Method for producing an emulsified composition

Abstract

To provide a production method of an emulsion composition that facilitates fibrillating cellulose fibers by using partially neutralized anion-modified cellulose fibers, is excellent in emulsion stability, and contains low-viscosity anion-modified cellulose fibers.SOLUTION: A production method of an emulsion composition includes a step 1 and a step 2 as follows: the step 1 of fibrillating partially neutralized anion-modified cellulose fibers and obtaining a water dispersion of the anion-modified cellulose fibers; and the step 2 of mixing the water dispersion of the anion-modified cellulose fibers, obtained in the step 1 with an oil agent and an organic compound having a cationic group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a method for producing an emulsified composition. [Background technology]

[0002] Emulsified compositions containing cellulose fibers have been known for some time. For example, Patent Document 1 discloses a viscous aqueous composition characterized by containing the following components (A) and (B): (A) Cellulose fiber having a maximum fiber diameter of 1000 nm or less and a number average fiber diameter of 2 to 150 nm, wherein the cellulose has a cellulose type I crystalline structure, and the hydroxyl group at the C6 position of each glucose unit in the cellulose molecule is selectively oxidized and modified into a carboxyl group, thereby having carboxyl groups at a ratio of 0.6 to 2.0 mmol / g, and the carboxyl group is a salt of a monoamine with an organic value of 300 or less in the organic conceptual diagram. (B) Water. Patent Document 1 describes that by bonding a monoamine with an organic value of 300 or less as a salt to anionically modified cellulose microfibers, a viscous aqueous composition with excellent shape retention, dispersion stability, salt resistance, and emulsification stability can be produced. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2012-126786 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, Patent Document 1 does not consider how to achieve both emulsification stability and viscosity in the resulting emulsified composition. A first aspect of the present invention relates to a method for producing an emulsified composition containing anionically modified cellulose fibers that have excellent emulsification stability and low viscosity. Conventionally, in order to obtain an aqueous dispersion of anionic modified cellulose fibers, when the anionic groups are in the free acid form, defibrillation treatment is difficult. Therefore, after completely neutralizing the anionic groups of the anionic modified cellulose fibers, defibrillation treatment has been carried out. A second aspect of the present invention relates to a method for producing an emulsified composition that can easily defibrillate cellulose fibers by using partially neutralized anionic modified cellulose fibers, and further contains anionic modified cellulose fibers having excellent emulsification stability and low viscosity.

Means for Solving the Problems

[0005] A first aspect of the present invention relates to the following [1] to [3]. 〔1〕 An aqueous dispersion of partially neutralized anionic modified cellulose fibers, An oil agent, and An organic compound having a cationic group A method for producing an emulsified composition, comprising a step of mixing them. 〔2〕 An emulsified composition produced by the production method according to [1] above. 〔3〕 A film obtained by drying the emulsified composition according to [2] above.

[0006] A second aspect of the present invention relates to the following [4] to [6]. 〔4〕 A method for producing an emulsified composition, comprising the following Step 1 and Step 2. Step 1: A step of defibrillating partially neutralized anionic modified cellulose fibers to obtain an aqueous dispersion of anionic modified cellulose fibers Step 2: A step of mixing the aqueous dispersion of anionic modified cellulose fibers obtained in Step 1, an oil agent, and an organic compound having a cationic group 〔5〕 An emulsified composition produced by the production method according to [4] above. 〔6〕 A film obtained by drying the emulsified composition according to [5] above.

Advantages of the Invention

[0007] According to the production method of the present invention, an emulsion composition containing an anionic modified cellulose fiber having excellent emulsion stability and showing a low viscosity can be easily produced.

Mode for Carrying Out the Invention

[0008] 〔Method for Producing Emulsion Composition〕 As a result of intensive studies by the present inventors to solve the above problems, a first aspect of the present invention is a production method in which a partially neutralized anionic modified cellulose fiber aqueous dispersion, an oil agent, and an organic compound having a cationic group are mixed, and it has been found that an emulsion composition having excellent emulsion stability and a low viscosity can be obtained.

[0009] To obtain an aqueous dispersion of an anionic modified cellulose fiber used in the first aspect of the present invention, it is preferable to use Step 1 of the second aspect of the present invention.

[0010] A second aspect of the present invention is a method for producing an emulsion composition having the following Step 1 and Step 2. Step 1: A step of defibrating a partially neutralized anionic modified cellulose fiber to obtain an aqueous dispersion of an anionic modified cellulose fiber Step 2: A step of mixing the aqueous dispersion of anionic modified cellulose fiber obtained in Step 1, an oil agent, and an organic compound having a cationic group

[0011] [Step 1 of Aspect 2] In Step 1, without completely neutralizing the anionic groups of the anionic modified cellulose fiber, preferably 2% or more and 90% or less of the anionic groups are neutralized with metal ions or ammonium ions, and surprisingly, sufficient defibrillation of the fiber can be achieved, and the present invention has an advantage in the production process that an emulsion composition can be prepared without returning the anionic groups to the free acid form after defibrillation. Step 2 in the second aspect is the same as that in the first aspect of the present invention.

[0012] [Anionic Modified Cellulose Fiber] Anionically modified cellulose fibers can be obtained by introducing anionic groups into cellulose fibers using known methods. From an environmental standpoint, natural cellulose fibers are preferred as raw materials, including 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. From the viewpoint of sugar chain cleavage efficiency, carboxyl groups, sulfonic acid groups, and phosphate groups are preferred as anionic groups, with carboxyl groups being more preferred. From the viewpoint of anionic group bonding stability, it is more preferable that the anionically modified cellulose fibers are carboxyl-modified cellulose fibers, and even more preferable that the cellulose fibers have a carboxyl group at the C6 position of the cellulose constituent unit. The average fiber diameter of the cellulose fibers used as raw material is not particularly limited, but from the viewpoint of handling and cost, it is preferably 1 μm or more, and preferably 300 μm or less.

[0013] Furthermore, while the average fiber length of the cellulose fibers used as raw materials is not particularly limited, from the viewpoint of availability and cost, it is preferably 100 μm or more, and preferably 5,000 μm or less.

[0014] One known method for producing anionically modified cellulose fibers is the method described in WO2019 / 235557, for example, which uses 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) as a catalyst. In this method, natural cellulose fibers are preferably used as the raw material cellulose fibers, and carboxyl groups as anionic groups are introduced into the cellulose fibers by TEMPO as a catalyst.

[0015] The average fiber diameter of the cellulose fibers in the anion-modified cellulose fibers used in step 1 is not particularly limited, but from the viewpoint of handling and cost, it is preferably 1 μm or more, and preferably 300 μm or less.

[0016] Anion-modified cellulose fibers preferably have a cellulose type I crystalline structure. From the viewpoint of strength development during film formation, the degree of crystallinity of the anion-modified cellulose fibers is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more. From the viewpoint of raw material availability, it is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, and even more preferably 75% or less. 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.

[0017] [Partially neutralized anion-modified cellulose fiber] In this specification, partially neutralized anion-modified cellulose fiber refers to anion-modified cellulose in which some of the anionic groups of anion-modified cellulose are neutralized with cations. In the present invention, an emulsion composition is produced using an aqueous dispersion of such partially neutralized anion-modified cellulose fiber.

[0018] The cations that neutralize some of the anionic groups of the anionic-modified cellulose are preferably one or more selected from the group consisting of monovalent cations, more preferably one or more selected from the group consisting of metal ions and onium ions, even more preferably one or more selected from alkali metal ions and ammonium ions, and even more preferably sodium ions, from the viewpoint of ease of defibration of the anionic-modified cellulose fibers and the emulsification stability of the final emulsion composition.

[0019] The degree to which the anionic groups of partially neutralized anionic-modified cellulose fibers are neutralized (sometimes referred to as "degree of neutralization of anionic groups" in this specification) is defined as the ratio of "number of moles of anionic groups × valence of anionic groups present in 1 g of anionic-modified cellulose fiber" to "number of moles of anionic groups × valence of anionic groups present in 1 g of anionic-modified cellulose fiber," and can be specifically determined by the method described in the examples.

[0020] The degree of neutralization of the anionic groups is preferably 2% or more, more preferably 5% or more, and even more preferably 10% or more, from the viewpoint of the ease of defibration of the anionically modified cellulose fibers and the emulsification stability of the final emulsion composition. On the other hand, the degree of neutralization of the anionic groups is preferably 90% or less, more preferably 80% or less, and even more preferably 70% or less, from the viewpoint of suppressing the thickening of the final emulsion composition.

[0021] One method for preparing partially neutralized anion-modified cellulose fibers from anion-modified cellulose fibers is to mix the anion-modified cellulose fibers with a base. Examples of bases include hydroxides of alkali metals (e.g., lithium, sodium, potassium, etc.), hydroxides of alkaline earth metals (e.g., beryllium, magnesium, calcium, etc.), and ammonia. Therefore, examples of metal ions that neutralize the anionic group include lithium ions, sodium ions, potassium ions, beryllium ions, magnesium ions, and calcium ions. From the viewpoint of dispersibility of anion-modified cellulose fibers, alkali metal ions, i.e., lithium ions, sodium ions, and potassium ions, are preferred as metal ions.

[0022] [Water dispersion] The aqueous dispersion in this invention contains partially neutralized anion-modified cellulose fibers. The content of partially neutralized anion-modified cellulose fibers in the aqueous dispersion is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, as a solid content, from the viewpoint of efficiently producing the dispersion. On the other hand, from the viewpoint of suppressing excessive thickening of the dispersion, it is preferably 20% by mass or less, more preferably 10% by mass or less.

[0023] The solvent in the aqueous dispersion, i.e., the aqueous solvent, may be water alone, or it may contain other solvents such as methanol, ethanol, dimethylformamide, acetone, 1-propanol, 2-propanol, dimethylacetamide, n-methylpyrrolidone, dimethyl sulfoxide, ethylene glycol, diethylene glycol, glycerin, propylene glycol, propylene glycol monomethyl ether, etc. If a solvent other than water is included, the proportion of the "solvent other than water" in the aqueous solvent is preferably 50% by mass or less, more preferably 30% by mass or less, from the viewpoint of dispersibility of the anionically modified cellulose fibers.

[0024] As described above, the aqueous solvent is as follows: During the defibration treatment, the ratio of partially neutralized anion-modified cellulose fiber to the aqueous solvent is preferably 1 part by mass or more, more preferably 10 parts by mass or more, of the aqueous solvent per 1 part by mass of the partially neutralized anion-modified cellulose fiber, while preferably 1000 parts by mass or less, more preferably 100 parts by mass or less.

[0025] By dissolving and dispersing an aqueous dispersion of partially neutralized anion-modified cellulose fibers, micrometer-scale cellulose can be refined to a nanometer scale.

[0026] For the defibration and dispersion process, known dispersers are preferably used. For example, dispersers, beaters, low-pressure homogenizers, high-pressure homogenizers, grinders, cutter mills, ball mills, jet mills, short-screw extruders, twin-screw extruders, ultrasonic stirrs, household juicer mixers, etc., can be used.

[0027] From the viewpoint of obtaining an emulsion composition, the anionic group content in the anionic-modified cellulose fibers in the aqueous dispersion of anionic-modified cellulose fibers obtained by defibration and dispersion treatment 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. Furthermore, from the viewpoint of the emulsion stability of the emulsion composition, 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 fibers, and is specifically measured by the method described in the examples below.

[0028] 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 obtaining an emulsion composition, and preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less, from the viewpoint of the emulsion stability of the emulsion composition. The average fiber diameter of the anion-modified cellulose fibers is measured by the method described in the examples below.

[0029] [Step 1 of Embodiment 1, and Step 2 of Embodiment 2] Step 2 of Embodiments 1 and 2 is a step of mixing a partially neutralized anion-modified cellulose fiber aqueous dispersion, an oil, and an organic compound having a cationic group.

[0030] Aqueous dispersion of partially neutralized anion-modified cellulose fibers is prepared by mixing partially neutralized anion-modified cellulose fibers with water. A preferred embodiment of the method for preparing the aqueous dispersion is step 1 of embodiment 2, which is a step of defibrating and dispersing the partially neutralized anion-modified cellulose fibers in an aqueous solvent, and it is preferable in the present invention to further include such a step.

[0031] [Oils] In this invention, the oil used has a solubility parameter of preferably 6.0 (cal / cm³) from the viewpoint of obtaining a film with improved water resistance and lubricity. 3 ) 0.5The above, more preferably 6.5 (cal / cm 3 ) 0.5 or more, and from the same perspective, the solubility parameter is preferably 10 (cal / cm 3 ) 0.5 or less, more preferably 9.5 (cal / cm 3 ) 0.5 or less, even more preferably 9.0 (cal / cm 3 ) 0.5 or less, even more preferably 8.5 (cal / cm 3 ) 0.5 or less.

[0032] The solubility parameter in this specification is the SP value calculated by the Fedors method, and is described in, for example, the reference "Fundamentals, Applications, and Calculation Methods of SP Values" (Information Organization, 2005), Polymer handbook Third edition (A Wiley-Interscience publication, 1989), etc.

[0033] As the oil agent used in the present invention, those having a solubility of 10 g or less in 100 g of water at 25°C are preferred, and those having a solubility of 1 g or less are more preferred.

[0034] Regarding the molecular weight of the oil agent used in the present invention, from the perspective of obtaining a film with improved water resistance and lubricity, it is preferably 100 or more, more preferably 200 or more, and from the same perspective, it is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less.

[0035] Preferred specific examples of such oils include, from the viewpoint of obtaining a low-viscosity emulsion composition with excellent storage stability, one or more selected from the group consisting of alcohol, ester oil, hydrocarbon oil, silicone oil, ether oil, fats and oils, fluorinated inert liquid, and fatty acid. Preferably, one or more selected from the group consisting of ester oil, silicone oil, ether oil, fats and oils, and fluorinated inert liquid, more preferably, one or more selected from the group consisting of silicone oil, ester oil, and ether oil, and even more preferably, silicone oil and / or ester oil.

[0036] Examples of silicone oils include dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. Examples of silicone oils used as lubricants in this invention include KF96-1cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-10cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-50cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-100cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-1000cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), and KF-96H-10,000cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3).

[0037] [Organic compounds containing cationic groups] Examples of cationic groups in organic compounds include amino groups (primary amines, secondary amines, tertiary amines), quaternary ammonium, phosphonium, amidine, guanidine, imidazolium, pyridinium, and imidazoline. From the viewpoint of compound availability, amino groups are preferred. In the present invention, examples of organic compounds having cationic groups include polymer compounds having cationic groups and hydrocarbon compounds having cationic groups.

[0038] [Polymer compounds containing cationic groups] From the viewpoint of availability, polymer compounds having cationic groups are preferably polymer compounds having amino groups. The polymer compounds having amino groups that can be preferably used in the present invention are commercially available or can be prepared according to known methods. One or more polymer compounds having amino groups may be used.

[0039] 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, and ali-aromatic polyamines. The position of the reactive group may be in the main chain, side chains, or terminals of the polymer compound. Among these, from the viewpoint of obtaining a film with synovial properties, it is preferable to use one or more selected from the group consisting of amino-modified silicones and polyoxyalkyleneamines.

[0040] (i) Amino-modified silicone 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.

[0041] The kinematic viscosity at 25°C can be determined using an Ostwald viscometer, and from the viewpoint of synovial properties, 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.

[0042] Furthermore, 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 properties, and 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 bonding to anion-modified cellulose fibers. Note that the amino equivalent is the molecular weight per nitrogen atom, and is calculated as amino equivalent (g / mol) = weight-average molecular weight / number of nitrogen atoms per molecule. Here, the weight-average molecular weight is the value obtained using gel permeation chromatography with polystyrene as the standard substance, and the number of nitrogen atoms can be determined by elemental analysis.

[0043] A specific example of an amino-modified silicone is the compound represented by general formula (a1).

[0044] [ka]

[0045] [In the formula, R 1a R represents a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom, and from the viewpoint of synovial properties, a methyl group or a hydroxyl group is preferred. 2a is a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, or a hydrogen atom, and from a similar viewpoint, a methyl group or a hydroxyl group is preferred. B represents a side chain having at least one amino group, and R 3a x represents an alkyl group or hydrogen atom having 1 to 3 carbon atoms. x and y represent the average degree of polymerization, and are selected such that the kinematic viscosity and amino equivalent of the compound at 25°C are within the above range. Note that R 1a , R 2a , R 3a These may be the same or different, and there may be multiple Rs. 2a They may be the same or different.

[0046] In the compound of general formula (a1), from the viewpoint of synovial properties, 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 between 2,000 and 1,000,000, more preferably between 5,000 and 100,000, and even more preferably between 8,000 and 50,000.

[0047] 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.)

[0048] 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)

[0049] Furthermore, as the amino-modified silicone, from the viewpoint of obtaining a film with high water resistance, it 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, and more preferably one or more selected from the group consisting of a compound in which the amino-group-containing side chain B is represented by -C3H6-NH2 [hereinafter referred to as component (a1-1)] and a compound in which the amino-group-containing side chain B is represented by -C3H6-NH-C2H4-NH2 [hereinafter referred to as component (a1-2)].

[0050] 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: 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 manufactured by Shin-Etsu Chemical Co., Ltd. (Kinematic viscosity: 1100, Amino equivalent: 1700), KF 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) are preferred. (In parentheses, kinematic viscosity is measured at 25°C (unit: mm) 2The value is expressed as ( / s), and the unit of amino equivalent is g / mol.

[0051] (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).

[0052] (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.

[0053] The silicone compound may have 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 Examples include alkoxy-carbonyl groups with 1 to 6 carbon atoms, such as carbonyl, 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; and dialkylamino groups with 1 to 6 carbon atoms in the alkyl group.

[0054] (ii) Polyoxyalkyleneamines In the present invention, a polyoxyalkyleneamine refers to an amine compound having a polyoxyalkylene structure. Preferably, the polyoxyalkylene structure and the nitrogen atom of the amine compound are bonded directly or via a linking group. The linking group is preferably a hydrocarbon group, and more preferably an alkylene group having 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. Examples of such alkylene groups include ethylene and propylene groups.

[0055] [Hydroxide compounds containing 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 obtaining a film with high water resistance, the total number of carbon atoms in the hydrocarbon compound having a cationic group is preferably 16 or more, more preferably 18 or more, and from the viewpoint of handling properties, preferably 40 or less, more preferably 30 or less, and even more preferably 26 or less.

[0056] 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.

[0057] Examples of hydrocarbon groups in the hydrocarbon compounds include chain-type saturated hydrocarbon groups, chain-type unsaturated hydrocarbon groups, cyclic saturated hydrocarbon groups, and aromatic hydrocarbon groups. From the viewpoint of availability, the number of carbon atoms in the hydrocarbon group is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Similarly, from the same viewpoint, it is preferably 40 or less, more preferably 30 or less, and even more preferably 24 or less. Unless otherwise specified, the number of carbon atoms in a hydrocarbon group refers to the number of carbon atoms in a single hydrocarbon group.

[0058] Specific examples of chain-type saturated hydrocarbon groups include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, pentyl group, tert-pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, octadecyl group, docosyl group, octacosanyl group, and the like.

[0059] Specific examples of chain-type unsaturated hydrocarbon groups include, for example, ethenyl group, propenyl group, butenyl group, isobutenyl group, isoprenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, and octadecenyl group.

[0060] Specific examples of cyclic saturated hydrocarbon groups include, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group, cyclotridecyl group, cyclotetradecyl group, and cyclooctadecyl group.

[0061] Aromatic hydrocarbon groups are selected from the group consisting of, for example, aryl groups and aralkyl groups. The aryl group and aralkyl group may be either substituted or unsubstituted aromatic rings.

[0062] Examples of aryl groups include phenyl, naphthyl, anthryl, phenanthryl, biphenyl, triphenyl, terphenyl groups, and groups in which these groups are substituted with substituents described later.

[0063] Examples of aralkyl groups include benzyl, phenethyl, phenylpropyl, phenylpentyl, phenylhexyl, phenylheptyl, and phenyloctyl groups, as well as groups in which the aromatic groups of these groups are further substituted with substituents.

[0064] 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.

[0065] 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.

[0066] [Other ingredients] In the manufacturing method of the present invention, the emulsified composition may contain, in addition to the above-mentioned components, 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, antifungal agents, antibacterial agents, 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.

[0067] [Mixing operation] An emulsified composition is obtained by mixing an aqueous dispersion of partially neutralized anion-modified cellulose fibers, an oil, and an organic compound having cationic groups. 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.

[0068] [Emulsifying composition] The emulsified composition of the present invention is a composition produced by the above-described manufacturing method, and may be either an o / w type emulsion or a w / o type emulsion, but is preferably an o / w type emulsion. The emulsifying composition of the present invention exhibits surprisingly high stability in its emulsified state and low viscosity, resulting in good handling.

[0069] In the emulsified composition, the content of partially neutralized anion-modified cellulose fibers is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, from the viewpoint of emulsifying power, while from the viewpoint of handling properties, it is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less.

[0070] In the emulsified composition, the oil content is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, from the viewpoint of maintaining the emulsified state, while from the viewpoint of solution viscosity and handling properties, it is preferably 70% by mass or less, more preferably 50% by mass or less, and even more preferably 20% by mass or less.

[0071] In the emulsified composition, the content of the organic compound having a cationic group is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, from the viewpoint of emulsifying power and maintaining the emulsified state, and preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of solution viscosity and handling properties.

[0072] 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.

[0073] The viscosity of the emulsified composition is not particularly limited, but the viscosity at 25°C is preferably 0.5 mPa·s or higher, more preferably 0.8 mPa·s or higher, and even more preferably 1 mPa·s or higher. From the viewpoint of handling, it is preferably 500 mPa·s or lower, more preferably 200 mPa·s or lower, and even more preferably 100 mPa·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.

[0074] The average particle size (volume median particle size) of the emulsion droplets in the emulsion composition, as measured by the laser diffraction method described later, is preferably 10 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more, from the viewpoint of suppressing biofouling and improving synovial properties and their durability. Similarly, it is preferably 2000 nm or less, more preferably 1000 nm or less, even more preferably 700 nm or less, and even more preferably 500 nm or less. Preferably, it is 10 nm to 2000 nm, more preferably 50 nm to 1000 nm, and even more preferably 100 nm to 500 nm.

[0075] 〔film〕 The emulsified composition of the present invention can be dried to produce a film. Preferably, such a film exhibits the synovial surface properties described in the literature (Technology of Superhydrophobic, Superoleophobic, and Synovial Surfaces / Publisher: Hiroshi Motoki / Distributor: Science & Technology Co., Ltd. / Published January 28, 2016).

[0076] The synovial surface properties can be measured, for example, by the method described in the "Slip Angle Measurement Test" in the examples below. A smaller slip angle value indicates higher synovial properties of the film.

[0077] The thickness of the film of the present invention is not particularly limited. From the viewpoint of film durability, it is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more. From the viewpoint of economic efficiency, it is preferably 2000 μm or less, more preferably 1200 μm or less, even more preferably 500 μm or less, and even more preferably 200 μm or less. The film thickness can be set to a desired value by adjusting the film thickness using an applicator or other coating tool, or by adjusting the ratio of the medium. The film thickness can be measured according to the method described in the examples below.

[0078] The film of the present invention is preferable because higher smoothness leads to higher synovial properties. Specifically, from the viewpoint of cost-effectiveness, the arithmetic mean roughness of the film immediately after manufacturing is preferably 0.3 μm or more, more preferably 0.5 μm or more, and even more preferably 0.8 μm or more. On the other hand, from the viewpoint of adhesion inhibition, it is preferably 40 μm or less, more preferably 35 μm or less, and even more preferably 30 μm or less. The arithmetic mean roughness of the film can be measured according to the method described in the examples below.

[0079] The film of the present invention may contain optional components that do not impair the effects of the present invention. The content of these optional components in the film is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0080] 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 excellent durability, allowing it to maintain its effect for a long period of time. Therefore, it can be suitably used in various applications, such as packaging materials for daily necessities, cosmetics, and home appliances, as interior materials for packaging containers such as blister packs, trays, and lunch box lids, food containers, industrial trays and transport pipes used for transporting and protecting industrial parts, and even as covering materials for roofs, building walls, ship bottoms, and electric wires. As a result, it can be suitably used as an antifouling film to suppress the adhesion of dust and other particles, a snow-proof film to suppress the adhesion of snow and ice, and a bio-adhesion-suppressing film to suppress the adhesion of aquatic organisms.

[0081] The emulsified composition of the present invention is useful as a biofouling inhibitor, antifouling agent, and snowproofing agent. By applying the emulsified composition of the present invention to the above-mentioned solid surfaces, it can be used as a method for inhibiting biofouling, an antifouling method, and a snowproofing method.

[0082] Such films can be manufactured, for example, as follows: Specifically, the emulsified composition is applied to a substrate, such as a solid surface made of glass, resin, metal, ceramics, concrete, wood, stone, or fiber, or to skin, hair, etc. Methods of application include, but are not limited to, using an applicator, bar coater, spin coater, etc., as well as brush application, hand application, spraying, dip coating, etc.

[0083] The thickness of the emulsion composition coating film on the substrate is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more, from the viewpoint of film durability, and preferably 2000 μm or less, and more preferably 1500 μm or less, from the viewpoint of coatability.

[0084] Next, the emulsion composition coating can be dried to obtain a coating film. The drying conditions can be under reduced pressure or atmospheric pressure, and the temperature range is preferably between 15°C and 75°C. The drying time is preferably between 1 hour and 24 hours. [Examples]

[0085] 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.

[0086] [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.

[0087] [Average fiber diameter, average fiber length, and average aspect ratio of anionically 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.

[0088] [Anionic group content of anionic-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)]

[0089] [Aldehyde group content of anionically modified cellulose fibers] The carboxyl group content of the 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 cellulose fiber 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 carboxy-modified cellulose fiber. After the reaction is complete, the material is washed with deionized water to obtain cellulose fiber 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 anionic group content described above to calculate the "carboxyl group content of the oxidized cellulose fiber." Subsequently, the aldehyde group content of the cellulose fiber to be measured is calculated using Equation 1.

[0090] Aldehyde group content (mmol / g) = (Carboxyle group content of oxidized cellulose fiber) - (Carboxyle group content of cellulose fiber to be measured) ... Equation 1

[0091] [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.

[0092] [Confirmation of crystalline structure in various cellulose fibers] The crystalline structure of 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. 2The 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.

[0093] <Formula A> Cellulose type I crystallinity (%) = [(I 22.6 -I 18.5 ) / I 22.6 ]×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°).

[0094] 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 formula B below can be used as the degree of crystallinity.

[0095] <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.

[0096] [Degree of neutralization of anionic groups] The degree of neutralization of the anionic groups in anion-modified cellulose fibers is determined as follows. Degree of neutralization (%) = [[[Amount of metal ions (mmol) bonded to anionic groups introduced in 1g of anionic-modified cellulose fiber × valence of metal ions] + [Amount of ammonium ions (mmol) bonded to anionic groups introduced in 1g of anionic-modified cellulose fiber × valence]] / [Amount of anionic groups introduced in 1g of anionic-modified cellulose fiber (mmol) × valence of anionic groups]] × 100

[0097] The amount of metal ions bonded to the anionic group can be determined by the following method. Approximately 1 g of dried anion-modified cellulose fiber is mixed with 100 g of deionized water, stirred at 20°C for 1 hour (100 rpm), and then filtered using filter paper (No. 5). This washing procedure is repeated a total of three times. The washed anion-modified cellulose fiber is freeze-dried, weighed, ashed, dissolved in hydrochloric acid, and the amount of metal ions is measured by inductively coupled plasma atomic emission spectrometry (ICP-AES). It is possible. The amount of ammonium ions bonded to the anionic group can be determined by the following method. Approximately 1 g of dried anionically modified cellulose fiber is mixed with 100 g of deionized water, stirred at 20°C for 1 hour (100 rpm), and then filtered using filter paper (No. 5). This washing procedure is repeated a total of three times. The washed anionically modified cellulose fiber is dried and weighed, and the amount of ammonia detected when an excess amount of sodium hydroxide is added to neutralize it to over 100% is measured and converted to the amount of ammonium ions.

[0098] Furthermore, if the metal ion is an alkali metal ion, its valency is 1; if the metal ion is an alkaline earth metal ion, its valency is 2; and the ammonium ion has a valency of 1.

[0099] [Measuring the particle size of emulsified droplets using laser diffraction] The particle size of emulsion droplets is measured using laser diffraction with a LA-960 laser meter manufactured by Horiba, Ltd. Measurement conditions: Water is added to the measurement cell, and the volume particle size distribution and volume median particle size (D50) are measured at a concentration that results in an appropriate absorbance range. The relative refractive index is 1.40, the temperature is 25°C, the circulation pump is ON, the circulation speed is 5, and the stirring speed is 5.

[0100] [Preparation of anionically modified cellulose fibers] Preparation Example 1 Bleached coniferous kraft pulp (Hinton, manufactured by Westfrother) was used as the raw material for the natural cellulose fiber. A commercially available product (Free radical, manufactured by Aldrich, 98% by mass) was used as the TEMPO. Commercially available products were used for sodium hypochlorite, sodium bromide, and sodium hydroxide.

[0101] First, 10 g of bleached kraft pulp fiber and 990 g of deionized water were weighed into a 2 L PP beaker equipped with a mechanical stirrer and stirring blades. After stirring at 25°C and 100 rpm for 30 minutes, 0.13 g of TEMPO, 1.3 g of sodium bromide, and 35.5 g of 10.5% by mass sodium hypochlorite aqueous solution were added to 10 g of pulp fiber in that order. Using an automatic titrator (Toa DKK Co., Ltd., AUT-701), pH stat titration was performed, and 0.5 M sodium hydroxide aqueous solution was added dropwise to maintain the pH at 10.5. The reaction was carried out at 25°C for 120 minutes at a stirring speed of 100 rpm, after which the addition of sodium hydroxide aqueous solution was stopped, and a suspension of anionically modified cellulose fiber (carboxylated cellulose fiber) was obtained.

[0102] The obtained suspension of anionically modified cellulose fibers was washed three times with 1M hydrochloric acid. Then, the filtrate was thoroughly washed with deionized water until its conductivity, measured using a compact electrical conductivity meter (Horiba, LAQUAtwin EC-33B), was 200 μs / cm or less. Following this, dehydration was performed to obtain anionically modified cellulose fiber 1. At this time, the degree of neutralization of anionically modified cellulose fiber 1 was 0% (below the detection limit). The carboxyl group content of anionically modified cellulose fiber 1 was 1.45 mmol / g, and the aldehyde group content was 0.23 mmol / g. The average fiber length of anionically modified cellulose fiber 1 was 2000 μm, and the average fiber diameter was 40 μm.

[0103] Preparation Example 2 Anionically modified cellulose fiber 2 was obtained in the same manner as in Preparation Example 1, except that the amount of sodium hypochlorite aqueous solution was 71 mL and the reaction time was 300 minutes. At this time, the degree of neutralization of anionically modified cellulose fiber 2 was 0% (below the detection limit). The carboxyl group content of this anionically modified cellulose fiber was 1.90 mmol / g, and the aldehyde group content was 0.20 mmol / g. The average fiber length of anionically modified cellulose fiber 2 was 800 μm, and the average fiber diameter was 50 μm.

[0104] Example 1 [Preparation of partially neutralized anion-modified cellulose fibers] Deionized water was added to the anionically modified cellulose fibers prepared in Preparation Example 1 to prepare a suspension (solid content 2.0% by weight) of 50 g. A 1 M sodium hydroxide aqueous solution was then added to achieve the predetermined degree of neutralization shown in Table 1, and further deionized water was added to prepare a dispersion of partially neutralized anionically modified cellulose fibers (solid content 1.0% by mass) of 100 g.

[0105] [Preparation of partially neutralized, finely textured anion-modified cellulose fibers] The dispersion of partially neutralized anion-modified cellulose fibers obtained in this manner was subjected to five defibrillation and dispersion treatments at 150 MPa using a high-pressure homogenizer (NanoVeta L-ES, manufactured by Yoshida Machinery Co., Ltd.) to obtain a dispersion of partially neutralized, finely milled anion-modified cellulose fibers (solid content 1.0 mass%). The average fiber length of the finely milled anion-modified cellulose fibers 1 at the degree of neutralization in Example 1 was 600 nm, and the average fiber diameter was 3.3 nm. The transmittance and nanofiber yield of the finally obtained dispersion were measured. The results are shown in Table 1.

[0106] [Preparation of Emulsified Compositions] 60.0 g (solid content 1.0 mass%) of the dispersion of partially neutralized finely pulverized anion-modified cellulose fiber 1 obtained in this manner was mixed with 6.0 g of silicone oil (Shin-Etsu Chemical Co., Ltd., KF-96-100cs) and 2.22 g of amino-modified silicone (Toray Dow Corning Co., Ltd., SS-3551). Deionized water was added to make a total of 100 g. 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 an emulsion composition containing modified cellulose fibers in which amino-modified silicone was ionically bonded to the anion-modified cellulose fibers. The stability and viscosity of this emulsion composition were evaluated. The results are shown in Table 1. The median volume particle size was 300 nm.

[0107] Examples 2-5 As shown in Table 1, 50 g of suspension (solid content 2.0% by weight) was prepared by adding deionized water to the anionically modified cellulose fibers prepared in Preparation Example 1 or Preparation Example 2. To this, 1 M sodium hydroxide aqueous solution or 1 M ammonia aqueous solution was added to achieve the predetermined degree of neutralization shown in Table 1, and then deionized water was added to prepare 100 g of dispersion of partially neutralized anionically modified cellulose fibers (solid content 1.0% by mass).

[0108] Next, in the same manner as in Example 1, partially neutralized micronized anion-modified cellulose fibers and emulsified compositions were prepared for each example, and evaluated for each evaluation item. The results are shown in Table 1.

[0109] Comparative Examples 1 and 3 As shown in Table 1, 100 g of a dispersion of anionically modified cellulose fibers (solid content 1.0 wt%) was prepared by adding deionized water to the anionically modified cellulose fibers prepared in Preparation Example 1 or Preparation Example 2.

[0110] Next, in the same manner as in Example 1, micronized anion-modified cellulose fibers and emulsified compositions were prepared for each comparative example, and each evaluation item was evaluated. The results are shown in Table 1.

[0111] Comparative Example 2 As shown in Table 1, 50 g of suspension (solid content 2.0% by weight) was prepared by adding deionized water to the anionically modified cellulose fibers prepared in Preparation Example 1. To this, 1 M sodium hydroxide aqueous solution was added to achieve the predetermined degree of neutralization shown in Table 1, and then deionized water was added to prepare 100 g of dispersion of anionically modified cellulose fibers (solid content 1.0% by mass) in which all anionic groups were neutralized.

[0112] Next, micronized anion-modified cellulose fibers and emulsified compositions were prepared in the same manner as in Example 1, and each evaluation item was assessed. The results are shown in Table 1.

[0113] [Table 1]

[0114] The evaluation method for each evaluation item in Table 1 is as follows: [Permeability of dispersion] The dispersion (solid content 1.0 wt%) was placed in a rectangular cell with a path length of 1 cm, and the light transmittance at 660 nm was measured using a spectrophotometer (AS ONE, ASV11D-H). The values ​​are shown as relative values, with deionized water set to 100%.

[0115] [Nanofiber yield] A dispersion (solid content 1.0 wt%) was diluted 40-fold with deionized water and centrifuged at an acceleration of 10,000 g for 20 minutes to settle cellulose fibers that had not been defibrated into nanofibers. 1 mL of this supernatant was measured into a 15 mL centrifuge tube, 1 mL of 5% phenol aqueous solution was added, and then 5 mL of concentrated sulfuric acid was vigorously added dropwise. After standing at room temperature for 30 minutes, the absorbance at a wavelength of 490 nm was measured using a spectrophotometer (AS ONE, ASV11D-H), and the amount of cellulose present in the supernatant was quantified using a calibration curve prepared with samples of known cellulose concentration. Similarly, the amount of cellulose in the sample before centrifugation was also quantified, and the percentage of cellulose remaining in the supernatant after centrifugation was defined as the nanofiber yield.

[0116] [Stability of the emulsified composition] Based on the following criteria, the stability of the emulsified composition stored at 25°C was evaluated on a three-point scale. 1: Creaming was observed within 3 days of preparation. 2: Creaming was observed within one week of preparation. 3: No creaming was observed even after more than one week had passed since preparation.

[0117] [Viscosity of emulsified compositions] A Type B viscometer (Toki Sangyo TVB-10) was used to measure the viscosity at 25°C, a rotation speed of 60 RPM, and after 1 minute.

[0118] Reference example 1 To 50 mL of the emulsified composition prepared in Example 1, 348 μL of 1 M sodium hydroxide aqueous solution (corresponding to 80% of the amount of carboxyl groups in the composition) was added, and the mixture was stirred with a magnetic stirrer for 10 minutes to perform further neutralization, thereby obtaining an emulsified composition with the same composition as Comparative Example 2.

[0119] Reference example 2 To 50 mL of the emulsified composition prepared in Example 3, 218 μL of 1 M sodium hydroxide aqueous solution (corresponding to 50% of the amount of carboxyl groups in the composition) was added, and the mixture was stirred with a magnetic stirrer for 10 minutes to perform further neutralization, thereby obtaining an emulsified composition with the same composition as Comparative Example 2.

[0120] Table 2 shows the evaluation results of the emulsified compositions finally prepared in Reference Example 1 and Reference Example 2.

[0121] [Table 2]

[0122] The dispersions of partially neutralized anion-modified cellulose fibers prepared in Examples 1-5 exhibited high light transmittance and nanofiber yield, indicating efficient defibration into fine fibers. Furthermore, the emulsified compositions prepared in Examples 1-5 showed high stability while exhibiting low viscosity and excellent handling properties. On the other hand, in Comparative Examples 1 and 3, where the anionically modified cellulose fibers were subjected to defibration and dispersion treatment with a degree of neutralization by metal ions of 0%, the defibration of the anionically modified cellulose fibers was insufficient, resulting in poor emulsion stability of the prepared emulsion composition. Furthermore, in Comparative Example 2, where the anionically modified cellulose fibers were subjected to defibration and dispersion treatment with a degree of neutralization by metal ions of 100%, the prepared emulsion composition exhibited excellent stability, but its viscosity was high, resulting in poor handling properties. In Reference Examples 1 and 2, an aqueous sodium hydroxide solution was added to the emulsified compositions prepared in Examples 1 and 3, resulting in a composition 100% neutralized by metal ions, similar to Comparative Example 2. However, the viscosity of the emulsified composition did not increase; in fact, it decreased.

[0123] [Preparation of a dried film] The emulsified compositions prepared in Examples 1-2 and Comparative Examples 1-2 were each coated in 400 μL on separate glass substrates (MATSUNAMI Micro Slide Glass S2112) and spread over the entire surface of the slide glass. The films were then dried for 24 hours at 1 atm, 25°C, and approximately 40% RH. The thickness of the film in Example 1 was measured to be 20 μm using the method described below.

[0124] [Measurement of film thickness] The thickness of the film after drying was measured using a laser microscope (Keyence VK-9710) under the following conditions: objective lens: 10x, light intensity: 3%, brightness: 1548, Z pitch: 0.5 μm. A portion of the film was scraped off with a metal spatula to expose the glass substrate. The height of the glass substrate and the height of the filmed portion were measured using the built-in image processing software, and the film thickness was determined by taking the difference between these two values.

[0125] [Water droplet fall angle measurement test] The dried films of Examples 1-2 and Comparative Examples 1-2, prepared as described above, were placed horizontally. Using a fully automatic contact angle meter (FAMAS, manufactured by Kyowa Interface Science Co., Ltd.), 8 μL of water (23°C) was dropped onto each film 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 droplet began to slide was measured. The measurement results are shown in the table below. However, if the droplet did not slide off even when tilted to 85°, the water droplet sliding angle was noted as "85 or greater". A smaller water droplet sliding angle indicates higher synovial properties of the film.

[0126] [Measurement of the arithmetic mean roughness of a film] The arithmetic mean roughness of the dried films of Examples 1-2 and Comparative Examples 1-2, prepared as described above, was measured. The arithmetic mean roughness of the films was measured using a laser microscope (Keyence Corporation, VK-9710) under the following conditions: objective lens: 10x, light intensity: 3%, brightness: 1548, Z pitch: 0.5 μm. The arithmetic mean roughness was measured at 5 points using the built-in image processing software, and the average value was used.

[0127] [Biological adhesion test] The emulsified compositions prepared in Examples 1-2 and Comparative Examples 1-2 were coated at a rate of 1.5 mL onto a SUS304 substrate (L50 mm × W50 mm × T3 mm) and dried for 24 hours at 1 atm, 25°C, and approximately 40% RH to produce a film. An untreated SUS304 substrate of L50 mm × W50 mm × T3 mm was used as Comparative Example 4. The aforementioned circuit boards were connected by chains and placed in seawater near Shimotsu Port in Wakayama Prefecture so that they were 2 meters below the water surface at low tide, and an immersion test was conducted in seawater. After one month of immersion, the degree of attachment of crustaceans and algae to the substrate was visually evaluated. The evaluation criteria were as follows: A smaller value indicates a higher effectiveness in inhibiting the attachment of aquatic organisms.

[0128] 1: A condition in which the attachment of aquatic organisms covers less than 2% of the substrate surface area. 2: A condition in which aquatic organisms are attached to more than 2% but less than 10% of the substrate surface. 3: A condition in which aquatic organisms are attached to more than 10% but less than 20% of the substrate surface. 4: A condition in which aquatic organisms are attached to more than 20% but less than 30% of the substrate surface. 5: A condition in which aquatic organisms are attached to more than 30% but less than 50% of the substrate surface. 6: A condition in which aquatic organisms are attached to more than 50% but less than 80% of the substrate surface. 7: A condition in which aquatic organisms are attached to more than 80% of the substrate surface.

[0129] [Removal of attached organisms] In the above biological fouling test, the removal efficiency of aquatic organisms attached to the substrate after 1 month and 3 months of immersion was evaluated according to the following criteria. Here, "low pressure" refers to a weak pressure, such as that used when spraying from a wash bottle. A smaller value indicates that the aquatic organisms can be removed more easily.

[0130] 1: Easily removed by low-pressure water washing. 2: Rinsing and scrubbing are required. 3. Tools are required (removed in one scraping step). 4: Requires multiple scraping operations with a tool, or is impossible to remove.

[0131] The results are shown in Table 3.

[0132] [Table 3]

[0133] Table 3 shows that the emulsifying composition and membrane of the present invention have excellent synovial properties, making it difficult for organisms to adhere to them, and allowing for easy removal of any organisms that do adhere. [Industrial applicability]

[0134] The emulsifying composition of the present invention has excellent lubricity and can form a film that is resistant to the adhesion of organisms, and can therefore be used in the field of coating various surfaces, such as ships and bridges.

Claims

1. Aqueous dispersion of partially neutralized anion-modified cellulose fibers, Oils and Organic compounds having cationic groups A method for producing an emulsified composition, comprising the step of mixing the following: The partially neutralized anion-modified cellulose fiber is anion-modified cellulose in which some of the anionic groups of anion-modified cellulose are neutralized with cations. The aforementioned cation is one or more cations selected from the group consisting of alkali metal ions and ammonium ions. The degree of neutralization of the anionic groups in the partially neutralized anion-modified cellulose fiber is 2% or more and 90% or less. A method for producing an emulsified composition.

2. A method for producing an emulsified composition, comprising the following steps 1 and 2. Step 1: A step of obtaining an aqueous dispersion of anionically modified cellulose fibers by defibrating partially neutralized anionically modified cellulose fibers, The partially neutralized anion-modified cellulose fiber is anion-modified cellulose in which some of the anionic groups of anion-modified cellulose are neutralized with cations. The aforementioned cation is one or more cations selected from the group consisting of alkali metal ions and ammonium ions. The process is such that the degree of neutralization of the anionic groups in the partially neutralized anion-modified cellulose fiber is 2% or more and 90% or less. Step 2: A step of mixing the aqueous dispersion of anionically modified cellulose fibers obtained in Step 1, an oil, and an organic compound having a cationic group.

3. The manufacturing method according to claim 1 or 2, wherein the anionic modified cellulose fiber is a carboxy-modified cellulose fiber.

4. The manufacturing method according to any one of claims 1 to 3, wherein the average fiber diameter of the anionically modified cellulose fibers in the aqueous dispersion is 0.1 nm or more and 200 nm or less.

5. The manufacturing method according to any one of claims 1 to 4, wherein the cationic group in the organic compound having the cationic group is an amino group.

6. The solubility parameter of the aforementioned oil, calculated by the Fedors method, is 6.0 (cal / cm³). ３ ) ０．５ More than 10 (cal / cm ３ ) ０．５ The manufacturing method according to any one of claims 1 to 5, which is as follows:

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