CELLULOSE PARTICLES

Description

Background(i) Technical Field

[0001] The present disclosure relates to a cellulosic particle.(ii) Related Art

[0002] In Japanese Unexamined Patent Application Publication No. 2022-099605, "resin beads obtained by surface treatment of core beads formed from a resin having cellulose as a main component by a solid surface treatment agent, in which the volume-based cumulative 50% particle size is 50 µm or less, the sphericity is 0.7-1.0, the surface smoothness is 70-100%, and the degree of crystallization is 60% or less." are proposed.

[0003] In Japanese Unexamined Patent Application Publication No. 2020-132616, "oily solid cosmetics containing surface-treated spherical cellulose powder with an average particle size of 1.0-30.0 µm." is proposed.

[0004] WO 2022 / 137679 A1 discloses resin beads formed of a resin containing cellulose as a main component, a method for producing the resin beads, and products such as cosmetics obtained by using the resin beads.

[0005] EP 4116357 A1 discloses resin beads containing a cellulose derivative as a main component, a method for producing the resin beads, and products, such as cosmetics, obtained using the resin beads.

[0006] CN 114555678 A discloses a cellulose particle and a method for producing a cellulose particle.Summary

[0007] The present disclosure is provided by the appended set of claims.

[0008] Accordingly, it is an object of the present disclosure to provide a cellulosic particle as defined in the appended claim 1 that has a fluffy feel compared with if at least one of the amount of the hydrocarbon ester and the amount of the ketone in the cellulosic particle is less than 3 ppm or more than 1000 ppm.

[0009] It should be noted that the "fluffy feel" is a measure represented in "Fluffy Feel Evaluations" in the Examples below.

[0010] According to the appended claim 2 of the present disclosure, there is provided a cellulosic particle that has a fluffy feel compared with if the cellulosic particle has a coating layer containing a silane compound.

[0011] According to the appended claim 3 of the present disclosure, there is provided a cellulosic particle that has a fluffy feel compared with if the fatty acid is a fatty acid having fewer than 16 or more than 22 carbon atoms or if the number of carbon atoms in the fatty acid metallic salt is fewer than 16 or more than 22.

[0012] According to the appended claim 4 of the present disclosure, there is provided a cellulosic particle that has a fluffy feel compared with if the fatty acid is an unsaturated fatty acid or if the fatty acid metallic salt is an unsaturated fatty acid metallic salt.

[0013] According to the appended claim 5 of the present disclosure, there is provided a cellulosic particle that has a fluffy feel compared with if the cellulosic particle has an intermediate layer containing arginine or dextrin.

[0014] According to the appended claim 6 of the present disclosure, there is provided a cellulosic particle that has a fluffy feel compared with if the cellulosic particle has no inorganic particle as an external additive.

[0015] According to the appended claim 7 of the present disclosure, there is provided a cellulosic particle that has a fluffy feel compared with if the volume-average particle diameter is less than 3 µm or 10 µm or more.

[0016] According to the appended claim 8 of the present disclosure, there is provided a cellulosic particle that has a fluffy feel compared with if the upper geometric standard deviation by number GSDv is less than 1.0 or greater than 1.7.

[0017] According to the appended claim 9 of the present disclosure, there is provided a cellulosic particle that has a fluffy feel compared with if the sphericity is less than 0.7.

[0018] According to the appended claim 10 of the present disclosure, there is provided a cellulosic particle that has a fluffy feel compared with if the surface smoothness is less than 50%.

[0019] According to the appended claim 11 of the present disclosure, there is provided a cellulosic particle that has a fluffy feel compared with if the number-average molecular weight of the cellulose is less than 37000.

[0020] According to the appended claim 12 of the present disclosure, there is provided a cellulosic particle that has a fluffy feel compared with if the number-average molecular weight of the cellulose is less than 45000.Detailed Description

[0021] Exemplary embodiments as examples of the present disclosure will now be described. These descriptions and the Examples are intended to illustrate exemplary embodiments and not intended to limit the scope of aspects of the present disclosure.

[0022] In a series of numerical ranges presented herein, an upper or lower limit specified in one numerical range may be substituted with the upper or lower limit of another numerical range in the same series.

[0023] A constituent may include multiple corresponding substances.

[0024] When the amount of a constituent in a composition is mentioned herein, and if multiple substances corresponding to the constituent are present in the composition, the mentioned amount represents the total amount of the multiple substances present in the composition unless stated otherwise.

[0025] "Step" refers not only to an independent step; even if a step cannot be clearly distinguished from another, the step is included in this term as long as its intended action is achieved.Cellulosic Particles

[0026] Cellulosic particles according to an exemplary embodiment contain cellulose as their base constituent and at least one selected from the group consisting of a hydrocarbon ester and a ketone, and at least one of the amount of the hydrocarbon ester and the amount of the ketone is 3 ppm or more and 1000 ppm or less.

[0027] Configured as described above, the cellulosic particles according to this exemplary embodiment are cellulosic particles having a fluffy feel. Possible reasons are as follows.

[0028] Known cellulosic particles tend to be lacking in fluffy feel because hydrogen bonding inside and outside the cellulose as their base constituent is firm.

[0029] The cellulosic particles according to this exemplary embodiment contain cellulose as their base constituent and at least one selected from the group consisting of a hydrocarbon ester and a ketone. Hydrocarbon esters tend to be likely to penetrate between cellulose molecules and, at the same time, are likely to weaken hydrogen bonding inside and outside the cellulose molecules because hydroxyl groups contained in the cellulose and the ester group in the hydrocarbon ester interact. Ketones, too, are likely to weaken hydrogen bonding inside and outside the cellulose molecules because they interact with hydroxyl groups contained in the cellulose molecules. The cellulosic particles according to this exemplary embodiment, furthermore, are likely to have an improved fluffy feel because the higher-order structure of the cellulose is disturbed by virtue of the presence of at least one selected from the group consisting of a hydrocarbon ester and a ketone.

[0030] The amount of the hydrocarbon ester or ketone, furthermore, is 3 ppm or more and 1000 ppm or less. By setting the amount of the hydrocarbon ester or ketone to 3 ppm or more, it is easier for these compounds to penetrate into cellulose molecules. By setting the amount of the hydrocarbon ester or ketone to 1000 ppm or less, their exudation from the cellulosic particles is reduced.

[0031] For these reasons, presumably, the cellulosic particles according to this exemplary embodiment are cellulosic particles having a fluffy feel.Constituents of the Cellulosic ParticlesCellulose

[0032] The cellulosic particles according to this exemplary embodiment contain cellulose as their base constituent.

[0033] In this context, containing cellulose as a base constituent means that the amount of cellulose relative to the cellulosic particles is 90% by mass or more.

[0034] When the cellulosic particles have the coating and intermediate layers described later herein, containing cellulose as a base constituent means that the cellulose content relative to the core particle is 90% by mass or more.

[0035] The number-average molecular weight of the cellulose may be 37000 or more, preferably 45000 or more.

[0036] There is no particular upper limit, but for example, the number-average molecular weight of the cellulose may be 100000 or less.

[0037] By setting the number-average molecular weight of the cellulose to 37000 or more, it is likely that the number of hydroxyl groups exposed on the surface of the cellulosic particles is small. It is, therefore, likely that dispersibility in a dispersion is improved. By setting the number-average molecular weight of the cellulose to 45000 or more, it is more likely that the number of hydroxyl groups exposed on the surface of the cellulosic particles is small. It is, therefore, more likely that dispersibility in a dispersion is improved.

[0038] The number-average molecular weight of the cellulose is measured by gel permeation chromatography (differential refractometer, Optilab T-rEX, Wyatt Technology; multiangle light scattering detector, DAWN HELEOS II, Wyatt Technology; columns, one TSKgel α-M and one α-3000, Tosoh) with dimethylacetamide (with the addition of 0.1 M lithium chloride) as the eluent.Hydrocarbon Ester

[0039] A hydrocarbon ester is a compound having at least one ester group and in which only a hydrocarbon group binds to the ester group.

[0040] The number of ester groups that the hydrocarbon ester contains may be one or two, preferably one.

[0041] The number of carbon atoms that the hydrocarbon ester contains may be one or more and eight or fewer, preferably one or more and five or fewer, more preferably one or more and three or fewer.

[0042] The hydrocarbon group that the hydrocarbon ester contains may be a saturated hydrocarbon group, and examples include the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, and octyl groups.

[0043] The hydrocarbon ester is at least one selected from the group consisting of ethyl acetate, butyl acetate, and ethyl propionate, preferably ethyl acetate.

[0044] By using at least one selected from the group consisting of ethyl acetate, butyl acetate, and ethyl propionate as the hydrocarbon ester, the penetration between cellulose molecules is encouraged. As a result, the fluffy feel of the cellulosic particles further improves.Ketone

[0045] A ketone is a compound having at least one carbonyl group and in which only a hydrocarbon group binds to the carbonyl group.

[0046] The number of carbonyl groups that the ketone contains may be one or two, preferably one.

[0047] The number of carbon atoms that the ketone contains may be one or more and eight or fewer, preferably one or more and five or fewer, more preferably one or more and three or fewer.

[0048] The hydrocarbon group that the ketone contains may be a saturated hydrocarbon group, and examples include the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, and octyl groups.

[0049] The ketone is at least one selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, and acetone, preferably methyl ethyl ketone.

[0050] By using at least one selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, and acetone as the ketone, the penetration between cellulose molecules is encouraged. As a result, the fluffy feel of the cellulosic particles further improves.At Least One of the Amount of the Hydrocarbon Ester and the Amount of the Ketone

[0051] At least one of the amount of the hydrocarbon ester and the amount of the ketone is 3 ppm or more and 1000 ppm or less and may be 10 ppm or more and 500 ppm or less, preferably 15 ppm or more and 200 ppm or less, more preferably 20 ppm or more and 100 ppm or less. It should be noted that at least one of the amount of the hydrocarbon ester and the amount of the ketone is an amount relative to the cellulosic particles. The "ppm" is by mass.

[0052] The amount of hydrocarbon ester and that of ketone are measured using a gas chromatograph. An example of a gas chromatograph that can be used is Shimadzu Corporation's Nexis GC-2030. The measurement procedure is as follows.

[0053] Sets of cellulosic particles in which the amount of hydrocarbon ester is 3 ppm, 10 ppm, 100 ppm, 500 ppm, 1000 ppm, and 2000 ppm are each prepared. Then these sets of cellulosic particles are subjected to measurement with a gas chromatograph, and a calibration curve for calculating the amount of hydrocarbon ester is constructed.

[0054] Sets of cellulosic particles in which the amount of ketone is 3 ppm, 10 ppm, 100 ppm, 500 ppm, 1000 ppm, and 2000 ppm are each prepared. Then these sets of cellulosic particles are subjected to measurement with a gas chromatograph, and a calibration curve for calculating the amount of ketone is constructed.

[0055] Then the cellulosic particles of interest are subjected to measurement with the gas chromatograph, and the amounts of hydrocarbon ester and ketone are calculated based on the calibration curves.Extra Constituents

[0056] The cellulosic particles according to this exemplary embodiment may contain extra constituents. If the cellulosic particles have the coating layer described later herein, the extra constituents are contained in the core particle, which is covered with the coating layer.

[0057] Examples of extra constituents include plasticizers, flame retardants, compatibilizers, release agents, light stabilizers, weathering agents, coloring agents, pigments, modifiers, anti-dripping agents, antistatic agents, anti-hydrolysis agents, fillers, reinforcing agents (glass fiber, carbon fiber, talc, clay, mica, glass flakes, milled glass, glass beads, crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, etc.), acid acceptors for preventing acetic acid release (oxides, such as magnesium oxide and aluminum oxide; metal hydroxides, such as magnesium hydroxide, calcium hydroxide, aluminum hydroxide, and hydrotalcite; calcium carbonate; talc; etc.), and reactive trapping agents (e.g., epoxy compounds, acid anhydride compounds, carbodiimides, etc.).

[0058] The amounts of the extra constituents may be 0% by mass or more and 5% by mass or less for each constituent in relation to the total amount of the cellulosic particles (or core particles). In this context, "0% by mass" means that the extra constituent is not contained.Cellulosic Particles Having a Coating Layer

[0059] The cellulosic particles according to this exemplary embodiment may be cellulosic particles having a core particle that contains cellulose as its base constituent (hereinafter also referred to as a cellulosic core particle) and a coating layer that covers the core particle and contains at least one selected from the group consisting of a fatty acid, a fatty acid metallic salt, and an amino acid compound (hereinafter also referred to as "cellulosic particles having a coating layer").

[0060] In this configuration, the cellulosic particles according to this exemplary embodiment assume a sponge-like structure, or a structure having spaces throughout, as a result of the carboxylic acid moiety of the fatty acid or fatty acid metallic salt being anchored by interacting with hydroxyl groups on the surface of the cellulose and the aliphatic groups, facing outward, repelling one another. The amino acid enhances flexibility as a result of its hydroxyl group becoming anchored by interacting with hydroxyl groups on the surface of the cellulose and its amino acid portion having a flexible structure. The fluffy feel of the cellulosic particles, therefore, further improves.Core Particle

[0061] The core particle contains cellulose as its base constituent.

[0062] The cellulose contained in the core particle is synonymous with the cellulose described above, and possible and preferred ranges are also the same as described above.Coating Layer

[0063] The coating layer contains at least one selected from the group consisting of a fatty acid, a fatty acid metallic salt, and an amino acid compound.- Fatty Acid

[0064] A fatty acid is a linear-chain or branched saturated or unsaturated fatty acid. The fatty acid may be a mixture of a saturated fatty acid and an unsaturated fatty acid.

[0065] The fatty acid may be a fatty acid having 16 or more and 22 or fewer carbon atoms (C16 to C22; preferably a C18 to C20 fatty acid). Specific examples of C16 to C22 linear-chain fatty acids include behenic acid, arachidic acid, and palmitic acid.

[0066] The amount of the fatty acid may be 2% by mass or more and 15% by mass or less, preferably 5% by mass or more and 10% by mass or less, of the cellulosic particles as a whole.

[0067] By using a C16 to C22 fatty acid as the fatty acid, it is easier to cover the surface of the core particle. As a result, it is more likely that the number of hydroxyl groups exposed on the surface of the cellulosic particles is small.- Fatty Acid Metallic Salt

[0068] A fatty acid metallic salt is a linear-chain or branched saturated or unsaturated fatty acid metallic salt. The fatty acid metallic salt may be a mixture of a saturated fatty acid metallic salt and an unsaturated fatty acid metallic salt.

[0069] Examples of fatty acid metallic salts include metallic salts of C16 to C22 (preferably C18 to C20) fatty acids. Examples of metallic salts of C16 to C22 fatty acids include metallic salts of stearic acid, metallic salts of behenic acid, and metallic salts of palmitic acid.

[0070] An example of a metal in a fatty acid metallic salt is a divalent metal.

[0071] Examples of metals in linear-chain fatty acid metallic salts include magnesium, calcium, aluminum, barium, and zinc.

[0072] The amount of the fatty acid metallic salt may be 2% by mass or more and 15% by mass or less, preferably 5% by mass or more and 10% by mass or less, of the cellulosic particles as a whole.

[0073] The number of carbon atoms in the fatty acid may be 16 or more and 22 or fewer, and the number of carbon atoms in the fatty acid metallic salt may be 16 or more and 22 or fewer.

[0074] By using C16 to C22 compounds as the fatty acid and the fatty acid metallic salt, the length is long enough that the aliphatic group produces its full effect and short enough that the affinity for the surface of the cellulosic particles is not impaired due to too strong hydrophobicity. As a result, the fluffy feel of the cellulosic particles further improves.

[0075] The fatty acid may be a saturated fatty acid, and the fatty acid metallic salt may be a saturated fatty acid metallic salt.

[0076] When the fatty acid and fatty acid metallic salt are a saturated fatty acid and a saturated fatty acid metallic salt, binding between aliphatic groups caused by the opening of an unsaturated portion is prevented. As a result, the fluffy feel of the cellulosic particles further improves.- Amino Acid Compound

[0077] "Amino acid compounds" refers to amino acids and amino acid derivatives.

[0078] Examples of amino acid compounds include lauryl leucine, lauryl arginine, and myristyl leucine.

[0079] The amount of the amino acid compound may be 2% by mass or more and 10% by mass or less of the cellulosic particles as a whole.

[0080] Cellulosic particles having a coating layer may have an intermediate layer between the core particle and the coating layer. The intermediate layer, furthermore, may contain at least one selected from the group consisting of a polyamine compound, a polyquaternium, a polysaccharide compound, and a polyacrylic acid.

[0081] When the cellulosic particles have an intermediate layer, the affinity between the coating layer and the cellulosic particles is stronger. As a result, the fluffy feel of the cellulosic particles further improves.

[0082] "Polyamine compound" is a generic term for aliphatic hydrocarbons having two or more primary amino groups.

[0083] Examples of polyamine compounds include a polyalkyleneimine, polyallylamine, polyvinylamine, and polylysine.

[0084] The polyalkyleneimine may be a polyalkyleneimine possessing a constituent unit having a C1 to C6 (preferably C1 to C4, more preferably C1 or C2), preferably polyethyleneimine, for improved biodegradability.

[0085] Examples of polyallylamines include homopolymers or copolymers of allylamine, allylamine amidosulfate, diallylamine, dimethylallylamine, etc.

[0086] Examples of polyvinylamines include polyvinylamines manufactured by hydrolyzing poly(N-vinylformamide) with an alkali, and a specific example is Mitsubishi Chemical's "PVAM-0595B."

[0087] The polylysine may be polylysine extracted from a natural substance, may be polylysine produced by a transformed microorganism, or may be chemically synthesized polylysine.

[0088] The amount of the polyamine compound may be 0.2% by mass or more and 2% by mass or less of the cellulosic particles as a whole.

[0089] Examples of polyquaterniums include polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-11, polyquaternium-51, polyquaternium-61, and polyquaternium-64.

[0090] The amount of the polyquaternium may be 0.2% by mass or more and 2% by mass or less of the cellulosic particles as a whole.

[0091] The amount of the polyacrylic acid may be 0.2% by mass or more and 2% by mass or less of the cellulosic particles as a whole.Amounts of Constituents in the Coating and Intermediate Layers

[0092] The total amount of the fatty acid, fatty acid metallic salt, and amino acid compound relative to the entire coating layer may be 90% by mass or more and 100% by mass or less, preferably 95% by mass or more and 100% by mass or less.

[0093] The total amount of the polyamine compound, polyquaternium, polysaccharide compound, and polyacrylic acid relative to the entire intermediate layer may be 90% by mass or more and 100% by mass or less, preferably 95% by mass or more and 100% by mass or less.External Additive

[0094] The cellulosic particles according to this exemplary embodiment may have inorganic particles as an external additive.

[0095] When the cellulosic particles have inorganic particles as an external additive, the inorganic particles are able to freely move up and down, following the flexibility of the surface of the cellulosic particles. As a result, the fluffy feel of the cellulosic particles further improves.

[0096] An example of an external additive is at least one selected from the group consisting of silicon-containing compound particles and metal oxide particles.

[0097] "Silicon-containing compound particles" indicates particles containing silicon.

[0098] The silicon-containing compound particles may be particles of silicon or may be particles containing silicon and one or more other elements.

[0099] The silicon-containing compound particles may be silica particles. The silica particles can be any particles containing silica, or SiO 2 , as their base constituent and may be crystalline or amorphous. The silica particles, furthermore, may be particles manufactured from a silicon compound, such as waterglass or an alkoxysilane, as a raw material or may be particles obtained by crushing quartz.

[0100] As for metal oxides, oxides of metals other than silicon can be applied.

[0101] Examples of metal oxides include zinc oxide, magnesium oxide, iron oxide, and aluminum oxide.

[0102] The volume-average particle diameter of the external additive may be 1 nm or more and 100 nm or less, preferably 5 nm or more and 30 nm or less, for texture (specifically, feel when touched) reasons.

[0103] The volume-average particle diameter of the external additive is measured in the same manner as the volume-average particle diameter of the cellulose.

[0104] The amount of the external additive may be 0.1% by mass or more and 2% by mass or less of the mass of the cellulosic particles (the cellulosic particles without the external additive on them) as a whole.Volume-Average Particle Diameter and Upper Geometric Standard Deviation by Number GSDv

[0105] The volume-average particle diameter of the cellulosic particles according to this exemplary embodiment may be 3 µm or more and less than 10 µm, preferably 4 µm or more and 9 µm or less, more preferably 5 µm or more and 8 µm or less.

[0106] When the volume-average particle diameter is 3 µm or more, the fluffy feel tends to be better because in that case the amount of deformation is large enough that the cellulosic particles can exhibit their flexibility.

[0107] When the volume-average particle diameter is less than 10 µm, a deterioration in feel and rugged feel caused by too large particle diameters are not felt, and the fluffy feel tends to be better. By virtue of a moderately large surface area, furthermore, biodegradation, which starts at the surface, is likely to progress uniformly, and biodegradability tends to be excellent.

[0108] The upper geometric standard deviation by number GSDv of the cellulosic particles according to this exemplary embodiment may be 1.0 or greater and 1.7 or less, preferably 1.0 or greater and 1.5 or less, more preferably 1.0 or greater and 1.3 or less.

[0109] When the GSDv is 1.0 or greater and 1.7 or less, hardness caused by fine particles and rugged feel caused by coarse particles are reduced, and the fluffy feel tends to improve.

[0110] The inhibition of biodegradation (which starts at the surface) by coarse particles (large particles greater than 10 µm) is also unlikely to occur.

[0111] The volume-average particle diameter and the upper geometric standard deviation GSDv of the cellulosic particles are measured as follows.

[0112] Particle diameters are measured using the LS particle size distribution analyzer "Beckman Coulter LS13 320 (Beckman Coulter)," and the cumulative distribution of particle diameters is plotted as a function of volume starting from the smallest diameter; then the particle diameter at which the cumulative percentage is 50% is determined as the volume-average particle diameter.

[0113] Separately, the cumulative distribution of particle diameters is plotted as a function of volume starting from the smallest diameter; the particle diameter at which the cumulative percentage is 50% is defined as the number-average particle diameter, D50v, and the particle diameter at which the cumulative percentage is 84% is defined as particle diameter D84v by number. The upper geometric standard deviation by number GSDv is calculated according to the equation GSDv = (D84v / D50v) 1 / 2< .

[0114] The sphericity of the cellulosic particles according to this exemplary embodiment may be 0.7 or greater, preferably 0.8 or greater, more preferably 0.9 or greater.

[0115] When the sphericity is 0.7 or greater, the particles are likely to uniformly deform in all directions, and the fluffy feel tends to improve. Decomposition by microorganisms, furthermore, proceeds along the most efficient path, from the surface toward the inner core, and biodegradability tends to be excellent.

[0116] Sphericity is given by (circumference of the equivalent circle) / (circumference) [(circumference of a circle having the same projected area as the particle's image) / (circumference of the particle's projected image)]. Specifically, sphericity is a value measured by the following method.

[0117] First, the cellulosic particles of interest are sampled by aspiration in such a manner that the sample will form a flat stream, and this flat stream is photographed with a flash to capture the figures of the particles in a still image; then the sphericity is determined by analyzing the particle images using a flow particle-image analyzer (Sysmex Corp. FPIA-3000). The number of particles sampled in determining the sphericity is 3500.

[0118] If the cellulosic particles have an external additive, the cellulosic particles of interest are dispersed in water containing a surfactant, then the dispersion is sonicated to give cellulosic particles from which the external additive has been removed, and the resulting cellulosic particles are used as the subject of measurement.Surface Smoothness

[0119] The surface smoothness of the cellulosic particles according to this exemplary embodiment may be 50% or more, preferably 60% or more and 99% or less, more preferably 70% or more and 98% or less.

[0120] When the smoothness is 50% or more, the expression of local hardness following surface irregularities is reduced, and the fluffy feel tends to improve. Biodegradability, furthermore, tends to be excellent; biodegrading microorganisms include species relatively large in size, and the particle surface in that case is accessible even to such large microorganisms.

[0121] The surface smoothness is measured through a procedure as described below.

[0122] An SEM image (magnification, 5,000 times) of the cellulosic particles, taken with a scanning electron microscope (SEM), is observed, and the smoothness M of the individual cellulosic particles is calculated according to the equation below. The arithmetic mean of the smoothness values M of ten or more randomly chosen cellulosic particles is reported as the surface smoothness. The closer the value of the smoothness M is to 1, the closer the surface of the cellulosic particles is to smoothness. M = 1 − S 3 / S 2 × 100

[0123] In this equation, S2 indicates the area that the cellulosic particle occupies in the image (projected area), and S3 indicates, when the cellulosic particle in the image and a circle having a projected area equal to S2 are superimposed, the sum of "the area outside the outline of the circle having a projected area equal to S2 and inside the outline of the cellulosic particle in the image" and "the area inside the outline of the circle having a projected area equal to S2 and outside the outline of the cellulosic particle in the image."

[0124] The method for superimposing the cellulosic particle in the image and a circle having a projected area equal to S2 is as follows.

[0125] The superposition is carried out in such a manner that when the cellulosic particle in the image and the circle having a projected area equal to S2 are superimposed, the area of the region shared by the two images (the area inside the outline of the circle having a projected area equal to S2 and inside the outline of the cellulosic particle in the image) is maximized.Method for Manufacturing the Cellulosic Particles

[0126] An example of a method for manufacturing the cellulosic particles according to this exemplary embodiment is as follows.Cellulosic Particle (core particle) Production Step

[0127] (1) First, cellulose acylate solution A is prepared by dissolving a cellulose acylate in organic solvent A. (2) Then cellulose acylate solution B is prepared by adding cellulose acylate solution A into a calcium carbonate dispersion, in which calcium carbonate has been dispersed in water, and stirring the resulting mixture. (3) Then cellulose acylate solution C is prepared by adding cellulose acylate solution B to a mixed solution of carboxymethylcellulose, organic solvent B, and water and rapidly stirring the resulting mixture. (4) Then sodium hydroxide is added to cellulose acylate solution C. Subsequently, cellulose acylate dispersion C is heated to remove water-dissolving organic solvents A and B, and hydrochloric acid is added to cause the formation of cellulose acylate particles. Then the cellulose acylate particles are isolated by filtration, and the isolated cellulose acylate particles are dispersed in water; in this manner, a cellulose acylate particle dispersion is prepared. (5) Then a cellulosic particle suspension is prepared by adding sodium hydroxide to the cellulose acylate particle dispersion and subsequently saponifying the cellulose acylate particles by warming the cellulose acylate particle dispersion in a weakly alkaline environment with stirring. (6) Then the pH of the cellulosic particle suspension is adjusted to near neutral (e.g., 6.5 or higher and 7 or lower) by adding hydrochloric acid to the suspension, and subsequently isolation by filtration and washing in purified water of the cellulosic particles are repeated. After the electrical conductivity of the filtrate reaches 10 µs / cm or less, the isolated cellulosic particles are dried.

[0128] Organic solvent A may be a hydrocarbon ester, and organic solvent B may be a ketone.

[0129] The amounts of hydrocarbon ester and ketone contained can be adjusted by changing the amount of the hydrocarbon ester used as organic solvent A and that of the ketone used as organic solvent B added.

[0130] In the foregoing, a cellulose acylate is a cellulose derivative in which at least one of the hydroxy groups of cellulose has been replaced with an aliphatic acyl group (acylated). Specifically, a cellulose acylate is a cellulose derivative in which at least one of the hydroxy groups of cellulose has been replaced with -CO-R AC< (R AC< represents an aliphatic hydrocarbon group.).Intermediate Layer and Coating Layer Formation Step

[0131] If cellulosic particles having a coating layer are manufactured, a step of forming the coating layer (coating layer formation step) may be included after the above cellulosic particle (core particle) production step.

[0132] If the coating layer formation step is carried out, the coating layer is formed using the particles obtained through the above cellulosic particle (core particle) production step as the core particles.

[0133] First, an aqueous dispersion in which the core particles have been dispersed is prepared. Before preparing the aqueous dispersion, the core particles may be cleaned with an acid.

[0134] Then the aqueous dispersion in which the core particles have been dispersed and an aqueous solution containing the compound that will form the intermediate layer are mixed together. Through that, the intermediate layer is formed, for example as a result of reaction between hydroxyl groups in the resin contained in the core particles and amine sites, carboxyl groups, amino groups, or any other moiety of the compound that will form the intermediate layer or as a result of hydrogen bonding between hydroxyl groups. Then the aqueous dispersion in which the core particles with the intermediate layer formed thereon are dispersed and an emulsion containing the compound that will form the coating layer are mixed together. Through that, the coating layer is formed.

[0135] If no intermediate layer is formed, the coating layer is formed by mixing together an aqueous dispersion in which the core particles obtained through the above cellulosic particle (core particle) production step have been dispersed and an emulsion containing the compound that will form the coating layer.

[0136] Then, from the mixture, the cellulosic particles having a coating layer are removed. The removal of the cellulosic particles having a coating layer is performed by, for example, filtering the mixture. The removed cellulosic particles having a coating layer may be washed with water. Through that, unreacted surface-treating polymers can be eliminated. Then, by drying the cellulosic particles having a coating layer, cellulosic particles according to this exemplary embodiment are obtained.Addition Step

[0137] To the resulting cellulosic particles, an external additive may be added.

[0138] An example of an addition step is a treatment in which the external additive is added to the cellulosic particles using equipment like a mixing mill, V-blender, Henschel mixer, or Lödige mixer.Applications

[0139] Applications of the cellulosic particles according to this exemplary embodiment include granular materials for use as cosmetics, a rolling agent, an abrasive, a scrubbing agent, display spacers, a material for bead molding, light-diffusing particles, a resin-strengthening agent, a refractive index control agent, a biodegradation accelerator, a fertilizer, water-absorbent particles, toner particles, and anti-blocking particles.

[0140] An application of the cellulosic particles according to this exemplary embodiment may be cosmetics.

[0141] In particular, an application of the cellulosic particles according to this exemplary embodiment may be a cosmetic additive.

[0142] The cellulosic particles according to this exemplary embodiment are superior in flexibility; when they are used as a cosmetic additive, therefore, it is likely that the spreading and hardness of the cosmetic on the skin to which the cosmetic is applied are good.

[0143] The cellulosic particles according to this exemplary embodiment can be applied as cosmetic additives, for example to base makeup cosmetics (e.g., foundation primer, concealer, foundation, and face powder); makeup cosmetics (e.g., lipstick, lip gloss, lip liner, blusher, eyeshadow, eyeliner, mascara, eyebrow powder, nail products, and nail care cosmetics); and skincare cosmetics (e.g., face wash, facial cleanser, toner, milky lotion, serum, face packs, face masks, and cosmetics for the care of the eye and mouth areas).

[0144] In particular, the resin particles according to this exemplary embodiment may be used as a cosmetic additive to makeup cosmetics because flexibility and biodegradability are required in such an application.Examples

[0145] Examples will now be described, but no aspect of the present disclosure is limited to these examples. In the following description, "parts" and "%" are all by mass unless stated otherwise.Preparation of Materials

[0146] The following materials are prepared.Cellulose Acylates

[0147] CA-1: Daicel Corporation's "L50," diacetyl cellulose, weight-average molecular weight = 8,000 CA-2: Daicel Corporation's "L20," diacetyl cellulose, weight-average molecular weight = 47,000 CA-3: Eastman Chemical "CAP482-20," cellulose acetate propionate, weight-average molecular weight = 75,000 CA-4: Eastman Chemical "CAB381-20," cellulose acetate butyrate, weight-average molecular weight = 70,000 CA-5: Eastman Chemical "CA398-6," diacetyl cellulose, weight-average molecular weight = 35,000 Coating Layer Formation MaterialsFatty Acids

[0148] ST-1: NOF Corporation's "NAA-222S," behenic acid (saturated fatty acid), the number of carbon atoms = 22 ST-2: NOF Corporation's "NAA-180," stearic acid (saturated fatty acid), the number of carbon atoms = 18 ST-3: Miyoshi Oil & Fat Co., Ltd.'s "Palmitic Acid 98," palmitic acid (saturated fatty acid), the number of carbon atoms = 16 ST-4: NOF Corporation's "NAA-142," myristic acid (saturated fatty acid), the number of carbon atoms = 14 ST-5: Tokyo Chemical Industry Co., Ltd.'s "Lignoceric Acid," lignoceric acid (saturated fatty acid), the number of carbon atoms = 24 ST-6: NOF Corporation's "EXTRA OS-85," oleic acid (unsaturated fatty acid with a degree of unsaturation of 1), the number of carbon atoms = 18 ST-7: NOF Corporation's "Linoleic Acid 90," linoleic acid (unsaturated fatty acid with a degree of unsaturation of 2), the number of carbon atoms = 18 Fatty Acid Metallic Salts

[0149] ST-8: NOF Corporation's "CALCIUM STEARATE VEGETABLE," calcium stearate (saturated fatty acid metallic salt), the number of carbon atoms = 18 ST-9: NOF Corporation's "MAGNESIUM STEARATE S," magnesium stearate (saturated fatty acid metallic salt), the number of carbon atoms = 18 ST-10: Nitto Chemical Industry Co., Ltd.'s "CS-7," calcium behenate (saturated fatty acid metallic salt), the number of carbon atoms = 22 ST-11: NOF Corporation's "NONSOUL PK-1," potassium palmitate (saturated fatty acid metallic salt), the number of carbon atoms = 16 ST-12: NOF Corporation's "POWDER BASE M," zinc myristate (saturated fatty acid metallic salt), the number of carbon atoms = 14 ST-13: Tokyo Chemical Industry Co., Ltd.'s "Calcium Lignocerate," calcium lignocerate (saturated fatty acid metallic salt), the number of carbon atoms = 24 ST-14: NOF Corporation's "NONSOUL ON-1N," sodium oleate (unsaturated fatty acid metallic salt with a degree of unsaturation of 1), the number of carbon atoms = 18 ST-15: Nitto Chemical Industry Co., Ltd.'s "BS-5," barium linoleate (unsaturated fatty acid metallic salt with a degree of unsaturation of 2), the number of carbon atoms = 18 Amino Acid Compounds ST-16: Ajinomoto Co., Inc.'s "AMIHOPE LL," lauroyl lysine ST-17: Yoneyama Yakuhin Kogyo Co., Ltd.'s "Glycylglycine," glycylglycine ST-18: New Japan Chemical Co., Ltd.'s "DL-ALANINE," alanine Silane Compound

[0150] ST-19: Shin-Etsu Chemical Co., Ltd.'s "KBE-3083," octyltriethoxysilane Intermediate Layer Formation MaterialsPolyamine Compounds

[0151] AA-1: Nippon Shokubai Co., Ltd.'s "PEI-1500," polyethyleneimine AA-2: BASF Japan Ltd.'s "Dehyquart H81," PEG-15 cocopolyamine AA-3: Ichimaru Pharcos Co., Ltd.'s "Polylysine 10," poly-ε-lysine Polyquaterniums AA-4: Nouryon Japan K.K.'s "CELQUAT SC230M," polyquaternium 10 AA-5: BASF Japan Ltd.'s "Luviquat PQ11AT1," polyquaternium 11 Polysaccharide Compounds AA-6: Sumitomo Pharma Food & Chemical Co., Ltd.'s "GLYLOID 6C," Tamarindus Indica seed gum AA-7: Sumitomo Pharma Food & Chemical Co., Ltd.'s "RHABALL GUM CG-M," cationized guar gum Arginine

[0152] AA-8: Ajinomoto Co., Inc.'s "L-Arginine, C grade," arginine Polysaccharide Compound AA-9: Koyo Chemical Co., Ltd.'s "KOYO Chitosan FLA-40," chitosan Dextrin AA-10: San-ei Sucrochemical Co., Ltd.'s "NSD300A," dextrin Polysaccharide Compound AA-11: Hayashibara Co., Ltd.'s "PULLULAN (cosmetic grade)," pullulan Polyacrylic Acids AA-12: Toagosei Co., Ltd.'s "JURYMER AC-10H," a polyacrylic acid, weight-average molecular weight = 150,000 AA-13: Toagosei Co., Ltd.'s "JURYMER AC-10SH," a polyacrylic acid, weight-average molecular weight = 1,000,000 External Additives

[0153] EA-1: Wacker Asahikasei Silicone Co., Ltd.'s "HDK N20," silica particles, volume-average particle diameter = 200 nm EA-2: Wacker Asahikasei Silicone Co., Ltd.'s "HDK T30," silica particles, volume-average particle diameter = 300 nm

[0154] The volume-average particle diameters of the external additives are measured through the same procedure as the volume-average particle diameters of the cellulosic particles.Examples 1 to 64 and Comparative Examples 1 to 8 (Example 19 is not included)Cellulose Acylate Formation

[0155] The cellulose acylate of the species and amount indicated in Tables 1-1 and 1-3 is dissolved in ethyl acetate, which is a hydrocarbon ester, in the amount (parts) indicated in Tables 1-1 and 1-3. The resulting solution, solution A, is added to a dispersion in which calcium carbonate in the amount (parts) indicated in Tables 1-1 and 1-3 has been dispersed in 500 parts by mass of purified water, and the resulting mixture is stirred for 5 hours.

[0156] Then the resulting solution, solution B, is added to a dispersion in which carboxymethylcellulose in the amount (parts) indicated in Tables 1-1 and 1-3 and methyl ethyl ketone, which is a ketone, in the amount (parts) indicated in Tables 1-1 and 1-3 have been dispersed in 800 parts by mass of purified water, and the resulting mixture is stirred for 10 minutes using a high-speed emulsifier.

[0157] Then sodium hydroxide in the amount (parts) indicated in Tables 1-1 and 1-3 is added to the resulting solution, solution C, the resulting mixture is stirred for the time indicated in Tables 1-1 and 1-3 at 80°C to remove the ethyl acetate and methyl ethyl ketone, and subsequently diluted hydrochloric acid in the amount (parts) indicated in Tables 1-1 and 1-3 is added to dissolve the calcium carbonate and form cellulose acylate particles. Then the particles are isolated by filtration, and the isolated particles are dispersed again in purified water to give a slurry of cellulose acylate particles.Saponification of Cellulose Acylate Particles

[0158] A 20% aqueous solution of sodium hydroxide in the amount (parts) indicated in Tables 1-1 and 1-3 is added to 500 parts by mass of the slurry of cellulose acylate particles (solids content, 50 parts by mass), and saponification is performed by stirring the resulting mixture at the reaction temperature and for the time indicated in Tables 1-1 and 1-3 to form cellulosic particles.

[0159] Then hydrochloric acid is added dropwise to the resulting slurry of cellulosic particles until the pH of the slurry reaches the pH in Tables 1-1 and 1-3. Subsequently, the slurry is filtered, the residue is washed with an excess of purified water, and the filtration and washing are repeated until the electrical conductivity of the filtrate reaches 10 µs / cm or less. The final cake of residue is filtered, and the resulting residue is lyophilized to give cellulosic particles (core particles).Surface Treatment

[0160] In certain Examples and Comparative Examples, the cellulosic particles obtained through the saponification of cellulose acylate particles are used as core particles, and the core particles are subjected to the surface treatment described below.

[0161] The cake of residue after the repeated filtration and washing until the electrical conductivity of the filtrate reaches 10 µs / cm or less is reslurried with purified water to give a slurry of the core particles.

[0162] Then the intermediate layer formation material of the type and amount indicated in Tables 1-2-1, 1-2-2, 1-4-1, and 1-4-2 is added to 500 parts by mass of the slurry of the core particles (solids content, 50 parts by mass), and the resulting mixture is stirred for 3 hours at 30°C. Through that, an intermediate layer is formed on the surface of the core particles.

[0163] Then an emulsified form of the coating layer formation material of the type and amount indicated in Tables 1-2-1, 1-2-2, 1-4-1, and 1-4-2 is added to the slurry of core particles having an intermediate layer, and the resulting mixture is stirred for 24 hours. Through that, a coating layer is formed on the surface of the core particles having an intermediate layer.

[0164] Then the slurry of core particles having intermediate and coating layers is filtered, the residue is washed with purified water, and the resulting slurry is filtered again. This operation is repeated, and when the electrical conductivity of the filtrate reaches 10 µs / cm or less, the residue is lyophilized to give cellulosic particles having intermediate and coating layers. In addition, the treated surface of the cellulosic particles having intermediate and coating layers is smoothened by stirring the particles using FM Mixer (FM40, Nippon Coke & Engineering) for 3 hours at a frequency of 2000 min -1< while the mixer temperature is maintained at 25°C.

[0165] Then the external additive of the type and amount (parts) indicated in Tables 1-2-1, 1-2-2, 1-4-1, and 1-4-2 is added to 100 parts of the cellulosic particles having intermediate and coating layers, and the materials are mixed together using a mixing mill (WONDER CRUSHER, Osaka Chemical) to give cellulosic particles having an external additive.

[0166] In certain Examples and Comparative Examples, cellulosic particles composed of a core particle and a coating layer formed thereon without an intermediate layer or cellulosic particles composed of a core particle, a coating layer formed thereon without an intermediate layer, and a subsequently added external additive are produced. Table 1-1Particle numberCellulosic core particlesCellulose acylate particlesSaponificationCellulose acylateCalcium carbonateEthyl acetateCarboxymethylcelluloseMethyl ethyl ketoneSodium hydroxideStirring timeDiluted hydrochloric acid20% aqueous solution of sodium hydroxideReaction temperatureStirring timepHCompoundParts by massParts by massParts by massParts by massParts massParts by masshrParts by massParts by mass°Chours-Example 1PTC-1CA120060125054001010202040127Example 2PTC-2CA220060125054001010202040127Example 3PTC-3CA320060125054001010202040127Example 4PTC-4CA420060125054001010202040127Example 5PTC-5CA520060125054001010202040127Example 6PTC-6CA120060105053201010202040127Example 7PTC-7CA120060150055001010202040127Example 8PTC-8CA120060125074001010202040127Example 9PTC-9CA120060125094001010202040127Example 10PTC-10CA120060125044001010202040127Example 11PTC-11CA120060125024001010202040127Example 12PTC-12CA120050125054001010202040127Example 13PTC-13CA12004012505400107202040127Example 14PTC-14CA120060125054001010202540127Example 15PTC-15CA120060125054001010201540127Example 16PTC-16CA120060125054001010201540127Example 17PTC-17CA12006012505400710202040127Example 18PTC-18CA12006012505400410202040127Example 20PTC-20CA1200601250540010202040127Example 21PTC-21CA1200601250540010202040127Example 22PTC-22CA1200601250540010202040127Example 23PTC-23CA1200601250540010202040127Example 24PTC-24CA1200601250540010202040127Example 25PTC-25CA1200601250540010202040127Example 26PTC-26CA1200601250540010202040127Example 27PTC-27CA1200601250540010202040127Example 28PTC-28CA1200601250540010202040127Example 29PTC-29CA1200601250540010202040127Example 30PTC-30CA1200601250540010202040127Example 31PTC-31CA1200601250540010202040127Example 32PTC-32CA1200601250540010202040127Example 33PTC-33CA1200601250540010202040127Example 34PTC-34CA1200601250540010202040127Example 35PTC-35CA1200601250540010202040127Example 36PTC-36CA1200601250540010202040127Example 37PTC-37CA1200601250540010202040127Example 38PTC-38CA1200601250540010202040127Example 39PTC-39CA1200601250540010202040127 Table 1-2-1 Surface treatmentCellulosic core particlesIntermediate layer formation materialCoating layer formation materialExternal additiveParts by massCompoundParts by massCompoundParts by massCompoundParts by massExample 150Example 250Example 350Example 450Example 550Example 650Example 750Example 850Example 950Example 1050Example 1150Example 1250Example 1350Example 1450Example 1550Example 1650Example 1750Example 1850Example 2050ST-25Example 2150ST-35Example 2250ST-45Example 2350ST-55Example 2450ST-65Example 2550ST-75Example 2650ST-85Example 2750ST-95Example 2850ST-105Example 2950ST-115Example 3050ST-125Example 3150ST-135Example 3250ST-145Example 3350ST-155Example 3450ST-165Example 3550ST-175Example 3650ST-185Example 3750ST-195Example 3850ST-83Example 3950ST-87 Table 1-2-2 Particle characteristicsParticle diameterGSDvSphericitySurface smoothnessMnPercentage biodegradabilityHydrocarbon ester contentKetone contentµm--%-%ppmppmExample 17.51.40.929058000972520Example 27.81.380.929047000982018Example 37.41.420.949252000962222Example 47.81.350.949178000982518Example 56.51.340.888831000972722Example 67.41.440.9191580009644Example 77.61.380.93925800096995993Example 83.31.550.888556000952729Example 92.81.610.898157000962827Example 109.51.210.939258000972926Example 1110.21.220.928858000973024Example 127.21.680.969057000973129Example 137.81.730.878756000953319Example 147.31.310.999357000943023Example 157.21.290.759258000962827Example 167.31.350.688858000952725Example 177.21.560.815459000962828Example 1871.660.84858000962925Example 207.71.550.919157000922622Example 2181.440.929056000912526Example 227.81.430.918658000922829Example 237.71.450.898557000912728Example 247.81.550.888758000922826Example 257.71.430.888556000932629Example 267.91.340.939058000922527Example 277.71.380.939157000912425Example 287.81.350.929158000932926Example 297.71.330.939256000922828Example 307.61.420.888755000922722Example 317.81.380.878856000913029Example 327.81.440.878658000902728Example 337.71.410.888757000912925Example 347.61.350.919058000922528Example 357.71.390.929157000922826Example 367.81.380.929158000912926Example 377.71.350.878758000923823Example 387.61.350.939259000913625Example 397.71.380.939256000933527 Table 1-3 Particle numberCellulosic core particlesCellulose acylate particlesSaponificationCellulose acylateCalcium carbonateEthyl acetateCarboxymethylcelluloseMethyl ethyl ketoneSodium hydroxideStirring timeDiluted hydrochloric acid20% aqueous solution of sodium hydroxideReaction temperatureStirring timepHCompoundParts by massParts by massParts by massParts by massParts by massParts by masshrParts by massParts by mass°Chours-Example 40PTC-40CA1200601250540010202040127Example 41PTC-41CA1200601250540010202040127Example 42PTC-42CA1200601250540010202040127Example 43PTC-43CA1200601250540010202040127Example 44PTC-44CA1200601250540010202040127Example 45PTC-45CA1200601250540010202040127Example 46PTC-46CA1200601250540010202040127Example 47PTC-47CA1200601250540010202040127Example 48PTC-48CA1200601250540010202040127Example 49PTC-49CA1200601250540010202040127Example 50PTC-50CA1200601250540010202040127Example 51PTC-51CA1200601250540010202040127Example 52PTC-52CA1200601250540010202040127Example 53PTC-53CA1200601250540010202040127Example 54PTC-54CA1200601250540010202040127Example 55PTC-55CA1200601250540010202040127Example 56PTC-56CA1200601250540010202040127Example 57PTC-57CA1200601250540010202040127Example 58PTC-58CA1200601250540010202040127Example 59PTC-59CA1200601250540010202040127Example 60PTC-60CA1200601250540010202040127Example 61PTC-62CA12006090054001010202040127Example 62PTC-63CA120060125052701010202040127Example 63PTC-65CA120060175054001010202040127Example 64PTC-66CA120060125056001010202040127Comparative Example 1PTC-61CA12006090052701010202040127Comparative Example 2PTC-64CA120060175056001010202040127Comparative Example 3PTC-57CA12006090052701010202040127Comparative Example 4PTC-68CA120060175056001010202040127Comparative Example 5PTC-69CA12006090052701010202040127Comparative Example 6PTC-70CA120060175056001010202040127Comparative Example 7PTC-71CA12006090052701010202040127Comparative Example 8PTC-72CA120060175056001010202040127 Table 1-4-1 Surface treatmentCellulosic core particlesIntermediate layer formation materialCoating layer formation materialExternal additiveParts by massCompoundParts by massCompoundParts by massCompoundParts by massExample 4050AA-10.5ST-85Example 4150AA-20.5ST-85Example 4250AA-30.5ST-85Example 4350AA-40.5ST-85Example 4450AA-50.5ST-85Example 4550AA-60.5ST-85Example 4650AA-70.5ST-85Example 4750AA-80.5ST-85Example 4850AA-90.5ST-85Example 4950AA-100.5ST-85Example 5050AA-110.5ST-85Example 5150AA-120.5ST-85Example 5250AA-130.5ST-85Example 5350AA-10.25ST-85Example 5450AA-11.5ST-85Example 5550AA-10.5ST-83Example 5650AA-10.5ST-87Example 5750AA-10.5ST-85EA-10.5Example 5850AA-10.5ST-85EA-20.5Example 5950AA-10.5ST-85EA-15Example 6050ST-85EA-10.5Example 6150Example 6250Example 6350Example 6450Comparative Example 150Comparative Example 250Comparative Example 350ST-85Comparative Example 450ST-85Comparative Example 550AA-10.5ST-85Comparative Example 650AA-10.5ST-85Comparative Example 750AA-10.5ST-85EA-10.5Comparative Example 850AA-10.5ST-85EA-10.5 Table 1-4-2 Particle characteristicsParticle diameterGSDvSphericitySurface smoothnessMnPercentage biodegradabilityHydrocarbon ester contentKetone contentµm--%-%ppmppmExample 407.81.410.949358000782525Example 417.61.40.959458000772729Example 427.51.380.949358000742921Example 437.71.390.969257000782528Example 447.81.420.959158000762823Example 457.71.420.949057000722327Example 467.81.380.959058000742824Example 477.71.550.898658000782526Example 487.61.580.888759000762729Example 497.71.620.878656000752833Example 507.81.580.99058000752420Example 517.81.580.99058000742939Example 527.81.580.99059000732628Example 537.51.440.959058000732727Example 547.41.380.949156000722420Example 557.51.330.939257000712526Example 567.71.320.949358000722829Example 5781.350.919056000682633Example 5881.370.919055000692740Example 598.11.340.929054000682835Example 6081.350.919055000672527Example 617.41.440.91915600068230Example 627.41.440.91915800069252Example 637.61.380.93925700068105025Example 647.61.380.93925600069301050Comparative Example 17.41.440.9191550006922Comparative Example 27.61.380.9392560006710501050Comparative Example 37.81.450.8989550006722Comparative Example 47.61.380.8987560006810501050Comparative Example 57.51.440.8887570006622Comparative Example 67.31.420.8788560006710501050Comparative Example 77.91.410.8887580006822Comparative Example 88.11.430.8988570006910501050 Comparative Examples 9 to 13

[0167] The following particles are used as cellulosic particles of these Comparative Examples.

[0168] Comparative Example 9: CELLULOBEADS D10 (Daito Kasei, cellulosic particles containing cellulose as their base constituent. No intermediate layer, no coating layer, and no external additive.)

[0169] Comparative Example 10: CELLUFLOW C25 (JNC, cellulosic particles containing cellulose as their base constituent. No intermediate layer, no coating layer, and no external additive.)

[0170] Comparative Example 11: CELLUFLOW T25 (JNC, cellulosic particles containing cellulose acetate as their base constituent. No intermediate layer, no coating layer, and no external additive.)

[0171] Comparative Example 12: OTS-0.5A CELLULOBEADS D10 (Daito Kasei, cellulosic particles having a core particle containing cellulose as its base constituent and a coating layer containing triethoxyoctylsilane. No external additive.)

[0172] Comparative Example 13: S-STM CELLULOBEADS D-5 (Daito Kasei, cellulosic particles having a core particle containing cellulose as its base constituent and a coating layer containing magnesium stearate. No external additive.)Comparative Example 14

[0173] Cellulosic particles are obtained according to the procedure described in Example 1 in Japanese Patent No. 6921293. The specific production process is as follows.

[0174] An oil phase is prepared by dissolving 150 parts of cellulose acetate (trade name "CA-398-6," Eastman Chemical; the percentage of acetyl groups, 39.8%) in 1,350 parts of ethyl acetate (solubility in water, 8 g / 100 g). A water phase is prepared by dissolving 100 parts of polyvinyl alcohol in 1,250 parts of deionized water. The oil phase is added to the prepared water phase, the two phases are mixed together, and the resulting mixture is stirred for 3 minutes at 1,000 rpm using a dissolver. The mixture is further stirred for 10 minutes at 2,000 rpm using a dissolver to give a suspension in which oil droplets are uniformly dispersed. The volume-average particle diameter of the oil droplets measured through observation under an optical microscope and image analysis is 18 µm.

[0175] While the resulting suspension is stirred at 500 rpm using a dissolver, 42,000 parts of deionized water is introduced over 90 minutes to give a resin particle dispersion. After filtration and washing, the resin particles are deflocculated in deionized water and stirred. The resin particles are collected by filtration and washed, and the washed resin particles are dispersed in 2,500 parts of deionized water. The pH is adjusted to 13.0 or lower by adding sodium hydroxide, and hydrolysis is performed through heating to 50°C. After the end of the hydrolysis, the dispersion is neutralized with hydrochloric acid. After filtration and washing, the product is deflocculated in deionized water. Then, after filtration and washing, drying and crushing are performed to give core beads having a median diameter (D50) of 9 µm.

[0176] Fifty grams of the resulting core beads and 1.5 g of zinc stearate (trade name "SPZ-100F," Sakai Chemical Industry; a powder of sheet-shaped particles; average particle diameter, 0.4 µm; thickness, 0.1 µm; aspect ratio, 3) are put into a small-sized mixer. The surface of the core beads is treated with the zinc stearate through dry mixing for 3 minutes to give resin beads.

[0177] The resulting resin beads are used as cellulosic particles of Comparative Example 14.Comparative Example 15

[0178] Cellulosic particles are obtained according to the procedure described in Example 2 in Japanese Patent No. 6921293. The specific production process is as follows.

[0179] Resin beads are obtained in the same manner as in Example 1 in Japanese Patent No. 6921293, except that 2.5 g of magnesium stearate (trade name "SPX-100F," Sakai Chemical Industry; a powder of sheet-shaped particles; average particle diameter, 0.7 µm; thickness, 0.1 µm; aspect ratio, 4) is used instead of the zinc stearate.

[0180] The resulting resin beads are used as cellulosic particles of Comparative Example 15. Table 2Product nameManufacturerCore particlesAnchoring agentSurface treatment agentExternal additiveParticle diameterGSDvSphericitySurface smoothnessMnPercentage biodegradabilityHydrocarbon ester contentKetone contentComparative Example 9PTC-101CELLULOBEADS D10Daito KaseiCelluloseNoneNoneNone141.170.97941100007901Comparative Example 10PTC-102CELLUFLOW C25JNCCelluloseNoneNoneNone101.860.9788450007801250Comparative Example 11PTC-103CELLUFLOW T25JNCCellulose acetateNoneNoneNone121.940.9888480001701300Comparative Example 12PTC-104OTS-0.5A CELLULOBEADS D-10 (Example 1 in Japanese Unexamined Patent Application Publication No. 2020-132616)Daito KaseiCelluloseNoneTriethoxyoctylsilaneNone141.320.98851100002501Comparative Example 13PTC-105S-STM CELLULOBEADS D-5 (Example 2 in Japanese Unexamined Patent Application Publication No. 2020-132616)Daito KaseiCelluloseNoneMagnesium stearateNone101.860.97561100002400Related artCore particlesAnchoring agentSurface treatment agentExternal additiveParticle diameterGSDvSphericitySurface smoothnessMnPercentage biodegradabilityHydrocarbon ester contentKetone contentComparative Example 14PTC-111Example 1 in Japanese 6921293Patent No.CelluloseNoneZinc stearateNone91.450.9692330008502Comparative Example 15PTC-112Example 2 in Japanese 6921293Patent No.CelluloseNoneMagnesium stearateNone91.550.9692320008802 Characteristics EvaluationParticle Characteristics

[0181] For the cellulosic particles obtained in the Examples and Comparative Examples, the following particle characteristics are measured according to the methods described above. Volume-average particle diameter ("Particle diameter" in the tables) Upper geometric standard deviation by number ("GSDv" in the tables) Sphericity Surface smoothness Number-average molecular weight of cellulose ("Mn" in the tables) Amounts of hydrocarbon ester and ketone Percentage Biodegradability

[0182] The 60-day percentage biodegradability in activated sludge of the cellulosic particles obtained in the Examples and Comparative Examples is measured by a method according to OECD 306F.Cosmetics EvaluationProduction of Cosmetics

[0183] Of the cellulosic particles of the Examples and Comparative Examples, the cellulosic particles indicated in Tables 4-1 and 4-3 are used to produce a variety of cosmetics. Specifically, the following is performed.Liquid Foundation

[0184] According to the formula presented in Table 3-1, liquid foundation is obtained by a known method. Table 3-1 Liquid FoundationFormulaCompoundProduct name (manufacturer)Parts by massParticlesParticlesThe cellulosic particles specified in Tables 4-1 and 4-310Ingredients other than the particlesPropylene glycolPropylene Glycol JSQI (Dow Toray)5BentoniteOVWIL BR (Mizusawa Industrial Chemicals)1TriethanolamineTriethanolamine 99% (Dow Toray)1Stearic acidNAA172 (NOF)3Stearyl alcoholNAA45 (NOF)1Liquid paraffinMORESCO-VIOLESS (MORESCO)8Isopropyl myristateIPM-R (NOF)5PetrolatumNOMCORT W (Nisshin OilliO)2Stearic acid monoglycerideEXCEL 84 (Kao Chemicals)2POE (20) stearyl etherEMALEX 602 (Nihon Emulsion)1Titanium oxideNMR-1 (Sakai Chemical)8KaolinBERACLAY 20061 AMAZONIAN WHITE CLAY (BERECA)5Iron oxideC33-128 Sun CROMA RED Iron Oxide (Sun Chemical)0.5PreservativeOPTIPHEN HD (Ashland Japan)0.5FragranceBisabolol rac. (BASF Japan)0.3Purified water46.5Total100 Milky Lotion

[0185] According to the formula presented in Table 3-2, a milky lotion is obtained by a known method. Table 3-2 Milky LotionFormulaCompoundProduct name (manufacturer)Parts by massParticlesParticlesAs in the Example or Comparative Example2Ingredients other than the particlesPropylene glycolPropylene Glycol JSQI (Dow Toray)5Polyethylene glycol 1500PEG#1500 (NOF)3Carboxy vinyl polymerNTC-CARBOMER 380 (Nikko Chemicals)0.1TriethanolamineTriethanolamine 99% (Dow Toray)1Stearic acidNAA172 (NOF)2Cetyl alcoholNAA44 (NOF)1.5Liquid paraffinMORESCO-VIOLESS (MORESCO)10PetrolatumNOMCORT W (Nisshin OilliO)3Glyceryl oleateNIKKOL MGO (Nikko Chemicals)1POE (20) sorbitan oleateNIKKOL TO -0V (Nikko Chemicals)1PreservativeOPTIPHEN HD (Ashland Japan)0.2FragranceBisabolol rac. (BASF Japan)0.1Purified water70.1Total100 Loose Powder

[0186] The ingredients listed in Table 3-3 are mixed together in a blender, the resulting mixture is milled in a mill, and then the resulting particles are sieved through a 250-µm mesh sieve to give a loose powder. Table 3-3 Loose PowderFormulaCompoundProduct name (manufacturer)Parts by massParticlesParticlesThe cellulosic particles specified in Tables 4-1 and 4-310Ingredients other than the particlesTalcTalc CT-25 (Yamaguchi Mica)65KaolinBERACLAY 20061 AMAZONIAN WHITE CLAY (BERECA)5Titanium oxideMKR-1 (Sakai Chemical)3Zinc myristatePOWDER BASE M (NOF)5Magnesium carbonateNatrasorb HFB (Nouryon Japan)5SericiteSericite FSE (Sanshin Mining Ind.)7Total100 Powder Foundation

[0187] According to the formula presented in Table 3-4, the particles and powders are mixed together, the binders are mixed together separately, the mixture of particles and powders is gradually added into the binders with stirring, and then the mixture is mixed to give powder foundation. Table 3-4 Powder FoundationFormulaCompoundProduct name (manufacturer)Parts by massParticlesParticlesThe cellulosic particles specified in Tables 4-1 and 4-38Powders other than the particlesTalcTalc CT-25 (Yamaguchi Mica)52.5MicaMica FA450 (Yamaguchi Mica)16Titanium oxideMKR-1 (Sakai Chemical)12Black iron oxideC33-134 Sun CROMA Black Iron Oxide (Sun Chemical)0.2Red iron oxideC33-128 Sun CROMA Red Iron Oxide (Sun Chemical)0.4Yellow iron oxideC33-210 Sun CROMA Yellow Iron Oxide (Sun Chemical)2.4BindersDiisostearyl malateNeosolue-DiSM (Nippon Fine Chemical)3Caprylic / capric triglycerideCaprylic / Capric Triglyceride (FUJIFILM Wako Pure Chemical)2Neopentyl glycol dicaprateNPDC (Kokyu Alcohol Kogyo)2Pentylene glycolDIOL PD (Kokyu Alcohol Kogyo)1.5Total100 Sunscreen Cream

[0188] According to the formula presented in Table 3-5, oil phase (1) is warmed to 50°C until dissolution, then oil phase (2) is added, and the two phases are mixed together. Water phase (2) is brought into dissolution and mixed with water phase (1). After the particles and the powders are added to the mixture of oil phases (1) and (2) and dispersed and mixed, emulsification is performed by gradually adding the mixture of water phases (1) and (2), giving a sunscreen cream. Table 3-5 Sunscreen CreamFormulaCompoundProduct name (manufacturer)Parts by massParticlesParticlesThe cellulosic particles specified in Tables 4-2 and 4-45Powders other than the particlesQuaternium-18 hectoriteSUMECTON-SAN (Kunimine Industries)1Titanium oxideMKR-1 (Sakai Chemical)8Oil phase (1)Ethylhexyl methoxycinnamateUvinul MC80 (BASF Japan)4t-Butyl methoxydibenzoylmethaneEusolex 9030 (Merck KGaA)0.5Bis-ethylhexyloxyphenol methoxyphenyl triazineTinosorb S (BASF Japan)2Isopropyl sebacateIsopropyl Sebacate (FUJIFILM Wako Pure Chemical)6Caprylic / capric triglycerideCaprylic / Capric Triglyceride (FUJIFILM Wako Pure Chemical)2Oil phase (2)Cetyl PEG / PPG-10 / 1 dimethiconeKF-6048 (Shin-Etsu Chemical)4Sorbitan isostearateEMALEX SPIS 100 (Nihon Emulsion)0.4CyclopentasiloxaneKF-995 (Shin-Etsu Chemical)16Ethylhexylglycerin, glyceryl caprylateNIKKOL NIKKOGUARD 88 (Nikko Chemicals)0.4Water phase (1)PEG-240 / HDI copolymer bis-decyltetradeceth-20 etherADEKA NOL GT 7001GlycerinRG-CO-P (NOF)41,3-Butylene glycolHAISUGARCANE BG (Kokyu Alcohol Kogyo)4Pentylene glycolDIOL PD (Kokyu Alcohol Kogyo)1PhenoxyethanolPhenoxetol (Clariant Japan)0.3Water phase (2)Magnesium sulfateMagnesium Sulfate (FUJIFILM Wako Pure Chemical)0.3Purified water40.1Total100 All-in-One Gel

[0189] According to the formula presented in Table 3-6, water phases (1) and (2) are mixed together. Then oil phase (1) is mixed and added to the mixture of water phases (1) and (2). After oil phase (2) is warmed to 70°C, the particles are added to give a dispersion. The resulting dispersion is added to the mixture of water phases (1) and (2) and oil phase (1), and emulsification is performed by stirring and mixing the resulting mixture. After the neutralizing agent is added, the emulsion is stirred and cooled to give an all-in-one gel. Table 3-6 All-in-One GelFormulaCompoundProduct name (manufacturer)Parts by massParticlesParticlesThe cellulosic particles specified in Tables 4-2 and 4-44Oil phase (1)Xanthan gumNOMCORT Z (The Nisshin OilliO Group)0.1Hydrogenated lecithinCOATSOME NC-21 (NOF)0.1GlycerinRG-CO-P (NOF)5IsopentyldiolIsoprene Glycol (Kuraray)4Oil phase (2)Polyglyceryl-10 isostearateSunsoft Q-18S-C (Taiyo Kagaku)1.2Polyglyceryl-4 isostearateNIKKOL Tetraglyn 1-SV (Nikko Chemicals)0.3Behenyl alcoholNAA-422 (NOF)1.8OctyldodecanolRISONOL 20SP (Kokyu Alcohol Kogyo)0.8Cetyl ethylhexanoateFineNeo-CIO (Nippon Fine Chemical)3.2SqualaneNIKKOL Olive Squalane (Nikko Chemicals)0.6TocopherolTocopherol 100 (The Nisshin OilliO Group)0.6Ethylhexylglycerin, glyceryl caprylateNIKKOL NIKKOGUARD 88 (Nikko Chemicals)0.6Water phase (1)Carboxy vinyl polymerNTC-CARBOMER 380 (Nikko Chemicals)0.4Pentylene glycolDIOL PD (Kokyu Alcohol Kogyo)1PhenoxyethanolPhenoxetol (Clariant Japan)0.3Sodium dilauramidoglutamide lysine, waterPellicer LB 100 (Asahi Kasei Finechem)0.1Water phase (2)Citric acidCitric Acid (FUJIFILM Wako Pure Chemical)0.1Purified water1.4Neutralizing agent A 10% aqueous solution of sodium hydroxideTotal100 Foundation Primer

[0190] According to the formula presented in Table 3-7, the particles are dispersed in component A, and the resulting mixture is stirred. Component B is added, and the resulting mixture is stirred to give a foundation primer. Table 3-7 Foundation PrimerFormulaCompoundProduct name (manufacturer)Parts by massParticlesParticlesThe cellulosic particles specified in Tables 4-2 and 4-410Component ADimethicone / PEG-10 / 15 crosspolymer, dimethiconeKSG-210 (Shin-Etsu Chemical)3.5PEG-9 polydimethylsiloxyethyl dimethiconeKF-6028 (Shin-Etsu Chemical)2DimethiconeKF-7312K (Shin-Etsu Chemical)5Isononyl isononanoateKAK99 (Kokyu Alcohol Kogyo)4.5Ethylhexyl methoxycinnamateNOMCORT TAB (The Nisshin OilliO Group)10Quaternium-18 hectoriteSUMECTON-SAN (Kunimine Industries)1.2Dimethicone / vinyl dimethicone crosspolymer, dimethiconeKSG-16 (Shin-Etsu Chemical)5CyclomethiconeDOWSIL SH245 Fluid (Dow Toray)25Component B1,3-Butylene glycolHAISUGARCANE BG (Kokyu Alcohol Kogyo)5Sodium citrateTrisodium Citrate (Jungbunzlauer International AG)2PreservativeOPTIPHEN HD (Ashland Japan)0.3Purified water26.5Total100 Lip Primer

[0191] According to the formula presented in Table 3-8, component B is heated to 60°C and mixed. The particles are dispersed in the mixture, component A is added, heating in a microwave is performed until dissolution, the resulting solution is mixed, and then the resulting mixture is poured into a mold and cooled. The resulting solid is set into a lipstick case to give a lip primer. Table 3-8 Lip PrimerFormulaCompoundProduct name (manufacturer)Parts by massParticlesParticlesThe cellulosic particles specified in Tables 4-2 and 4-410Component ACeresinCERESIN #810 (Nikko Rika)4.27Microcrystalline waxRefined Microcrystalline Wax (Nikko Rika)1.55Candelilla waxRefined Candelilla Wax No. 1 (Nippon Wax)5.03ParaffinRefined Paraffin Wax (Nikko Rika)3.07Component BDiisostearyl malateNeosolue-DiSM (Nippon Fine Chemical)17.95Dipentaerythrite fatty acid esterCOSMOL 168 EV (The Nisshin OilliO Group)6.22Adsorption refined lanolinSUPER STEROL LIQUID (Croda Japan)2.52Liquid lanolin acetateACELAN SP (Croda Japan)13.34EthylhexylglycerylGLYMOIST (NOF)19.02Liquid paraffinHYDROBRITE 380 PO (Sonneborn)7.28Isotridecyl isononanoateKAK139 (Kokyu Alcohol Kogyo)3.21Polyglyceryl-2 triisostearateEMALEX TISG-2 (Nihon Emulsion)4.01Methylphenyl polysiloxaneBELSIL PDM 20 (Wacker Asahikasei Silicone)2.41MethylparabenNipagin M (Clariant Japan)0.07TocopherolTocopherol 100 (The Nisshin OilliO Group)0.05Total100 Body Powder

[0192] A body powder is obtained by mixing together the ingredients listed in Table 3-9 using a laboratory mixer. Table 3-9 Body PowderFormulaCompoundProduct name (manufacturer)Parts by massParticlesParticlesThe cellulosic particles specified in Tables 4-2 and 4-410Ingredients other than the particlesTalcTalc CT-25 (Yamaguchi Mica)89.7FragranceBisabolol rac. (BASF Japan)0.3 Solid Powder Eyeshadow

[0193] According to the formula presented in Table 3-10, the particles and powders are mixed together, the binder is uniformly dissolved, the resulting solution is added to the powder mixture, the resulting mixture is further mixed, and then the resulting mixture is compression-molded to give a solid powder eyeshadow. Table 3-10 Solid Powder EyeshadowFormulaCompoundProduct name (manufacturer)Parts by massParticlesParticlesThe cellulosic particles specified in Tables 4-2 and 4-451Powders other than the particlesMicaTalc CT-25 (Yamaguchi Mica)15SericiteSericite FSE (Sanshin Mining Ind.)5PigmentUnipure Blue LC 621 (Sensient Technologies Japan)15Pearl pigmentTWINCLEPEARL (Nihon Koken Kogyo10BinderMethyl polysiloxaneBELSIL DM 10 (Wacker Asahikasei Silicone)2OthersSorbitan sesquioleateEMALEX SPO-150 (Nihon Emulsion)2Total100 Fluffy Feel Evaluations

[0194] The fluffy feel of the resulting cellulosic particles and cosmetics is evaluated as follows.

[0195] It should be noted that the greater the compression energy, described below, is, the greater the resilience after being pressed is, and thus the better the fluffy feel is; and the greater the work of recovery is, the better the recovery from compression is, and thus the better the fluffy feel is.Evaluation of the Fluffy Feel of Cellulosic Particles

[0196] The cellulosic particles are packed into a 60-mm square and 20-mm deep SUS vat, and compression energy and the work of recovery are measured using a texture tester (KES-G5, Kato Tech).Evaluation of the Fluffy Feel of Solid Cosmetics

[0197] For the loose powder, powder foundation, body powder, and solid powder eyeshadow, the fluffy feel is evaluated as follows.

[0198] Compression energy and the work of recovery are evaluated in the same manner as the cellulosic particles, except that the cosmetic is packed into the SUS vat.Evaluation of the Fluffy Feel of Liquid or Cream Cosmetics

[0199] For the cosmetics other than the loose powder, powder foundation, body powder, and solid powder eyeshadow, the fluffy feel is evaluated as follows.

[0200] The cosmetic is applied to artificial skin (Exseal, As One), and compression energy and the work of recovery are evaluated using a texture tester (KES-G5, Kato Tech) on the coated surface. Table 4-1Particle numberPercentage biodegradability (%)Fluffy feelParticlesLiquid foundationMilky lotionLoose powderPowder foundationCompression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Example 1PTC-1972.250.770.220.070.210.072.130.722.020.69Example 2PTC-2982.240.750.210.070.220.072.110.692.010.68Example 3PTC-3962.210.740.220.070.220.082.160.711.990.67Example 4PTC-4982.230.730.230.080.220.072.140.711.980.66Example 5PTC-5971.880.590.150.040.170.041.870.551.810.55Example 6PTC-6962.120.750.220.080.230.082.110.681.990.69Example 7PTC-7962.210.710.230.070.210.072.080.671.970.69Example 8PTC-8952.230.720.230.080.220.072.10.691.990.67Example 9PTC-9961.890.590.170.040.160.041.870.561.790.54Example 10PTC-10972.210.710.220.070.220.082.140.712.010.66Example 11PTC-11971.920.580.170.040.170.051.880.571.770.52Example 12PTC-12972.220.720.210.070.210.082.130.711.980.68Example 13PTC-13951.870.570.180.040.170.041.850.561.780.53Example 14PTC-14942.250.710.220.080.20.072.120.711.990.69Example 15PTC-15962.230.710.230.080.210.072.110.681.980.67Example 16PTC-16951.850.570.170.040.180.041.830.551.760.55Example 17PTC-17962.220.710.220.070.20.082.250.692.010.69Example 18PTC-18961.860.580.170.040.170.041.840.541.740.54Example 20PTC-20922.660.890.360.10.280.152.581.112.330.97Example 21PTC-21912.650.880.350.120.290.142.571.132.320.98Example 22PTC-22922.350.650.270.080.220.12.110.9920.77Example 23PTC-23912.380.680.260.080.230.12.120.992.010.76Example 24 PTC-24922.360.670.270.070.220.092.110.982.020.74Example 25PTC-25932.380.660.280.080.210.12.090.992.030.75Example 26PTC-26922.680.890.350.120.280.132.581.122.340.97Example 27PTC-27912.660.90.360.130.290.172.591.222.320.96Example 28PTC-28932.670.880.360.150.270.152.591.122.340.96Example 29PTC-29922.650.870.370.140.290.162.581.152.330.97Example 30PTC-30922.360.650.250.080.210.092.120.992.010.73Example 31PTC-31913.350.630.270.070.20.092.110.982.020.77Example 32PTC-32902.390.640.280.080.220.12.120.9920.75Example 33PTC-33912.370.610.270.070.210.092.10.982.020.74Example 34PTC-34922.680.890.360.130.280.172.581.122.320.97Example 35PTC-35922.720.880.370.120.290.162.591.132.350.96Example 36PTC-36912.650.870.350.130.280.162.591.122.360.96Example 37PTC-37922.220.620.260.080.210.12.110.992.010.72Example 38PTC-38912.670.870.340.120.280.152.591.132.340.97Example 39PTC-39932.680.890.350.130.290.162.581.132.320.96 Table 4-2 Fluffy feelSunscreen creamAll-in-one gelFoundation primerLip primerBody powderSolid powder eyeshadowCompression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Example 10.350.090.210.072.130.722.020.692.250.712.450.81Example 20.330.090.220.072.110.692.010.682.220.692.380.78Example 30.340.090.220.082.160.711.990.672.230.672.410.77Example 40.330.080.220.072.140.711.980.662.230.672.380.76Example 50.280.060.170.041.870.551.810.551.890.592.110.54Example 60.340.090.230.082.110.681.990.692.240.692.380.77Example 70.330.080.210.072.080.671.970.692.350.672.410.73Example 80.340.090.220.072.10.691.990.672.210.672.390.72Example 90.290.060.160.041.870.561.790.541.880.572.090.57Example 100.330.080.220.082.140.712.010.662.220.682.380.76Example 110.280.060.170.051.880.571.770.521.870.552.090.56Example 120.340.090.210.082.130.711.980.682.210.692.380.77Example 130.280.060.170.041.850.561.780.531.870.592.080.55Example 140.350.090.20.072.120.711.990.692.210.662.370.76Example 150.330.080.210.072.110.681.980.672.190.682.360.75Example 160.270.060.180.041.830.551.760.551.870.572.080.55Example 170.340.090.20.082.250.692.010.692.150.672.330.76Example 180.280.060.170.041.840.541.740.541.860.542.070.55Example 200.560.140.280.142.650.92.220.992.531.032.691.02Example 210.550.150.290.132.650.892.230.982.521.012.71.01Example 220.390.090.240.12.230.672.010.752.330.872.430.88Example 230.370.080.230.112.350.691.990.762.340.882.410.89Example 240.380.090.240.12.330.681.990.772.350.862.410.88Example 250.370.080.230.12.340.6920.762.340.872.420.87Example 260.570.140.290.142.640.92.210.972.5112.711Example 270.550.160.290.152.630.912.230.982.521.012.691.01Example 280.540.130.290.152.650.882.220.992.511.032.71Example 290.580.150.280.142.640.882.210.982.521.042.681Example 300.360.080.240.112.320.691.980.782.350.882.430.88Example 310.380.090.230.092.320.6920.752.360.872.420.89Example 320.390.080.230.12.310.692.010.762.350.872.410.87Example 330.380.090.240.12.330.692.010.772.350.882.420.88Example 340.550.130.290.142.640.892.210.982.5512.681.02Example 350.570.140.290.142.630.882.210.972.521.012.671Example 360.580.150.280.142.630.872.190.982.5112.661Example 370.390.080.230.112.330.681.990.772.360.872.410.89Example 380.560.150.280.142.650.872.230.992.511.022.711.01Example 390.570.140.290.132.640.882.210.982.511.012.71.01 Table 4-3 Particle numberPercentage biodegradability (%)Fluffy feelParticlesLiquid foundationMilky lotionLoose powderPowder foundationCompression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Example 40PTC-40783.151.010.440.190.380.242.881.452.881.55Example 41PTC-41773.110.990.450.180.370.222.891.442.871.68Example 42PTC-42743.121.010.410.180.370.242.891.452.861.58Example 43PTC-43783.1510.530.170.380.232.881.452.891.57Example 44PTC-44763.030.990.430.180.370.222.891.472.871.55Example 45PTC-45723.151.030.450.190.360.212.881.432.871.58Example 46PTC-46743.111.030.420.180.370.222.891.452.881.57Example 47PTC-47782.760.860.350.150.290.162.661.152.551.23Example 48PTC-48763.091.010.430.170.370.232.91.442.891.56Example 49PTC-49752.710.880.540.140.280.152.651.22561.33Example 50PTC-50753.081.010.430.180.360.232.881.482.881.57Example 51PTC-51743.151.020.450.190.360.222.891.432.891.55Example 52PTC-52733.130.990.420.170.370.232.91.432.871.56Example 53PTC-53733.151.050.420.180.360.242.911.452.881.55Example 54PTC-54723.151.030.430.190.370.232.881.432.891.54Example 55PTC-55713.111.030.420.180.350.222.871.422.871.57Example 56PTC-56723.121.020.420.190.360.232.851.422.861.56Example 57PTC-57683.331.230.510.260.440.313.051.663.011.88Example 58PTC-58693.341.220.50.240.420.293.031.643.011.89Example 59PTC-59653.121.020.430.20.360.222.851.412.861.56Example 60PTC-60673.361.210.510.220.420.33.081.6531.86Example 61PTC-62682.220.720.220.070.210.072.120.681.990.67Example 62PTC-63692.210.730.210.080.220.082.140.71.980.68Example 63PTC-65682.220.730.220.080.210.072.150.712.010.67Example 64PTC-66692.230.710.210.070.220.072.140.692.010.68Comparative Example 1PTC-61690.630.310.060.010.080.011.230.220.980.22Comparative Example 2PTC-64670.620.330.060.010.070.011.220.210.990.21Comparative Example 3PTC-67670.990.430.090.020.110.021.560.381.450.38Comparative Example 4PTC-68680.980.440.090.020.120.021.550.371.440.39Comparative Example 5PTC-69660.980.450.080.020.120.021.570.361.430.37Comparative Example 6PTC-70670.970.440.090.020.110.021.560.381.40.38Comparative Example 7PTC-71680.980.430.080.020.120.021.570.381.410.39Comparative Example 8PTC-72690.970.450.090.020.110.021.550.371.440.39Comparative Example 9PTC-101790.630.310.060.010.080.011.240.220.980.19Comparative Example 10PTC-102780.610.330.060.010.070.011.220.230.990.21Comparative Example 11PTC-103170.980.420.090.020.120.021.540.391.410.37Comparative Example 12PTC-104250.990.440.090.020.110.021.530.381.420.38Comparative Example 13PTC-105240.970.450.090.020.110.021.540.381.410.37Comparative Example 14PTC-111850.960.450.090.020.120.021.550.381.40.38Comparative Example 15PTC-112880.970.430.090.020.110.021.540.371.420.37 Table 4-4 Fluffy feelSunscreen creamAll-in-one gelFoundation primerLip primerBody powderSolid powder eyeshadowCompression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Compression energy (J)Work of recovery (W)Example 400.820.250.420.253.111.332.881.652.991.553.121.57Example 410.820.240.410.243.121.322.871.642.981.513.131.55Example 420.810.230.420.243.121.322.881.662.981.533.111.56Example 430.870.240.430.253.131.332.851.642.991.543.111.55Example 440.80.240.420.263.121.322.821.632.981.533.091.56Example 450.790.220.410.243.121.312.831.622.991.533.091.56Example 460.810.250.420.253.131.312.821.612.981.523.091.54Example 470.660.190.350.212.881.112.661.442.771.242.881.37Example 480.810.240.410.243.111.322.831.62.971.533.011.36Example 490.670.20.360.22.891.122.61.422.751.252.881.36Example 500.790.250.410.253.111.332.821.612.971.543.111.56Example 510.80.250.420.243.091.322.821.622.971.543.091.55Example 520.820.250.410.253.11.312.841.612.971.543.081.55Example 530.810.240.420.243.081.332.831.62.961.553.11.54Example 540.80.230.410.253.091.322.821.622.961.563.111.54Example 550.790.240.420.263.071.352.811.632.981.543.11.55Example 560.80.230.420.243.071.322.821.642.971.553.091.56Example 570.990.290.460.293.251.492991.83.121.713.311.71Example 580.980.280.460.283.281.4831.83.121.73.291.72Example 590.810.230.430.253.061.332.811.632.961.553.091.55Example 600.970.290.470.283.271.482.991.793.091.73.291.71Example 610.340.090.220.072120.692.010.682.250.692.410.78Example 620.350.090.210.082.110.7120.692.220.682.390.77Example 630.360.090.210.082130.691.990.682.210.672.420.78Example 640.350.090.230.072120.71.980.692.250.682.390.79Comparative Example 10.090.010.080.011.210.211.110.251.020.211.330.16Comparative Example 20.090.010.070.011.190.221.120.251.040.221.320.17Comparative Example 30.190.040.120.021.550.391.550.311.340.311.520.28Comparative Example 40.190.040.110.021.560.381.510.331.330.311.510.27Comparative Example 50.180.040.120.021.550.381.50.311.320.321.510.27Comparative Example 60.190.040.110.021.570.391.530.321.330.311.510.25Comparative Example 70.190.040.110.021.580.381.550.311.340.311.520.24Comparative Example 80.180.030.110.021.560.371.50.331.320.311.510.24Comparative Example 90.090.010.080.011.190.21.120.281.040.211.320.17Comparative Example 100.090.010.070.011.190.211.130.261.030.221.331.16Comparative Example 110.190.040.120.021.560.371.530.31.320.311.50.24Comparative Example 120.180.030.120.021.550.371.540.311.330.321.530.25Comparative Example 130.190.030.110.021.560.361.50.31.310.311.520.22Comparative Example 140.190.040.110.021.570.371.510.321.320.311.510.21Comparative Example 150.190.040.110.021.570.371.510.311.320.311.520.23

[0201] From these results, it can be seen that the cellulosic particles of the Examples have a fluffy feel.

[0202] The foregoing description of the exemplary embodiments of the present disclosure has been provided for the purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure to the precise forms disclosed. Obviously, many modifications and variations will be apparent to practitioners skilled in the art. The embodiments were chosen and described in order to best explain the principles of the disclosure and its practical applications, thereby enabling others skilled in the art to understand the disclosure for various embodiments and with the various modifications as are suited to the particular use contemplated. It is intended that the scope of the disclosure be defined by the following claims.

Claims

1. A cellulosic particle comprising: cellulose as a base constituent; and at least one selected from the group consisting of a hydrocarbon ester and a ketone, wherein: the hydrocarbon ester is at least one selected from the group consisting of ethyl acetate, butyl acetate, and ethyl propionate, the ketone is at least one selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, and acetone, at least one of an amount of the hydrocarbon ester and an amount of the ketone is 3 ppm or more and 1000 ppm or less relative to the cellulosic particles, ppm being by mass, and the amount of the hydrocarbon ester and the amount of the ketone are measured in accordance with the method outlined the description, and an amount of the cellulose relative to the cellulosic particle is 90% by mass or more.

2. The cellulosic particle according to claim 1, wherein: the cellulosic particle has: a core particle with a cellulose content relative to the core particle of 90% by mass or more; and a coating layer covering the core particle and containing at least one selected from the group consisting of a fatty acid, a fatty acid metallic salt, and an amino acid compound.

3. The cellulosic particle according to claim 2, wherein: the fatty acid is a fatty acid having 16 or more and 22 or fewer carbon atoms; and a number of carbon atoms in the fatty acid metallic salt is 16 or more and 22 or fewer.

4. The cellulosic particle according to claim 2 or 3, wherein: the fatty acid is a saturated fatty acid; and the fatty acid metallic salt is a saturated fatty acid metallic salt.

5. The cellulosic particle according to any one of claims 2 to 4, wherein: the cellulosic particle has an intermediate layer between the core particle and the coating layer; and the intermediate layer is at least one selected from the group consisting of a polyamine compound, a polyquaternium, a polysaccharide compound, and a polyacrylic acid.

6. The cellulosic particle according to any one of claims 1 to 5, wherein: the cellulosic particle has an inorganic particle as an external additive.

7. The cellulosic particle according to any one of claims 1 to 6, wherein: a volume-average particle diameter of the cellulosic particles is 3 µm or more and less than 10 µm and measured in accordance with the method outlined in the description.

8. The cellulosic particle according to any one of claims 1 to 7, wherein: an upper geometric standard deviation by number GSDv of the cellulosic particles is 1.0 or greater and 1.7 or less and measured in accordance with the method outlined in the description.

9. The cellulosic particle according to any one of claims 1 to 8, wherein: sphericity of the cellulosic particle is 0.7 or greater and measured in accordance with the method outlined in the description.

10. The cellulosic particle according to any one of claims 1 to 9, wherein: surface smoothness of the cellulosic particle is 50% or more and measured in accordance with the method outlined in the description.

11. The cellulosic particle according to any one of claims 1 to 10, wherein: a number-average molecular weight of the cellulose is 37000 or more and measured by gel permeation chromatography.

12. The cellulosic particle according to claim 11, wherein: the number-average molecular weight of the cellulose is 45000 or more.