Hard surface treatment agent

Abstract

To provide a hard surface modifier that can easily impart synovial properties. [Solution] A hard surface treatment agent containing an oil-in-water type Pickering emulsion; and the hard surface treatment agent used as a snow-repellent paint, an antifouling paint, an antibacterial paint, a flow resistance reducing agent, or a mold release agent.

Description

Technical Field

[0001] The present invention relates to a hard surface treatment agent.

Background Art

[0002] Conventionally, attempts have been made to prevent the adhesion of dirt by imparting water repellency to an object. Recently, a Slippery Liquid Infused Porous Surface (SLIPS) in which a liquid lubricant is impregnated in a network structure or a fine concavo-convex structure has been reported, and liquids such as water can slide off with a slight inclination compared to conventional water repellent techniques. This property is called slipperiness. For example, Patent Document 1 describes a method of forming a water-repellent film composed of one or more silicones on the surface of a substrate by applying an anionic silica particle dispersion liquid to the surface of the substrate and then applying a silicone emulsion.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In the method of Patent Document 1, since the treatment process is complicated, an agent that can impart slipperiness with a simple operation is required.

[0005] The problem of the present invention relates to a hard surface modifier that can easily impart slipperiness.

Means for Solving the Problems

[0006] The present invention relates to the following [1] to [2]. [1] A hard surface treatment agent containing an oil-in-water type pickering emulsion. 〔2〕 The hard surface treatment agent according to 〔1〕 above, wherein the hard surface treatment agent is used as an anti-snow paint, an anti-fouling paint, an antibacterial paint, a fluid resistance reducing agent, or a mold release agent.

Advantages of the Invention

[0007] By using the hard surface treatment agent provided by the present invention, a film excellent in synovial fluid properties can be easily produced on a hard surface.

Brief Description of the Drawings

[0008] [Figure 1] FIG. 1 is a schematic diagram of a pressure loss measuring device.

Embodiments for Carrying Out the Invention

[0009] As a result of intensive studies by the present inventors to solve the above problems, it has been found that an agent containing an oil-in-water type Pickering emulsion can easily provide a film having synovial fluid properties on a hard surface, and the present invention has been completed. A Pickering emulsion is an emulsion stabilized by solid particles adsorbed on the liquid-liquid interface, in which solid particles having appropriate wettability for both the oil phase and the water phase are adsorbed to the oil-water interface to stabilize the emulsion. By applying the oil-in-water type Pickering emulsion of the present invention to a hard surface and drying it, a film having synovial fluid properties can be formed. Although the mechanism by which such characteristics are expressed is not clear, it is presumed that the solid particles that formed the Pickering emulsion form a network structure with drying, and a film in which an oil agent is held therein can be formed. By using a Pickering emulsion, a stable emulsion can be obtained without reducing or blending the amount of surfactant.

[0010] 1. Hard surface treatment agent The hard surface treatment agent of the present invention contains an oil-in-water type Pickering emulsion. A Pickering emulsion, for example, includes solid particles and an organic compound that binds to them, and it is preferable that the organic compound is bound to the solid particles, from the viewpoint of providing sufficient stability to the emulsion.

[0011] <Solid particles> The solid particles used in the Pickering emulsion may be inorganic or organic, but from the viewpoint of producing the Pickering emulsion, anionic solid particles are preferred. Inorganic particles or crystalline organic particles are more preferred as the anionic solid particles. Even more preferred solid particles are one or more selected from the group consisting of anionic modified cellulose fibers having a type I crystal structure, silica particles, and carbon-based compounds having anionic groups.

[0012] Inorganic materials include metal particles (metals such as gold, silver, copper, aluminum, silicon, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zinc, palladium, platinum, iridium, and rhodium, and their alloys), metal oxides (silica, alumina, titanium oxide, zinc oxide, iron oxide, etc.), natural minerals (mica, talc, kaolin, bentonite, smectite, etc.), insoluble salts (metal carbonates, sulfates, phosphates, etc.), semiconductor nanoparticles (CdSe, ZnS, InP, CdS, PbS, etc.), and carbon-based materials (carbon black, graphene, graphene oxide, nanodiamonds, metal carbides, etc.).

[0013] Examples of organic materials include polysaccharides (cellulose nanofibers, cellulose particles, starch), oil and fat powders, metal soaps, organic pigments, and polymer powders (fluororesins, silicone resins, polystyrene, polyolefins, polyamides, polyesters, acrylic resins, methacrylic resins). Among these, crystalline organic particles, such as cellulose nanofibers, cellulose particles, and metal soaps, are preferred from the viewpoint of emulsion stability.

[0014] Inorganic solid particles and organic solid particles may be modified with anionic groups such as carboxyl groups, or cationic groups such as hydroxyl groups and amino groups. The solid particles are preferably anionic solid particles, and more preferably solid particles having a carboxyl group. Specific examples of compounds include carbon black with anionic groups and polysaccharides with anionic groups, which are solid particles containing anionic groups. These compounds are commercially available and can be easily obtained.

[0015] The solid particles can take any shape, including spherical, amorphous, fibrous, and sheet-like forms. The maximum length of the solid particles is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less, from the viewpoint of suppressing aggregation between emulsions, while from the viewpoint of ensuring sufficient adsorption force to the liquid-liquid interface, it is preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 10 nm or more. The maximum length of these particles refers to the numerical average of the major axis (the length of the straight line connecting the furthest points on the surface of the particles) of 50 randomly selected powders observed with an optical microscope or electron microscope.

[0016] When the solid particles are fibrous, such as cellulose nanofibers, i.e., when the aspect ratio is 5 or more, the average fiber diameter is preferably 1 nm or more, more preferably 2 nm or more, from the viewpoint of ensuring sufficient adsorption to the liquid-liquid interface, while from the viewpoint of suppressing aggregation between emulsions, it is preferably 5 μm or less, more preferably 1 μm or less, and even more preferably 500 nm or less. Furthermore, when the solid particles are fibrous, such as cellulose nanofibers, the average fiber length is preferably 10 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more, from the viewpoint of ensuring sufficient adsorption to the liquid-liquid interface, while from the viewpoint of suppressing aggregation between emulsions, it is preferably 1 mm or less, more preferably 100 μm or less, and even more preferably 10 μm or less. The average fiber diameter and average fiber length can be determined by the method described later.

[0017] Furthermore, when the solid particles are in the form of a sheet, their thickness is preferably 500 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less, from the viewpoint of suppressing aggregation between emulsions.

[0018] An example of cellulose nanofibers is polysaccharides having anionic groups. Examples of polysaccharides having anionic groups include cellulose fibers that have been anion-modified to contain anionic groups within the cellulose fibers.

[0019] [Anionic modified cellulose fiber] The anionically modified cellulose fibers used in this invention are cellulose fibers that have been anionically modified to contain anionic groups within the cellulose fibers.

[0020] Anion-modified cellulose fibers have a cellulose type I crystalline structure. From the viewpoint of strength development during film formation, the degree of crystallinity of 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.

[0021] 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.

[0022] 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 at least one compound selected from the group consisting of compounds having carboxyl groups, acid anhydrides of compounds having carboxyl groups, and derivatives thereof. The method for oxidizing the hydroxyl groups of the cellulose is not particularly limited, but for example, a method 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 can be applied. More specifically, known methods, such as the method described in Japanese Patent Application Publication No. 2011-140632, can be referred to.

[0023] 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, such cellulose fibers may be referred to as "oxidized cellulose fibers." Oxidized cellulose fibers are preferred because they are easier to prepare than other anionically modified cellulose fibers.

[0024] 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.

[0025] 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.

[0026] <Organic compounds with bonding properties> In the present invention, the organic compound having bonding properties is an organic compound that has bonding properties to solid particles. When the solid particles are anionic solid particles, the organic compound is preferably an organic compound having a cationic functional group.

[0027] As organic compounds having cationic functional groups, organic compounds having amino groups are preferred, and examples of organic compounds having amino groups include polymer compounds having amino groups and hydrocarbon compounds having amino groups.

[0028] (i) Polymer compounds having an amino group 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. 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 lipoaromatic polyamines. The reactive group may be located in the main chain, side chains, or terminals of the polymer compound. Among these, amino-modified silicones are preferred from the viewpoint of obtaining a film with synovial properties.

[0029] 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.

[0030] The kinematic viscosity at 25°C can be determined using an Ostwald viscometer, and from the viewpoint of obtaining a film with excellent release properties, a 20 mm film 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.

[0031] Also, from the viewpoint of obtaining a film with excellent releasability, the amino equivalent is preferably 400 g / mol or more, more preferably 600 g / mol or more, still more preferably 800 g / mol or more. From the viewpoint of ease of bonding to an anion-modified cellulose fiber, it is preferably 16,000 g / mol or less, more preferably 14,000 g / mol or less, still more preferably 12,000 g / mol or less. The amino equivalent is the molecular weight per nitrogen atom and is determined by amino equivalent (g / mol) = weight average molecular weight / number of nitrogen atoms per molecule. 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 elemental analysis.

[0032] Specific examples of the amino-modified silicone include compounds represented by the general formula (a1).

[0033] [Chemical formula]

[0034] [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 viewpoint of obtaining a film with excellent releasability. 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 viewpoint. 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. ]

[0035] In the compound of general formula (a1), from the viewpoint of obtaining a film with excellent mold release 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 2,000 to 1,000,000, more preferably 5,000 to 100,000, and even more preferably 8,000 to 50,000.

[0036] 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.)

[0037] 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)

[0038] Furthermore, as the amino-modified silicone, from the viewpoint of obtaining a film with excellent mold release properties, 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)].

[0039] 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.

[0040] (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).

[0041] (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.

[0042] Furthermore, amino-modified silicones 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 groups. 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.

[0043] (ii) hydrocarbon compounds having an amino group A hydrocarbon compound having an amino group is a compound in which one or more hydrocarbon groups are bonded to one amino group. From the viewpoint of obtaining a film with excellent release properties, the total number of carbon atoms in the hydrocarbon compound having an amino 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.

[0044] In hydrocarbon compounds containing an amino group, if the amino group is a primary amine, secondary amine, tertiary amine, quaternary ammonium compound, phosphonium, etc., the hydrocarbon group is directly bonded to a nitrogen atom or phosphorus atom via a covalent bond. Hydrocarbon compounds containing an amino group are more preferably those that do not contain an oxyalkylene group.

[0045] (Hydrogen group) 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, even more preferably 3 or more, even more preferably 12 or more, and even more preferably 16 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] The hydrocarbon compounds having an amino 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.

[0054] [Hydrophobic modified cellulose fibers] In a Pickering emulsion, when the solid particles are anionic modified cellulose fibers having a type I crystalline structure, and the binding organic compound is an amino-modified silicone or a hydrocarbon amine, the two combine to form hydrophobic modified cellulose fibers. In the hydrophobic modified cellulose fibers, modifying groups derived from the amino-modified silicone or hydrocarbon amine are bonded to specific groups of the anionic modified cellulose fibers having a type I crystalline structure. The bonding sites for the modifying groups are one or more groups selected from the group consisting of anionic groups and hydroxyl groups.

[0055] When the bonding site is a hydroxyl group of an anionically modified cellulose fiber, the bonding mode is a covalent bond, and examples include ether bonds, ester bonds, carbonate bonds, etc.

[0056] When the bonded site is an anionic group of anion-modified cellulose fiber, the bonded mode is either ionic or covalent. When the bonded mode is ionic, it refers to a state where a modifying compound having a cationic group is bonded via electrostatic interaction. When the bonded mode is covalent, it refers to a state where it is bonded via ester bonds, amide bonds, etc. In particular, with respect to the carboxyl group of carboxyl group-containing cellulose fiber, it refers to a state where it is bonded via ester bonds, amide bonds, carbonate bonds, urethane bonds, etc.

[0057] For example, the compound for introducing a modifying group (referred to as "modifying compound" in this specification) is an amino-modified silicone (referred to as "H2N-[alkylsilicone skeleton]"), and the anionic-modified cellulose fiber is a carboxyl-containing cellulose fiber (referred to as "[cellulose skeleton]-C 6 Let's assume (=O)-OH. In the case where the bonding mode is an ionic bond, the hydrophobic modified cellulose fiber is "[cellulose backbone]-C 6 (=O)-O-H3N + The structure becomes like "-[alkylsilicone skeleton]", and the modifying group is "-[alkylsilicone skeleton]". On the other hand, if the bonding mode is an amide bond, the hydrophobic modified cellulose fiber becomes "[cellulose skeleton]-C 6 The structure becomes like "(=O)-NH-[alkylsilicone skeleton]", and the modifying group becomes "-[alkylsilicone skeleton]". Thus, the structure of the modifying group depends on the structure of the modifying compound used. Note that "C 6 " refers to the carbon atom at position 6 of the cellulose constituent unit.

[0058] One preferred embodiment of a hydrophobic modified cellulose fiber, which is formed by bonding amino-modified silicone to a cellulose fiber, has a structure represented by the following general formula (T-Ce).

[0059] [ka]

[0060] (In the formula, X is -CH2OH, -CH2O-R) 1 -C(=O)OH, -C(=O)OR 1 -C(=O)-O-H3N + -R 1 and -C(=O)-NH-R 1 One or more groups selected from the group consisting of R 1 R is a modifying group, and each R is independently a hydrogen atom or a modifying group. 1 And R may be the same or different, and multiple R 1At least one of R is a modifying element. m is an integer between 20 and 3,000.

[0061] In hydrophobic modified cellulose fibers, which are formed by bonding amino-modified silicone to anion-modified cellulose fibers having a type I crystalline structure, the modifying group is a group derived from the amino-modified silicone, and the modifying group (i.e., R in formula (T-Ce) above) 1 The structure of (and R) depends on the structure of the amino-modified silicone used. The mode of attachment of the modifying group to the cellulose fiber is preferably covalent or ionic. From the viewpoint of ease of manufacture, ionic bonding is preferred, and from the viewpoint of the stability of the formed film, covalent bonding is preferred.

[0062] <Water> The hard surface treatment agent of the present invention contains water. Water serves as a solvent in the preparation of the Pickering emulsion and as one of the components of the hard surface treatment agent of the present invention.

[0063] <Oils> The hard surface treatment agent of the present invention contains an oil. As an oiling agent, an organic compound that is liquid at 25°C and 1 atm is preferred. At 25°C and 1 atm, the solubility of a liquid organic compound in water is preferably 10g or less, and more preferably 1g or less, per 100g of water at 25°C. From the viewpoint of obtaining a film with improved lubricity, the molecular weight of the oil is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less, and from the same viewpoint, preferably 100 or more, and more preferably 200 or more.

[0064] As for the oiling agent, from the viewpoint of obtaining a film with improved lubricity, examples include one or more selected from the group consisting of alcohol, ester oil, hydrocarbon oil, silicone oil, ether oil, fat and oil, fluorinated inert liquid, and fatty acid. One or more selected from the group consisting of ester oil, silicone oil, ether oil, fat and oil, and fluorinated inert liquid is preferred, one or more selected from the group consisting of silicone oil, SL oil, and ether oil is more preferred, and silicone oil and / or SL oil is even more preferred.

[0065] 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.

[0066] Examples of silicone oils include dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.

[0067] 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.

[0068] From the viewpoint of producing a Pickering emulsion, the oil compound 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.

[0069] In this specification, SP value refers to the solubility parameter calculated by the Fedors method (unit: (cal / cm³) 3 ) 1 / 2This 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).

[0070] Examples of oils with an SP value of 10 or less used in this 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 fluorine. 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: 7) Examples include 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.

[0071] <Polyether-modified silicone compound> The hard surface treatment agent of the present invention may further contain a polyether-modified silicone compound. By incorporating such a component into the hard surface treatment agent, a film with improved mold release properties can be obtained. An example of a polyether-modified silicone compound is a compound having a methyl silicone chain as the main chain and side chains consisting of polyoxyethylene groups, and specifically, a compound represented by the following general formula can be mentioned.

[0072] [ka]

[0073] (In the formula, R 1 R is a methylene group, an ethylene group, or a trimethylene group. 2 is an alkyl group having 1 to 4 carbon atoms, where m is an integer from 0 to 50, n is an integer from 1 to 10, p is an integer from 1 to 50, and q is an integer from 0 to 50. -R 1 (C2H4O) p (C3H6O) q R 2 In the group shown, (C2H4O) p and (C3H6O) q (It can be random or blocky.)

[0074] From the viewpoint of obtaining a film with excellent release properties obtained by drying the hard surface treatment agent, the HLB value of the polyether-modified silicone compound is preferably within a specific range, specifically preferably 1 or higher, more preferably 5 or higher, even more preferably 10 or higher, preferably 18 or lower, and more preferably 16 or lower.

[0075] When using two or more polyether-modified silicones with different HLB values, the weighted average of these values ​​should fall within the above range. The HLB value is an index representing the balance between hydrophilicity and lipophilicity, and in this invention, it refers to the value obtained by the following Griffin formula. HLB value = 20 × sum of molecular weights of hydrophilic bases / molecular weight

[0076] The kinematic viscosity of the polyether-modified silicone compound at 25°C is preferably within a specific range from the viewpoint of obtaining a film with excellent release properties obtained by drying the hard surface treatment agent. Specifically, it is preferably 1 mm. 2 / s or more, more preferably 5mm 2 The value is 1 / s or more, preferably 1000 mm 2 / s or less, more preferably 500mm 2 / s or less, more preferably 200 mm 2 It is less than or equal to / s.

[0077] Polyether-modified silicone compounds are commercially available, including KF-615A, KF-640, KF-642, KF-643, KF-644, KF-351A, KF-354L, KF-355A, KF-6011, KF-6012, KF-6015, KF-6016, KF-6017, KF-6020, KF-6043, etc., manufactured by Shin-Etsu Chemical Co., Ltd. From the viewpoint of obtaining a film with excellent release properties obtained by drying a hard surface treatment agent, KF-640, KF-642, KF-643, KF-351A, KF-354L, KF-355A, etc., can be suitably used. Commercially available products with structures that do not correspond to the above general formula (for example, KF-6028 and KF-6038 manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as polyether-modified silicone compounds.

[0078] <Volatile organic compounds> The hard surface treatment agent in the present invention is an organic compound other than the oil agent, and may further contain an organic compound that is volatile at 25°C and 1 atm (such an organic compound is referred to as a "volatile organic compound" in this specification). It is preferable to incorporate such a component into the Pickering emulsion or hard surface treatment agent because it makes it easier to form a film on the substrate. In this specification, an organic compound that is volatile at 25°C and 1 atm means an organic compound whose vapor pressure at such conditions is 10 Pa or more.

[0079] Examples of such components include N-methylpyrrolidone, 2-propanol, 1-propanol, ethanol, methanol, t-butanol, 1-butanol, 2-butanol, toluene, xylene, methyl ethyl ketone, acetone, ethyl acetate, dimethylformamide, methyl isobutyl ketone, acetonitrile, dimethyl sulfoxide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, hexane, cyclohexane, cyclohexanone, 1,4-dioxane, chloroform, dichloromethane, diethyl ether, and mixtures thereof.

[0080] <Polymer compounds> The hard surface treatment agent in the present invention may further contain polymer compounds other than the above-mentioned polymer compounds having amino groups, for example, one or more selected from the group consisting of polymer compound (X) and polymer compound (Y) below. Incorporating such components into the emulsified composition is preferable because it can improve the durability of the film. Polymer compound (X): Methacrylic or acrylic polymer having an ester group or amide group in its side chain. Polymeric compound (Y): A polymeric compound having an ester group, amide group, urethane group, ether group, or carbonate group in its main chain.

[0081] The weight-average molecular weight of the polymer compound (X) is preferably 1,000 or more from the viewpoint of improving the durability of the film, and preferably 500,000 or less from the same viewpoint. Examples of polymer compounds (X) include polyalkyl(meth)acrylates such as polymethyl(meth)acrylate, polyethyl(meth)acrylate, and polybutyl(meth)acrylate; copolymers with acrylics such as styrene-acrylic and urethane-acrylic; and poly(meth)acrylamides such as poly(meth)acrylamide, polyN-methyl(meth)acrylamide, polyN,N-dimethyl(meth)acrylamide, and polyN-phenyl(meth)acrylamide.

[0082] 2. Method for manufacturing hard surface treatment agent The hard surface treatment agent of the present invention can be manufactured, for example, by mixing the aforementioned components (A), (B), (C), etc.

[0083] By mixing the components, emulsification occurs, yielding a Pickering emulsion. 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.

[0084] 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.

[0085] The preferred range of content of each component during mixing is the same as the preferred range of content of each component in the Pickering emulsion of the present invention described above.

[0086] Regarding the blending ratio of anionic solid particles to an organic compound having cationic functional groups, from the viewpoint of synovial properties and durability, the amount of the organic compound having cationic functional groups is preferably 0.1 equivalents or more, more preferably 0.3 equivalents or more, and even more preferably 0.5 equivalents or more relative to the anionic groups of the anionic solid particles. On the other hand, from the viewpoint of the stability of the Pickering emulsion, it is preferably 3 equivalents or less, more preferably 2 equivalents or less, and even more preferably 1.5 equivalents. The following applies:

[0087] Alternatively, the total number of moles of amino groups in amino-modified silicone and amino groups in hydrocarbon amines, relative to the number of moles of anionic groups in anionic solid particles, is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more, from the viewpoint of obtaining a film with improved synovial properties and durability, and preferably 3 or less, more preferably 2 or less, and even more preferably 1.5 or less, from the viewpoint of film formation. The number of moles of anionic groups in anionic-modified cellulose fibers can be obtained by multiplying the amount of anionic-modified cellulose fibers used (g) by the anionic group content (mmol / g), and the number of moles of amino groups in amino-modified silicone can be obtained by dividing the amount of amino-modified silicone used (g) by the amino equivalent (g / mol).

[0088] Furthermore, the mass ratio of the organic compound having a cationic functional group to the oil ([organic compound having a cationic functional group] / [oil]) is preferably 0.0001 or more, more preferably 0.001 or more, even more preferably 0.004 or more, even more preferably 0.01 or more, and even more preferably 0.04 or more, from the viewpoint of obtaining a film with improved lubricity and durability, and preferably 20 or less, more preferably 10 or less, even more preferably 5 or less, even more preferably 3 or less, and even more preferably 2 or less, from the viewpoint of film formation. From these viewpoints, it is preferably 0.0001 or more and 20 or less, more preferably 0.001 or more and 10 or less, even more preferably 0.004 or more and 5 or less, even more preferably 0.01 or more and 3 or even more preferably 0.04 or more and 2 or even more.

[0089] 3. Properties of hard surface treatment agents The hard surface treatment agent of the present invention is an emulsified composition containing the above-mentioned components as essential components. Emulsification in the present invention is performed by applying mechanical force to a mixture of water and a liquid organic compound at 25°C and 1 atm, resulting in a state in which droplets of the other liquid are finely dispersed in one liquid. The emulsion type is an oil-in-water emulsion.

[0090] The content of [total amount of solid particles and organic compounds that bind to them] in or during the mixing of the Pickering emulsion is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the viewpoint of emulsifying power, while from the viewpoint of 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.

[0091] The water content in the Pickering emulsion or during mixing is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of maintaining an emulsified state, and preferably 98% by mass or less, from the viewpoint of effective content.

[0092] From the viewpoint of maintaining an emulsified state, the oil content in the Pickering emulsion or during mixing is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. On the other hand, from the viewpoint of solution viscosity and handling properties, it is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0093] The mass ratio of the components [total of solid particles and organic compounds that bind to them] to the oil in the Pickering emulsion or during mixing ([total of solid particles and organic compounds that bind to them] / [oil]) is preferably 0.0001 or more, more preferably 0.001 or more, even more preferably 0.004 or more, even more preferably 0.01 or more, and even more preferably 0.04 or more from the viewpoint of obtaining a film with improved synovial properties, and preferably 20 or less, more preferably 10 or less, even more preferably 5 or less, even more preferably 3 or less, and even more preferably 2 or less from the viewpoint of film formation. From these viewpoints, it is preferably 0.0001 to 20 or less, more preferably 0.001 to 10 or less, even more preferably 0.004 to 5 or less, even more preferably 0.01 to 3 or even more preferably 0.04 to 2 or less.

[0094] When the hard surface treatment agent of the present invention contains a polyether-modified silicone compound, the content of the polyether-modified silicone compound is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, while preferably 2% by mass or less, more preferably 1% by mass or less.

[0095] When the hard surface treatment agent of the present invention contains the volatile organic compound, the content of such organic compound is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more, while preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0096] When the hard surface treatment agent of the present invention contains one or more selected from the group consisting of polymer compound (X) and polymer compound (Y), the content of one or more selected from the group consisting of polymer compound (X) and polymer compound (Y) is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, on the other hand preferably 10% by mass or less, more preferably The amount is 8% by mass or less, and more preferably 6% by mass or less.

[0097] The viscosity of the Pickering emulsion is not particularly limited, but from a handling standpoint, 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. Similarly, from the same standpoint, it is preferably 30 Pa·s or lower, more preferably 20 Pa·s or lower, and even more preferably 10 Pa·s or lower. Here, the 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.

[0098] The average particle size of the emulsion droplets in the Pickering emulsion, as measured by SEM observation as 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 improving synovial properties and 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.

[0099] 4. Application of hard surface treatment agents to hard surfaces The hard surface treatment agent of the present invention is applied to a hard surface and dried to form a film on the hard surface.

[0100] Specifically, the treatment agent is applied to a hard surface, such as a solid surface made of glass, resin, metal, ceramics, concrete, wood, stone, paper, etc. Methods of application include, but are not limited to, using an applicator, bar coater, spin coater, roller, brush application, hand application, air spray, airless spray, trigger spray, aerosol can spray, dip coating, etc.

[0101] From the viewpoint of film durability, the thickness of the Pickering emulsion coating film on a hard surface is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. From the viewpoint of coatability, it is preferably 2000 μm or less, and more preferably 1500 μm or less.

[0102] Next, the Pickering emulsion coating can be dried to obtain the film. The drying conditions can be either under reduced pressure or at 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.

[0103] The dried film formed by the above method preferably 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).

[0104] 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.

[0105] The film's durability is further improved by including the aforementioned polyether-modified silicone compound.

[0106] There are no particular restrictions on the film thickness. 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 a coating tool such as an applicator, or by adjusting the ratio of the medium. The film thickness can be measured according to the method described in the examples below.

[0107] The smoother the film, the better its synovial properties, which is preferable. Specifically, from the viewpoint of cost-effectiveness, the arithmetic mean roughness of the film surface 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 surface roughness of the film can be measured as the arithmetic mean roughness according to the method described in the examples below.

[0108] It is preferable for the film to have high durability. The durability of the film can be evaluated, for example, by the degree of increase in the arithmetic mean roughness of the film after contact with water for a certain period of time, or by the presence or absence of synovial properties. Specifically, if the substrate on which these films are deposited is held horizontally, and water is continuously dripped onto the substrate from a height of 40 cm at a flow rate of 50 mL / second for 5 minutes, and the arithmetic mean roughness of the film is less than twice the roughness before dripping, and the film retains synovial properties after 5 minutes of dripping, then the film can be evaluated as having high durability.

[0109] The amount of solid particles in the membrane is preferably 1% by mass or more, more preferably 10% by mass or more, from the viewpoint of membrane durability, and preferably 65% ​​by mass or less, more preferably 36% by mass or less, and even more preferably 16% by mass or less, from the viewpoint of the membrane's synovial properties. The amount of hydrophobic modified cellulose fibers in the membrane is calculated considering the amount of volatile components in the Pickering emulsion.

[0110] The film 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.

[0111] By applying the hard surface treatment agent of the present invention to a hard surface, the hard surface can be modified into a synovial surface. The formed film not only has excellent synovial properties but also excellent durability, allowing its effect to be maintained for a long period of time. Therefore, it is useful for various applications, such as snow-proof paints, antifouling paints, antibacterial paints, flow resistance reducing agents, and mold release agents. Applicable surfaces include ships (hull bottoms, propellers, etc.), houses (e.g., roofs, walls, housing equipment, etc.), vehicles, building materials, piping, equipment, tools, panels, containers, etc. By applying the pickering emulsion of the present invention to the hard surfaces mentioned above, it can be used as a snow-proofing method, antifouling method, antibacterial method, flow resistance reducing method, and mold release method. [Examples]

[0112] 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.

[0113] [Average fiber diameter, average fiber length, and average aspect ratio of anionically modified cellulose fibers and hydrophobically modified cellulose fibers] Water is added to the cellulose fibers to be measured to prepare a dispersion with a 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 image is analyzed using the AFM. The height at which the fiber is extended can be considered as the fiber diameter.

[0114] [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.

[0115] [Anionic group content of anionic-modified cellulose fibers and hydrophobic-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)]

[0116] [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.

[0117] Aldehyde group content (mmol / g) = (Carboxyle group content of oxidized cellulose fiber) - (Carboxyle group content of oxidized cellulose fiber to be measured) ... Equation 1

[0118] [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.

[0119] [Confirmation of the crystal structure in hydrophobic modified cellulose fibers] The crystal structure of hydrophobic 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.

[0120] <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°).

[0121] 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.

[0122] <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 The peak area of ​​the amorphous region (diffraction angle 2θ = 18.5°) is shown, and each peak area is obtained by fitting the obtained X-ray diffraction chart with a Gaussian function.

[0123] [Cellulose fiber (equivalent amount) in hydrophobic modified cellulose fibers] The cellulose fiber (equivalent amount) in hydrophobic modified cellulose fibers is measured by the following method. (1) When only one type of "modifying compound" is added The amount of cellulose fiber (converted amount) is calculated using the following formula C. <Formula C> Cellulose fiber content (converted amount) (g) = Mass of hydrophobic modified cellulose fiber (g) / [1 + Molecular weight of modifying compound (g / mol) × Amount of modifying group bonded (mmol / g) × 0.001] (2) When there are two or more types of "modifying compounds" added The amount of cellulose fiber (converted amount) is calculated by considering the molar ratio of each compound (i.e., the molar ratio when the total molar amount of the added compounds is set to 1).

[0124] [Measurement of viscosity of Pickering emulsion] Using a Type B viscometer (Toki Sangyo TVB-10) with rotor No. 1, the viscosity was measured at 25°C, a rotation speed of 60 RPM, and after 1 minute.

[0125] [Observation of Pickering emulsion using Cryo-SEM] Observation of Pickering emulsions using Cryo-SEM is performed using a Scios DualBeam field emission scanning electron microscope manufactured by FEI. Observation is carried out while gradually sublimating the water from a frozen Pickering emulsion. Observation is performed at an acceleration voltage of 2kV and a magnification of 25,000x.

[0126] [Measuring the particle size of emulsified droplets using laser diffraction] The particle size of emulsion droplets is measured using the LA-960 laser diffraction method manufactured by Horiba, Ltd. Measurement conditions: Water is added to the measurement cell, and the volume particle size distribution and the median volume particle size (D) are measured at a concentration that allows the absorbance to fall within the appropriate range. 50 The following conditions are met: relative refractive index 1.20, temperature 25°C, circulation pump ON, circulation speed 5, and stirring speed 5.

[0127] [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.

[0128] 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 was obtained.

[0129] The suspension of the obtained anionically modified cellulose fibers was adjusted to pH=2 by adding 0.01 M hydrochloric acid. The filtrate was then thoroughly washed with deionized water until its conductivity, measured using a compact electrical conductivity meter (Horiba, Ltd., LAQUAtwin EC-33B), was 200 μs / cm or less. The fibers were then dehydrated to obtain anionically modified cellulose fibers. The carboxyl group content of these anionically modified cellulose fibers was 1.50 mmol / g, and the aldehyde group content was 0.23 mmol / g.

[0130] Preparation Example 2 (Production of finely textured anion-modified cellulose fibers) In Preparation Example 1, 100 g of a suspension (solid content 2.0% by mass) was prepared by adding deionized water to the anionically modified cellulose fibers finally obtained. A 0.5 M sodium hydroxide aqueous solution was added to adjust the pH to 8, and then deionized water was added to bring the total volume to 200 g. This suspension was subjected to three micronization treatments at 150 MPa using a high-pressure homogenizer (Yoshida Machinery Co., Ltd., NanoVeta L-ES) to obtain a dispersion of micronized anionically modified cellulose fibers (solid content 1.0% by mass). The counterions of the carboxyl groups in these micronized anionically modified cellulose fibers were sodium ions. These micronized anionically modified cellulose fibers are abbreviated as "TCNF (Na type)".

[0131] Preparation Example 3 (Production of finely textured anionic modified cellulose fibers with reduced aldehyde groups) 182 g of the finely pulverized anionic modified cellulose fiber dispersion (solid content 1.0% by mass) obtained in Preparation Example 2 was weighed out, and deionized water was 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 were added, and the mixture was stirred at 25°C for 4 hours. Next, 9 mL of 1 M hydrochloric acid was added to carry out protonation. After the reaction was complete, the mixture was filtered, and the resulting cake was washed six times with deionized water to remove the salt and hydrochloric acid, obtaining a finely pulverized anionic modified cellulose fiber dispersion (solid content 0.9% by mass) in which the aldehyde groups had been reduced. The carboxyl group content of the obtained cellulose fibers was 1.50 mmol / g, and the aldehyde group content was 0.02 mmol / g. The carboxyl groups in these finely pulverized anionic modified cellulose fibers are in the free acid form (COOH), and are abbreviated as "TCNF (H type)". The crystallinity of these finely textured anion-modified cellulose fibers was 30%, the average fiber diameter was 3.3 nm, and the average fiber length was 600 nm.

[0132] Preparation Example 4 (Synthesis of silica nanoparticles with an average particle size of 400 nm) 500 g of ethanol, 45 g of deionized water, 20 g of aqueous ammonia, and 30 g of tetraethoxysilane were mixed in a flask and stirred at room temperature for 12 hours. After that, silica fine particles were separated from the solution by centrifugation (10,000 g, 10 minutes), and the separated particles were resuspended in water and freeze-dried to obtain a powder. Five g of this powder was suspended in ion-exchanged water to a concentration of 10% by mass, and dispersed for five minutes using an ultrasonic homogenizer (US-300E, probe diameter 12 mm, manufactured by Nippon Seiki Seisakusho Co., Ltd.) to obtain silica nanoparticles dispersed in water. The number-average particle size, measured by observation with a scanning electron microscope (JEOL Ltd., JSM-IT500HR, acceleration voltage 10 kV, magnification 50,000x), was 400 nm.

[0133] [Preparation of Pickering emulsion] Example 1 20 g of the finely milled anion-modified cellulose fiber dispersion (solid content 0.9% by mass) obtained in Preparation Example 3, 1.8 g of 10 cs of silicone oil, and 0.6 g of amino-modified silicone were weighed into a beaker, and deionized water was added to make a total of 30 g. This solution was dispersed for 5 minutes using an ultrasonic homogenizer (Nippon Seiki Seisakusho, US-300E, probe diameter 12 mm) to obtain a Pickering emulsion stabilized by finely milled anion-modified cellulose fibers. This Pickering emulsion was used as a hard surface treatment agent.

[0134] Examples 2-6 A Pickering emulsion stabilized by fine particles was obtained in the same manner as in Example 1, except that the proportions of each component were as shown in Table 1. This Pickering emulsion was used as a hard surface treatment agent.

[0135] Comparative Example 1 1.8 g of 10 cs silicone oil and 0.6 g of amino-modified silicone were weighed into a beaker, and deionized water was added to make a total of 30 g. This solution was dispersed for 5 minutes using an ultrasonic homogenizer (US-300E, 12 mm probe diameter, manufactured by Nippon Seiki Seisakusho), but it immediately separated into two layers, and an emulsion could not be obtained.

[0136] Comparative Example 2 1.8 g of 10 cs silicone oil, 0.6 g of amino-modified silicone, and 60 mg of Emulgen 109P were weighed into a beaker, and deionized water was added to make a total of 30 g. This solution was dispersed for 5 minutes using an ultrasonic homogenizer (Nippon Seiki Seisakusho, US-300E, probe diameter 12 mm) to obtain an emulsion that was stably emulsified by the surfactant.

[0137] [Emulsion Stability] The Pickering emulsions prepared in Examples 1-6 and the emulsion prepared in Comparative Example 2 were measured into vials of 5 mL each and left to stand at room temperature. No separation was observed for more than one week, and the emulsions remained stable.

[0138] [Preparation of a dry film] 400 μL each of the Pickering emulsions prepared in Examples 1-6 and the emulsion prepared in Comparative Example 2 were coated onto separate glass substrates (MATSUNAMI Micro Slide Glass S2112) and spread over the entire surface of the slide glass. Then, the films were 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 measurement method described below.

[0139] [Measurement of film thickness] The thickness of the film after drying was measured using a laser microscope (Keyence Corporation, VK-9710) as follows: Measurements were taken under fixed conditions. The measurement conditions were: 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, and the sample was measured. The height of the glass substrate and the height of the portion with the film were measured using built-in image processing software, and the film thickness was determined by taking the difference between these two values.

[0140] [Slip angle measurement test] The dried films of Examples 1-6 and Comparative Example 2, prepared as described above, were placed horizontally. Using a fully automatic contact angle meter (FAMAS, 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.

[0141] Table 1 below summarizes the composition (mass%) and evaluation results of each composition.

[0142] [Table 1]

[0143] The following was learned from the above experiment. Within the scope of the present invention, a film obtained by applying and drying a Pickering emulsion on a substrate has been found to have excellent lubricity, allowing even minute water droplets to slide off with only a slight incline. In contrast, when no surfactant or solid particles were added (Comparative Example 1), a stable Pickering emulsion could not be produced. Furthermore, the film created by applying the emulsion prepared with a surfactant (Comparative Example 2) to a substrate did not exhibit synovial properties.

[0144] Preparation Example 5 In a beaker, 66.7 g (solid content 0.9% by mass) of the finely milled anion-modified cellulose fiber dispersion obtained in Preparation Example 3, 12 g of 100 cs of silicone oil, and 1.91 g of amino-modified silicone were weighed out, and 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 a Pickering emulsion stabilized by the finely milled anion-modified cellulose fibers. 0.2 g of polyether-modified silicone was added to this, and the mixture was stirred at 25°C for 30 minutes to obtain a Pickering emulsion. The average emulsion particle size measured by laser diffraction was 300 nm, and the viscosity was 10 mPa·s. The final obtained Pickering emulsion was used as a hard surface treatment agent.

[0145] Preparation Example 6 In a beaker, 66.7 g (solid content 0.9% by mass) of the finely milled anionic modified cellulose fiber dispersion obtained in Preparation Example 3, 6 g of 10 cs of silicone oil, and 1.91 g of amino-modified silicone were mixed, and 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 a Pickering emulsion stabilized by the finely milled anionic modified cellulose fibers. 0.2 g of polyether-modified silicone was added to this, and the mixture was stirred at 25°C for 30 minutes to obtain a Pickering emulsion. The final obtained Pickering emulsion was used as a hard surface treatment agent.

[0146] Preparation Example 7 In a beaker, 66.7 g of the finely milled anionic modified cellulose fiber dispersion obtained in Preparation Example 3 (solid content 0.9% by mass), 6 g of 100 cs of silicone oil, and 2.68 g of amino-modified silicone were mixed, and 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 a Pickering emulsion stabilized by the finely milled anionic modified cellulose fibers. The final obtained Pickering emulsion was used as a hard surface treatment agent.

[0147] Preparation Example 8 In a beaker, 66.7 g (solid content 0.9 mass%) of the finely pulverized anionic modified cellulose fiber dispersion obtained in Preparation Example 3, 12 g of 10 cs of silicone oil, and 1.91 g of amino-modified silicone were mixed, and 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 a Pickering emulsion stabilized by the finely pulverized anionic modified cellulose fibers. 0.2 g of polyether-modified silicone was added to this, and the mixture was stirred at 25°C for 30 minutes to obtain a Pickering emulsion. The final obtained Pickering emulsion was used as a hard surface treatment agent.

[0148] Preparation Example 9 In a beaker, 66.7 g of the finely milled anionic modified cellulose fiber dispersion obtained in Preparation Example 3 (solid content 0.9% by mass), 6 g of 100 cs of silicone oil, and 2.68 g of amino-modified silicone were mixed, and 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 a Pickering emulsion stabilized by finely milled anionic modified cellulose fibers. To this, 0.2 g of polyether-modified silicone, 13.5 g of styrene acrylic (solid content 44.5% by mass), and 10 g of N-methylpyrrolidone were added, and the mixture was stirred at 25°C for 30 minutes to obtain a Pickering emulsion. The final obtained Pickering emulsion was used as a hard surface treatment agent.

[0149] Table 2 below summarizes the composition (mass%) of each emulsion.

[0150] [Table 2]

[0151] [Main ingredients used] Details of the representative components used in the examples are summarized below. [Solid particles] Micronized anion-modified cellulose fibers (prepared in Preparation Example 3) Graphene oxide (10 mg / mL aqueous dispersion): Manufactured by Tokyo Chemical Industry Co., Ltd. Nanodiamond (particle size: <10nm) (carboxylic acid group modified): Manufactured by Tokyo Chemical Industry Co., Ltd. Silica microparticles 1, Aerosil 300: Manufactured by Nippon Aerosil Co., Ltd. Silica nanoparticles 2 (average particle size 400 nm): synthesized according to Preparation Example 4. [Reagents used in Preparation Example 4] Ethanol (99.5%): Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Tetraethoxysilane: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. 28% Ammonia Solution: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [Oils] Silicone oil 10cs: Manufactured by Shin-Etsu Chemical Co., Ltd., KF-96-10cs Silicone oil 100cs: Manufactured by Shin-Etsu Chemical Co., Ltd., KF-96-100cs Liquid paraffin: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [Organic compounds with bonding properties] Amino-modified silicone: Dow-Toray SS-3551 Oleylamine: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [Surfactants] Emulgen 109P (Polyoxyethylene Lauryl Ether): Manufactured by Kao Corporation [Polyether-modified silicone] Polyether-modified silicone 1: KF-640 manufactured by Shin-Etsu Chemical Co., Ltd. Polyether-modified silicone 2: KF-642 manufactured by Shin-Etsu Chemical Co., Ltd. [Polymer compound] Styrene-acrylic: DSM Corporation, NeoCryl XK-188 (44.5% solids by mass) [Volatile organic compounds] N-methylpyrrolidone: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0152] [Snow accumulation test] <Preparation of dried film> Example 7 2.4 mL of the hard surface treatment agent prepared in Preparation Example 5 was applied to a glass substrate (10 cm × 10 cm × 5 mm thick), and dried at 1 atm, 25°C, and approximately 40% RH humidity for 24 hours to form a film, which was used as the substrate for Example 7. The water droplet sliding angle of this film was 7°.

[0153] Comparative Example 3 Comparative Example 3 used a glass substrate (10cm x 10cm x 5mm thick) that had not been treated with a hard surface treatment agent.

[0154] Comparative Example 4 In Comparative Example 4, a commercially available snow-preventing paint, "Rakuyuki Paint" manufactured by Kansai Paint, was applied with a brush to the same glass substrate used in Comparative Example 3, and dried for 24 hours at 1 atmosphere, 25°C, and approximately 40% RH humidity. The paint thickness after drying was 20 μm.

[0155] <Skiing performance evaluation> The skidability was evaluated in the low-temperature test chamber (1°C) of MTS Snow and Ice Research Institute. A 1cm x 2cm x 2mm thick stainless steel piece was attached to the back of each substrate in Example 7 and Comparative Examples 3-4 using double-sided tape (Scotch Super Multipurpose Double-Sided Tape, 12mm wide, manufactured by 3M). The substrates were then placed on a magnetic mounting stand at a 90° angle. Artificial snow was then blown onto the front of the substrates at a wind speed of 5m / s for 30 minutes to evaluate their snow-sliding properties. On the substrate in Example 7, the snow slid off within 10 minutes of the start of the artificial snow blowing, whereas on the substrates in Comparative Examples 3 and 4, the snow did not slide off within 30 minutes. In other words, it was found that the substrate in Example 7, coated with the hard surface treatment agent, had excellent snow-sliding properties.

[0156] [Flow Resistance Test] <Preparation of dried film> Example 8 The hard surface treatment agent prepared in Preparation Example 5 was applied to a SUS304 substrate (L200mm × W50mm × T3mm), and dried at 1 atmosphere, 25°C, and approximately 40% RH humidity for 24 hours to form a film, which was used as the substrate for Example 8. The thickness of the dried film was 20 μm.

[0157] Example 9 An acrylic resin-based coating (SEAFLO NEO CF Z, manufactured by Chugoku Marine Paints Co., Ltd.) was spread onto a SUS304 substrate (L200mm × W50mm × T3mm) using a brush and dried for 24 hours at 1 atmosphere, 25°C, and approximately 40% RH humidity. The coating thickness after drying was 20 μm. Next, the hard surface treatment agent prepared in Preparation Example 9 was applied on top of it and dried in the same manner to form a film, which served as the substrate for Example 9. The thickness of the dried film was 20 μm.

[0158] Example 10 Except for using an epoxy resin-based paint (Banno 500, manufactured by Chugoku Marine Paints Co., Ltd.) instead of an acrylic resin-based paint, a substrate was prepared in the same manner as in Example 9 by coating the epoxy resin-based paint with the hard surface treatment agent prepared in Preparation Example 9, and this was used as the substrate for Example 10. The thickness of the dried film was 20 μm.

[0159] Comparative Example 5 Comparative Example 5 used a SUS304 substrate (L200mm × W50mm × T3mm) that had not been coated with paint or treatment agents.

[0160] Comparative Example 6 Comparative Example 6 used a SUS304 substrate (L200mm x W50mm x T3mm) that had not been coated with any paint or treatment agent, to which an acrylic resin-based paint (SEAFLO NEO CF Z, manufactured by Chugoku Marine Paints Co., Ltd.) was applied and dried.

[0161] Comparative Example 7 As Comparative Example 7, a SUS304 substrate (L200mm × W50mm × T3mm) that had not been coated with paint or treatment agents was coated with epoxy resin paint (Banno 500, manufactured by Chugoku Marine Paints Co., Ltd.) and dried.

[0162] Comparative Example 8 Comparative Example 8 used a PVC (polyvinyl chloride) substrate (L200mm × W50mm × T3mm) that had not been coated with paint or treatment agents.

[0163] <Measuring fluid resistance> As shown in Figure 1, pressure loss was measured when tap water (viscosity at 30°C: 0.8 mPa·s) was flowed through a slit flow channel device made of SUS304. A 4 mm thick PTFE (polytetrafluoroethylene) spacer was sandwiched between substrates (Examples 8-10, Comparative Examples 5-8), and under conditions of a pressure port distance of 230 mm, a slit width of 30 mm, a slit height of 4 mm, and a flow rate of 13.3 L / min, transparent tubes were connected to the inlet and outlet pressure ports. At a room temperature of 20°C and a water temperature of 32°C, a water tap was connected to the liquid supply port with a hose, and the pressure loss was compared after water was flowed for 30 minutes. The difference in water level in the silicone tubes connected to the inlet and outlet was measured to determine the hydrostatic pressure and evaluate the pressure loss. The results are shown in Table 3.

[0164] [Measurement of film surface roughness] The surface roughness (Rz) of the film 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. Rz was measured at 5 points using the built-in image processing software, and the average value was used.

[0165] [Table 3]

[0166] Table 3 shows that the substrates of Examples 8-10 had lower pressure loss values ​​than the substrates of Comparative Examples 5-8. This indicates that the substrates coated with the hard surface treatment agent in Examples 8-10 have the effect of reducing flow resistance. Furthermore, since Example 8 was coated on the substrate of Comparative Example 5, Example 9 on the substrate of Comparative Example 6, and Example 10 on the substrate of Comparative Example 7, it was found that the present invention can provide the effect of reducing the flow resistance of various types of substrates. Moreover, although the surface roughness of Example 9 and Comparative Example 8 were similarly low, it was found that Example 9 could achieve an even lower pressure loss.

[0167] [Durability test of flow resistance] Seawater from near Shimotsu Port in Wakayama Prefecture was pumped into a circulating water tank, and half of the seawater was replaced every two weeks in an environment exposed to sunlight. The substrates of Example 9 and Comparative Example 6 were immersed in this system for seven months, and the degree of contamination and the pressure loss reduction rate were evaluated at the third and seventh months. The evaluation criteria for the degree of contamination are as follows, and the pressure loss reduction rate was based on the initial state of Comparative Example 6. The results are shown in Table 4. A lower score indicates better contamination, and a higher pressure loss reduction rate indicates a greater effect in reducing pressure loss, i.e., a greater effect in lowering flow resistance.

[0168] <Contamination Assessment> 1: The amount of attached material is less than 10% of the total surface area. 2: The deposits cover more than 10% but less than 30% of the entire surface. 3: The deposits cover 30% to less than 50% of the entire surface. 4: The surface area has deposits covering 50% to less than 70% of the total surface area. 5: The surface area has deposits covering 70% to less than 90% of the total surface area. 6: More than 90% of the surface is covered with deposits.

[0169] [Table 4]

[0170] Table 4 revealed the following: Compared to Comparative Example 6, Example 9 showed a higher effect in suppressing fouling when immersed in circulating seawater, and also showed a greater reduction in pressure loss at 3 and 7 months of immersion. Furthermore, while Comparative Example 6's pressure loss worsened by 44% over 7 months, Example 9's deterioration was limited to 6.2% from the beginning, indicating that the substrate coated with the hard surface treatment agent in Example 9 had high durability in terms of the persistence of its pressure loss reduction effect, i.e., the durability of its flow resistance reduction effect.

[0171] [Aquatic organism attachment test] Example 11 1.5 mL of the hard surface treatment agent prepared in Preparation Example 6 was applied to a SUS304 substrate (L50 mm × W50 mm × T3 mm), and dried at 1 atm, 25°C, and approximately 40% RH humidity for 24 hours to form a film, which was used as the substrate for Example 11. The water droplet sliding angle of this film was 6°.

[0172] Comparative Example 9 For comparison, an untreated SUS304 substrate measuring L50mm x W50mm x T3mm was used as Comparative Example 9.

[0173] 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. A 3-month immersion test was then conducted in seawater.

[0174] Three months after immersion, the degree of attachment of crustaceans and algae to the substrates was visually evaluated. In the substrate of Example 11, no crustaceans were observed, and the area of ​​algal attachment was less than 30% of the substrate. The attached aquatic organisms could be easily removed by washing with water. On the other hand, in the substrate of Comparative Example 9, crustaceans were attached to more than 30% of the substrate area, and algae were attached to more than 80%. These organisms could not be removed without repeated scrubbing with a tool. In other words, it was found that the substrate coated with the hard surface treatment agent of Example 11 had excellent effects in suppressing the attachment of aquatic organisms and removing attached aquatic organisms.

[0175] [Antibacterial test] <Preparation of dried film> Example 12 0.4 mL of the hard surface treatment agent prepared in Preparation Example 7 was applied to a glass substrate (MATSUNAMI: Micro Slide Glass S2112), and dried at 1 atm, 25°C, and approximately 40% RH humidity for 24 hours to form a film, which was used as the substrate for Example 12. The water droplet sliding angle of this film was 5°.

[0176] Comparative Example 10 Comparative Example 10 is a glass substrate without a treatment agent applied (MATSUNAMI: Micro Sli de Glass S2112 was used.

[0177] <Preparation of bacterial suspension> A glycerol stock solution of Staphylococcus aureus (NBRC13276) was pre-cultured at 37°C for 24 hours using Luria-Bertani Agar (LB Agar Medium "Daigo," manufactured by Nippon Pharmaceutical Co., Ltd.). 10 mL of Luria-Bertani (manufactured by Nippon Pharmaceutical Co., Ltd., LB medium "Daigo") was placed in a 50 mL centrifuge tube, and one loopful of colonies prepared in the pre-culture was inoculated into it. The culture was then incubated with shaking at 37°C / 200 rpm / 24 hours. After culturing, the absorbance at a wavelength of 600 nm (OD600nm) was measured using a spectrophotometer (Funakoshi Co., Ltd., WPA biowave CO8000). The bacterial suspension, diluted to an absorbance of 0.4, was then diluted 100-fold in LB medium to prepare the bacterial suspension for evaluation.

[0178] <Evaluation of Biofilm Formation Inhibition Effect: Colony Counting Method> The substrates of Example 12 and Comparative Example 10 were sterilized by irradiating them with UV light for 10 minutes. The sterilized substrates were placed in a rectangular 4-well dish (AS ONE, Multi-dish for suspension cells 267061), 6 mL of the previously prepared bacterial solution was added to each well, and the mixture was incubated at 37°C for 24 hours to form a biofilm on the substrate. Using a pipette gun, the bacterial suspension from the well was aspirated, and 6 mL of physiological saline was added to the well and shaken. Next, physiological saline was aspirated with a pipette gun and 6 mL of physiological saline was added to the well and shaken. Next, physiological saline was aspirated with a pipette gun and the substrate (15 cm) 2 The surface of the sample was wiped with a swab test kit (Elmex, ST-25), and the bacteria were extracted into 10 mL of phosphate-buffered saline. The sample was then diluted 10-fold with a diluent (Nippon Pharmaceutical Co., Ltd., LP Diluent "Daigo"). These were then prepared using serial dilution to create bacterial suspensions. 100 μL of each suspension was spread onto LB agar medium using plating beads (Fujifilm Wako Pure Chemical Industries, Ltd., Bac 'n' Roll Beads) and incubated at 30°C for 48 hours. By counting the colonies that grew on the agar medium after culturing and determining the number of bacteria attached to the test plate, it was found that the substrate of Example 12 suppressed bacterial adhesion by 98% compared to the glass substrate of Comparative Example 10. In other words, the substrate coated with the hard surface treatment agent of Example 12 was found to have excellent antibacterial properties.

[0179] [Release Test] <Preparation of dried film> Example 13 The hard surface treatment agent prepared in Preparation Example 8 was uniformly applied at a rate of 3 g to a stainless steel deep-type bat (manufactured by Sanbo Co., Ltd., external dimensions: 135 × 106 × H59 mm, volume 650 mL) using an air spray (Anest Iwata, WIDER1-10E1G, nozzle diameter Φ1.0 mm). The bat was dried at 1 atm, 25°C, and approximately 40% RH humidity for 1 hour to form a film, which was used as the bat for Example 13. The film thickness was 7 μm, and the water droplet sliding angle of this film was 10°.

[0180] Comparative Example 11 Comparative Example 11 used a stainless steel deep tray (manufactured by Sanbo Co., Ltd., external dimensions: 135 x 106 x H59 mm, volume 650 mL) that had not been treated with the treatment agent.

[0181] Comparative Example 12 As Comparative Example 12, 3g of a commercially available silicone-based mold release agent (Shin-Etsu Chemical Co., Ltd., KM-9782, effective content 10%) was uniformly applied to a stainless steel deep-type mixed tray (Sanbo Co., Ltd., external dimensions: 135 x 106 x H59 mm, volume 650 mL) that had not been treated with the release agent, using an air sprayer (Anest Iwata, WIDER1-10E1G, nozzle diameter Φ1.0 mm). A film was then prepared by drying at 1 atmosphere, 25°C, and approximately 40% RH humidity for 1 hour.

[0182] <Resin mold release properties evaluation> Amorphous polyester resin (Toyobo Co., Ltd., Byron 600™) in a stainless steel container was softened on a hot plate heated to 300°C. 500g of this resin was poured into a stainless steel deep tray treated with the coating agents of Example 13 and Comparative Example 12, or into an untreated stainless steel deep tray (Comparative Example 11). After cooling and curing at room temperature for 12 hours, the release properties of the resin were evaluated according to the following criteria. In Example 13, the resin fell off the bat simply by turning it over, and the same release properties were maintained even after repeating the same experiment 10 times. On the other hand, in Comparative Example 12, it was necessary to strike the bottom of the bat with a hammer to release the resin. In Comparative Example 11, the resin did not release even after being struck with a hammer 5 times. In other words, it was found that the bat coated with the hard surface treatment agent in Example 13 had excellent release properties.

[0183] In summary, the coating obtained by applying and drying the hard surface treatment agent of the present invention to a substrate has excellent antifouling properties due to its lubricating properties, and is also excellent in inhibiting the adhesion of aquatic organisms in the sea, inhibiting the adhesion of snow (snowproof effect), antibacterial properties, and resin release properties. [Industrial applicability]

[0184] The hard surface treatment agent of the present invention has snow-preventive, antifouling, antibacterial, flow resistance reduction, or mold release improvement effects, and can therefore be used as a snow-preventive paint, antifouling paint, antibacterial paint, flow resistance reducing agent, or mold release agent, etc. [Explanation of symbols]

[0185] PG pressure gauge

Claims

1. A hard surface treatment agent containing an oil-in-water pickering emulsion.

2. The hard surface treatment agent according to claim 1, wherein the emulsion contains solid particles to which an organic compound having binding properties to solid particles is bound.

3. The hard surface treatment agent according to claim 2, wherein the solid particles are anionic solid particles and the binding organic compound is an organic compound having a cationic functional group.

4. The hard surface treatment agent according to claim 3, wherein the organic compound having a cationic functional group is an organic compound having an amino group.

5. The hard surface treatment agent according to claim 3 or 4, wherein the anionic solid particles are inorganic particles or crystalline organic particles.

6. The hard surface treatment agent according to any one of claims 2 to 5, wherein the solid particles are one or more selected from the group consisting of anionic modified cellulose fibers having a type I crystal structure, silica particles, and carbon-based compounds having anionic groups.

7. The hard surface treatment agent according to any one of claims 1 to 6, wherein the hard surface treatment agent is used as a snow-repellent paint, an antifouling paint, an antibacterial paint, a flow resistance reducing agent, or a mold release agent.

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