Adhesion inhibitor for wet powders

Abstract

The present invention relates to an adhesion inhibitor for wet powers which is obtained by mixing the following components (A), (B), and (C): component (A), an organic compound that is liquid at 25°C and 1 atm; component (B), anion-modified cellulose fibers; and component (C), a hydrophobic compound having a cationic functional group (the hydrophobic compound being not one falling under the component (A)). The present invention can provide an agent which has excellent handleability at outdoor and other sites and can inhibit wet powders, e.g., water-containing earth, from adhering to hard surfaces.

Description

Wet powder adhesion inhibitor

[0001] The present invention relates to a wet powder adhesion inhibitor.

[0002] The adhesion of wet powder containing liquid is a problem in various fields. For example, in manufacturing sites that handle large amounts of powder, such as food, pharmaceutical, chemical, molded, and cosmetic products, adhesion of wet powder to hoppers and discharge sections can reduce work efficiency, and moisture-absorbing wet powder can adhere to walls and ceilings, significantly increasing the cleaning load. Furthermore, in civil engineering and construction projects such as dredging, heavy machinery is used to extract and transport wet soil. After transportation, soil often adheres to or sticks to the dump truck bed, requiring considerable effort to remove the soil from the bed. Patent Document 1 discloses a method for preventing soil adhesion and sticking, in which a friction-reducing coating-forming agent, a powdered compound containing a powdered water-soluble polymer, is supplied to the vessel wall before contact with the wet granules / sludge.

[0003] Patent No. 6287091

[0004] The present invention relates to the following [1] to

[12] . [1] A wet powder adhesion inhibitor comprising the following components (A), (B), and (C): (A) an organic compound that is liquid at 25°C and 1 atmosphere; (B) an anion-modified cellulose fiber; and (C) a hydrophobic compound having a cationic functional group (excluding those corresponding to component (A)). [2] The wet powder adhesion inhibitor according to [1] above, wherein the blending amount of component (A) is 0.1% by mass or more and 70% by mass or less. [3] The wet powder adhesion inhibitor according to [1] or [2] above, wherein the blending amount of component (B) is 0.02% by mass or more and 15% by mass or less. [4] The wet powder adhesion inhibitor according to any one of [1] to [3] above, wherein the blending amount of component (C) is 0.5% by mass or more and 20% by mass or less. [5] The wet powder adhesion inhibitor according to any one of [1] to [4] above, further comprising the following component (D): (D) a polymer compound having an anionic functional group and having one or more counter cations selected from the group consisting of ammonium ions and organic ammonium ions (excluding those corresponding to component (A) or component (B)). [6] The wet powder adhesion inhibitor according to any one of [1] to [5] above, further comprising the following component (E): (E) a wetting agent. [7] The wet powder adhesion inhibitor according to [6] above, wherein the blending amount of component (E) is 0.1 parts by mass or more and 100 parts by mass or less per 100 parts by mass of component (A). [8] The wet powder adhesion inhibitor according to [6] or [7] above, wherein the blending amount of component (E) is 10 parts by mass or more and 300 parts by mass or less per 100 parts by mass of component (B). [9] The wet powder adhesion inhibitor according to any one of [6] to [8] above, which is obtained by blending two or more types of component (E).

[10] A method for inhibiting the adhesion of wet powder to a hard surface, comprising the steps of: applying to a hard surface a wet powder adhesion inhibitor comprising a blend of the following components (A), (B), and (C), and forming a film of the wet powder adhesion inhibitor on the hard surface. (A) An organic compound that is liquid at 25°C and 1 atmosphere (B) Anion-modified cellulose fiber (C) A hydrophobic compound having a cationic functional group (excluding those corresponding to component (A) above).)

[11] The method according to claim 10, wherein the weight ratio of the liquid to the powder contained in the wet powder is 10% by mass or more.

[12] A composition comprising the following components (A), (B), (C), (D), and (E'), wherein the composition comprises two or more types of component (E'): (A) an organic compound that is liquid at 25°C and 1 atmosphere (B) anion-modified cellulose fiber (C) a hydrophobic compound having a cationic functional group (excluding those corresponding to component (A)) (D) a polymer compound having an anionic functional group and having one or more counter cations selected from the group consisting of ammonium ions and organic ammonium ions (excluding those corresponding to component (A) or component (B)) (E') one or more selected from the group consisting of polyether-modified silicone-type surfactants, acetylene glycol-based surfactants, and alkyl glyceryl ether-type surfactants. Detailed Description of the Invention

[0005] The technology described in Patent Document 1 supplies powdered medicine to the wall of the container, so when trying to supply the medicine outdoors or elsewhere, it is difficult to supply the medicine evenly because the powder gets blown around by the wind, making it difficult to handle on site.

[0006] Therefore, the present invention relates to providing an agent that is easy to handle on-site, such as outdoors, and that can inhibit wet powders such as water-containing soil and sand from adhering to hard surfaces.

[0007] According to the present invention, it is possible to provide an agent that is easy to handle on-site, such as outdoors, and that can inhibit the adhesion of wet powders, such as water-containing soil and sand, to hard surfaces.

[0008] As a result of investigations, the inventors have found that adhesion of wet powder can be suppressed by applying to a hard surface a composition containing an organic compound that is liquid at 25°C and 1 atmosphere, an anion-modified cellulose fiber, and a hydrophobic compound having a cationic group, and have completed the present invention.

[0009] The mechanism by which this effect is exhibited is thought to be that when this composition dries on a hard surface, the film that forms exhibits a sliding property, which inhibits the adhesion of wet powders such as soil and sand mixed with water or seawater to the hard surface.Furthermore, the film that is formed upon drying is thought to be formed by the interaction of the anionic groups of (B) the anion-modified cellulose fiber with the cationic groups of (C) the hydrophobic compound having a cationic functional group, which increases the affinity for (A) organic compounds that are liquid at 25°C and 1 atmosphere, thereby allowing the (A) component to be retained on the surface of the film and thereby exhibiting a stable sliding property.

[0010] In the present invention, the term "wet powder" refers to a powder composition that (a) contains at least a powder and a liquid (such as a dispersion medium), and (b) the weight ratio of the liquid to the powder is 5% by mass or more and less than 200% by mass.

[0011] Examples of powders include inorganic substances such as soil, sand, cement, silicon dioxide, calcium carbonate, iron oxide, titanium dioxide, calcium sulfate, aluminum sulfate, calcium nitrate, phosphate, copper sulfate, zinc sulfate, talc, and mica; natural polymers such as starches such as corn starch and wheat flour; synthetic polymers such as polyethylene powder and polypropylene powder; and powders of coal and charcoal. The particle size of the powder is not particularly limited, but is preferably 0.1 μm or more and preferably 5 mm or less. Examples of liquids include water, seawater, aqueous solutions, organic solvents, oils, colloidal solutions, and mixtures thereof.

[0012] As described above, the weight ratio of liquid to powder is 5% by mass or more but less than 200% by mass, preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint of exhibiting the adhesion-inhibiting effect, and from the same viewpoint, preferably 150% by mass or less, more preferably 100% by mass or less. Here, the weight ratio of liquid to powder is 50% by mass when 50 g of liquid is used per 100 g of powder. Therefore, specific examples of wet powder include soil containing fresh water such as seawater or water from rivers or lakes, moist starches, and powder raw materials or products mixed with moisture or other liquids at manufacturing sites. Furthermore, in the present invention, "inhibiting adhesion" of wet powder not only means reducing the amount of wet powder adhering to hard surfaces, but also includes making it possible to easily remove wet powder adhering to hard surfaces.

[0013] The wet powder adhesion inhibitor of the present invention is a blend of the following components (A) to (C): (A) an organic compound that is liquid at 25°C and 1 atmosphere, (B) anion-modified cellulose fiber, and (C) a hydrophobic compound having a cationic functional group (excluding those corresponding to component (A) above). Because the inhibitor of the present invention contains a liquid component such as component (A), it is liquid at around room temperature, allowing it to be easily applied even outdoors or at other locations.

[0014] <Component (A)> Component (A) in the present invention is an organic compound that is liquid at 25°C and 1 atmosphere. The solubility of component (A) in water is preferably 10 g or less, and more preferably 1 g or less, per 100 g of water at 25°C. The molecular weight of component (A) (weight average molecular weight in the case of a polymer or mixture) is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less, from the viewpoint of handleability, and is preferably 100 or more, more preferably 200 or more, from the viewpoint of stability in suppressing wet powder adhesion.

[0015] Specific examples of component (A) in the present invention include oils, organic solvents, polymerizable monomers, prepolymers, etc. Component (A) in the present invention is preferably an oil, and examples of the oil, from the viewpoint of suppressing adhesion of wet powder, include one or more selected from the group consisting of higher alcohols, ester oils, hydrocarbon oils, silicone oils, ether oils, fats and oils, fluorine-based inert liquids, and fatty acids, preferably one or more selected from the group consisting of ester oils, silicone oils, ether oils, fats and oils, and fluorine-based inert liquids, more preferably one or more selected from the group consisting of silicone oils, ester oils, and ether oils, and even more preferably silicone oils and / or ester oils.

[0016] Examples of higher alcohols include alcohols having a saturated or unsaturated, linear or branched alkyl chain having 8 to 22 carbon atoms, such as 1-octanol, 2-octanol, 1-decanol, 2-decanol, oleyl alcohol, isostearyl alcohol, and behenyl alcohol.

[0017] Examples of ester oils include monoester oils, diester oils, and triester oils, and specific examples include aliphatic or aromatic monocarboxylic or dicarboxylic acid esters having 2 to 18 carbon atoms, such as isopropyl myristate, octyldodecyl myristate, myristyl myristate, 2-hexyldecyl myristate, isopropyl palmitate, glycerol tri-2-ethylhexanoate, and glycerol triisostearate.

[0018] Examples of silicone oils include siloxane compounds such as dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane, and modified silicones such as phenyl-modified silicones, alkyl-modified silicones, and fluorine-modified silicones, but the silicone oils that can be used as component (A) do not have cationic functional groups in their molecules.

[0019] Examples of fats and oils include vegetable oils such as soybean oil, coconut oil, linseed oil, cottonseed oil, rapeseed oil, and castor oil, as well as animal oils.

[0020] From the viewpoint of suppressing adhesion of wet powder, component (A) preferably has an SP value of 10 or less, more preferably 9.5 or less, even more preferably 9.0 or less, and even more preferably 8.5 or less, and from the same viewpoint, preferably 6.0 or more, more preferably 6.5 or more. For example, an oil agent having an SP value of 10 or less, as described below, can be exemplified as a preferred example.

[0021] The SP value in this specification refers to the solubility parameter calculated by the Fedors method (unit: (cal / cm 3 ) 1 / 2 ) and are described in, for example, references such as "SP Value Basics, Applications and Calculation Methods" (Johokikansha, 2005) and Polymer Handbook Third Edition (A Wiley-Interscience publication, 1989).

[0022] Examples of oils having an SP value of 10 or less that can be suitably used in the present invention include oleic acid (SP value: 9.2), D-limonene (SP value: 9.4), PEG400 (SP value: 9.4), dimethyl succinate (SP value: 9.9), neopentyl glycol dicaprate (SP value: 8.9), hexyl laurate (SP value: 8.6), isopropyl laurate (SP value: 8.5), isopropyl myristate (SP value: 8.5), isopropyl palmitate (SP value: 8.5), isopropyl oleate (SP value: 8.6), hexadecane (SP value: 8.0), olive oil (SP value: 9.3), jojoba oil (SP value: 8.6), squalane (SP value: 7.9), liquid paraffin (SP value: 7.9), and fluorine-based inert liquids (e.g., fluorine-based inert liquids). 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 oil (e.g., KF96-1cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-10cs (manufactured by Shin-Etsu Chemical Co., Ltd.) , SP value: 7.3), KF-96-50cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-100cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-1000cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-3000cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96H-10,000cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), etc. All of these oils are liquid at 25°C and 1 atmosphere.

[0023] <Component (B)> Component (B) is an anion-modified cellulose fiber. Anion-modified cellulose fiber is a cellulose fiber that has been anion-modified so as to contain anionic groups. Component (B), alone or together with other components, functions as an emulsifier that emulsifies component (A) and water when used in combination with water.

[0024] Anion-modified cellulose fibers have a cellulose type I crystal structure derived from the raw cellulose fibers. From the viewpoint of emulsion stability when used in combination with water, the degree of crystallinity of the anion-modified cellulose fibers is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more. From the viewpoint of raw material availability, the degree of crystallinity is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, and even more preferably 75% or less.

[0025] In this specification, the crystallinity of various cellulose fibers refers to the cellulose type I crystallinity calculated from the diffraction intensity value obtained 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 cellulose type I crystallinity refers to the proportion of crystalline regions in the entire 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.

[0026] Examples of the anionic group contained in the anion-modified cellulose fiber include a carboxy group, a sulfonic acid group, and a phosphate group. The anionic group is preferably a carboxy group from the viewpoint of bonding with component (C). As the anion-modified cellulose fiber, a carboxy group-containing cellulose fiber in which the anionic group is a carboxy group is more preferred from the viewpoints of ease of preparation and mild reaction conditions.

[0027] Examples of counter ions to the anionic groups in anion-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, ammonium ions, and organic ammonium ions that are generated by substituting these metal ions with acids.

[0028] The anionic group content in the anion-modified cellulose fiber 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 bonding strength with component (C). Furthermore, from the viewpoint of improving handleability, it is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, and even more preferably 1.8 mmol / g or less. The "anionic group content" refers to the total amount of anionic groups in the cellulose constituting the cellulose fiber, and is specifically measured by the method described in the Examples below.

[0029] The average fiber diameter of the anion-modified cellulose fiber is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more from the viewpoint of handleability, and is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less from the viewpoint of strength when formed into a film. The average fiber diameter of the anion-modified cellulose fiber is measured by the method described in the examples below.

[0030] [Method for producing anionically modified cellulose fibers] The anionically modified cellulose fibers used in the present invention can be obtained by subjecting raw cellulose fibers to an oxidation treatment or an anionic group addition treatment, thereby introducing one or more anionic groups per glucose residue and anionically modifying the fibers.

[0031] The cellulose fibers to be anionically modified, i.e., the cellulose fibers used as the raw material for anionically modified cellulose fibers, are preferably natural cellulose fibers from an environmental perspective, and examples thereof include wood pulps such as softwood pulp and hardwood pulp; cotton pulps such as cotton linter and cotton lint; non-wood pulps such as straw pulp and bagasse pulp; and bacterial cellulose, and these may be used alone or in combination of two or more.

[0032] From the viewpoints of handleability and cost, the average fiber diameter of the raw cellulose fibers is preferably 1 μm or more and preferably 300 μm or less. Furthermore, from the viewpoints of availability and cost, the average fiber length of the raw cellulose fibers is preferably 100 μm or more and preferably 5,000 μm or less. The average fiber diameter and average fiber length of the raw cellulose fibers can be measured according to the method described in the Examples below. From the viewpoint of dispersibility, it is preferable to use cellulose fibers that have been subjected to a fiber shortening treatment such as alkaline hydrolysis or acid hydrolysis, and have an average fiber length of 1 μm or more and 1,000 μm or less.

[0033] The anionic group to be introduced includes a carboxy group, a sulfonic acid group, or a phosphoric acid group.

[0034] (i) Introducing carboxy groups as anionic groups into cellulose fibers Examples of methods for introducing carboxy groups into cellulose fibers include a method of converting hydroxy groups of cellulose into carboxy groups by oxidizing them, and a method of reacting the hydroxy groups of cellulose with one or more compounds selected from the group consisting of compounds having carboxy groups, acid anhydrides of compounds having carboxy groups, and derivatives thereof.

[0035] As a method for oxidizing the hydroxy groups of the cellulose, for example, a method of reacting an oxidizing agent such as sodium hypochlorite and a bromide such as sodium bromide using 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) as a catalyst can be applied. For more details, known methods, such as the method described in JP 2011-140632 A, can be referred to.

[0036] By oxidizing cellulose fibers using TEMPO as a catalyst, the hydroxymethyl group (-CH ２(OH) is selectively converted to a carboxy group. This method is particularly advantageous in that it has excellent selectivity for the hydroxy group at the C6 position, which is the target of oxidation on the surface of the raw cellulose fiber, and the reaction conditions are mild. Therefore, a preferred embodiment of the anion-modified cellulose fiber of the present invention is a cellulose fiber in which the C6 position of the cellulose structural unit is a carboxy group. In this specification, cellulose fibers obtained by oxidizing hydroxy groups in the cellulose structural unit may be referred to as "oxidized cellulose fibers," and cellulose fibers obtained by oxidizing cellulose fiber using TEMPO as a catalyst and in which the C6 position of the cellulose structural unit is a carboxy group may be referred to as "TEMPO-oxidized cellulose fibers." Oxidized cellulose fibers, particularly TEMPO-oxidized cellulose fibers, are preferred because they are easier to prepare than other anion-modified cellulose fibers.

[0037] By further subjecting the oxidized cellulose fibers to a further oxidation treatment or reduction treatment, it is possible to prepare oxidized cellulose fibers from which the remaining aldehyde groups have been removed.

[0038] An example of a method for introducing phosphate groups as anionic groups into cellulose fibers is the method described in Japanese Patent No. 7196051, in which raw cellulose fibers are impregnated with a mixed aqueous solution of ammonium dihydrogen phosphate and urea to convert hydroxy groups in the cellulose fibers into phosphoric acid esters. (ii) Introducing sulfonic acid groups or phosphate groups as anionic groups into cellulose fibers. Examples of a method for introducing sulfonic acid groups as anionic groups into cellulose fibers include adding sulfuric acid to cellulose fibers and heating the fibers. Examples of a method for introducing phosphate groups as anionic groups into cellulose fibers include mixing a powder or aqueous solution of phosphoric acid or a phosphoric acid derivative with dry or wet cellulose fibers, or adding an aqueous solution of phosphoric acid or a phosphoric acid derivative to a dispersion of cellulose fibers. When these methods are employed, dehydration and heating treatments are generally performed after mixing or adding a powder or aqueous solution of phosphoric acid or a phosphoric acid derivative.

[0039] <Component (C)> Component (C) is a hydrophobic compound having a cationic functional group (excluding those corresponding to the above-mentioned component (A)). The term "hydrophobic" in component (C) refers to the property of having a solubility in water at 25°C of 5% by mass or less. Only one type of component (C) may be used, or two or more types may be used.

[0040] From the viewpoint of suppressing adhesion of wet powder, component (C) is preferably one or more compounds selected from the group consisting of polymeric compounds having a cationic functional group and hydrocarbon-based compounds having a cationic functional group.

[0041] Examples of the cationic functional group in component (C) include an amino group, an ammonium group, and an imidazolium group, and from the viewpoint of availability, an amino group is preferred. In this specification, the term "amino group" refers to a monovalent functional group obtained by removing one hydrogen atom from ammonia, a primary amine, or a secondary amine.

[0042] (i) Polymer Compound Having Cationic Functional Group From the viewpoint of strength during film formation, the weight-average molecular weight of the polymer compound having a cationic functional group is preferably 2,000 or more, more preferably 5,000 or more, and even more preferably 8,000 or more, and from the same viewpoint, is preferably 1,000,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. From the viewpoint of ease of modification, examples of the polymer compound include silicone having a cationic functional group, polyoxyalkylene oxide, poly(meth)acrylate, polyvinyl, polyester, polyamide, polycarbonate, etc., and more preferably silicone having an amino group.

[0043] The silicone has a polysiloxane structure with a siloxane bond as the main chain, which may further include an alkylene group. The polysiloxane structure may have a substituent, which will be described later.

[0044] [Substituents] Examples of the 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; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, and sec-butoxycarbonyl; Examples of such an alkoxycarbonyl group include an alkoxy group having 1 to 6 carbon atoms, such as a carboxyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, and an isopentyloxycarbonyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; an acyl group having 1 to 6 carbon atoms, such as an acetyl group and a propionyl group; an aralkyl group; an aralkyloxy group; an alkylamino group having 1 to 6 carbon atoms; and a dialkylamino group having an alkyl group having 1 to 6 carbon atoms.

[0045] [Amino-modified silicone] From the viewpoint of the stability of the emulsion composition that results when used in combination with water, component (C) is preferably a silicone having an amino group (referred to herein as "amino-modified silicone").

[0046] The amino-modified silicone has a kinematic viscosity of 10 mm at 25°C. ２ / s or more 20,000mm ２ Further, amino-modified silicones having an amino equivalent of 400 g / mol or more and 16,000 g / mol or less are preferred.

[0047] The kinematic viscosity at 25°C can be determined using an Ostwald viscometer, and from the viewpoint of strength during film formation, it is more preferably 20 mm ２ / s or more, more preferably 50 mm ２ / s or more, and from the viewpoint of handling, it is more preferably 10,000 mm ２ / s or less, more preferably 5,000 mm ２ / s or less.

[0048] From the viewpoint of strength during film formation, 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, and from the viewpoint of ease of bonding to anion-modified cellulose fibers, it is preferably 16,000 g / mol or less, more preferably 14,000 g / mol or less, and even more preferably 12,000 g / mol or less. The amino equivalent is the molecular weight per nitrogen atom and can be determined by quantifying the amount of nitrogen atoms in a sample by elemental analysis and calculating the mass of the sample containing 1 mol of nitrogen atoms.

[0049] Specific examples of amino-modified silicones include compounds represented by general formula (a1).

[0050]

[0051] [In the formula, R １ａ R represents a group selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom, and is preferably a methyl group or a hydroxy group from the viewpoint of suppressing adhesion of wet powder. ２ａ is a group selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom, and from the same viewpoint, is preferably a methyl group or a hydroxy group. B represents a side chain having at least one amino group, and R ３ａ represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. x and y each represent an average degree of polymerization, where x is an integer of 0 or more and y is an integer of 1 or more, and are selected so that the kinematic viscosity at 25°C and amino equivalent of the compound fall within the above-mentioned ranges. １ａ , R ２ａ , R ３ａ may be the same or different, and multiple R ２ａ may be the same or different.

[0052] In the compound of general formula (a1), from the viewpoint of suppressing adhesion of wet powder, x is preferably a number of 10 or more and 10,000 or less, more preferably a number of 20 or more and 5,000 or less, and even more preferably a number of 30 or more and 3,000 or less. y is preferably a number of 1 or more and 1,000 or less, more preferably a number of 1 or more and 500 or less, and even more preferably a number of 1 or more and 200 or less. From the viewpoint of strength during film formation, the weight-average molecular weight of the compound of general formula (a1) is preferably 2,000 or more, more preferably 5,000 or more, and even more preferably 8,000 or more, and from the same viewpoint, it is preferably 1,000,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0053] In the general formula (a1), examples of the side chain B having an amino group include the following: ３ H ６ -NH ２ -C ３ H ６ -NH-C ２ H ４ -NH ２ -C ３ H ６ -NH-[C ２ H ４ -NH] ｅ -C ２ H ４ -NH ２ -C ３ H ６ -NH(CH ３ ) -C ３ H ６ -NH-C ２ H ４ -NH(CH ３ ) -C ３ H ６ -NH-[C ２ H ４ -NH ｆ -C ２ H ４ -NH(CH ３ ) -C ３ H ６ -N(CH ３ ) ２ -C ３ H ６ -N(CH ３ )-C２ H ４ -N(CH ３ ) ２ -C ３ H ６ -N(CH ３ )-[C ２ H ４ -N(CH ３ )] ｇ -C ２ H ４ -N(CH ３ ) ２ -C ３ H ６ -NH-cyclo-C ５ H １１ (where e, f, and g are numbers from 1 to 30.)

[0054] The amino-modified silicone used in the present invention can be produced, for example, by hydrolyzing an organoalkoxysilane represented by general formula (a2) with excess water to obtain a hydrolyzate, and then heating the resulting hydrolyzate with dimethylcyclopolysiloxane in the presence of a basic catalyst such as sodium hydroxide at 80 to 110°C to cause an equilibrium reaction, and then neutralizing the basic catalyst with an acid when the reaction mixture reaches the desired viscosity (see JP-A-53-98499). ２ N (CH ２ ) ２ NH (CH ２ ) ３ Si(CH ３ ) (OCH ３ ) ２ (a2)

[0055] From the viewpoint of strength during film formation, the amino-modified silicone is preferably at least one selected from the group consisting of monoamino-modified silicones having one amino group in one side chain B and diamino-modified silicones having two amino groups in one side chain B, and more preferably, the side chain B having an amino group is -C ３ H ６ -NH ２ [hereinafter referred to as component (a1-1)] and a compound represented by the formula (a1-1) in which the side chain B having an amino group is -C ３ H ６ -NH-C ２ H ４ -NH２ The compound is at least one selected from the group consisting of compounds represented by the following formula (hereinafter referred to as component (a1-2)):

[0056] In terms of performance, the amino-modified silicones used in the present invention include TSF4703 (kinematic viscosity: 1000, amino equivalent: 1600) and TSF4708 (kinematic viscosity: 1000, amino equivalent: 2800) manufactured by Momentive Performance Materials, Inc., and SS-3551 (kinematic viscosity: 1000, amino equivalent: 1700), SF8457C (kinematic viscosity: 1200, amino equivalent: 1800), SF8417 (kinematic viscosity: 1200, amino equivalent: 1700), SF8452C (kinematic viscosity: 600, amino equivalent: 6400), BY16-209 (kinematic viscosity: 500, amino equivalent: 1800), BY16-892 (kinematic viscosity: 1500, amino equivalent: 2000), and BY16-209 (kinematic viscosity: 500, amino equivalent: 1800) manufactured by Dow-Toray Industries, Inc. 6-898 (kinematic viscosity: 2000, amino equivalent: 2900), FZ-3710 (kinematic viscosity: 1000, amino equivalent: 1700), 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-8004 (kinematic viscosity: 800, amino equivalent: 1500), KF-8005 (kinematic viscosity: 1200, amino equivalent: 11000), KF-867 (kinematic viscosity: 1300, amino equivalent: 1700), KF-864 (kinematic viscosity: 1700, amino equivalent: 3800), KF-859 (kinematic viscosity: 60, amino equivalent: 6000). In parentheses, kinematic viscosity is measured at 25°C (unit: mm ２ / s), and the unit of amino equivalent is g / mol.

[0057] As the component (a1-1), BY16-213 (kinematic viscosity: 55, amino equivalent: 2700) and BY16-853U (kinematic viscosity: 14, amino equivalent: 450) are more preferred.

[0058] As the component (a1-2), SF8417 (kinematic viscosity: 1200, amino equivalent: 1700), BY16-209 (kinematic viscosity: 500, amino equivalent: 1800), FZ-3710 (kinematic viscosity: 1000, amino equivalent: 1700), 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.

[0059] (ii) Hydrocarbon Compound Having a Cationic Functional Group A hydrocarbon compound having a cationic functional group is a compound in which one or more hydrocarbon groups are bonded to one cationic functional group. The total carbon number of the hydrocarbon compound having a cationic functional group is preferably 16 or more, more preferably 18 or more, from the viewpoint of suppressing adhesion of wet powder, and is preferably 40 or less, more preferably 30 or less, and even more preferably 26 or less, from the viewpoint of handleability. When the cationic functional group is a primary amine, secondary amine, tertiary amine, or quaternary ammonium, the hydrocarbon compound having a cationic functional group is a compound in which the hydrocarbon group is directly bonded to a nitrogen atom via a covalent bond. When the cationic functional group is an imidazolium, pyridinium, imidazoline, or the like, the hydrocarbon compound is a compound in which at least one hydrocarbon group is bonded to any position of the ring structure via a covalent bond.

[0060] (Hydrocarbon Group) Examples of the hydrocarbon group in the hydrocarbon compound having a cationic functional group include a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, a cyclic saturated hydrocarbon group, and an aromatic hydrocarbon group. From the viewpoint of availability, the number of carbon atoms in the hydrocarbon group is preferably 16 or more, more preferably 18 or more, and from the same viewpoint, it is preferably 40 or less, more preferably 30 or less, and even more preferably 24 or less. The number of carbon atoms in a hydrocarbon group refers to the number of carbon atoms in one hydrocarbon group, unless otherwise specified. Specific examples of chain saturated hydrocarbon groups include a hexadecyl group, an octadecyl group, a docosyl group, and an octacosanyl group. Specific examples of chain unsaturated hydrocarbon groups include a hexadecenyl group and an octadecenyl group. Specific examples of cyclic saturated hydrocarbon groups include a cyclohexadecyl group and a cyclooctadecyl group. The hydrocarbon compounds may further have some hydrogen atoms substituted. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxy group, a methoxy group, an ethoxy group, a carboxy group, an aldehyde group, a ketone group, and a thiol group.

[0061] The hydrocarbon compound having a cationic functional group is preferably a hydrocarbon compound having an amino group, such as a primary amine, a secondary amine, a tertiary amine, or a quaternary ammonium (referred to as a "hydrocarbon amine" in this specification.) Specific examples of such hydrocarbon amines include hexadecylamine, stearylamine, oleylamine, dioctylamine, didecylamine, didodecylamine, trihexylamine, trioctylamine, tetrabutylammonium salt, tetrahexylammonium salt, dimethyldioctylammonium salt, dimethyldidecylammonium salt, and trimethylhexadecylammonium salt.

[0062] <Component (D)> Component (D) is a "polymer compound having an anionic functional group, the counter cation of which is one or more selected from the group consisting of ammonium ions and organic ammonium ions" (however, excluding those corresponding to component (A) or component (B) above). By incorporating component (D) into the adhesion inhibitor of the present invention, it is possible to expect a further effect of improving the stability of the emulsion composition when used in combination with water. Component (D) may be used alone or in combination of two or more types.

[0063] The weight average molecular weight of component (D) is preferably 500 or more, more preferably 1,000 or more, from the viewpoint of the aggregation suppression effect, and is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less, also from the viewpoint of the aggregation suppression effect.

[0064] Examples of the anionic functional group in component (D) include a carboxy group, a sulfonic acid group, a sulfate group, a phosphorous acid group, and a phosphate group. Among these, a carboxy group is preferred from the viewpoint of easy availability. The functional group equivalent of component (D) is preferably 50 g / mol or more, more preferably 60 g / mol or more, from the viewpoint of the water resistance of the resulting membrane, and is preferably 300 g / mol or less, more preferably 200 g / mol or less, from the viewpoint of the aggregation suppression effect. Here, "functional group equivalent" refers to the molecular weight per anionic functional group (i.e., the molecular weight of component (D) / the number of anionic functional groups), and is determined by quantifying the amount of anionic functional groups in a sample by neutralization titration and calculating the mass of the sample containing 1 mol of anionic functional groups.

[0065] Examples of polymer compounds having such an anionic functional group include polyacrylic acid, polymethacrylic acid, polymaleic acid copolymers, polyallylsulfonic acid, and copolymers containing these constituent monomers. Among these, polyacrylic acid is preferred from the viewpoint of easy availability.

[0066] The counter cation in component (D) is one or more selected from the group consisting of ammonium ions and organic ammonium ions. The organic ammonium ions may be any of primary ammonium cations, secondary ammonium cations, tertiary ammonium cations, and quaternary ammonium cations, all of which have an organic group. The number of carbon atoms in the organic group of the organic ammonium ion is preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less, from the viewpoint of the water resistance of the resulting film.

[0067] The organic ammonium ion is generated by protonation of the organic amine. Specific examples of organic amines that provide the organic ammonium ion include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, ethylenediamine, triethanolamine, dimethylaminoethanol, aniline, pyrrolidine, and piperidine. From the viewpoint of suppressing adhesion of wet powder, a counter cation component that volatilizes from the adhesion inhibitor of the present invention when the adhesion inhibitor of the present invention is dried to form a film is preferred. From this viewpoint, ammonia (boiling point: −33° C.), triethylamine (boiling point: 89° C.), and dimethylaminoethanol (boiling point: 133° C.) are more preferred as compounds that provide the counter cation.

[0068] When preparing the wet powder adhesion inhibitor of the present invention, component (D) may be blended in the form of a salt of a "polymeric compound having an anionic functional group" and one or more compounds selected from the group consisting of ammonia and organic amines, or the "polymeric compound having an anionic functional group" and one or more compounds selected from the group consisting of ammonia and organic amines may be blended separately. When component (D) is blended in the form of a salt, specific preferred examples of the salt are ammonium polyacrylate and ammonium polycarboxylate.

[0069] <Component (E)> Component (E) is a "wetting agent". In the present invention, the wetting agent is a component that exhibits the effect of improving the wet spreadability of the wet powder to inhibit adhesion to a hard surface. By blending component (E) with the adhesion inhibitor of the present invention, it is possible to expect an even greater effect of stably exhibiting the wet powder adhesion inhibitory effect. Component (E) may be used alone or in combination of two or more types.

[0070] As the wetting agent, any agent used in the field of the present invention can be used without limitation. Specific examples of the wetting agent include the following nonionic surfactants (excluding those corresponding to the component (A)).

[0071] [Nonionic Surfactants] Examples of nonionic surfactants that can be used as wetting agents include polyether-modified silicone surfactants, polyoxyalkylene fatty alcohol ether surfactants, acetylene glycol surfactants, alkyl glyceryl ether surfactants, polyoxyethylene alkylphenyl ether surfactants, oxyethylene-oxypropylene block polymers, and polyoxyethylene alkylamine alkylalkanolamides.

[0072] The HLB value of the nonionic surfactant that can be used as a wetting agent is preferably within a specific range from the viewpoint of suppressing adhesion of wet powder to the film obtained by drying the adhesion inhibitor; specifically, it is preferably 1 or more, more preferably 5 or more, and even more preferably 8 or more, and is preferably 18 or less, more preferably 16 or less.

[0073] When two or more nonionic surfactants with different HLB values ​​are used, the HLB value of component (E) should be determined by their weighted average within the above range. The HLB value is an index that represents the balance between hydrophilicity and lipophilicity, and in the present invention refers to the value calculated by the following Griffin formula: HLB value = 20 x sum of molecular weights of hydrophilic groups / molecular weight

[0074] [Polyether-modified silicone surfactant] Examples of polyether-modified silicone surfactants include compounds having a methylsilicone chain as a main chain and a polyoxyethylene group as a side chain, and specifically include compounds represented by the following general formula:

[0075]

[0076] In the formula, R １ is a methylene group, an ethylene group, or a trimethylene group, and R ２ represents an alkyl group having 1 to 4 carbon atoms, m represents an integer of 0 to 50, n represents an integer of 1 to 10, p represents an integer of 1 to 50, and q represents an integer of 0 to 50. １ (C ２ H ４ O) ｐ (C ３ H ６ O) ｑ R ２ In the group represented by (C ２ H ４ O) ｐ and (C ３ H ６ O) ｑ can be random or block.

[0077] The kinematic viscosity of the polyether-modified silicone surfactant at 25°C is preferably within a specific range from the viewpoint of suppressing adhesion of the wet powder of the film obtained by drying the adhesion inhibitor, and specifically, is preferably within 1 mm ２ / s or more, more preferably 5 mm ２ / s or more, more preferably 10 mm ２ / s or more, preferably 1000 mm ２ / s or less, more preferably 500 mm ２ / s or less, more preferably 200 mm ２ / s or less, more preferably 100 mm ２ / s or less.

[0078] The weight average molecular weight of the polyether-modified silicone surfactant is preferably 300 or more, more preferably 500 or more, from the viewpoint of improving the adhesion inhibitory properties of the wet powder of the film obtained by drying the adhesion inhibitor, and from the same viewpoint, is preferably 9000 or less, more preferably 5000 or less, and even more preferably 3000 or less.

[0079] Polyether-modified silicone compounds that can be preferably used as component (E) 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 manufactured by Shin-Etsu Chemical Co., Ltd. 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 having structures that do not fall within the general formula (for example, KF-6028 and KF-6038 manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as component (E).

[0080] [Polyoxyalkylene Fatty Alcohol Ether Surfactants] Examples of polyoxyalkylene fatty alcohol ether surfactants include alkylene oxide adducts having a saturated or unsaturated, straight-chain or branched-chain hydrocarbon group having 6 to 22 carbon atoms.

[0081] From the viewpoint of suppressing adhesion of wet powder, the number of carbon atoms in the hydrocarbon group is preferably 8 or more, more preferably 9 or more, and even more preferably 10 or more. From the same viewpoint, the number of carbon atoms in the hydrocarbon group is preferably 17 or less, more preferably 15 or less, and even more preferably 13 or less.

[0082] Examples of polyoxyalkylene fatty alcohol ether surfactants include polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, and polyoxyethylene polyoxypropylene alkyl ethers, with polyoxyethylene alkyl ethers being preferred. From the viewpoint of suppressing adhesion of wet powder, the average number of moles of alkylene oxide added in the polyoxyalkylene fatty alcohol ether surfactant is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more. From the same viewpoint, it is preferably 20 or less, more preferably 15 or less, even more preferably 12 or less, and particularly preferably 8 or less.

[0083] [Acetylene glycol surfactants] Examples of acetylene glycol surfactants include acetylene glycols having 8 to 22 carbon atoms and ethylene adducts of the acetylene glycols, preferably one or more selected from the group consisting of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,4-dimethyl-5-hexyn-3-ol, and ethylene oxide adducts thereof, more preferably one or more selected from the group consisting of 2,4,7,9-tetramethyl-5-decyne-4,7-diol and ethylene oxide adducts thereof, and even more preferably 2,4,7,9-tetramethyl-5-decyne-4,7-diol. Examples of commercially available acetylene glycol surfactants include the Surfynol series manufactured by Air Products & Chemicals and the Acetylenol series manufactured by Kawaken Fine Chemicals Co., Ltd.

[0084] [Alkyl glyceryl ether surfactants] Examples of alkyl glyceryl ether surfactants include glyceryl ethers and polyglyceryl ether compounds having a saturated or unsaturated, linear or branched hydrocarbon group having 4 to 18 carbon atoms. From the viewpoint of suppressing adhesion of wet powder, the number of carbon atoms in the hydrocarbon group of the alkyl glyceryl ether surfactant is preferably 6 or more, more preferably 7 or more, and even more preferably 8 or more. From the same viewpoint, the number of carbon atoms is preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. The hydrocarbon group is preferably branched, and from the viewpoint of suppressing adhesion of wet powder, 2-ethylhexyl glyceryl ether, isononyl glyceryl ether, or 2-propylheptyl glyceryl ether is preferred.

[0085] As described above, from the viewpoint of stably exhibiting the effect of inhibiting the adhesion of wet powder, it is more preferable to use, as the wetting agent, one or more components selected from the group consisting of polyether-modified silicone surfactants, acetylene glycol surfactants, and alkyl glyceryl ether surfactants (such components will be referred to as "component (E')"), and it is even more preferable to blend two or more types of component (E'). Therefore, the present invention encompasses the following composition. Such a composition can be preferably used as an agent for inhibiting the adhesion of wet powder. A composition comprising the following components (A), (B), (C), (D), and (E'), wherein the composition comprises two or more types of component (E'). (A) an organic compound that is liquid at 25°C and 1 atmosphere; (B) an anion-modified cellulose fiber; (C) a hydrophobic compound having a cationic functional group (excluding those corresponding to the component (A) above); (D) a polymer compound having an anionic functional group, the counter cation of which is one or more selected from the group consisting of ammonium ions and organic ammonium ions (excluding those corresponding to the component (A) or the component (B) above); (E') one or more selected from the group consisting of polyether-modified silicone surfactants, acetylene glycol surfactants, and alkyl glyceryl ether surfactants.

[0086] Here, the properties and specific examples of component (A), component (B), component (C), and component (D), as well as the polyether-modified silicone surfactant, acetylene glycol surfactant, and alkyl glyceryl ether surfactant, are as described above, and the content and blending amount of each component are the same as those of the wet powder adhesion inhibitor described below.

[0087] <Water> The adhesion inhibitor of the present invention may contain water. Water serves as a solvent during preparation or as one of the components of the adhesion inhibitor. When the adhesion inhibitor of the present invention contains water, the adhesion inhibitor may be in an emulsified state.

[0088] <Other Components> In addition to the above components, the wet powder adhesion inhibitor of the present invention may contain antibacterial compounds (e.g., organic synthetic antibacterial agents, natural product antibacterial agents, inorganic antibacterial agents, etc.), film reinforcing agents, thickeners, plasticizers, crystal nucleating agents, fillers (inorganic fillers, organic fillers), hydrolysis inhibitors, flame retardants, antioxidants, lubricants such as hydrocarbon waxes and anionic surfactants, UV absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, foaming agents, surfactants; polysaccharides such as starches and alginic acid; natural proteins such as gelatin, glue, and casein; inorganic compounds such as tannin, zeolite, ceramics, and metal powder; fragrances; flow adjusters; leveling agents; conductive agents; UV dispersants; deodorizers, etc., within the range that does not impair the effects of the present invention. Similarly, other polymeric materials and other compositions may also be added within the range that does not impair the effects of the present invention.

[0089] <Properties of the Wet Powder Adhesion Inhibitor> The wet powder adhesion inhibitor of the present invention contains the above-mentioned components (A), (B), and (C) as essential components, and when it further contains water, it is an emulsified composition. The emulsified state is determined by visually observing the wet powder adhesion inhibitor, and if it is cloudy, it is considered to be in an emulsified state. When the wet powder adhesion inhibitor of the present invention is an emulsion composition, it may be either an O / W type emulsion or a W / O type emulsion, but is preferably an O / W type emulsion.

[0090] The average particle size of the droplets in the emulsion composition is preferably 10 nm or more, more preferably 50 nm or more, from the viewpoint of the water resistance of the film to be formed, and is preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1.5 μm or less, from the viewpoint of the stability of the emulsion state. The average particle size of the droplets is measured by the method described in the Examples below.

[0091] The content of component (A) in the wet powder adhesion inhibitor or the amount of component (A) blended when preparing the wet powder adhesion inhibitor is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of maintaining an emulsified state when used in combination with water, while from the viewpoint of viscosity and handleability, it is preferably 70% by mass or less, more preferably 40% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0092] The content of component (B) in the wet powder adhesion inhibitor or the amount of component (B) blended when preparing the wet powder adhesion inhibitor is preferably 0.02% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, from the viewpoint of reliably emulsifying each component and creating an emulsified state when used in combination with water, while from the viewpoint of handleability it is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0093] The content of component (C) in the wet powder adhesion inhibitor or the amount of component (C) to be blended when preparing the wet powder adhesion inhibitor is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, from the viewpoints of the stability of the emulsion state when used in combination with water and the water resistance of the film formed by drying the wet powder adhesion inhibitor, and from the same viewpoints, it is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0094] When component (D) is blended, the content of component (D) in the adhesion inhibitor of the present invention or the blending amount of component (D) when preparing the adhesion inhibitor is preferably 0.01 mass% or more, more preferably 0.03 mass% or more, and even more preferably 0.05 mass% or more, from the viewpoint of maintaining an emulsified state, while from the viewpoint of viscosity and handleability, it is preferably 1 mass% or less, more preferably 0.5 mass% or less, and even more preferably 0.2 mass% or less.

[0095] When water is blended, the content of water in the adhesion inhibitor of the present invention or the amount of water blended when preparing the adhesion inhibitor is, from the viewpoint of maintaining an emulsified state, preferably 10% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more, and from the same viewpoint, preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.

[0096] When component (E) is blended, the content of component (E) in the adhesion inhibitor of the present invention or the blending amount of component (E) when preparing the adhesion inhibitor is preferably 0.1 mass % or more, more preferably 0.2 mass % or more, and even more preferably 0.5 mass % or more from the viewpoint of wettability, and is preferably 5 mass % or less, more preferably 3 mass % or less, and even more preferably 2 mass % or less from the viewpoint of the water resistance of the film formed by drying the wet powder adhesion inhibitor. The blending amount of each component in the wet powder adhesion inhibitor of the present disclosure as described above can be considered to be the content of each component in the wet powder adhesion inhibitor of the present disclosure.

[0097] When component (E) is blended, the mass ratio of component (E) to component (A) is, from the viewpoint of wettability, preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 5 parts by mass or more, of component (E) per 100 parts by mass of component (A); on the other hand, from the viewpoint of the water resistance of the film formed by drying the wet powder adhesion inhibitor, it is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 20 parts by mass or less.

[0098] When component (E) is blended, the mass ratio of component (E) to component (B) is, from the viewpoint of wettability, preferably 10 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 100 parts by mass or more of component (E) per 100 parts by mass of component (B); on the other hand, from the viewpoint of the water resistance of the film formed by drying the wet powder adhesion inhibitor, preferably 300 parts by mass or less, more preferably 250 parts by mass or less, and even more preferably 200 parts by mass or less.

[0099] The wet powder adhesion inhibitor of the present invention can be applied to a hard surface (e.g., a metal surface, a resin surface, a glass surface, a ceramic surface, or the like) and dried at room temperature and normal pressure, or by heating or reducing the pressure as necessary, to form a wet powder adhesion inhibitor film. In the formed film, the anion-modified cellulose fiber of component (B) and the hydrophobic compound having a cationic functional group of component (C) are thought to form a salt.

[0100] Therefore, examples of uses of the wet powder adhesion inhibitor of the present invention include application to heavy machinery during construction work such as shield construction, tunneling work, and dredging work; application to manufacturing equipment such as hoppers and discharge sections at manufacturing sites; application to outdoor equipment such as tents, greenhouses, and solar panels; and application to walls and ceilings inside and outside buildings.

[0101] The wet powder adhesion inhibitor of the present invention can be prepared by mixing the components. Known devices that can be used for mixing include, without limitation, magnetic stirrers, mechanical stirrers, homomixers, vacuum emulsifiers, low-pressure homogenizers, high-pressure homogenizers, grinders, cutter mills, ball mills, jet mills, single-screw extruders, twin-screw extruders, ultrasonic agitators, and household juicer mixers. The mixing process may be performed by combining two or more types of operations. Water may be added during mixing, and in this case, emulsification occurs when the components are mixed, resulting in an emulsion composition.

[0102] The temperature and time during mixing of the components are not particularly limited, but are preferably in the range of 5 to 50°C and 1 minute to 3 hours, for example. The preferred ranges of the amounts of the components to be mixed are the same as those of the wet powder adhesion inhibitor of the present invention described above.

[0103] In the step (I), it is preferable to further mix a water-soluble cationic compound. By mixing a water-soluble cationic compound, a more stable emulsified state can be maintained. In this specification, water-soluble means that 1 g or more of the compound dissolves in 100 g of water at 25°C.

[0104] Examples of the water-soluble cationic compound include ammonia, amine compounds (for example, primary amines having from 1 to 8 carbon atoms, such as methylamine, ethylamine, propylamine, butylamine, hexylamine, and octylamine; diamines having from 1 to 12 carbon atoms, such as dimethylamine, diethylamine, dipropylamine, dibutylamine, and dihexylamine; and tertiary amines, such as trimethylamine, triethylamine, dimethylaminoethanol, and triethanolamine), and ammonium compounds (salts of the above amine compounds, and tetrabutylammonium). Among these, from the viewpoint of ensuring the stability of the emulsion composition, one or more compounds selected from the group consisting of ammonia, amine compounds, and ammonium compounds are preferred, and one or more compounds selected from the group consisting of ammonia and amine compounds are more preferred.

[0105] The boiling point of the water-soluble cationic compound is preferably 200° C. or lower, more preferably 150° C. or lower, and even more preferably 100° C. or lower, from the viewpoint of improving the water resistance of the film obtained by applying the emulsion composition and suppressing adhesion of wet powder. Therefore, among the specific compounds listed above, ammonia (boiling point: −33° C.), triethylamine (boiling point: 89° C.), and dimethylaminoethanol (boiling point: 133° C.) are more preferred.

[0106] The water-soluble cationic compound may be used alone or in combination of two or more. The amount of the water-soluble cationic compound to be added is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 100 mol% or more, based on the anionic group, preferably the carboxyl group, of component (C), from the viewpoints of the stability of the emulsion composition and the water resistance and suppression of adhesion of wet powder of the film obtained by drying the emulsion composition, and from the same viewpoints, is preferably 300 mol% or less, more preferably 200 mol% or less, and even more preferably 180 mol% or less.

[0107] At any stage in the production process of the wet powder adhesion inhibitor, the components or composition containing the anionically modified cellulose fibers of component (B) can be subjected to a micronization treatment, thereby reducing the average fiber diameter of the anionically modified cellulose fibers to the nanometer scale. Since reducing the average fiber diameter of the anionically modified cellulose fibers to the nanometer scale improves the stability of the wet powder adhesion inhibitor and the strength of the film when formed, it is preferable to carry out such a micronization treatment step.

[0108] A known dispersing machine is preferably used as the apparatus used in the micronization treatment. For example, a disintegrator, a beater, a low-pressure homogenizer, a high-pressure homogenizer, a grinder, a cutter mill, a ball mill, a jet mill, a single-screw extruder, a twin-screw extruder, an ultrasonic agitator, a household juicer mixer, etc. can be used. In addition, the solid content of the target material in the micronization treatment is preferably 50% by mass or less. The operating conditions of the apparatus during the micronization treatment can be appropriately set by a person skilled in the art based on known operating conditions or the operating conditions described in the instruction manual of each apparatus.

[0109] Anion-modified cellulose fibers that have been subjected to a micronization treatment (referred to as "micronized cellulose fibers") have a cellulose type I crystal structure derived from the raw cellulose fibers. The preferred range of the crystallinity of the micronized cellulose fibers is the same as the preferred range of the crystallinity of the anion-modified cellulose fibers described above.

[0110] The average fiber diameter of the pulverized 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 handleability, and is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less from the viewpoint of strength when formed into a film. The average fiber diameter of the pulverized cellulose fibers is measured by the method described in the Examples below.

[0111] The average fiber length of the pulverized cellulose fibers is preferably 10 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more from the viewpoint of handleability, and from the same viewpoint, is preferably 750 nm or less, more preferably 500 nm or less, and even more preferably 250 nm or less. The average fiber diameter of the pulverized cellulose fibers is measured by the method described in the Examples below.

[0112] In relation to the above-described embodiment, the present invention further discloses the following wet powder adhesion inhibitor, method for inhibiting adhesion of wet powder to a hard surface, and composition containing component (A) and the like.

[0113] <1> A wet powder adhesion inhibitor comprising the following components (A), (B), and (C): (A) an organic compound that is liquid at 25°C and 1 atmosphere; (B) an anion-modified cellulose fiber; and (C) a hydrophobic compound having a cationic functional group (excluding those corresponding to component (A)).

[0114] <2> The wet powder adhesion inhibitor according to <1>, wherein component (A) contains one or more selected from the group consisting of higher alcohols, ester oils, hydrocarbon oils, silicone oils, ether oils, oils and fats, fluorinated inert liquids, and fatty acids. <3> The wet powder adhesion inhibitor according to <1> or <2>, wherein component (A) contains one or more selected from the group consisting of ester oils and silicone oils. <4> The wet powder adhesion inhibitor according to any one of <1> to <3>, wherein the anionic group in component (B) contains one or more selected from the group consisting of a carboxy group, a sulfonic acid group, and a phosphate group. <5> The wet powder adhesion inhibitor according to any one of <1> to <4>, wherein component (B) has a degree of crystallinity of preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more. <6> The wet powder adhesion inhibitor according to any one of <1> to <5>, wherein the crystallinity of component (B) is preferably 90% or less, more preferably 85% or less, and even more preferably 80% or less. <7> The wet powder adhesion inhibitor according to any one of <1> to <6>, wherein component (B) is a micronized cellulose fiber and the average fiber diameter thereof is preferably 0.1 nm or more, more preferably 1.0 nm or more, and even more preferably 2.0 nm or more. <8> The wet powder adhesion inhibitor according to any one of <1> to <7>, wherein component (B) is a micronized cellulose fiber and the average fiber diameter thereof is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. <9> The wet powder adhesion inhibitor according to any one of <1> to <8>, wherein component (B) is a micronized cellulose fiber and the average fiber length thereof is preferably 10 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more. <10> The wet powder adhesion inhibitor according to any one of <1> to <9>, wherein the component (B) is a micronized cellulose fiber having an average fiber length of preferably 750 nm or less, more preferably 500 nm or less, and even more preferably 250 nm or less.

[0115] <11> The wet powder adhesion inhibitor according to any one of <1> to <10>, wherein component (C) comprises one or more compounds selected from the group consisting of polymeric compounds having a cationic functional group and hydrocarbon compounds having a cationic functional group. <12> The wet powder adhesion inhibitor according to any one of <1> to <11>, wherein component (C) comprises a silicone having an amino group. <13> The wet powder adhesion inhibitor according to any one of <1> to <12>, wherein the blending amount of component (A) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more. <14> The wet powder adhesion inhibitor according to any one of <1> to <13>, wherein the blending amount of component (A) is preferably 70% by mass or less, more preferably 40% by mass or less, even more preferably 20% by mass or less, and still more preferably 10% by mass or less. <15> The wet powder adhesion inhibitor according to any one of <1> to <14>, wherein the blending amount of component (B) is preferably 0.02% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. <16> The wet powder adhesion inhibitor according to any one of <1> to <15>, wherein the blending amount of component (B) is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. <17> The wet powder adhesion inhibitor according to any one of <1> to <16>, wherein the blending amount of component (C) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more. <18> The wet powder adhesion inhibitor according to any one of <1> to <17>, wherein the blending amount of component (C) is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. <19> The wet powder adhesion inhibitor according to any one of <1> to <18>, further comprising the following component (D): (D) A polymeric compound having an anionic functional group, the counter cation of which is one or more cations selected from the group consisting of ammonium ions and organic ammonium ions (excluding those corresponding to the aforementioned component (A) or the aforementioned component (B)).<20> The wet powder adhesion inhibitor according to <19>, wherein the polymer compound having an anionic functional group in component (D) is one or more selected from the group consisting of polyacrylic acid, polymethacrylic acid, polymaleic acid copolymer, polyallylsulfonic acid, and copolymers containing these constituent monomers (excluding those corresponding to component (A) or component (B)).

[0116] <21> The wet powder adhesion inhibitor according to <19> or <20>, wherein the compound providing the counter cation in component (D) is one or more selected from the group consisting of ammonia, triethylamine, and dimethylaminoethanol. <22> The wet powder adhesion inhibitor according to any one of <19> to <21>, wherein component (D) is at least one selected from the group consisting of ammonium polyacrylate and ammonium polycarboxylate. <23> The wet powder adhesion inhibitor according to any one of <1> to <12>, further comprising the following component (E): (E) a wetting agent. <24> The wet powder adhesion inhibitor according to <23>, wherein component (E) is a nonionic surfactant. <25> The wet powder adhesion inhibitor according to <23> or <24>, wherein component (E) comprises one or more selected from the group consisting of polyether-modified silicone surfactants, acetylene glycol surfactants, and alkyl glyceryl ether surfactants. <26> The wet powder adhesion inhibitor according to any one of <23> to <25>, which contains two or more types of component (E). <27> The wet powder adhesion inhibitor according to any one of <23> to <26>, wherein the amount of component (E) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and even more preferably 5 parts by mass or more, per 100 parts by mass of component (A). <28> The wet powder adhesion inhibitor according to any one of <23> to <27>, wherein the amount of component (E) is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of component (A). <29> The wet powder adhesion inhibitor according to any one of <23> to <28>, wherein the amount of component (E) is preferably 10 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 100 parts by mass or more, per 100 parts by mass of component (B). <30> The wet powder adhesion inhibitor according to any one of <23> to <29>, wherein the blending amount of component (E) is preferably 300 parts by mass or less, more preferably 250 parts by mass or less, and even more preferably 200 parts by mass or less, per 100 parts by mass of component (B).

[0117] <31> A wet powder adhesion inhibitor comprising the following components (A), (B), and (C): (A) one or more organic compounds that are liquid at 25°C and 1 atmosphere, selected from the group consisting of higher alcohols, ester oils, hydrocarbon oils, silicone oils, ether oils, fats and oils, fluorinated inert liquids, and fatty acids; (B) anion-modified cellulose fibers in which the anionic group contains one or more selected from the group consisting of carboxy groups, sulfonic acid groups, and phosphate groups; and (C) one or more hydrophobic compounds selected from the group consisting of polymeric compounds having a cationic functional group and hydrocarbon compounds having a cationic functional group (excluding those corresponding to component (A)). <32> A wet powder adhesion inhibitor comprising the following components (A), (B), and (C): (A) one or more organic compounds that are liquid at 25°C and 1 atmosphere, selected from the group consisting of ester oils and silicone oils; (B) anion-modified cellulose fibers, the anionic group of which contains one or more anionic groups selected from the group consisting of carboxyl groups, sulfonic acid groups, and phosphate groups; and (C) a silicone having an amino group (excluding those corresponding to the above-mentioned component (A)). <33> A wet powder adhesion inhibitor comprising a blend of the following components (A), (B), (C), (D), and (E'), wherein the wet powder adhesion inhibitor comprises a blend of two or more types of component (E'). (A) an organic compound that is liquid at 25°C and 1 atmosphere; (B) anion-modified cellulose fiber; (C) a hydrophobic compound having a cationic functional group (excluding those corresponding to the component (A) above); (D) a polymer compound having an anionic functional group and having one or more counter cations selected from the group consisting of ammonium ions and organic ammonium ions (excluding those corresponding to the component (A) or the component (B) above); (E') one or more surfactants selected from the group consisting of polyether-modified silicone surfactants, acetylene glycol surfactants, and alkyl glyceryl ether surfactants. <34> A method for inhibiting the adhesion of wet powder to a hard surface, comprising the steps of: applying to a hard surface a wet powder adhesion inhibitor comprising a blend of the following components (A), (B), and (C); and forming a film of the wet powder adhesion inhibitor on the hard surface.(A) an organic compound that is liquid at 25°C and 1 atmospheric pressure; (B) an anion-modified cellulose fiber; and (C) a hydrophobic compound having a cationic functional group (excluding those corresponding to the component (A) above). <35> A method for inhibiting adhesion of a wet powder onto a hard surface, comprising: a step of applying to a hard surface a wet powder adhesion inhibitor formed by blending the following components (A), (B), and (C), and a step of forming a film of the wet powder adhesion inhibitor on the hard surface, wherein the weight ratio of liquid to powder contained in the wet powder is 10 mass% or more. (A) an organic compound that is liquid at 25°C and 1 atmosphere (B) anion-modified cellulose fibers (C) a hydrophobic compound having a cationic functional group (excluding those corresponding to the component (A) above). <36> A composition comprising the following components (A), (B), (C), (D), and (E'), wherein the composition comprises two or more types of component (E'): (A) an organic compound that is liquid at 25°C and 1 atmosphere (B) anion-modified cellulose fibers (C) a hydrophobic compound having a cationic functional group (excluding those corresponding to the component (A) above). (D) a polymer compound that has an anionic functional group and whose counter cation is one or more selected from the group consisting of ammonium ions and organic ammonium ions (excluding those corresponding to the component (A) or the component (B) above). (E') one or more surfactants selected from the group consisting of polyether-modified silicone surfactants, acetylene glycol surfactants, and alkyl glyceryl ether surfactants.

[0118] 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 are not intended to limit the scope of the present invention. Note that "normal pressure" refers to 101.3 kPa, and "normal temperature" refers to 25°C.

[0119] [Average Fiber Diameter, Average Fiber Length, and Average Aspect Ratio of Anion-Modified Cellulose Fibers] Water is added to the cellulose fibers to be measured to prepare a dispersion with a content of 0.0001% by mass. The dispersion is dropped onto mica and dried to form an observation sample. The fiber height (height difference between fiber-containing and non-fiber-containing areas) of the cellulose fibers in the observation sample is measured using an atomic force microscope (AFM) (Digital Instruments, Nanoscope II Tapping mode AFM; Nanosensors, Point Probe (NCH) probe). At this time, 100 or more cellulose fibers are extracted from a microscopic image in which the cellulose fibers can be seen, and the average fiber diameter is calculated from their fiber height. The average fiber length is calculated from the distance in the fiber direction. The average aspect ratio is calculated by dividing the average fiber length by the average fiber diameter. The height analyzed in the AFM image can be considered the fiber diameter.

[0120] [Average Fiber Diameter and Average Fiber Length of Raw Cellulose Fibers] Deionized water is added to the cellulose fibers to be measured to prepare a dispersion with a cellulose content of 0.01% by mass. The dispersion is measured using a wet dispersion type image analysis particle size distribution analyzer (IF-3200, manufactured by JUSCO International Co., Ltd.) under the following conditions: front lens: 2x, telecentric zoom lens: 1x, image resolution: 0.835 μm / pixel, syringe inner diameter: 6515 μm, spacer thickness: 500 μm, image recognition mode: ghost, threshold: 8, analysis sample volume: 1 mL, and sampling: 15%. At least 100 cellulose fibers are measured, and the average ISO fiber diameter and average ISO fiber length are calculated as the average fiber diameter and average fiber length, respectively.

[0121] [Anionic Group Content of Anion-Modified Cellulose Fiber] 0.5 g of the cellulose fiber to be measured (dry mass) is placed in a 100 mL beaker, and deionized water or a 2:1 methanol / water mixed solvent is added to make a total of 55 mL. 5 mL of 0.01 M aqueous sodium chloride solution is added to the beaker to prepare a dispersion. The dispersion is stirred until the cellulose fiber to be measured is sufficiently dispersed. 0.1 M hydrochloric acid is added to the dispersion to adjust the pH to 2.5-3. Using an automatic titrator (DKK-TOA Corporation, AUT-701), 0.05 M aqueous sodium hydroxide solution is added dropwise to the dispersion with a waiting time of 60 seconds, and the conductivity and pH values ​​are measured every minute. Measurements are continued until the pH reaches approximately 11, and a conductivity curve is obtained. The sodium hydroxide titration amount is determined from this conductivity curve, and the anionic group content of the cellulose fiber to be measured is calculated using the following formula: Anionic group content (mmol / g) = [sodium hydroxide titration amount × sodium hydroxide aqueous solution concentration (0.05 M)] / [mass of cellulose fiber to be measured (0.5 g)]

[0122] [Solid content in various solutions and dispersions] This is measured using a halogen moisture meter (Shimadzu Corporation; MOC-120H). Measurements are made every 30 seconds for 1 g of sample at a constant temperature of 150°C, and the value at which the mass loss is 0.1% or less of the initial amount of the sample is taken as the solid content.

[0123] [Confirmation of Crystalline Structure in Various Cellulose Fibers] The crystal structure of various cellulose fibers is confirmed by measurement using an X-ray diffractometer (MiniFlex II, manufactured by Rigaku Corporation) under the following conditions. The measurement conditions are: X-ray source: Cu / Kα-radiation, tube voltage: 30 kV, tube current: 15 mA, measurement range: diffraction angle 2θ = 5 to 45°, X-ray scan speed: 10° / min. The measurement sample has an area of ​​320 mm. ２ The degree of crystallinity of the cellulose type I crystal structure is calculated from the obtained X-ray diffraction intensity according to the following formula A.

[0124] <Equation A> Cellulose I type crystallinity (%) = [(I ２２．６ -I １８．５ ) / I ２２．６ ]×100 [wherein, I２２．６ is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6°) in X-ray diffraction, I １８．５ indicates the diffraction intensity of the amorphous portion (diffraction angle 2θ=18.5°).

[0125] On the other hand, when the crystallinity obtained by the above formula A is 35% or less, from the viewpoint of improving calculation accuracy, it is preferable to calculate based on the following formula B in accordance with the description on pages 199-200 of "Wood Science Experiment Manual" (edited by the Japan Wood Research Society; published in April 2000). Therefore, when the crystallinity obtained by the above formula A is 35% or less, the value calculated based on the following formula B can be used as the crystallinity.

[0126] <Equation B> Cellulose type I crystallinity (%) = [A ｃ / (A ｃ +A ａ )]×100 [In the formula, A ｃ is the sum of the peak areas of the lattice planes (002 plane) (diffraction angle 2θ=22.6°), (011 plane) (diffraction angle 2θ=15.1°) and (0-11 plane) (diffraction angle 2θ=16.2°) in X-ray diffraction, A ａ indicates the peak area of ​​the amorphous portion (diffraction angle 2θ = 18.5°), and each peak area is determined by fitting the obtained X-ray diffraction chart with a Gaussian function.

[0127] [Anion-modified cellulose fiber] As anion-modified cellulose fiber 1, TEMPO-oxidized cellulose fiber having the physical properties shown in Table 1 was used.

[0128]

[0129] Such anion-modified cellulose fiber 1 can be prepared, for example, by the method described in the TEMPO oxidation treatment below.

[0130] [TEMPO oxidation treatment] 10 g of bleached coniferous kraft pulp fiber as the raw natural cellulose fiber and 990 g of deionized water were weighed into a 2 L PP beaker equipped with a mechanical stirrer and stirring blades and stirred at 25°C and 100 rpm for 30 minutes. Next, 0.13 g of TEMPO, 1.3 g of sodium bromide, and 35.5 g of a 10.5 wt% aqueous sodium hypochlorite solution were added to the 10 g of pulp fiber in this order. Next, pH stat titration was performed using an automatic titrator, and 0.5 M aqueous sodium hydroxide solution was added dropwise to maintain the pH at 10.5. The reaction was carried out at 25°C for 120 minutes with a stirring speed of 100 rpm.

[0131] Next, 1 M hydrochloric acid is added to the suspension while stirring to adjust the pH of the suspension to 2. Next, the solid content is separated by suction filtration. The operation of dispersing the solid content in deionized water and separating the solid content by suction filtration is repeated until the conductivity of the filtrate reaches 200 μs / cm or less. The resulting solid content is subjected to a dehydration treatment to obtain anion-modified cellulose fiber 1.

[0132] [Preparation of Micronized Cellulose Fiber Dispersion] Preparation Example 1 7.69 g of the suspension of anion-modified cellulose fiber 1 (solid content 26.0% by mass) and 4.23 mL of 1 M aqueous ammonia (4.23 mmol as ammonia) were weighed into a flask equipped with a stirrer, and deionized water was added to make a total of 200 g. This mixture was heated at 75°C while stirring for 9 hours, allowed to cool to room temperature, and then subjected to a micronization treatment by one pass at 150 MPa using a high-pressure homogenizer (Yoshida Kikai Co., Ltd., Nanovaita L-ES) to obtain a micronized cellulose fiber dispersion (solid content 1.0% by mass). The crystallinity of the micronized cellulose fibers was 60%, the average fiber diameter was 3.3 nm, and the average fiber length was 165 nm.

[0133] [Preparation of Wet Powder Adhesion Inhibitor] Example 1 60 g (solid content 1.0 mass%) of the micronized cellulose fiber dispersion obtained in Preparation Example 1, 6 g of silicone oil 1, 3.6 g of amino-modified silicone 1 (corresponding to 2.5 equivalents relative to the carboxy groups of the anion-modified cellulose fiber), and 0.8 g of ammonium polyacrylate 1 (10 mass% aqueous solution) were weighed and mixed in a beaker, and deionized water was added to make a total of 100 g. This solution was processed five times in a high-pressure homogenizer (NanoVita L-ES, manufactured by Yoshida Kikai Co., Ltd.) at 150 MPa to obtain a composition. Visual observation of this composition revealed a uniform white turbidity, and this composition was determined to be an emulsion composition. The average droplet size was 1.1 μm. The emulsion composition prepared as described above was designated as Wet Powder Adhesion Inhibitor 1.

[0134] Example 2 50 g of wet powder adhesion inhibitor 1 was placed in a beaker, to which 0.25 g of polyether-modified silicone 1 and 0.25 g of 2-ethylhexyl glyceryl ether were added, and the mixture was stirred and mixed with a magnetic stirrer to obtain wet powder adhesion inhibitor 2. The average particle size of the droplets was 1.1 μm.

[0135] Example 3 An emulsion composition was prepared in the same manner as in Example 1, except that component (D) was not added, by blending components (A) to (C) and water in the ratios shown in Table 2. This emulsion composition was designated wet powder adhesion inhibitor 3.

[0136] Examples 4 to 11 In the same manner as in Example 1, emulsion compositions were prepared by blending components (A) to (D) and water shown in Table 2 in the ratios shown in Table 2. Next, in the same manner as in Example 2, component (E) was blended in the ratio shown in Table 2, to prepare wet powder adhesion inhibitors 4 to 11.

[0137] The composition of each example is shown in Table 2. The amount of each component in Table 2 is in mass %.

[0138]

[0139] Reference Example 1 A water-in-oil emulsion of a copolymer of sodium acrylate and acrylamide was used as the wet powder adhesion inhibitor of Reference Example 1 (40% by mass of sodium acrylate / acrylamide copolymer, 35% by mass of water, 25% by mass of hydrocarbon solvent). The copolymer of sodium acrylate and acrylamide can be synthesized by known methods, for example, those described in JP-A-50-72982.

[0140] Details of the main components used in the Preparation Examples and Examples are summarized below. [Component (A)] Silicone oil 1: KF-96-3000cs, manufactured by Shin-Etsu Chemical Co., Ltd. (SP value: 7.3. This silicone oil is liquid at 25°C and 1 atmosphere.) Silicone oil 2: KF-96H-10,000cs, manufactured by Shin-Etsu Chemical Co., Ltd. (SP value: 7.3. This silicone oil is liquid at 25°C and 1 atmosphere.) Silicone oil 3: KF-96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd. (SP value: 7.3. This silicone oil is liquid at 25°C and 1 atmosphere.) Isopropyl palmitate: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (SP value: 8.5. This compound is liquid at 25°C and 1 atmosphere.) [Component (C)] Amino-modified silicone 1: DOWSIL, manufactured by Dow-Toray Industries, Inc. ＴＭ FZ-3710, (Kinematic viscosity at 25 ° C: 1,000 mm ２ / s, amino equivalent: 1,700 g / mol. The solubility of this amino-modified silicone 1 in water at 25°C is 5% by mass or less.) [Component (D)] Ammonium polyacrylate 1: Aron A30-SL (weight average molecular weight = 6,000, functional group equivalent = 99 g / mol), manufactured by Toagosei Co., Ltd. [Component (E)] 2-Ethylhexyl glyceryl ether: Tokyo Chemical Industry Co., Ltd. 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD): Tokyo Chemical Industry Co., Ltd. Polyether-modified silicone 1: KF-642, manufactured by Shin-Etsu Chemical Co., Ltd.

[0141] [Preparation of Dry Films] The wet powder adhesion inhibitors of Examples 1 to 11 and the sodium acrylate / acrylamide copolymer of Reference Example 1 were each applied to separate glass substrates (Micro Slide Glass S2112, manufactured by Matsunami Co., Ltd.) or cold-rolled steel (SPCC) substrates (SPCC-SD, 25 × 100 × t 1.6 mm, manufactured by Standard Test Piece Co., Ltd.) degreased with acetone, and dried at 1 atmosphere, 25°C, and approximately 40% RH for 24 hours to prepare films on the substrates. The thickness of each film was measured using the following method, and was found to be 10 μm in all cases.

[0142] [Measurement of film thickness] A portion of the dried film prepared as described above was scraped off with a metal spatula to expose the surface of the glass slide. Images of the surface of the dried film and the surface of the glass slide were taken with a laser microscope (Lasertec Corporation, OPTELICS HYBRID+, light source: xenon lamp, objective lens: Nikon TU Plan Fluor 10x, NA: 0.30). The heights of the surface of the glass slide and the surface of the dried film were calculated using the built-in image software, and the difference between them was taken as the thickness of the dried film.

[0143] Comparative Examples 1 and 2 In Comparative Example 1, the above-mentioned glass substrate with no coating was used, and in Comparative Example 2, the above-mentioned SPCC substrate with no coating was used after being degreased with acetone.

[0144] Test Example 1 (Evaluation of Wet Powder Residualness) JIS Z 8901 Test Powder 1 Type 8 (Kanto Loam Calcined Product) was used as the powder. 75 g (75% by weight) of deionized water was added to 100 g of powder and stirred to prepare Wet Powder 1. The wet powder was then placed on top of each horizontal substrate according to the conditions shown in Table 3, tilted vertically (i.e., 90°), and allowed to stand for 10 seconds. The weight of the remaining wet powder was measured. The wet powder residual rate [%] was calculated using the following formula. A smaller wet powder residual rate indicates greater suppression of wet powder adhesion. Wet Powder Residual Rate [%] = (Wet Powder Residual Weight) / (Wet Powder Weight on Substrate) × 100. Furthermore, 50 g (50% by weight) of deionized water was added to 100 g of powder and stirred to prepare Wet Powder 2, which was then tested in the same manner.

[0145]

[0146] Test Example 2 [Measurement of Oil-Bleeding Rate] Wet powder adhesion inhibitors 1 to 11 were applied to the above-mentioned glass substrate, and the oil-bleeding rate of the dried film was measured. The oil-bleeding rate was measured as follows. For each dried film, a PP porous film (GATSBY oil blotting film, manufactured by Mandom Corporation) was pressed against the entire surface to remove component (A) that had bled onto the film surface. This operation was repeated twice, and the weight of absorbed component (A) was quantified from the change in weight of the dried film before and after removal. Next, the oil-bleeding rate of component (A) was measured using the following formula: (Oil-bleeding rate) [wt%] = (Weight of component (A) absorbed by the PP porous film) / (Weight of dried film before oil removal) × 100

[0147] It is thought that a high oil-bleed rate will enhance the wet powder adhesion suppression effect, but since the effect cannot be expected to be sustainable, it can be judged to be inferior in practicality. On the other hand, the lower the oil-bleed rate, the higher the durability, and in particular, an oil-bleed rate of less than 10% can be said to be particularly high durability. Therefore, the wet powder adhesion suppression of the present invention can be evaluated as preferable because it exhibits a high wet powder adhesion suppression effect while having a low oil-bleed rate.

[0148] The composition of each component in the dried film obtained using the composition of each example and the evaluation results are shown in Tables 4 to 7. The numerical value of each component in Tables 4 to 7 is a relative value when the mass of the microfibrillated cellulose fiber, which is component (B), is taken as 10.

[0149]

[0150]

[0151]

[0152]

[0153] Tables 4 and 5 show that, when used on glass substrates, the wet powder adhesion inhibitor of the present invention exhibited a superior adhesion inhibitory effect compared to Comparative Example 1, in which nothing was applied to the substrate surface, and Reference Example 1, in which a copolymer was applied. Examples 1, 2, and 4 to 6 show that the addition of component (E) further enhances the wet powder adhesion inhibitory effect. While the reason for this is unclear, it is believed that the enhanced wettability of the wet powder adhesion inhibitor to the substrate surface allows for the formation of a more uniform film on the substrate surface. Examples 2, 7, and 8 show that low-viscosity silicone oils are relatively more effective, and Example 11 shows that even an ester oil with an SP value of 8.5 can be effective. Furthermore, Examples 8 to 10 show that the higher the proportion of component (A) in the wet powder adhesion inhibitor, the greater the effect.

[0154] Furthermore, Tables 6 and 7 show that, similarly to the above, when an SPCC substrate was used, the wet powder adhesion inhibitor of the present invention had a superior adhesion inhibitory effect compared to Comparative Example 2, in which nothing was applied to the substrate surface, and Reference Example 1, in which the copolymer was applied. This suggests that the wet powder adhesion inhibitor of the present invention can inhibit the adhesion of wet powder regardless of differences in the substrate material.

[0155] For the wet powder adhesion inhibitor 10, Comparative Example 1, and Comparative Example 2, evaluation was carried out in the same manner as in Test Example 1, and in Test Examples 3 and 4 shown below, using wet powders 3 to 10 shown in Table 8. The results are shown in Tables 9 and 10.

[0156]

[0157] Test Example 3 [Evaluation of Wet Powder Adhesion Amount] 50 mL of wet powder was placed in a 100 mL plastic cup, and each substrate was placed in and removed 50 times. After 50 times, the wet powder adhering to the back surface of the substrate was removed, and the weight of the wet powder adhering to the front surface was measured. Here, the front surface refers to the surface to which the wet powder adhesion inhibitor was applied.

[0158] Test Example 4 (Evaluation of Wet Powder Removability) Starch (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the powder. 75 g (75% by weight) of deionized water was added to 100 g of powder and stirred to prepare wet powder 8. Next, wet powder 8 was spread on each substrate and rubbed 10 times with Kimwipes (registered trademark). Then, a starch reaction iodine solution (manufactured by Hayashi Pure Chemical Industries, Ltd.) was spread and the removability of the wet powder was evaluated according to the following criteria. Areas where starch remained turned purple, and the smaller the area of ​​the substrate surface that turned purple, the better the removability of the wet powder. Here, "dry wiping" in the table refers to rubbing 10 times with a dry Kimwipe (registered trademark), and "wet wiping" refers to rubbing 10 times with a Kimwipe (registered trademark) moistened with water.

[0159] 1: A state in which 2 area% or less of the substrate surface is colored purple. 2: A state in which more than 2 area% and 10 area% or less of the substrate surface is colored purple. 3: A state in which more than 10 area% and 20 area% or less of the substrate surface is colored purple. 4: A state in which more than 20 area% and 30 area% or less of the substrate surface is colored purple. 5: A state in which more than 30 area% and 50 area% of the substrate surface is colored purple. 6: A state in which more than 50 area% and 80 area% of the substrate surface is colored purple. 7: A state in which more than 80 area% of the substrate surface is colored purple.

[0160] Furthermore, 50 g (50% by weight) and 30 g (30% by weight) of deionized water were added to 100 g of powder and mixed to prepare wet powders 9 and 10, respectively, and tests were carried out in the same manner.

[0161]

[0162]

[0163] Table 9 shows that, when used on a glass substrate, the wet powder adhesion inhibitor of the present invention is superior in its adhesion-inhibiting effect on a wide range of wet powders, including clay soil, charcoal, and starch, compared to Comparative Example 1, where nothing was applied to the substrate surface. Furthermore, it was found that not only does it facilitate sliding when tilted, but it also has an excellent adhesion-inhibiting effect when inserted and removed, even for wet powders with relatively low moisture content that tend to adhere. Furthermore, it was found to be excellent in ease of removal even for wet powders that become sticky due to moisture, such as starch. This evaluation confirmed that the wet powder adhesion inhibitor of the present invention is excellent in ease of removal of wet powder, even with dry wiping, which is usually difficult to remove. Furthermore, Table 10 shows that, similarly to the above, these effects were also exhibited when used on an SPCC substrate, compared to Comparative Example 2, where nothing was applied to the substrate surface, indicating that the wet powder adhesion inhibitor of the present invention had a superior adhesion-inhibiting effect. This suggests that the wet powder adhesion inhibitor of the present invention can inhibit wet powder adhesion regardless of the substrate material.

[0164] Production Example 1 (Production of an anion-modified cellulose wet powder adhesion inhibitor) Even if anion-modified cellulose fiber 2 into which phosphoric acid has been introduced is used instead of TEMPO-oxidized cellulose fiber into which a carboxy group has been introduced, a wet powder adhesion inhibitor similar to those of Examples 1 to 11 can be obtained. Such anion-modified cellulose fiber 2 can be prepared by the following phosphorylation treatment.

[0165] [Phosphorylation Treatment] 100 parts by mass of solids of bleached softwood kraft pulp fiber as the raw natural cellulose fiber is impregnated with a mixed aqueous solution of ammonium dihydrogen phosphate and urea, and then compressed to obtain 56 parts by mass of ammonium dihydrogen phosphate and 150 parts by mass of urea, to obtain chemical-impregnated fiber. The chemical-impregnated fiber is dried in a dryer at 105°C to evaporate water. The evaporated fiber is heated for 4 minutes in a fan dryer set at 140°C. 10,000 parts by mass of deionized water is added to 100 parts by mass of the obtained fiber, and the fiber is dispersed by stirring, and the solids are then filtered off by suction filtration. 10,000 parts by mass of deionized water is added to 100 parts by mass of the solids in the filtered cake, and the fiber is dispersed by stirring, and the solids are then filtered off by suction filtration. To the resulting cake, 10,000 parts by mass of deionized water is added, and while stirring, a 1 N aqueous sodium hydroxide solution is added dropwise to obtain a slurry with a pH of 12 to 13. Next, while stirring, 0.01 M hydrochloric acid is added to the suspension to adjust the pH to 2. The solid content is then separated by suction filtration. The resulting cake is dispersed in deionized water, and the cake is separated by suction filtration. This operation is repeated until the conductivity of the filtrate reaches 200 μS / cm or less. The resulting solid content is subjected to a dehydration treatment to obtain anion-modified cellulose fiber 2.

[0166] By applying the wet powder adhesion inhibitor of the present invention to the bucket or the like of a power shovel, etc., adhesion of soil (including water) to the surface of the bucket, etc. can be inhibited, and therefore the wet powder adhesion inhibitor of the present invention can be used in civil engineering fields that handle soil and sand containing water. Furthermore, by applying the wet powder adhesion inhibitor of the present invention to devices, equipment, and surrounding walls, ceilings, windows, etc. that handle wet powder, adhesion of wet powder to these devices, etc. can be inhibited, and therefore the wet powder adhesion inhibitor of the present invention can be used to reduce the production and cleaning burden at production sites, food factories, etc.

Claims

1. A wet powder adhesion inhibitor comprising the following components (A), (B), and (C): (A) an organic compound that is liquid at 25°C and 1 atmosphere; (B) an anion-modified cellulose fiber; and (C) a hydrophobic compound with a cationic functional group (excluding those corresponding to component (A) above).

2. The wet powder adhesion inhibitor according to claim 1, wherein the amount of component (A) is 0.1% by mass or more and 70% by mass or less.

3. A wet powder adhesion inhibitor according to claim 1 or 2, wherein the amount of component (B) is 0.02 mass % or more and 15 mass % or less.

4. A wet powder adhesion inhibitor according to any one of claims 1 to 3, wherein the amount of component (C) blended is 0.5% by mass or more and 20% by mass or less.

5. The wet powder adhesion inhibitor according to any one of claims 1 to 4, further comprising the following component (D): (D) a polymeric compound having an anionic functional group, the counter cation of which is one or more selected from the group consisting of ammonium ions and organic ammonium ions (excluding those corresponding to the component (A) or the component (B)).

6. The wet powder adhesion inhibitor according to any one of claims 1 to 5, further comprising the following component (E): (E) Wetting Agent 7. A wet powder adhesion inhibitor according to claim 6, wherein the amount of component (E) blended is 0.1 parts by mass or more and 100 parts by mass or less per 100 parts by mass of component (A).

8. A wet powder adhesion inhibitor according to claim 6 or 7, wherein the amount of component (E) blended is 10 parts by mass or more and 300 parts by mass or less per 100 parts by mass of component (B).

9. The wet powder adhesion inhibitor according to any one of claims 6 to 8, which comprises a blend of two or more types of component (E).

10. A method for inhibiting the adhesion of wet powder to a hard surface, comprising the steps of: applying to a hard surface a wet powder adhesion inhibitor comprising a blend of the following components (A), (B), and (C), and forming a film of the wet powder adhesion inhibitor on the hard surface: (A) an organic compound that is liquid at 25°C and 1 atmosphere, (B) anion-modified cellulose fiber, and (C) a hydrophobic compound having a cationic functional group (excluding those corresponding to component (A) above).

11. The method according to claim 10, wherein the weight ratio of liquid to powder contained in the wet powder is 10% by mass or more.

12. A composition comprising the following components (A), (B), (C), (D), and (E'), wherein the composition contains two or more types of component (E'): (A) an organic compound that is liquid at 25°C and 1 atmosphere (B) anion-modified cellulose fiber (C) a hydrophobic compound having a cationic functional group (excluding those corresponding to component (A) above) (D) a polymer compound having an anionic functional group and having one or more counter cations selected from the group consisting of ammonium ions and organic ammonium ions (excluding those corresponding to component (A) or (B) above) (E') one or more selected from the group consisting of polyether-modified silicone surfactants, acetylene glycol surfactants, and alkyl glyceryl ether surfactants

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