary ammonium salt compounds of copolymers of phosphate ester monomers; dicyanamide-diethylenetriamine-ammonium chloride condensates, dicyandiamide-polyalkylene polyamine ammonium polycondensates, and cationic polymers (reaction products of partially deacetylated compounds of (poly-β-1,4)-N-acetyl-D-glucosamine and hexamethylenebis(3-chloro-2-hydroxypropyldimethylammonium chloride)). The above-mentioned quaternary ammonium salt may be a halogenated compound such as a chloride, a carboxylate, or a dialkyl phosphate.

[0081] Phenolic antimicrobial agents are antimicrobial agents having a structure in which one or more hydrogen atoms of the aromatic hydrocarbon nucleus are replaced by a hydroxyl group. Examples include 5-chloro-2-(2,4-dichlorophenoxy)phenol (common name: triclosan), 4,4'-dichloro-2-hydroxydiphenyl ether (common name: diclosan), o-benzyl-p-chlorophenol (chlorophene), isopropylmethylphenol (3-methyl-4-isopropylphenol, IPMP), and parachlorometaxylenol (4-chloro-3,5-dimethylphenol, PCMX).

[0082] Examples of pyridine-based antibacterial agents include zinc pyrithione, zinc pyrithione, copper pyrithione, and copper pyrithione.

[0083] Examples of inorganic antimicrobial agents include metal-based inorganic antimicrobial agents, photocatalytic inorganic antimicrobial agents, and oxide / natural product-based inorganic antimicrobial agents. Examples of metal-based inorganic antibacterial agents include silicates such as zeolites, clay minerals, silica gel, silica / alumina, magnesium aluminometasilicate, and glass; phosphates such as zirconium phosphate and calcium phosphate (apatite); and other metal-based agents such as activated carbon, titanium dioxide, and complex salts. Furthermore, examples of photocatalytic systems include titanium dioxide such as anatase-type titanium dioxide, platinum-supported titanium dioxide, apatite-coated titanium dioxide, and nitrogen-doped titanium dioxide; and other photocatalytic systems such as silver-supported zirconium phosphate and silver-supported acrylic fibers. Examples of oxides / natural products include metal oxides such as magnesium oxide, calcium oxide, and zinc oxide, as well as calcined scallop shells, calcined oyster shells, and natural minerals (dolomite, calcite).

[0084] <Other ingredients> In addition to the components mentioned above, the emulsifying composition of the present invention may contain plasticizers, nucleating agents, fillers (inorganic fillers, organic fillers), hydrolysis inhibitors, flame retardants, antioxidants, hydrocarbon waxes and anionic surfactants as lubricants, ultraviolet absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, foaming agents, surfactants; starches, polysaccharides such as alginic acid; natural proteins such as gelatin, glue, and casein; inorganic compounds such as tannins, zeolites, ceramics, and metal powders; fragrances; flow regulators; leveling agents; conductive agents; ultraviolet dispersants; deodorants, etc., to the extent that they do not impair the effects of the present invention. Similarly, other polymer materials and other compositions may be added to the extent that they do not hinder the effects of the present invention.

[0085] <Properties of emulsified compositions> The emulsified composition of the present invention is an emulsified composition containing the above-mentioned components (A), (B), (C), and (D) as essential components. The emulsified composition of the present invention may be either an o / w type emulsion or a w / o type emulsion, but is preferably an o / w type emulsion.

[0086] The content of component (A) in the emulsified composition or during the preparation of the emulsified composition is preferably 0.02% by mass or more, more preferably 0.1% by mass or more, and even more preferably 1% by mass or more, from the viewpoint of emulsifying power, while from the viewpoint of handling properties, it is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0087] The content of component (B) in the emulsified composition or during the preparation of the emulsified composition is preferably 10% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more, from the viewpoint of maintaining the emulsified state, and preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less, from the viewpoint of effective content.

[0088] The content of component (C) in the emulsified composition or during the preparation of the emulsified composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of maintaining the emulsified state, while from the viewpoint of viscosity and handling properties, it is preferably 70% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0089] The content of component (D) in the emulsified composition or during the preparation of the emulsified composition is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, and even more preferably 0.01% by mass or more, from the viewpoint of improving the antibacterial properties of the film, and from the same viewpoint, preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less.

[0090] The mass ratio ((D) / (A)) of component (D) to component (A) in or during the preparation of the emulsified composition is preferably 0.0001 or higher, more preferably 0.0005 or higher, and more preferably 0.001 or higher, from the viewpoint of improving the antibacterial properties of the film. Similarly, it is preferably 0.1 or lower, more preferably 0.05 or lower, and even more preferably 0.04 or lower.

[0091] From the viewpoint of improving the antibacterial properties of the film, the mass ratio ((A) / (C)) of component (A) to component (C) in the emulsified composition or during the preparation of the emulsified composition is preferably 0.0001 or higher, more preferably 0.0002 or higher, even more preferably 0.0005 or higher, even more preferably 0.001 or higher, even more preferably 0.01 or higher, even more preferably 0.1 or higher, and even more preferably 0.4 or higher. Similarly, from the viewpoint of improving the antibacterial properties of the film, it is preferably 20 or less, more preferably 10 or less, even more preferably 1 or less, and even more preferably 0.5 or less.

[0092] From a handling standpoint, the viscosity of the emulsified composition is preferably 0.5 mPa·s or higher at 25°C, and similarly, preferably 30 Pa·s or lower. Here, viscosity was measured using a B-type viscometer with an appropriate rotor matched to the viscosity range of each sample, after stirring for 1 minute at 25°C and a rotation speed of 60 rpm.

[0093] The median of the particle size of the emulsion droplets in the emulsion composition is preferably 10 nm or larger, more preferably 50 nm or larger, even more preferably 100 nm or larger, and even more preferably 400 nm or larger, as measured by SEM observation as described later, from the viewpoint of improving the antibacterial properties, water resistance, synovial properties, and durability of the film. Similarly, it is preferably 1000 μm or smaller, more preferably 100 μm or smaller, even more preferably 50 μm or smaller, and even more preferably 30 μm or smaller.

[0094] Examples of applications for the emulsified composition of the present invention include biological adhesion inhibitors, antifouling agents, and antibacterial agents.

[0095] 2. Method for producing an emulsified composition The method for producing the emulsified composition of the present invention comprises the steps of mixing the aforementioned components (A), (B), (C), and (D), or the steps of mixing anionic modified cellulose fibers, modifying compounds, components (B), (C), and (D), etc.

[0096] Emulsification occurs when each component is mixed, yielding an emulsified 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, short-screw extruder, twin-screw extruder, ultrasonic stirrer, household juicer mixer, etc. The mixing process may also be carried out by combining two or more operations.

[0097] The temperature and time for mixing each component are not particularly limited, but for example, the temperature range is preferably 5 to 50°C, and the time range is preferably 1 minute to 3 hours.

[0098] The preferred range of content of each component during mixing is the same as the preferred range of content of each component in the emulsified composition of the present invention described above. Note that anionically modified cellulose fibers (component (A-1)) and a modifying compound (component (A-2)) may be used instead of component (A).

[0099] 3. Membrane The emulsifying composition, biofouling inhibitor, antifouling agent, or antibacterial agent of the present invention described above is applied to a hard surface (for example, a metal surface, resin surface, glass surface, ceramic surface, etc.) and a film is formed under normal temperature and pressure, or by heating or reducing pressure as necessary. Because the film has synovial properties and is also water-resistant, it can be used as a coating for applications where synovial properties are desired in water or seawater, such as ship hulls and propellers, bridge frameworks, piping, quays, cooling towers, tank interiors, offshore equipment, observation equipment, and fishing nets. [Examples]

[0100] The present invention will be specifically described below with reference to examples. Note that the following examples are merely illustrative of the present invention and do not imply any limitation.

[0101] [Average fiber diameter, average fiber length, and average aspect ratio of anionically modified cellulose fibers and modified cellulose fibers] Water is added to the cellulose fibers to be measured to prepare a dispersion with a water content of 0.0001% by mass. This dispersion is dropped onto mica and dried to create an observation sample. An atomic force microscope (AFM) (Digital Instruments, Nanoscope II Tappingmode AFM; probe used: Nanosensors, Point Probe (NCH)) is used to measure the fiber height (difference in height between areas with and without fibers) of the cellulose fibers in the observation sample. At that time, more than 100 cellulose fibers are extracted from the microscope image in which the cellulose fibers can be confirmed, and the average fiber diameter is calculated from their fiber heights. The average fiber length is calculated from the distance in the direction of the fibers. The average aspect ratio is calculated from the average fiber length / average fiber diameter. The height analyzed in the AFM image can be considered as the fiber diameter.

[0102] [Average fiber diameter and average fiber length of the cellulose fibers used as raw material] A dispersion containing 0.01% by mass of deionized water is prepared by adding deionized water to the cellulose fibers to be measured. This dispersion is measured using a wet dispersion type image analysis particle size distribution analyzer (Jusco International, 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, sampling: 15%. More than 100 cellulose fibers are measured, and their average ISO fiber diameter is used as the average fiber diameter, and their average ISO fiber length is used as the average fiber length.

[0103] [Anionic group content of anionic-modified cellulose fibers and modified cellulose fibers] Place 0.5 g of the cellulose fiber to be measured (dry mass) into a 100 mL beaker, add deionized water or a methanol / water = 1 / 2 mixture to make a total volume of 55 mL, and add 5 mL of 0.01 M sodium chloride aqueous solution to prepare a dispersion. Stir the dispersion until the cellulose fiber to be measured is sufficiently dispersed. Add 0.1 M hydrochloric acid to this dispersion to adjust the pH to 2.5-3, and using an automatic titrator (Toa DKK Co., Ltd., AUT-701), add 0.05 M sodium hydroxide aqueous solution dropwise to the dispersion with a waiting time of 60 seconds, and measure the conductivity and pH values ​​every minute. Continue the measurement until the pH reaches approximately 11 to obtain a conductivity curve. From this conductivity curve, determine the amount of sodium hydroxide titration, and calculate the anionic group content of the cellulose fiber to be measured using the following formula. Anionic group content (mmol / g) = [Sodium hydroxide titration volume × Sodium hydroxide aqueous solution concentration (0.05M)] / [Mass of cellulose fiber to be measured (0.5g)]

[0104] [Aldehyde group content of oxidized cellulose fibers] The carboxyl group content of the oxidized cellulose fiber to be measured is determined by the method for measuring the anionic group content described above. Separately, 100 g of an aqueous dispersion of the oxidized cellulose fibers to be measured (solid 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 are added to a beaker and stirred at 25°C for 16 hours to oxidize the aldehyde groups remaining in the oxidized cellulose fibers. After the reaction is complete, the fibers are washed with deionized water to obtain cellulose fibers from which the aldehyde groups have been oxidized. The reaction solution is freeze-dried, and the carboxyl group content of the resulting dried product is measured using the method for measuring the anionic group content described above to calculate the "carboxyl group content of the oxidized cellulose fibers." Subsequently, the aldehyde group content of the oxidized cellulose fibers to be measured is calculated using Equation 1. Aldehyde group content (mmol / g) = (Carboxyle group content of oxidized cellulose fiber) - (Carboxyle group content of oxidized cellulose fiber to be measured) ... Equation 1

[0105] [Solid content in the dispersion] Measurements are performed using a halogen moisture meter (Shimadzu Corporation, MOC-120H). Measurements are taken every 30 seconds at a constant temperature of 150°C for 1 g of sample, and the value at which the mass loss is 0.1% or less of the initial amount of sample is defined as the solid content.

[0106] [Confirmation of the crystalline structure in modified cellulose fibers] The crystalline structure of the modified cellulose fibers is confirmed by measuring it using an X-ray diffractometer (MiniFlexII, Rigaku Corporation) under the following conditions. The measurement conditions are as follows: X-ray source: Cu / Kα-radiation, tube voltage: 30kV, tube current: 15mA, measurement range: diffraction angle 2θ = 5~45°, X-ray scan speed: 10° / min. The sample area for measurement is 320mm². 2 The material is prepared by compressing it into pellets with a thickness of 1 mm. Furthermore, the degree of crystallinity of the cellulose type I crystal structure is calculated from the obtained X-ray diffraction intensity based on the following formula A.

[0107] <Formula A> Cellulose type I crystallinity (%) = [(I 22.6 -I 18.5 ) / I22.6 ]×100 [In the formula, I 22.6 This is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6°) in X-ray diffraction, I 18.5 This shows the diffraction intensity of the amorphous region (diffraction angle 2θ = 18.5°).

[0108] On the other hand, if the degree of crystallinity obtained by formula A above is 35% or less, from the viewpoint of improving calculation accuracy, it is preferable to calculate it based on the following formula B, in accordance with the description on pages 199-200 of the "Manual for Experiments in Wood Science" (edited by the Japan Wood Research Society; published April 2000). Therefore, if the degree of crystallinity obtained by formula A above is 35% or less, the value calculated based on the following formula B can be used as the degree of crystallinity.

[0109] <Formula B> Cellulose type I crystallinity (%) = [A c / ( A c +A a )] × 100 [In the ceremony, A c This 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 This shows the peak area of ​​the amorphous region (diffraction angle 2θ = 18.5°), and each peak area is obtained by fitting the obtained X-ray diffraction chart with a Gaussian function.

[0110] [Measurement of particle size of emulsion droplets by laser diffraction method] The particle size of emulsion droplets is measured using laser diffraction with a LA-960 laser diffractometer manufactured by Horiba, Ltd. Measurement conditions: Water is added to the measurement cell, and the volume particle size distribution and median (volume cumulative median particle size (D50)) are measured at a concentration that results in an appropriate absorbance range. The relative refractive index is 1.20, the temperature is 25°C, the circulation pump is ON, the circulation speed is 5, and the stirring speed is 5.

[0111] [Anionic modified cellulose fiber] Anionically modified cellulose fibers having the physical properties listed in Table 1 were used as raw materials.

[0112] [Table 1]

[0113] Such anionically modified cellulose fibers can be prepared, for example, by the TEMPO oxidation treatment described below.

[0114] [TEMPO oxidation treatment] In a 2L PP beaker equipped with a mechanical stirrer and stirring blades, weigh out 10g of bleached kraft pulp fiber from coniferous trees (as the raw material for natural cellulose fiber) and 990g of deionized water, and stir at 25°C and 100rpm for 30 minutes. Next, add 0.13g of TEMPO, 1.3g of sodium bromide, and 35.5g of 10.5% by mass sodium hypochlorite aqueous solution to 10g of pulp fiber in that order. Then, perform pH stat titration using an automatic titrator and add 0.5M sodium hydroxide aqueous solution dropwise to maintain the pH at 10.5. The reaction is carried out at 25°C for 120 minutes with a stirring speed of 100rpm.

[0115] Next, while stirring, 0.01 M hydrochloric acid is added to adjust the pH of the suspension to 2. Then, the solids are filtered off by suction filtration. The process of dispersing the solids in deionized water and filtering them off by suction filtration is repeated until the conductivity of the filtrate is 200 μs / cm or less. The resulting solids are then dehydrated to obtain anionically modified cellulose fibers.

[0116] [Preparation of reduced, finely textured anion-modified cellulose fibers] Preparation Example 1 The anionically modified cellulose fibers were subjected to a micronization treatment, followed by a reduction treatment, to prepare micronized anionically modified cellulose fibers having the physical properties listed in Table 2.

[0117] [Table 2]

[0118] Such finely milled anion-modified cellulose fibers can be prepared, for example, by the following milling and reduction treatments.

[0119] [Miniaturization process] A suspension (solid content 2.0% by mass) is prepared by adding deionized water to anionically modified cellulose fibers, and a 0.5 M sodium hydroxide aqueous solution is added to adjust the pH to 8. Then, deionized water is added to make a total of 200 g. This suspension is subjected to micronization treatment three times at 150 MPa using a high-pressure homogenizer to obtain a micronized anionically modified cellulose fiber dispersion (solid content 1.0% by mass).

[0120] [Reduction treatment] 182 g of a finely pulverized anionic modified cellulose fiber dispersion (solid content 1.0% by mass) is weighed out, and deionized water is added to make a total of 400 g. 1.2 mL of 0.1 M sodium hydroxide aqueous solution and 120 mg of sodium borohydride are added, and the mixture is stirred at 25°C for 4 hours. Next, 9 mL of 1 M hydrochloric acid is added and stirring is continued. After stirring is complete, the solids obtained by suction filtration are dispersed in deionized water, and the process of filtering out the solids by suction filtration is repeated 6 times. In this way, a finely pulverized anionic modified cellulose fiber dispersion (solid content 0.9% by mass) is obtained in which the aldehyde groups present in the finely pulverized anionic modified cellulose fibers are reduced.

[0121] [Production of modified cellulose fibers and emulsified compositions] Modified cellulose fibers and emulsified compositions of the examples and comparative examples were produced by the methods described below. The raw material compositions shown in the table represent the effective content of each raw material, and each raw material was used so that the effective content of each raw material was as indicated by mass % in the table.

[0122] Example 1 In a beaker, the finely milled anionically modified cellulose fiber dispersion (solid content 0.9% by mass) obtained in Preparation Example 1, silicone oil 1, and amino-modified silicone (corresponding to 1.25 equivalents relative to the carboxyl groups of the anionically modified cellulose fibers) were mixed, and deionized water was added to prepare the cellulose fiber dispersion. After stirring this solution with a mechanical stirrer for 5 minutes, it was subjected to 10 passes at 150 MPa using a high-pressure homogenizer (Yoshida Machinery Co., Ltd., NanoVeta L-ES) to obtain a dispersion containing modified cellulose fibers, i.e., modified cellulose fibers, in which amino-modified silicone was linked to the anionically modified cellulose fibers via ionic bonds. The obtained dispersion was a cloudy liquid, and since oil droplets were observed dispersed in water under an optical microscope, it was determined to be in an emulsified state. To the obtained dispersion, 1,2-benzoisothiazole-3(2H)-one was added and dispersed for 1 minute using an ultrasonic homogenizer UE-300E (manufactured by Nippon Seiki Seisakusho Co., Ltd., probe diameter 12 mm) to obtain an emulsified composition.

[0123] Examples 2-26, Comparative Examples 1, 5, 7, 8 Except for changing the formulation of the emulsified composition to that shown in the table below, the same procedure as in Example 1 was performed to obtain the emulsified composition. In the case where component D was a solution, the mixture was obtained by mixing for 30 seconds using a vortex mixer VORTEX-GENIE 2 (manufactured by Scientific Industries, Inc.) instead of an ultrasonic homogenizer.

[0124] Comparative Example 2 1,2-Benzisothiazole-3(2H)-one was diluted with deionized water to a concentration of 0.1% by mass and used as a surface treatment agent.

[0125] Comparative Example 3 Sanizol C was diluted with deionized water to a concentration of 0.1% by mass and used as a surface treatment agent.

[0126] The details of the representative components used in the examples are summarized below. [Component (A-2): Modifying compound] Amino-modified silicone: SS-3551, manufactured by Dow-Toray (kinematic viscosity: 1,000, amino equivalent: 1,700) Oleylamine: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (Amino equivalent: 267.5, Total number of carbon atoms: 18)

[0127] [Component (C)] Silicone oil 1: Shin-Etsu Chemical Co., Ltd., KF-96-100cs (SP value: 7.3) Isopropyl palmitate: Manufactured by Fujifilm Wako Pure Chemical Industries (SP value: 8.5) [Component (D): Antibacterial compound] 1,2-Benzisothiazole-3(2H)-one (abbreviated as BIT in the table): Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Proxel BDN (active ingredient: BIT): Manufactured by Lonza (effective concentration 33% by mass) Sanizol C: Manufactured by Kao Corporation (effective concentration 50% by mass) Zinc pyrithione: Manufactured by Fujifilm Wako Pure Chemical Industries. Copper pyrithione standard: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Furthermore, regarding zinc pyrithione and copper pyrithione, in order to improve their dispersibility when blended into an emulsified dispersion, polyether-modified silicone (Shin-Etsu Chemical Co., Ltd., KF-642, HLB:14) was added to the dispersion at a concentration of 0.2% by mass, and these were used as zinc pyrithione dispersion and copper pyrithione dispersion, respectively. Zinc oxide (290nm): Manufactured by Sakai Chemical Industry Co., Ltd., ST-ABZ-10 Zinc oxide (20 nm): Manufactured by Sakai Chemical Industry Co., Ltd., DIF-AQ-50 (effective content concentration 40% by mass, aqueous dispersion) Medetomidine: Dexmedetomidine, manufactured by Toronto Research Chemicals. Dichrosan: Manufactured by BASF Japan, Tinosan® HP 100 (effective content concentration 30% by mass) Proxel IB: Manufactured by Lonza (Active ingredient: Polyhexamethylene biguanide hydrochloride, effective concentration 20% by mass) Tralopiril: Manufactured by Janssen Pharmaceuticals, ECONEA® TECHNICAL

[0128] The emulsified compositions prepared as described above and the surface treatment agents of Comparative Examples 2-3 were evaluated as follows.

[0129] <Preparation of test specimens> 200 μL of each composition was applied to the transparent portion (61 × 26 [mm]) of a microscope slide (MATSUNAMI, Super Frost Slide Glass 76 × 26 [mm] S2441) and air-dried at room temperature. After drying, the surface was washed with sterile deionized water and then air-dried again at room temperature. On the other hand, substrates without any coating were used as the substrates for Comparative Examples 4 and 6.

[0130] <Evaluation of synovial properties> [Slip angle measurement test] The films of the examples and comparative examples prepared as described above were placed horizontally, and an 8 μL drop of water (23°C) was dropped onto each film using a fully automatic contact angle meter (FAMAS, Kyowa Interface Science Co., Ltd.) at 23°C, and allowed to stand for 1 second. Next, the film surface was tilted to 85° at a speed of 1° / s, and the angle at which the water droplet began to slide was measured. A smaller water droplet sliding angle indicates higher synovial properties of the film. The composition of each component (parts by mass in the film) and the evaluation results are shown in the table below. However, if the water droplet did not slide off even when tilted to 80°, the water droplet sliding angle was noted as "greater than 80". Films with a sliding angle "greater than 80" can be clearly evaluated as not having synovial properties.

[0131] <Evaluation of the effect of inhibiting biofilm formation> [Preparation of bacterial suspension] From glycerol-frozen samples of Staphylococcus aureus (S. aureus) NBRC13276, Escherichia coli (E. coli) NBRC3972, Methicillin-Resistant Staphylococcus aureus (MRSA) (Kao Corporation environmental isolate), Microbacterium oxydans (M. oxydans) (NBRC15586), Pseudomonas aeruginosa (P. aeruginosa) (NBRC12689), Stenotrophomonas maltophilia (S. maltophilia) (NBRC14161), and ESBL-producing Stenotrophomonas maltophilia (S. maltophila-ESBL) (Kao Corporation environmental isolate), samples were collected using disposable loop type 1 (AS ONE Corporation) and each was treated with Soybean. Pre-culture was performed at 32.5°C for 24 hours using Casein Digest agar medium (manufactured by Nippon Pharmaceutical Co., Ltd., standard agar medium "Daigo").

[0132] To conduct comparative tests of antibiotic-resistant and antibiotic-susceptible strains of the same bacterial species, samples were collected using disposable loop type 1 from glycerol-frozen samples of Enterococcus faecium (NBRC100480, ATCC51575), S. aureus (NBRC100910, ATCC BAA-41), Klebsiella pneumoniae (NBRC14940, ATCC BAA-2342), Acinetobacter baumannii (NBRC109757, ATCC BAA-1605), Pseudomonas aeruginosa (NBRC12689, ATCC BAA-2110), and Enterobacter cloacae (NBRC13535, ATCC BAA-2341) and then treated with Soybean Casein. Pre-culture was performed at 32.5°C for 24 hours using Digest agar medium (manufactured by Nippon Pharmaceutical Co., Ltd., standard agar medium "Daigo"). These bacterial species were obtained from a distribution institution.

[0133] 2 mL of Luria-Bertani (LB agar medium "Daigo" manufactured by Nippon Pharmaceutical Co., Ltd.) was placed in a test tube (Corning, PYREX® registered trademark, 18 × 150 mm), and a colony prepared in the pre-culture was inoculated with one loop of platinum. The culture was then incubated with shaking at 37°C / 200 rpm / 24 hours.

[0134] After culturing, the absorbance at a wavelength of 600 nm (OD600 nm) was measured using a spectrophotometer (Hitachi High-Technologies Corporation, U-5100), and the bacterial solutions were prepared so that the values ​​were E. coli: 1.0, P. aeruginosa: 0.2, S. maltophilia: 0.2, and other bacteria: 0.5. The bacterial solutions with the OD600 nm adjusted to the above values ​​were each diluted 100-fold on Soybean Casein Digest agar medium (Nippon Pharmaceutical Co., Ltd., Standard Agar Medium "Daigo") to prepare the bacterial solutions for evaluation.

[0135] [Evaluation of the effect of inhibiting biofilm formation] 100 μL of bacterial suspension was dropped onto each test specimen, and the specimens were sandwiched between other specimens treated with the same agent. These specimens were then placed in a sterile No. 2 square petri dish (140 × 100 × 14.5 [mm]: Eiken Chemical Co., Ltd.) and incubated at 32.5°C for 24 hours. The slide glass containing the bacterial suspension was washed with sterile deionized water using a 5 mL pipette, ensuring that the surface with the bacterial suspension was exposed. The surface of the test specimens was swabded using a wipe-check II (Eiken Chemical Co., Ltd.), and the container was vortexed for 30 seconds to suspend the bacterial cells. Bacterial suspensions were prepared by serial dilution in 10-fold increments, and 3 μL of each was added to Soybean Casein Digest agar medium (Nippon Pharmaceutical Co., Ltd., SCD agar medium "Daigo") packed in a sterile No. 2 square petri dish. Incubation was carried out at 32.5°C for 18 to 24 hours. In addition, 100 μL of the suspension stock solution was added to SCD agar medium packed in a sterile petri dish (Φ90 x 15 [mm]: manufactured by Ina Optica) to allow detection down to a lower limit of 10¹ cfu / mL. The antibacterial activity value was calculated using the following method. Antimicrobial activity value = log {(Number of viable bacteria after 24 hours of incubation in untreated specimen) - (Number of viable bacteria after 24 hours of incubation in treated specimen)} Furthermore, a higher antibacterial activity value indicates higher antibacterial properties of the emulsified composition used to prepare the treated test specimen. The results are shown in the table below.

[0136] [Table 3-1]

[0137] [Table 3-2]

[0138] [Table 4-1]

[0139] [Table 4-2]

[0140] [Table 5]

[0141] [Table 6]

[0142] The amounts of each component in Tables 3-6 represent the "effective content," excluding the amount of the medium, etc. The amount of water in component (B) includes the amount of water introduced as a medium when each component is used as a solution or suspension, etc.

[0143] From the evaluation results above, the following was found: Table 3 shows that the film made from the emulsified composition of the present invention exhibits high antibacterial activity regardless of whether the compound used as component (D) is an organic antibacterial agent or an inorganic antibacterial agent. Furthermore, it was found that the effect was overwhelmingly higher than that of the comparative example's antibacterial agent-only treated substrate. This is thought to be because the combination of the modified cellulose fiber film and component (D) effectively retains the antibacterial compound on the target surface. Furthermore, Table 4 shows that the effect of component D is achieved even with an extremely small amount. In addition, Table 5 shows that the antibacterial properties of the membrane according to the present invention can be applied to a wide range of bacterial species, including Gram-positive bacteria, Gram-negative bacteria, and antibiotic-resistant bacteria. Furthermore, Table 6 shows that the membrane made from the emulsified composition of the present invention is effective against both antibiotic-resistant and antibiotic-sensitive bacterial strains. [Industrial applicability]

[0144] The emulsifying composition of the present invention can form a film with excellent antibacterial properties, and furthermore, the film is expected to have durability. Therefore, it can be used as a surface treatment agent for walls, pipes, etc., in places where it is necessary to prevent various types of harm caused by microorganisms, such as infection and biofilm adhesion, such as medical institutions and food factories.

Claims

1. An emulsion composition containing the following components (A) to (D), wherein the mass ratio of component (D) to component (A) ((D) / (A)) is 0.0001 or more. (A) Cellulose fiber having a modifying group (B) Water (C) An organic compound that is liquid at 25°C and 1 atm (D) A compound having antibacterial properties

2. The emulsion composition according to Claim 1, wherein the content of component (D) is 0.0005% by mass or more and 5% by mass or less.

3. The emulsion composition according to Claim 1, wherein the mass ratio of component (A) to component (C) ((A) / (C)) is 0.0001 or more and 20 or less.

4. A biofouling inhibitor containing the emulsion composition according to Claim 1.

5. An antifouling agent containing the emulsion composition according to Claim 1.

6. An antibacterial agent containing the emulsion composition according to Claim 1.

7. A film obtained by applying the emulsion composition according to Claim 1, the biofouling inhibitor according to Claim 4, the antifouling agent according to Claim 5, or the antibacterial agent according to Claim 6.

8. A method for producing an emulsion composition, comprising a step of mixing the following components (A) to (D), wherein the mass ratio of component (D) to component (A) ((D) / (A)) is 0.0001 or more. (A) Cellulose fiber having a modifying group (B) Water (C) An organic compound that is liquid at 25°C and 1 atm (D) A compound having antibacterial properties