Emulsion composition for anti-icing and snow protection

Abstract

To provide a composition capable of forming a highly durable film capable of slipping ice and snow off, and expressing the effect for a long period of time regardless of change of an environmental temperature.SOLUTION: An emulsion composition for ice protection and snow protection includes following constituents (A)-(B). (A) is one or more modified cellulose(s) selected from the group consisting of the following constituent (a) and constituent (b), where (a) is an anion modified cellulose fiber having an I type crystal structure, and (b) is a hydrophobic modified cellulose fiber constituted by bonding modification group(s) to one or more group(s) selected from the group consisting of an anionic group and a hydroxyl group of an anion modified cellulose fiber having an I type crystal structure. (B) is water. (C) is an organic compound which is liquid at 25°C under 1 atmospheric pressure.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an anti-icing and anti-snow emulsified composition. More specifically, it relates to an anti-icing and anti-snow emulsified composition containing modified cellulose fibers having a specific structure.

Background Art

[0002] In heavy snow areas, traffic accidents occur due to snow accumulation on road signs and signals. Furthermore, the snow removal work on rooftops is extremely harsh, which not only places a great burden on residents but also causes painful accidents and problems such as snow falling on adjacent houses. In addition, there are also problems caused by snow accumulation in terms of the environment, such as a decrease in power generation efficiency due to snow accumulation on solar panels. For this reason, the development of paints with a snow prevention effect has been underway. For example, in Patent Document 1, it is described that a paint film formed by drying an organic solvent-based paint containing an oxidation-curable resin and a fluorine-based surfactant has an effect of making snow slippery for a long time.

[0003] On the other hand, a technique of making an object slippery by creating a surface that holds oil in a porous structure is known. For example, in Patent Document 2, it is disclosed that a surface with lubricating oil held on a rough surface (fine uneven structure) has a high ice adhesion suppression effect.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] Since the snow - proof paint described in Patent Document 1 has a hydrophilic surface, there is a concern that the snow on the paint surface does not melt partially to form a water film and thus does not exhibit sufficient effects, or that the water film freezes on the surface due to a decrease in air temperature, causing a performance decline.

[0006] In addition, the surface retaining lubricating oil in the uneven structure described in Patent Document 2 shows a certain anti - icing effect, but its durability is not sufficient, and there is a concern that the performance will decline if it is damaged or the lubricating oil is depleted.

[0007] Therefore, an object of the present invention is to provide a composition that can form a highly durable film capable of sliding off ice and snow regardless of changes in environmental temperature and expressing such effects over a long period.

Means for Solving the Problems

[0008] The present invention relates to the following [1] to [3]. 〔1〕An anti - icing and anti - snow emulsified composition containing the following components (A) to (C). (A) One or more modified cellulose fibers selected from the group consisting of the following components (a) and (b) (a) Anionic modified cellulose fibers having an I - type crystal structure (b) Hydrophobic modified cellulose fibers in which a modifying group is bonded to one or more groups selected from the group consisting of an anionic group and a hydroxy group of anionic modified cellulose fibers having an I - type crystal structure (B) Water (C) An organic compound that is liquid at 25°C and 1 atm 〔2〕A method for manufacturing an anti - icing and anti - snow film, including the step of applying and drying the anti - icing and anti - snow emulsified composition according to [1] above. 〔3〕A structure in which the anti - icing and anti - snow emulsified composition according to [1] above is dried to form a coating film.

Effects of the Invention

[0009] According to the present invention, it is possible to provide a composition that can form a film capable of effectively sliding off ice and snow adhered to various substrates. [Modes for carrying out the invention]

[0010] 1. Emulsified composition for anti-icing and snow protection The emulsified composition for ice and snow protection of the present invention contains the following components (A) to (C). In this specification, "for de-icing and snow protection" means at least one of the uses for de-icing and snow protection, preferably both.

[0011] <Ingredient (A)> Component (A) is one or more modified cellulose fibers selected from the group consisting of components (a) and (b) below. (a) Anionic modified cellulose fibers having a type I crystal structure (b) Hydrophobic modified cellulose fiber having a type I crystalline structure, wherein a modifying group is attached to one or more groups selected from the group consisting of anionic groups and hydroxyl groups.

[0012] In this specification, modified cellulose fiber refers to component (a) or component (b).

[0013] [Average fiber diameter of modified cellulose fibers] From the viewpoint of ease of handling, the average fiber diameter of the modified cellulose fibers is preferably 0.1 nm or more, more preferably 1.0 nm or more, and even more preferably 2.0 nm or more. From the viewpoint of strength when a film is formed, it is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. The average fiber diameter of the modified cellulose fibers is measured by the method described in the examples below.

[0014] [Anionic modified cellulose fiber (a)] 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.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] The average fiber diameter of the anion-modified cellulose fibers is preferably 0.1 nm or more, more preferably 1.0 nm or more, and even more preferably 2.0 nm or more, from the viewpoint of handling ease, and preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less, from the viewpoint of film strength. The average fiber diameter of the anion-modified cellulose fibers is measured by the method described in the examples below.

[0019] 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.

[0020] [Hydrophobic modified cellulose fiber (b)] The hydrophobic modified cellulose fiber of component (b) has a modifying group attached to a specific group of anionic modified cellulose fiber having a type I crystal structure. The attachment site for the modifying group is one or more groups selected from the group consisting of anionic groups and hydroxyl groups.

[0021] 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.

[0022] 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 in which a modifying compound having a cationic group is bonded via electrostatic interaction. When the bonded mode is covalent, it refers to a state in which 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 in which it is bonded via ester bonds, amide bonds, carbonate bonds, urethane bonds, etc.

[0023] For example, the compound for introducing a modifying group (referred to as "modifying compound" in this specification) is a polymer compound, such as 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.

[0024] One preferred embodiment of the hydrophobic modified cellulose fiber of component (b), that is, the hydrophobic modified cellulose fiber in which a polymer compound is bonded to a cellulose fiber, has a structure represented by the following general formula (T-Ce).

[0025] [ka]

[0026] (wherein X is -CH2OH, -CH2O-R 1 , -C(=O)OH, -C(=O)O-R 1 , -C(=O)-O-H3N + -R 1 and -C(=O)-NH-R 1 is one or more groups selected from the group consisting of, and R 1 is a modifying group, and each R is independently a hydrogen atom or a modifying group, and R 1 and R may be the same or different, and at least one of the plurality of R 1 and R is a modifying group. m is an integer of 20 or more and 3,000 or less.)

[0027] In the hydrophobic modified cellulose fiber formed by binding a polymer compound to an anion-modified cellulose fiber having an I-type crystal structure, the modifying group is a group derived from the polymer compound, and the structure of the modifying group (that is, R 1 and R in the above formula (T-Ce)) depends on the structure of the polymer compound used. The bonding mode of the modifying group to the cellulose fiber is preferably a covalent bond or an ionic bond. From the viewpoint of manufacturing simplicity, an ionic bond is preferred, and from the viewpoint of the stability of the formed film, a covalent bond is preferred.

[0028] Further, examples of the modifying compound include hydrocarbon-based compounds having a cationic group. The modifying group in the hydrophobic modified cellulose fiber formed by binding such a hydrocarbon-based compound via an ionic bond preferably has a cationic group, for example, a group derived from a hydrocarbon-based compound having a total carbon number of 16 or more and 40 or less. In this case, the bonding mode of the modifying group to the anionic group of the anion-modified cellulose fiber is an ionic bond, and the hydrophobic modified cellulose fiber is in a state where the cationic group of the modifying group is adsorbed to the anionic group on the surface of the anion-modified cellulose fiber via electrostatic interaction.

[0029] The inventors have discovered that by coating a substrate with an emulsion composition containing hydrophobic modified cellulose fibers, which are cellulose fibers bonded to a polymer compound or a specific hydrocarbon compound, and an organic compound that is liquid at 25°C and 1 atm, and then drying it, it is possible to produce a film that exhibits high ice-sliding and snow-sliding properties regardless of changes in ambient temperature, and has excellent durability. The mechanism by which this effect occurs is not clear, but it is presumed that in the emulsion composition, the hydrophobic modified cellulose fibers form particulate structures containing the organic compound that is liquid at 25°C and 1 atm, and that these particulate structures layer and form a film as it dries. The film thus formed is thought to be highly durable because, due to the mobility of the lubricating oil held in the particulate structure, ice and snow can slide off even if they do not melt, and the particulate structure firmly holds the lubricating oil.

[0030] The amount (mmol / g) and introduction rate (mol%) of modifying groups in hydrophobic modified cellulose fibers refer to the amount and proportion of modifying groups introduced into the hydrophobic modified cellulose fibers. The amount and introduction rate of modifying groups can be adjusted by the amount and type of modifying compound added, the reaction temperature, the reaction time, the solvent, etc.

[0031] From the viewpoint of obtaining a film with improved ice and snow resistance, the amount of modifying groups attached to the hydrophobic modified cellulose fibers is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, and even more preferably 0.5 mmol / g or more. Furthermore, from the viewpoint of reactivity, it is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less, and even more preferably 2 mmol / g or less.

[0032] Furthermore, from the viewpoint of obtaining a film with improved ice and snow resistance, the rate of introduction of modifying groups in hydrophobic modified cellulose fibers is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 40 mol% or more, and even more preferably 50 mol% or more. From the viewpoint of reactivity, it is preferably 99 mol% or less, more preferably 97 mol% or less, even more preferably 95 mol% or less, and even more preferably 90 mol% or less.

[0033] [Method for producing modified cellulose fibers] Among the modified cellulose fibers of component (A), the "anionic modified cellulose fiber having a type I crystal structure" of component (a) can be produced, for example, by a method that includes the step of introducing anionic groups into raw cellulose fibers to obtain anionic modified cellulose fibers.

[0034] Furthermore, component (b), "hydrophobic modified cellulose fiber having a type I crystalline structure, wherein a modifying group is bonded to one or more groups selected from the group consisting of anionic groups and hydroxyl groups," can be described by, for example, a method that includes (2) a step of bonding a modifying compound to an anionic modified cellulose fiber obtained by a method including the step of (1) above to obtain hydrophobic modified cellulose fiber.

[0035] One embodiment of the process described in (2) above is: Ingredients (A-1) Anionic modified cellulose fiber, Component (A-2): One or more compounds selected from the group consisting of amino-modified silicones and hydrocarbon compounds having cationic groups. Ingredient (B) Water, and Components (C): Organic compounds that are liquid at 25°C and 1 atm. One example is the step of mixing the components. This embodiment is the same as the step in the method for producing the emulsified composition of the present invention described later, namely the step of mixing components (A-1), (A-2), (B), and (C). According to this embodiment, hydrophobic modified cellulose fibers and the emulsified composition of the present invention can be produced in the same process, and therefore it can be said to be a more preferable production method.

[0036] (1) Process for obtaining anionic modified cellulose fibers The anionically modified cellulose fibers used in the present invention can be obtained by subjecting raw material cellulose fibers to an oxidation treatment or an anionic group addition treatment to introduce at least one anionic group and thereby anionically modify them.

[0037] The cellulose fibers to be anionically modified, i.e., the cellulose fibers used as raw materials for hydrophobically modified cellulose fibers and anionically modified cellulose fibers, are preferably natural cellulose fibers from an environmental standpoint. Examples include wood pulp such as coniferous pulp and hardwood pulp; cotton pulp such as cotton linters and cotton lint; non-wood pulp such as straw pulp and bagasse pulp; and bacterial cellulose. One of these can be used alone or in combination of two or more.

[0038] The average fiber diameter of the cellulose fibers used as raw materials is not particularly limited, but from the viewpoint of handling ease and cost, it is preferably 1 μm or more, and preferably 300 μm or less.

[0039] Furthermore, while the average fiber length of the raw cellulose fibers is not particularly limited, from the viewpoint of availability and cost, it is preferably 100 μm or more, and preferably 5,000 μm or less. The average fiber diameter and average fiber length of the raw cellulose fibers can be measured according to the method described in the examples below. From the viewpoint of dispersibility, it is preferable to use cellulose fibers in which the average fiber length is 1 μm or more and 1,000 μm or less, obtained by shortening the raw cellulose fibers through alkaline hydrolysis treatment, acid hydrolysis treatment, etc.

[0040] Examples of anionic groups that can be introduced include carboxyl groups, sulfonic acid groups, or phosphate groups.

[0041] (i) When introducing a carboxyl group as an anionic group into cellulose fibers Methods for introducing carboxyl groups into cellulose fibers include, for example, oxidizing the hydroxyl groups of cellulose to convert them into carboxyl groups, or reacting the hydroxyl groups of cellulose with at least one compound selected from the group consisting of compounds having carboxyl groups, acid anhydrides of compounds having carboxyl groups, and derivatives thereof.

[0042] 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.

[0043] 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 that is to be oxidized 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. Therefore, one preferred embodiment of the hydrophobically modified cellulose fiber in the present invention is a hydrophobicly modified cellulose fiber obtained by bonding an amino-modified silicone to a carboxyl group-containing cellulose fiber.

[0044] By further oxidation or reduction treatment of oxidized cellulose fibers, oxidized cellulose fibers from which the remaining aldehyde groups have been removed can be prepared.

[0045] (ii) When introducing a sulfonic acid group or a phosphate group as an anionic group into cellulose fibers Methods for introducing sulfonic acid groups as anionic groups into cellulose fibers include adding sulfuric acid to the cellulose fibers and heating them. Methods for introducing phosphate groups as anionic groups into cellulose fibers include mixing cellulose fibers in a dry or wet state with powder or aqueous solution of phosphate or a phosphate derivative, or adding an aqueous solution of phosphate or a phosphate derivative to a dispersion of cellulose fibers. When these methods are employed, generally, after mixing or adding powder or aqueous solution of phosphate or a phosphate derivative, dehydration and heat treatment are performed.

[0046] (iii) Anionic modified cellulose fibers (component (A-1)) The anionic groups contained in the anionically modified cellulose fibers obtained in this way include, for example, carboxyl groups, sulfonic acid groups, and phosphate groups. From the viewpoint of the efficiency of introducing modifying groups into cellulose fibers, the anionic group is preferably a carboxyl group. Examples of counterions that pair with the anionic groups in the anionically 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.

[0047] 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.

[0048] The average fiber diameter of the anion-modified cellulose fibers is preferably 0.1 nm or more, more preferably 1.0 nm or more, and even more preferably 2.0 nm or more, from the viewpoint of handling ease, and preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less, from the viewpoint of film strength. The average fiber diameter of the anion-modified cellulose fibers is measured by the method described in the examples below.

[0049] (2) Process for obtaining hydrophobic modified cellulose fibers The hydrophobic modified cellulose fibers of component (b) can be produced by bonding one or more compounds selected from the group consisting of polymer compounds and hydrocarbon compounds having cationic groups to the anionic modified cellulose fibers. As such a production method, a known method, for example, the method described in Japanese Patent Application Publication No. 2015-143336, can be used.

[0050] (i) Polymer compounds The polymer compounds used as modifying compounds in this invention can be commercially available or prepared according to known methods. One polymer compound may be used, or two or more polymer compounds may be used.

[0051] The polymer compounds used as modifying compounds in the present invention are preferably polymer compounds having a repeating structure linked by an oxygen atom, more preferably polymer compounds having a repeating structure linked by an oxygen atom, such as a polyoxyalkylene structure or a polysiloxane structure, and even more preferably silicone compounds. Examples of silicone compounds include amino-modified silicones, epoxy-modified silicones, carboxy-modified silicones, carbinol-modified silicones, and hydrogen-modified silicones, and the position of the reactive group may be either a side chain or a terminal of the silicone compound. Among these, amino-modified silicones are preferred from the viewpoint of ease of modification.

[0052] (ii) Amino-modified silicone Amino-modified silicones are silicone compounds that contain amino groups. For example, an amino-modified silicone has a kinematic viscosity of 10 mmHg at 25°C. 2 / s or more 20,000mm 2 A concentration of less than or equal to / s is preferred. Furthermore, amino-modified silicones with an amino equivalent of 400 g / mol to 16,000 g / mol are preferred.

[0053] The kinematic viscosity at 25°C can be determined using an Ostwald viscometer, and from the viewpoint of anti-icing and anti-snow properties, it is more preferable to use 20 mm 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.

[0054] Furthermore, the amino equivalent is preferably 400 g / mol or more, more preferably 600 g / mol or more, and even more preferably 800 g / mol or more, from the viewpoint of ice-proofing and snow-proofing properties, and preferably 16,000 g / mol or less, more preferably 14,000 g / mol or less, and even more preferably 12,000 g / mol or less, from the viewpoint of ease of bonding to anion-modified cellulose fibers. Note that the amino equivalent is the molecular weight per nitrogen atom, and is calculated as amino equivalent (g / mol) = mass-average molecular weight / number of nitrogen atoms per molecule. Here, the mass-average molecular weight is the value obtained using polystyrene as a standard substance by gel permeation chromatography, and the number of nitrogen atoms can be determined by elemental analysis.

[0055] A specific example of an amino-modified silicone is the compound represented by general formula (a1).

[0056] [ka]

[0057] [In the formula, R 1aR represents a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom, and from the viewpoint of anti-icing and anti-snow properties, a methyl group or a hydroxyl group is preferred. 2a is a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, or a hydrogen atom, and from a similar viewpoint, a methyl group or a hydroxyl group is preferred. B represents a side chain having at least one amino group, and R 3a x represents an alkyl group or hydrogen atom having 1 to 3 carbon atoms. x and y represent the average degree of polymerization, and are selected such that the kinematic viscosity and amino equivalent of the compound at 25°C are within the above range. Note that R 1a , R 2a , R 3a These may be the same or different, and there may be multiple Rs. 2a They may be the same or different.

[0058] In the compound of general formula (a1), from the viewpoint of anti-ice and anti-snow 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 mass-average molecular weight of the compound of general formula (a1) is preferably between 2,000 and 1,000,000, more preferably between 5,000 and 100,000, and even more preferably between 8,000 and 50,000.

[0059] 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.)

[0060] 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)

[0061] Furthermore, as the amino-modified silicone, from the viewpoint of obtaining a film with high anti-ice and anti-snow 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)].

[0062] 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 Industries, Inc. (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-8 Preferred grades are 004 (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.

[0063] (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).

[0064] (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.

[0065] The silicone compound may have substituents. Examples of substituents include alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, and hexyloxy groups; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, and sec-butoxycarbonyl Examples include alkoxy-carbonyl groups with 1 to 6 carbon atoms, such as carbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, and isopentyloxycarbonyl groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; acyl groups with 1 to 6 carbon atoms, such as acetyl and propionyl groups; aralkyl groups; aralkyloxy groups; alkylamino groups with 1 to 6 carbon atoms; and dialkylamino groups with 1 to 6 carbon atoms in the alkyl group.

[0066] (iii) hydrocarbon compounds having a cationic group In the present invention, a hydrocarbon compound having a cationic group is one in which one or more hydrocarbon groups are bonded to one cationic group. The total number of carbon atoms in the hydrocarbon compound having a cationic group is preferably 16 or more, more preferably 18 or more, from the viewpoint of obtaining a film with high anti-ice and anti-snow properties, and preferably 40 or less, more preferably 30 or less, and even more preferably 26 or less, from the viewpoint of handling properties.

[0067] Hydrocarbon compounds containing a cationic group are compounds in which the hydrocarbon group is directly bonded to a nitrogen atom or phosphorus atom via a covalent bond when the cationic group is a primary amine, secondary amine, tertiary amine, quaternary ammonium, phosphonium, etc. When the cationic group is an amidine, guanidine, etc., it is a compound in which the hydrocarbon group is covalently bonded to at least one of the nitrogen atoms or carbon atoms of the functional group. When the cationic group is an imidazolium, pyridinium, imidazoline, etc., it is a compound in which at least one hydrocarbon group is covalently bonded to any position in the ring structure. Hydrocarbon compounds having cationic groups are more preferably those that do not contain oxyalkylene groups.

[0068] (vi) hydrocarbon 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, and from the same viewpoint, 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] The hydrocarbon compounds having the cationic group described above are preferably hydrocarbon compounds having an amino group, such as primary amines, secondary amines, tertiary amines, and quaternary ammonium compounds (hereinafter referred to as "hydrocarbon amines"). Specific examples of such hydrocarbon amines include hexadecylamine, stearylamine, oleylamine, dioctylamine, didecylamine, didodecylamine, trihexylamine, trioctylamine, tetrabutylammonium salt, tetrahexylammonium salt, dimethyldioctylammonium salt, dimethylddecylammonium salt, and trimethylhexadecylammonium salt.

[0077] (v) Amount of modifying compound used In the process of obtaining hydrophobic modified cellulose fibers, the equivalent amount of functional groups in the modifying compound used that can react with the anionic groups in the anionic modified cellulose fibers is preferably 0.1 equivalents or more, more preferably 0.5 equivalents or more, and even more preferably 1 equivalent or more, from the viewpoint of ice prevention, snow prevention and durability. Similarly, it is preferably 20 equivalents or less, more preferably 10 equivalents or less, and even more preferably 2 equivalents or less.

[0078] (3) Miniaturization process By refining the cellulose at any stage of the method for producing modified cellulose fibers, micrometer-scale cellulose can be refined to a nanometer scale. Since reducing the average fiber diameter to nanometer size improves the strength during film formation, it is preferable to further perform the refinement process.

[0079] For the micronization process, known dispersers are preferably used. For example, disintegrators, beaters, low-pressure homogenizers, high-pressure homogenizers, grinders, cutter mills, ball mills, jet mills, short-screw extruders, twin-screw extruders, ultrasonic stirrers, household juicer mixers, etc., can be used. Furthermore, the solid content of the reactant fibers in the micronization process is preferably 50% by mass or less.

[0080] <Ingredient (B)> In this invention, component (B) is water. Component (B) serves as a solvent in the production of modified cellulose fibers and as one of the constituent components of the emulsified composition of this invention.

[0081] <Ingredient (C)> In this invention, component (C) is a liquid organic compound at 25°C and 1 atm. Component (C) may also be a solvent used in the production of hydrophobic modified cellulose fibers. 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 ice-preventive and snow-preventive properties, the molecular weight of component (C) is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less, and from the same viewpoint, preferably 100 or more, and more preferably 200 or more.

[0082] Component (C) in the present invention specifically includes oils, organic solvents, polymerizable monomers, prepolymers, etc. Component (C) in the present invention is preferably an oil, and as an oil, from the viewpoint of obtaining a film with improved anti-icing and anti-snow properties, examples include one or more selected from the group consisting of alcohols, ester oils, hydrocarbon oils, silicone oils other than modifying compounds, ether oils, fats and oils, fluorinated inert liquids, and fatty acids. Preferably, one or more selected from the group consisting of ester oils, silicone oils other than modifying compounds, ether oils, fats and oils, and fluorinated inert liquids are preferred, more preferably one or more selected from the group consisting of silicone oils other than modifying compounds, SL oils, and ether oils are preferred, and silicone oil and / or SL oil are even more preferred.

[0083] 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.

[0084] Examples of silicone oils other than modifying compounds include dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. 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.

[0085] From the viewpoint of obtaining a film with improved anti-freezing and anti-snow properties, the compound of component (C) preferably has an SP value of 10 or less, more preferably 9.5 or less, even more preferably 9.0 or less, and even more preferably 8.5 or less, and from the same viewpoint, preferably 6.0 or more, more preferably 6.5 or more.

[0086] In this specification, SP value refers to the solubility parameter calculated by the Fedors method (unit: (cal / cm³) 3 ) 1 / 2 This is shown in references such as "SP Value Basics, Applications, and Calculation Methods" (Information Organization Co., Ltd., 2005) and "Polymer Handbook Third Edition" (A Wiley-Interscience publication, 1989).

[0087] 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.

[0088] <Ingredient (D)> The emulsified composition of the present invention may contain polyether-modified silicone compounds other than the modifying compound for component (D). By incorporating such component (D) into the emulsified composition, a film with improved anti-ice and anti-snow properties can be obtained. An example of component (D) 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.

[0089] [ka]

[0090] (In the formula, R 1R 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.)

[0091] The HLB value of the polyether-modified silicone compound is preferably within a specific range from the viewpoint of the durability of the film obtained by drying the emulsified composition. Specifically, it is 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.

[0092] 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

[0093] The kinematic viscosity of the polyether-modified silicone compound at 25°C is preferably within a specific range from the viewpoint of the durability of the film obtained by drying the emulsion composition, and specifically, 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.

[0094] Polyether-modified silicone compounds that can be preferably used as component (D) are commercially available, and examples of commercially available products include "KF-615A", "KF-640", "KF-642", "KF-643", "KF-644", "KF-351A", "KF-354L", "KF-355A", "KF-6011", "KF-6012", "KF-6015", "KF-6016", "KF-6017", "KF-6020", and "KF-6043" (all are trade names) manufactured by Shin-Etsu Chemical Co., Ltd., and from the viewpoint of the durability of the film obtained by drying the emulsion composition, "KF-640", "KF-642", "KF-643", "KF-351A", "KF-354L", and "KF-355A" can be preferably used. Commercially available products 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. (both are product names)) can also be used as component (D).

[0095] <Component (E): Polymer compounds other than components (A) and (D)> The emulsifying composition of the present invention may further contain a polymer compound other than component (A) and component (D) (component (E)). From the viewpoint of obtaining a film with high anti-ice and anti-snow properties, it is preferable that the polymer compound be one or more selected from the group consisting of polymer compound (X) and polymer compound (Y) described below. Polymeric compound (X): A polymeric compound having an ester group, amide group, urethane group, amino group, ether group, or carbonate group in its main chain (however, polymeric compounds that fall under either component (A) or component (D) are not treated as polymeric compound (X)). Polymer compound (Y): Methacrylic or acrylic polymer having an ester group or amide group in its side chain.

[0096] The mass-average molecular weight of the polymer compound is preferably 1,000 or more from the viewpoint of obtaining a film with high anti-ice and anti-snow properties, and preferably 500,000 or less from the same viewpoint.

[0097] [High molecular compound (X)] Examples of polymer compounds (X) having an ester group in the main chain include condensates of dicarboxylic acids such as adipic acid, sebacic acid, dodecanediic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and alkenyl succinic acid with diols such as ethylene glycol, propylene glycol, and butanediol, or condensates of compounds such as glycolic acid and lactic acid that have both a hydroxyl group and a carboxyl group in one molecule.

[0098] Examples of polymer compounds (X) having an amide group in the main chain include condensates of dicarboxylic acids such as adipic acid, sebacic acid, dodecanediic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and alkenyl succinic acid with diamines such as aliphatic diamines such as ethylenediamine, hexamethylenediamine, and propylenediamine.

[0099] Examples of polymer compounds (X) having a urethane group in the main chain include polymers of diisocyanates such as triresin diisocyanate, diphenyl isocyanate, xylylene diisocyanate, and hexamethylene diisocyanate with diols such as ethylene glycol, propylene glycol, and butanediol.

[0100] Examples of polymer compounds (X) having amino groups in the main chain include polymers of alkylimines such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, and hexyleneimine.

[0101] Examples of polymer compounds (X) having an ether group in the main chain include polymers of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, and polymers of formaldehyde.

[0102] Examples of polymer compounds (X) having a carbonate group in the main chain include condensates of polyols such as 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, and 1,1-bis(4-hydroxyphenyl)cyclohexane with phosgene.

[0103] [High molecular compound (Y)] Examples of methacrylic or acrylic polymers having ester or amide groups in their side chains (hereinafter also simply referred to as (meth)acrylic polymers) 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. In the present invention, from the viewpoint of obtaining a film with high anti-ice and anti-snow properties, it is preferable that component (E) is a polymer compound containing a (meth)acrylic polymer.

[0104] <Other ingredients> In addition to the components mentioned above, the emulsifying composition of the present invention may contain plasticizers, nucleating agents, fillers (inorganic fillers, organic fillers), hydrolysis inhibitors, flame retardants, antioxidants, hydrocarbon waxes and anionic surfactants as lubricants, ultraviolet absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, antifungal agents, antibacterial agents, foaming agents, surfactants; starches, polysaccharides such as alginic acid; natural proteins such as gelatin, glue, and casein; inorganic compounds such as tannins, zeolites, ceramics, and metal powders; fragrances; flow regulators; leveling agents; conductive agents; ultraviolet dispersants; deodorants, etc., to the extent that they do not impair the effects of the present invention. Similarly, other polymer materials and other compositions may be added to the extent that they do not hinder the effects of the present invention.

[0105] <Properties of Emulsified Compositions for Ice and Snow Prevention> The emulsified composition for de-icing and snow protection of the present invention is an emulsified composition containing the above-mentioned components (A), (B), and (C) 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. Either an o / w type emulsion or a w / o type emulsion may be used, but an o / w type emulsion is preferred.

[0106] The content of component (A) in the emulsified composition or when mixed 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.

[0107] The content of component (B) in the emulsified composition 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 the emulsified state, and preferably 98% by mass or less, from the viewpoint of effective content.

[0108] The content of component (C) in the emulsified composition 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, from the viewpoint of maintaining the emulsified state, while from the viewpoint of solution viscosity and handling properties, it is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0109] The mass ratio (A / C) of component (A) to component (C) in the emulsified composition or when mixed is preferably 0.0001 or higher, more preferably 0.001 or higher, even more preferably 0.004 or higher, even more preferably 0.01 or higher, and even more preferably 0.04 or higher, from the viewpoint of obtaining a film with improved anti-freezing and anti-snowing properties, and preferably 20 or lower, more preferably 10 or lower, even more preferably 5 or lower, even more preferably 3 or lower, and even more preferably 2 or lower. From these viewpoints, it is preferably 0.0001 to 20 or lower, more preferably 0.001 to 10 or lower, even more preferably 0.004 to 5 or lower, even more preferably 0.01 to 3 or even more preferably 0.04 to 2 or lower.

[0110] When the emulsified composition of the present invention contains component (D), the content of component (D) in the emulsified composition or during mixing is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the viewpoint of film durability, while from the viewpoint of suppressing an increase in composition viscosity, it is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.

[0111] When the emulsified composition of the present invention contains component (E), the content of component (E) in the emulsified composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of film durability, while preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of suppressing an increase in the viscosity of the composition.

[0112] The viscosity of the emulsified composition 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.

[0113] From the viewpoint of improving ice and snow resistance and their durability, the average particle size of the emulsion droplets in the emulsion composition is preferably 10 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more, as measured by SEM observation described later. Similarly, it is preferably 2000 nm or less, more preferably 1000 nm or less, even more preferably 700 nm or less, even more preferably 500 nm or less, preferably 10 nm to 2000 nm, more preferably 50 nm to 1000 nm, and even more preferably 100 nm to 500 nm.

[0114] 2. Method for producing an emulsified composition for de-icing and snow protection. The present invention provides a method for producing an emulsified composition for ice and snow protection, comprising the step of mixing the aforementioned components (A), (B), (C), etc. Here, a liquid organic compound may be mixed with an aqueous dispersion of modified cellulose fibers at 25°C and 1 atm, or the organic compound dispersion of modified cellulose fibers may be mixed with water.

[0115] Alternatively, a method for producing the emulsified composition of the present invention includes a step of mixing component (A-1), component (A-2), component (B), and component (C). This method is more preferable because the step of obtaining hydrophobic modified cellulose fibers and the step of obtaining the emulsified composition can be achieved in a single step. There are no restrictions on the mixing order in this method. For example, component (A-1), component (A-2), and component (B) may be mixed first, followed by component (C), or component (A-1), component (A-2), and component (C) may be mixed first, followed by component (B). Preferably, the manufacturing method includes a step of mixing component (A-1) and component (A-2) in the presence of component (B) and component (C). Therefore, a preferred embodiment of the emulsified composition of the present invention contains component (A-1), component (A-2), component (B), and component (C). In this case, the content of component (A) is the total content of component (A-1) and component (A-2).

[0116] When component (D) and / or component (E) are included, component (D) and / or component (E) may be mixed together with component (A-1), component (A-2), component (B), and component (C), and component (D) and / or component (E) may be added to the emulsified composition obtained using these components.

[0117] Emulsification occurs when each component is mixed, yielding an emulsified composition. For this mixing process, a magnetic stirrer, mechanical stirrer, homomixer, vacuum emulsifier, low-pressure homogenizer, high-pressure homogenizer, grinder, cutter mill, ball mill, jet mill, short-screw extruder, twin-screw extruder, ultrasonic stirrer, household juicer mixer, etc. The mixing process may also be carried out by combining two or more operations.

[0118] 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.

[0119] The preferred range for the content of each component during mixing is the same as the preferred range for the content of each component in the emulsified composition of the present invention described above.

[0120] When using components (A-1) and (A-2) instead of component (A), it is preferable that the upper and lower limits of the preferred content of component (A) be set as the upper and lower limits of the total amount of both components. Here, the mixing ratio of component (A-1) and component (A-2) is such that, from the viewpoint of anti-freezing, anti-snow protection and durability, component (A-2) 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 group of component (A-1), while from the viewpoint of the stability of the emulsified composition, it is preferably 3 equivalents or less, more preferably 2 equivalents or less, and even more preferably 1.5 equivalents or less.

[0121] Alternatively, the ratio of the total number of moles of [the number of amino groups of amino-modified silicone in component (A-2)] and [the number of moles of hydrocarbon compounds with a total of 16 to 40 carbon atoms having cationic groups] to the number of moles of anionic groups of component (A-1) ([total number of moles of component (A-2)] / [number of moles of anionic groups of component (A-1)]) is preferably 0.1 or higher, more preferably 0.3 or higher, and even more preferably 0.5 or higher from the viewpoint of obtaining a film with improved ice-proofing and snow-proofing properties and durability, and preferably 3 or lower, more preferably 2 or lower, and even more preferably 1.5 or lower from the viewpoint of film-forming properties. 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).

[0122] Furthermore, the mass ratio (A-2 / C) of component (A-2) to component (C) is preferably 0.0001 or higher, more preferably 0.001 or higher, even more preferably 0.004 or higher, even more preferably 0.01 or higher, and even more preferably 0.04 or higher, from the viewpoint of obtaining a film with improved ice-proofing and snow-proofing properties and durability. From the viewpoint of film-forming properties, it is preferably 20 or lower, more preferably 10 or lower, even more preferably 5 or lower, even more preferably 3 or lower, and even more preferably 2 or lower. From these viewpoints, it is preferably 0.0001 to 20 or lower, more preferably 0.001 to 10 or lower, even more preferably 0.004 to 5 or lower, even more preferably 0.01 to 3 or even more preferably 0.04 to 2 or lower.

[0123] 3. Method for manufacturing anti-icing and anti-snow coatings The present invention provides a method for producing a membrane containing modified cellulose fibers, which includes the steps of applying and drying the emulsified composition of the present invention.

[0124] Specifically, the emulsified composition is applied to a substrate, such as a solid surface made of glass, resin, metal, ceramics, concrete, wood, stone, or fiber, or to skin, hair, etc. Methods of application include, but are not limited to, application using an applicator, bar coater, spin coater, roller, etc., as well as brush application, hand application, spraying methods such as air spray, airless spray, trigger spray, and dip coating.

[0125] The thickness of the emulsion composition coating film on the substrate is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more, from the viewpoint of film durability, and preferably 2000 μm or less, and more preferably 1500 μm or less, from the viewpoint of coatability.

[0126] Next, the emulsion composition coating can be dried to obtain a coating film. The drying conditions can be under reduced pressure or atmospheric pressure, and the temperature range is preferably between 15°C and 75°C. The drying time is preferably between 1 hour and 24 hours.

[0127] 4.Anti-ice / snow membrane The anti-icing and anti-snow film obtained by the above manufacturing 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). A smaller value for the sliding angle indicates higher synovial properties of the film.

[0128] The anti-ice and snow-prevention film's durability is further improved by including the aforementioned polyether-modified silicone compound.

[0129] The thickness of the film of the present invention is not particularly limited. From the viewpoint of film durability, it is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more. From the viewpoint of economic efficiency, it is preferably 2000 μm or less, more preferably 1200 μm or less, even more preferably 500 μm or less, and even more preferably 200 μm or less. The film thickness can be set to a desired value by adjusting the film thickness using an applicator or other coating tool, or by adjusting the ratio of the medium. The film thickness can be measured according to the method described in the examples below.

[0130] The film of the present invention is preferable because higher smoothness leads to higher synovial properties. Specifically, from the viewpoint of cost-effectiveness, the arithmetic mean roughness of the film immediately after manufacturing is preferably 0.3 μm or more, more preferably 0.5 μm or more, and even more preferably 0.8 μm or more. On the other hand, from the viewpoint of adhesion inhibition, it is preferably 40 μm or less, more preferably 35 μm or less, and even more preferably 30 μm or less. The arithmetic mean roughness of the film can be measured according to the method described in the examples below.

[0131] The film of the present invention is preferably highly durable. 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 arithmetic mean roughness of the film after dropping for 5 minutes is 2 times or less of the roughness before dropping, and the film retains synovial properties after dropping for 5 minutes, the film can be evaluated as highly durable.

[0132] The amount of modified cellulose fibers in the film of the present invention is preferably 1% by mass or more, more preferably 10% by mass or more, from the viewpoint of film durability, and 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 anti-ice and anti-snow properties. The amount of modified cellulose fibers in the film can be determined by considering the amount of volatile components (e.g., water and some oils) in the emulsified composition. The preferred range of amounts of component (C) and / or component (E) in the film of the present invention also corresponds to the preferred range of amounts of those components in the emulsified composition.

[0133] The film of the present invention may contain optional components that do not impair the effects of the present invention. The content of these optional components in the film is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0134] 5. Structure When the anti-icing and anti-snow emulsifying composition of the present invention is dried and a coating film is formed on the substrate, the surface of the substrate can be modified to a lubricating surface. The film of the present invention can be suitably used as a coating material for roofs, building walls and fences, solar panels, road equipment such as signs and billboards and traffic lights, airplanes, automobiles, train cars and power lines, or clothing. As a result, it can be suitably used as an anti-icing and anti-snow film that suppresses the adhesion of snow and ice.

[0135] The emulsified composition of the present invention is useful as an anti-icing agent and a snow-preventing agent, and can be used as an anti-icing method or a snow-preventing method by applying the emulsified composition of the present invention to the above substrate.

[0136] The film in the present invention can be obtained by drying the emulsifying composition of the present invention, for example, (A) One or more modified cellulose fibers selected from the group consisting of the following components (a) and (b), (a) Anionic modified cellulose fibers having a type I crystal structure (b) Hydrophobic modified cellulose fibers having a type I crystalline structure, wherein a modifying group is attached to one or more groups selected from the group consisting of anionic groups and hydroxyl groups, and (C) Liquid organic compounds at 25℃ and 1 atm. It is a film containing and having a particulate structure.

[0137] It is believed that when the water in the emulsified composition is removed by drying, the cellulose fibers that formed the emulsified particles form a networked particulate structure. Furthermore, it is presumed that the durability is improved because at least a portion of component (C) is included in the particulate structure.

[0138] The maximum length of the particles is preferably 10 to 2000 nm, more preferably 50 to 1000 nm, from the viewpoint of improving anti-icing and anti-snow properties and their durability, as observed by SEM. The maximum length refers to the longest length among the length, width, and height, assuming that the particles are contained in the smallest possible rectangular parallelepiped. The preferred numerical ranges and embodiments of each component of the film are the same as the preferred numerical ranges and embodiments in the emulsified composition described above. [Examples]

[0139] 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.

[0140] [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 water content of 0.0001% by mass. This dispersion is dropped onto mica and dried to create an observation sample. An atomic force microscope (AFM) (Digital Instruments, Nanoscope II Tappingmode AFM; probe used: Nanosensors, Point Probe (NCH)) is used to measure the fiber height (difference in height between areas with and without fibers) of the cellulose fibers in the observation sample. At that time, more than 100 cellulose fibers are extracted from the microscope image in which the cellulose fibers can be confirmed, and the average fiber diameter is calculated from their fiber heights. The average fiber length is calculated from the distance in the direction of the fibers. The average aspect ratio is calculated from the average fiber length / average fiber diameter. The height analyzed in the AFM image can be considered as the fiber diameter.

[0141] [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 Co., Ltd., product name: IF-3200) under the following conditions: front lens: 2x, telecentric zoom lens: 1x, image resolution: 0.835 μm / pixel, syringe inner diameter: 6515 μm, spacer thickness: 500 μm, image recognition mode: ghost, threshold: 8, analysis sample volume: 1 mL, 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.

[0142] [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., product name "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)]

[0143] [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.

[0144] Aldehyde group content (mmol / g) = (Carboxyle group content of oxidized cellulose fiber) - (Carboxyle group content of oxidized cellulose fiber to be measured) ... Equation 1

[0145] [Solid content in the dispersion] The measurement is performed using a halogen moisture meter (Shimadzu Corporation; product name "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.

[0146] [Confirmation of crystalline structure in various types of cellulose fibers] The various crystal structures of hydrophobic modified cellulose fibers and other materials are confirmed by measuring them 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.

[0147] <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°).

[0148] 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.

[0149] <Formula B> Cellulose type I crystallinity (%) = [A c / ( A c +A a )] × 100 [In the ceremony, A c This is the sum of the peak areas of the lattice planes (002 plane) (diffraction angle 2θ = 22.6°), (011 plane) (diffraction angle 2θ = 15.1°), and (0-11 plane) (diffraction angle 2θ = 16.2°) in X-ray diffraction, A a This shows the peak area of ​​the amorphous region (diffraction angle 2θ = 18.5°), and each peak area is obtained by fitting the obtained X-ray diffraction chart with a Gaussian function.

[0150] [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 attached (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).

[0151] [Measurement of viscosity of emulsified compositions] 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.

[0152] [Observation of emulsified compositions using Cryo-SEM] Observation of the emulsified composition using Cryo-SEM is performed using a Scios DualBeam field emission scanning electron microscope manufactured by FEI. Observation is performed while gradually sublimating the water from the frozen emulsified composition. Observation is performed at an acceleration voltage of 2kV and a magnification of 25,000x.

[0153] [Measuring the particle size of emulsified droplets using laser diffraction] The particle size of emulsion droplets is measured using laser diffraction with a LA-960 laser meter manufactured by Horiba, Ltd. Measurement conditions: Add water to the measurement cell and measure the volume particle size distribution and the volume median particle size (D) at a concentration that allows the absorbance to be 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.

[0154] [Preparation of anionically modified cellulose fibers] Preparation Example 1 Bleached coniferous kraft pulp (manufactured by Westfrey, trade name: Hinton) was used as the raw material for the natural cellulose fiber. A commercially available TEMPO (manufactured by Aldrich, Free Radical, 98% by mass) was used. Commercially available sodium hypochlorite, sodium bromide, and sodium hydroxide were also used.

[0155] 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., product name: 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.

[0156] 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.

[0157] Preparation Example 2 (Production of finely textured anion-modified cellulose fibers) In Preparation Example 1, 100 g of 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., product name: 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)".

[0158] 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.

[0159] [Preparation of hydrophobic modified cellulose fibers and emulsified compositions] Example 1 In a beaker, 66.7 g (solid content 0.9 mass%) of the finely pulverized anion-modified cellulose fiber dispersion obtained in Preparation Example 3, 6.0 g of silicone oil 1, and 1.91 g of amino-modified silicone 1 as a modifying compound (corresponding to 1.25 equivalents relative to the carboxyl groups of the anion-modified cellulose fibers) were mixed, and deionized water was added to make a total of 100 g. This dispersion was stirred with a mechanical stirrer at room temperature for 5 minutes, and then subjected to 10 passes at 150 MPa using a high-pressure homogenizer (Yoshida Machinery Co., Ltd., product name: NanoVeta L-ES) to obtain an emulsion composition containing hydrophobic modified cellulose fibers in which amino-modified silicone was ionically bonded to the anion-modified cellulose fibers. The obtained composition was a turbid liquid, and since oil droplets were observed to be dispersed in water using an optical microscope, it was determined to be an emulsion composition. The average emulsion particle size measured by laser diffraction was 300 nm.

[0160] Example 2 100 g of the emulsified composition obtained in Example 1 was weighed into a beaker, 0.2 g of polyether-modified silicone 1 was added thereto, and the mixture was stirred at 25°C for 30 minutes to obtain the emulsified composition.

[0161] Example 3 An emulsion composition containing hydrophobic modified cellulose fibers, in which amino-modified silicone is bonded to anionic-modified cellulose fibers via ionic bonds, was obtained in the same manner as in Example 1, except that the amount of silicone oil 1 was 2.0 g. To 100 g of the obtained emulsion composition, 0.2 g of polyether-modified silicone 1 was added and stirred to obtain an emulsion composition.

[0162] Example 4 An emulsion composition containing hydrophobic modified cellulose fibers, in which amino-modified silicone was bonded to anionic-modified cellulose fibers via ionic bonds, was obtained in the same manner as in Example 1, except that silicone oil 2 was used instead of silicone oil 1. To 100 g of the obtained emulsion composition, 0.2 g of polyether-modified silicone 1 was added and stirred to obtain an emulsion composition.

[0163] Example 5 An emulsion composition containing hydrophobic modified cellulose fibers, in which amino-modified silicone was bonded to anionic-modified cellulose fibers via ionic bonds, was obtained in the same manner as in Example 1, except that silicone oil 3 was used instead of silicone oil 1. To 100 g of the obtained emulsion composition, 0.2 g of polyether-modified silicone 1 was added and stirred to obtain an emulsion composition.

[0164] Example 6 To the emulsified composition of Example 2, 3.3 g of styrene acrylic 1 emulsion (45% solids content) was added and stirred to obtain an emulsified composition.

[0165] Example 7 To the emulsified composition of Example 2, 6.6 g of styrene acrylic 1 emulsion (45% solids content) was added and stirred to obtain an emulsified composition.

[0166] Example 8 To the emulsion composition of Example 2, 13.2 g of styrene acrylic 1 emulsion (45% solids content) was added and stirred to obtain an emulsion composition.

[0167] Example 9 To the emulsion composition of Example 2, 20.3 g of urethane 1 emulsion (solids content 29.5%) was added and stirred to obtain an emulsion composition.

[0168] Example 10 An emulsion composition was prepared in the same manner as in Example 1, except that 0.30 g of oleylamine (corresponding to 1.25 equivalents relative to the carboxyl groups of the anionically modified cellulose fibers) was added instead of amino-modified silicone 1. To 100 g of the obtained emulsion composition, 0.2 g of polyether-modified silicone 1 was added and stirred to obtain an emulsion composition.

[0169] Example 11 An emulsion composition was prepared in the same manner as in Example 1, except that isopropyl palmitate was used instead of silicone oil 1. To 100 g of the obtained emulsion composition, 0.2 g of polyether-modified silicone 1 was added and stirred to obtain an emulsion composition.

[0170] Comparative Example 1 As Comparative Example 1, a commercially available snow-repellent paint, "Kansai Paint's Rakuyuki Paint," was used as the coating liquid. This snow-repellent paint is a paint in which an acrylic synthetic resin and pigment are dispersed in an organic solvent, and therefore does not fall under the category of the emulsified composition of the present invention.

[0171] Comparative Example 2 As a comparative example 2, a surface with a textured structure coated with lubricating oil was prepared. Specifically, a water-repellent sheet with a textured structure (Toyal Ultra Lotus®, manufactured by Toyo Aluminum Co., Ltd.) was attached to a glass substrate (10 cm x 10 cm x 5 mm thick) with cellophane tape. 100 cm of water-repellent sheet 2 0.19 g of silicone oil 1, used as a lubricant, was applied to the surface to create a lubricant-coated surface film with a thickness of 20 μm.

[0172] Details of the representative components used in the examples are summarized below. [Modification compound] Amino-modified silicone 1: DOWSIL manufactured by Dow Toray Corporation TM SS-3551, kinematic viscosity: 1,000, amino equivalent: 1,700 Oleylamine: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [Component (C)] Silicone oil 1: Shin-Etsu Chemical Co., Ltd. "KF-96-100cs", SP value: 7.3 Silicone oil 2: Shin-Etsu Chemical Co., Ltd. "KF-96-10cs", SP value: 7.3 Silicone oil 3: Shin-Etsu Chemical Co., Ltd. "KF-96-3000cs", SP value: 7.3 Isopropyl palmitate: Manufactured by Fujifilm Wako Pure Chemical Industries, SP value: 8.5 [Component (D)] Polyether-modified silicone 1: Shin-Etsu Chemical Co., Ltd. "KF-640", HLB: 14 [Component (E)] Styrene-acrylic 1: Daicel Ornex Co., Ltd. "VIACRYL VSC 6286w / 45WA" Urethane 1: Daicel Ornex Co., Ltd., DAOTAN TW 6450 / 30WA, solids content 29.5%

[0173] [Preparation of a dried film] The emulsified compositions prepared in Examples 1-11 and the coating solution prepared in Comparative Example 1 were each applied to separate glass substrates (10 cm × 10 cm × 5 mm thick) and spread over the entire surface of the glass substrate. Then, the substrates were dried for 24 hours at 1 atmosphere, 25°C, and approximately 40% RH to form films. The thickness of each film was measured using the method described below, and all were found to be 20 μm. For Comparative Example 1, the coating solution was spread with a brush onto the same glass substrate as in the example, so that the film thickness after drying was 20 μm. The film was then dried for 24 hours at 1 atmosphere, 25°C, and approximately 40% RH.

[0174] [Measurement of film thickness] The thickness of the film after drying was measured using a laser microscope (Keyence VK-9710) under the following conditions: objective lens: 10x, light intensity: 3%, brightness: 1548, Z pitch: 0.5 μm. A portion of the film was scraped off with a metal spatula to expose the glass substrate. The height of the glass substrate and the height of the filmed portion were measured using the built-in image processing software, and the film thickness was determined by taking the difference between these two values.

[0175] Test Example 1 <Ice-Sliding Performance Evaluation Test> Each substrate with the aforementioned film formed on it, as well as the glass substrate itself, was fixed to a 45° inclined stand using double-sided tape (Scotch Super Multi-Purpose Double-Sided Tape, 12mm wide, manufactured by 3M). Next, in a room at 2°C, crushed ice was sprinkled onto the surface of each substrate using an electric ice shaver (DTY19, manufactured by Doshisha), and the amount of ice remaining on the substrate was measured. The specific criteria for evaluating ice-sliding properties are as follows; a higher value indicates that the film has higher ice-sliding properties. The specific gravity of the crushed ice was 0.49 g / cm³. 3 That was the case.

[0176] 5: More than 90% of the ice slid off. 4: More than 80% but less than 90% of the ice slid off. 3: More than 50% but less than 80% of the ice slid off. 2: More than 20% but less than 50% of the ice slid down. 1: Less than 20% of the ice slid off.

[0177] Test Example 2 <Snow-Sliding Performance Evaluation Test> The snow-sliding properties were evaluated in a low-temperature test chamber (1°C) manufactured by MTS Snow and Ice Research Institute. A 1cm x 2cm x 2mm thick stainless steel piece was attached to the back of each substrate with the above-mentioned film formed on it, as well as the glass substrate itself, using double-sided tape (Scotch Super Multi-Purpose Double-Sided Tape, 12mm wide, manufactured by 3M). The substrates were then placed on a magnetic stand at a 90° angle. Next, artificial snow was blown onto the front of the substrate at a wind speed of 5m / s for 30 minutes, and the snow-sliding properties were evaluated according to the following criteria. A higher value indicates that the film has higher snow-sliding properties. The specific gravity of the artificial snow was 0.29 g / cm³. 3That was the case.

[0178] Skiing within 5:10. Skiing within 4:15. Skiing within 3 hours and 20 minutes. Ski within 2 hours and 30 minutes. I did not ski within the 1 hour and 30 minute test time.

[0179] Test Example 3 <Scratch Resistance Evaluation> The film surface was observed using a laser microscope after the snow-skid performance evaluation test, and scratch resistance was evaluated according to the following criteria. A higher numerical value indicates greater scratch resistance of the film. Note that the number of scratches on the film before the snow-skid performance evaluation test was less than 10% of the film area in the observation field.

[0180] 4: The damaged area accounts for less than 10% of the surface area of ​​the film in the observation field, and the surface condition is almost the same as the initial state. 3: The damaged area covers more than 10% but less than 20% of the membrane area in the field of view. 2: The damaged area covers more than 20% but less than 50% of the membrane area in the observation field. 1: The damaged area covers more than 50% of the membrane area in the field of view.

[0181] Test Example 4 <Weather Resistance Evaluation> Using a Super Xenon Weather Meter SX75 (manufactured by Suga Test Instruments), the irradiance was measured at 180 W / m². 2 Accelerated weathering tests were conducted on substrates on which the films produced in Example 2 and Comparative Example 2 were formed, under the conditions of BPT: 63°C, humidity: 50%RH, and 3000 hours. As a result, the film prepared from the emulsified composition of Example 2 did not yellow even after 3000 hours and maintained high de-icing properties, indicating excellent weather resistance. On the other hand, the film of Comparative Example 2 yellowed severely after 3000 hours and disintegrated, indicating low weather resistance, i.e., low film durability.

[0182] The composition and evaluation results of each component are shown in Tables 1 and 2. The amounts of each component in Tables 1 and 2 are in mass percent. Note that due to rounding, the sum of each component may not equal 100 mass percent.

[0183] [Table 1]

[0184] [Table 2]

[0185] Tables 1 and 2 show that the films formed using the emulsified composition of the present invention exhibit excellent effects in breaking ice and sliding off artificial snow. In particular, the film formed using the emulsified composition of Example 2 was able to slide off even a small amount of accumulated snow within 10 minutes, demonstrating a high snow-prevention effect. It was also found that films containing the polymer of component (E) exhibited higher scratch resistance. [Industrial applicability]

[0186] The emulsifying composition of the present invention can form a film with anti-icing and anti-snowing properties, and can therefore be used in various fields such as coatings on road equipment such as signs, markers, and traffic lights in snowy areas, vehicles such as automobiles, airplanes, and trains, headlights, solar panels, power lines, and roofs and windows of buildings.

Claims

1. An emulsified composition for ice and snow protection containing the following components (A) to (C). (A) Modified cellulose fibers of component (b) below (b) Hydrophobic modified cellulose fiber having a type I crystalline structure, wherein one or more modifying compounds selected from the group consisting of polymer compounds and hydrocarbon compounds having cationic groups are bonded to one or more groups selected from the group consisting of anionic groups and hydroxyl groups of an anionic modified cellulose fiber, wherein the polymer compound is an amino-modified silicone and the hydrocarbon compound having cationic groups is a compound selected from the group consisting of primary amines, secondary amines, tertiary amines and quaternary ammonium compounds. (B) Water (C) An organic compound that is liquid at 25°C and 1 atm, wherein the organic compound is one or more organic compounds selected from the group consisting of ester oils, hydrocarbon oils, silicone oils other than the modifying compounds, ether oils, fats and oils, fluorinated inert liquids, and fatty acids.

2. The anti-ice and snow-prevention emulsified composition according to claim 1, wherein the silicone oil other than the modifying compound in component (C) is one or more selected from the group consisting of dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.

3. The anti-ice and anti-snow emulsifying composition according to claim 1 or 2, further comprising the following component (D). (D) Polyether-modified silicone compound

4. The emulsified composition for ice and snow protection according to claim 3, further comprising the following component (E). (E) Polymer compounds other than components (A) and (D)

5. The anti-ice and anti-snow emulsifying composition according to claim 4, wherein component (E) is a polymer compound containing a (meth)acrylic polymer.

6. A step of applying and drying the anti-ice / anti-snow emulsified composition according to any one of claims 1 to 5. A method for manufacturing anti-ice and anti-snow membranes, including [the specified element].

7. A structure having been formed by drying the anti-ice and anti-snow emulsified composition according to any one of claims 1 to 5 to form a coating film.

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