JP2022135891A - Polysaccharide-containing particle, method for producing the particle, and applications for the particle - Google Patents

Abstract

To provide a polysaccharide-containing particle having excellent light-scattering properties, a method for producing the particle, and applications for the particle.SOLUTION: A polysaccharide-containing particle has at least one crater-like recess on its surface. Preferably, the circularity is 0.70 or more and 0.97 or less, the aspect ratio is 0.60 or more and 0.85 or less, the polysaccharide has a crosslinked structure, the polysaccharide is a cellulose derivative, the volume average particle diameter is 0.1 μm-100 μm, the index of light scattering is 0.6-1.0, and the degree of swelling is 1.0-5.0.SELECTED DRAWING: None

Description

The present invention relates to polysaccharide-containing particles, methods for producing the particles, and uses of the particles.

BACKGROUND ART Conventionally, spherical particles containing polysaccharides have been used in a wide range of applications as additives for cosmetics, pharmaceuticals, foods, paints, etc., due to their good lubricity.

For example, Patent Document 1 describes an emulsified cosmetic containing porous spherical cellulose powder.

Patent Document 2 describes spherical porous cellulose fine particles having an outer shell layer and a porous inner core, the inner core having a porosity of 5 to 50%.

Patent Document 3 describes true spherical particles containing a water-soluble polymer such as a water-soluble cellulose derivative.

Patent Document 4 describes spherical particles composed of a polyvalent cation salt of carboxymethylcellulose.

Japanese Patent Publication No. 6-45534 JP-A-6-254373 JP-A-5-222208 JP-A-2009-51781

However, since the spherical particles containing the cellulose derivatives described in Patent Documents 1 to 4 have smooth surfaces, they are inferior in light scattering properties, and have a sufficient soft focus effect to correct skin defects such as wrinkles and spots. However, there was a problem that it could not be obtained, and further improvement was required.

The present invention has been made in view of the above, and an object of the present invention is to provide polysaccharide-containing particles having excellent light scattering properties, a method for producing the particles, and uses of the particles.

As a result of intensive studies aimed at achieving the above object, the inventors of the present invention have found that the above object can be achieved by forming a specific shape on the surface of the polysaccharide-containing particles. The present invention has been completed through further research.

The present invention provides inventions of the following aspects.
Section 1.
A polysaccharide-containing particle having at least one crater-shaped recess on its surface.
Section 2.
Item 2. The polysaccharide-containing particles according to Item 1, having a circularity of 0.70 or more and 0.97 or less.
Item 3.
Item 3. The polysaccharide-containing particles according to Item 1 or 2, having an aspect ratio of 0.60 or more and 0.85 or less.
Section 4.
Item 4. The polysaccharide-containing particle according to any one of Items 1 to 3, wherein the polysaccharide has a crosslinked structure.
Item 5.
Item 5. The polysaccharide-containing particle according to any one of Items 1 to 4, wherein the polysaccharide is a cellulose derivative.
Item 6.
Item 6. The polysaccharide-containing particles according to any one of Items 1 to 5, having a volume average particle size of 0.1 μm to 100 μm.
Item 7.
Item 7. The polysaccharide-containing particles according to any one of Items 1 to 6, which have a light scattering index of 0.6 to 1.0.
Item 8.
Item 8. The polysaccharide-containing particles according to any one of Items 1 to 7, having a swelling degree of 1.0 to 5.0.
Item 9.
Item 9. A method for producing polysaccharide-containing particles according to any one of Items 1 to 8,
a spray-drying step of spray-drying a solution containing a polysaccharide to obtain a precursor;
A heat treatment step of heating the precursor obtained in the spray drying step to obtain polysaccharide-containing particles;
A method for producing polysaccharide-containing particles.
Item 10.
Item 10. The method for producing polysaccharide-containing particles according to Item 9, wherein in the heat treatment step, the precursor obtained in the spray drying step is heated at a temperature of 60 to 300° C. for 1 hour or more.
Item 11.
Item 9. An external preparation comprising the polysaccharide-containing particles according to any one of Items 1 to 8.
Item 12.
A coating material comprising the polysaccharide-containing particles according to any one of Items 1 to 8.
Item 13.
Item 9. A resin composition comprising the polysaccharide-containing particles according to any one of items 1 to 8.
Item 14.
Item 9. An antiblocking agent comprising the polysaccharide-containing particles according to any one of items 1 to 8.
Item 15.
Item 9. A light diffusion film comprising the polysaccharide-containing particles according to any one of Items 1 to 8.

Since the polysaccharide-containing particles of the present invention have at least one crater-shaped concave portion on the surface, they are excellent in light scattering properties. In particular, since the polysaccharide-containing particles of the present invention have excellent light-scattering properties, they can be expected to exhibit a soft focus effect when blended in external preparations such as cosmetics.

1 is a photograph of polysaccharide-containing particles obtained in Example 1 taken with a scanning electron microscope (SEM) at a magnification of about 3000. FIG. 2 is a photograph of polysaccharide-containing particles obtained in Example 2, taken with an SEM at a magnification of about 3000. FIG. 1 is a photograph of the powder obtained in Comparative Example 1 taken with a SEM at a magnification of about 3000. FIG. 2 is a photograph of the powder obtained in Comparative Example 2 taken with an SEM at a magnification of about 3000. FIG. 2 is a photograph of the powder obtained in Comparative Example 3 taken with a SEM at a magnification of about 3000. FIG. 10 is a photograph of the powder obtained in Comparative Example 4 taken with a SEM at a magnification of about 3000. FIG. 2 is a photograph of particles obtained in Comparative Example 5, taken with a SEM at a magnification of about 3000. FIG. 2 is a SEM photograph of particles obtained in Comparative Example 6 at a magnification of about 3000. FIG.

Preferred embodiments of the present invention are described in detail below.

As used herein, the expressions "contain" and "include" include the concepts "contain", "include", "consist essentially of" and "consist only of".

In the numerical ranges described stepwise in this specification, the upper limit value or lower limit value of the numerical range in one step can be arbitrarily combined with the upper limit value or lower limit of the numerical range in another step. In addition, in the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with values shown in Examples or values that can be uniquely derived from Examples. Furthermore, in this specification, a numerical value connected with "-" means a numerical range including the numerical values before and after "-" as lower and upper limits.

1. Polysaccharide-Containing Particle The polysaccharide-containing particle of the present invention is characterized by containing a polysaccharide and having at least one crater-shaped concave portion on the surface of the particle. The polysaccharide-containing particles of the present invention are excellent in light scattering properties due to such a configuration. In addition, since the polysaccharide-containing particles of the present invention have excellent light scattering properties, they can be expected to exhibit a soft focus effect, and can be particularly suitably used for external preparations such as cosmetics.

Hereinafter, the polysaccharide-containing particles of the present invention may be simply referred to as "the present invention", "the particles of the present invention", or "polysaccharide-containing particles".

As used herein, the term “crater-shaped depression” means not only a partially depressed portion in the smooth portion of the particle surface, but also a depression having a bulge in the periphery of the depression (a raised depression surrounding the periphery of the depression). recesses with portions) are also meant. When the crater-shaped depressions on the surface of the polysaccharide-containing particles of the present invention are viewed from above, the shape of the depressions may be circular or elliptical.

As used herein, the term "crater-like depressions" does not mean wrinkled or wrinkled relief structures such as groove-like knots having a wrinkled or wrinkled appearance. In addition, in the present specification, the term “crater-shaped depressions” does not mean irregular concave-convex structures found in petal-shaped particles.

The crater-shaped recess preferably has a major axis of 0.1 μm to 70 μm. The crater-like depressions preferably have a depth of 0.1 μm to 50 μm.

The long diameter of the crater-shaped recesses is preferably 5% or more, more preferably 10% or more, and even more preferably 15% of the long diameter of the polysaccharide-containing particles, from the viewpoint of good light scattering properties. From the viewpoint of good light scattering properties, the content is preferably 50% or less, more preferably 40% or less, and even more preferably 30% or less. The major diameter of the crater-shaped depressions and the major diameter of the polysaccharide-containing particles can be measured by observing the polysaccharide-containing particles with an SEM at a magnification of about 3000, for example.

The maximum depth of the crater-shaped recesses is preferably 2% or more, more preferably 3% or more, and still more preferably 3% or more of the major diameter of the polysaccharide-containing particles, from the viewpoint of good light scattering properties. It is 5% or more, and from the viewpoint of good light scattering properties, it is preferably 90% or less, more preferably 80% or less, and even more preferably 70% or less. The maximum depth of the crater-shaped depressions can be measured, for example, by observing the polysaccharide-containing particles with an SEM at a magnification of about 3000 times.

In the polysaccharide-containing particles of the present invention, the number of crater-shaped recesses per particle is at least 1, preferably 2 to 20, from the viewpoint of good light scattering properties and excellent oil absorption. , more preferably 3 to 15, even more preferably 4 to 10.

From the viewpoint of further improving the strength of the particles, the polysaccharide-containing particles of the present invention are preferably solid particles having a solid structure. As used herein, solid particles having a solid structure mean particles that do not have a hollow structure or particles that do not have a porous structure. Here, the hollow structure means a structure in which the inside surrounded by the shell is hollow (a completely hollow state), or a structure in which at least one void is present inside the particle. The term "void" as used herein means a portion that becomes a hole inside the particle, which can be confirmed when the cross section of the particle is observed with an SEM or the like. The polysaccharide-containing particles of the present invention more preferably have a solid structure whose interior is filled with a cellulose derivative, and more preferably have a solid structure whose interior is filled with a cellulose derivative having a crosslinked structure. preferable.

In the present invention, the degree of circularity is preferably 0.70 or more and 0.97 or less, more preferably 0.75 or more and 0.96 or less, from the viewpoint of having a highly uniform reflected light intensity. It is preferably 80 or more and 0.95 or less. In the present specification, the degree of circularity means the degree of circularity obtained by the measuring method described in the section of Examples below.

The polysaccharide-containing particles of the present invention have an aspect ratio of 0.60 or more and 0.85 or less, and have at least one crater-shaped concave portion on the surface, from the viewpoint of moderate slipperiness and adhesion to the skin. Deformed particles (ie, polysaccharide-containing deformed particles) are preferred. As used herein, the term "irregularly shaped particles" means non-spherical particles (non-spherical particles). Moreover, in this specification, the aspect ratio means the aspect ratio obtained by the measuring method described in the section of Examples described later.

In the present invention, the polysaccharide preferably has a crosslinked structure from the viewpoint of water resistance and solvent resistance. A crosslinked structure means a structure in which polysaccharides are crosslinked. In the present invention, when the polysaccharide has a crosslinked structure, the toughness (elastic modulus) described below is further improved. In the present invention, it is more preferable to have a structure in which polysaccharides are crosslinked by hydrogen bonding. In the present invention, the cellulose derivative having a crosslinked structure is generally obtained by crosslinking cellulose derivatives used as raw materials. In addition, in this specification, the cellulose derivative used as a raw material means the cellulose derivative which does not have a crosslinked structure.

In the present invention, the polysaccharide is preferably a cellulose derivative. A cellulose derivative (a cellulose derivative not having a crosslinked structure) used as a raw material in this specification means a water-soluble polymer in which a part of the hydroxyl groups of cellulose is substituted with other substituents.

Examples of cellulose derivatives include methylcellulose, ethylcellulose, ethylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxyethylcellulose, carboxymethylcellulose sodium, carboxymethylcellulose potassium, carboxymethylcellulose calcium, carboxymethylcellulose ammonium and the like. . These cellulose derivatives can be used alone or in combination of two or more. In the present invention, the cellulose derivative is at least one selected from the group consisting of ethylcellulose, ethylmethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxyethylcellulose, carboxymethylcellulose sodium, carboxymethylcellulose potassium, carboxymethylcellulose calcium and carboxymethylcellulose ammonium. is preferred. In the present invention, the cellulose derivative is more preferably at least one selected from the group consisting of sodium carboxymethylcellulose, potassium carboxymethylcellulose, calcium carboxymethylcellulose and ammonium carboxymethylcellulose. In the present invention, carboxymethylcellulose ammonium is particularly preferred as the cellulose derivative.

In the present invention, the volume average particle size is preferably 0.1 μm to 100 μm from the viewpoint of tactile properties. As used herein, the volume-average particle size means the volume-average particle size obtained by the measurement method described in the Examples section below.

In the present invention, the light scattering index is preferably 0.6 to 1.0 from the viewpoint of obtaining highly uniform reflected light intensity. By setting the light scattering index within this range, the light scattering property is further improved, and when the particles of the present invention are blended in a cosmetic or the like, the soft focus property is further improved. In the present invention, the light scattering index is preferably 0.65-0.95, more preferably 0.7-0.9. As used herein, the light scattering index means the light scattering index obtained by the measurement method described in the Examples section below.

In the present invention, the degree of swelling is preferably 1.0 to 5.0, more preferably 1.5 to 4.5, still more preferably 2.0, from the viewpoint of the effect on touch and appearance in aqueous formulations. ~4.0. In the present specification, the degree of swelling means the degree of swelling obtained by the measuring method described in the Examples section below.

In the present invention, from the viewpoint of durability against external force in processing steps such as stirring and mixing, the higher the robustness, the better. As used herein, toughness means elastic modulus (MPa) obtained by the measurement method described in the Examples section below.

In the present invention, from the viewpoint of durability, the toughness (elastic modulus) is preferably 110 MPa or more and 270 MPa or less, more preferably 120 MPa or more and 240 MPa or less, and even more preferably 130 MPa or more and 210 MPa or less.

2. Method for producing polysaccharide-containing particles The production method of the present invention comprises a spray-drying step of obtaining a precursor by spray-drying a solution containing a polysaccharide, and heating the precursor obtained in the spray-drying step to obtain polysaccharide-containing particles. and a heat treatment step for obtaining particles. With such a configuration, the production method of the present invention can produce polysaccharide-containing particles having at least one crater-shaped concave portion on the surface by a simple method.

The details of the polysaccharide-containing particles produced by the production method of the present invention are as described in the above "1. Polysaccharide-containing particles" unless otherwise specified.

The method for producing polysaccharide-containing particles of the present invention will be described in detail below.

(Spray drying process)
The spray-drying step is a step of obtaining a precursor by spray-drying a solution containing a polysaccharide.

Preferably, the polysaccharide used in the spray drying process is a cellulose derivative.

Examples of cellulose derivatives include methylcellulose, ethylcellulose, ethylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxyethylcellulose, carboxymethylcellulose sodium, carboxymethylcellulose potassium, carboxymethylcellulose calcium, carboxymethylcellulose ammonium and the like. . These cellulose derivatives can be used alone or in combination of two or more. In the present invention, the cellulose derivative is at least one selected from the group consisting of ethylcellulose, ethylmethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, carboxyethylcellulose, carboxymethylcellulose sodium, carboxymethylcellulose potassium, carboxymethylcellulose calcium and carboxymethylcellulose ammonium. is preferred. In the present invention, the cellulose derivative is more preferably at least one selected from the group consisting of sodium carboxymethylcellulose, potassium carboxymethylcellulose, calcium carboxymethylcellulose and ammonium carboxymethylcellulose. In the present invention, carboxymethylcellulose ammonium is particularly preferred as the cellulose derivative.

The solution used in the spray drying process is preferably prepared by mixing the polysaccharide in a solvent in a container. The type of container is not particularly limited, and for example, a wide range of known containers can be used. Examples of the solvent include water, organic solvents, and mixed solvents of water and organic solvents. Among these, water is preferred. Examples of water include natural water, purified water, distilled water, ion-exchanged water, and pure water. Among these, ion-exchanged water is preferred. Examples of organic solvents include aliphatic monohydric alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aromatic compounds such as toluene and xylene. In this specification, organic solvents do not include polyhydric alcohols such as polyethylene glycol, polyvinyl alcohol, and erythritol.

The solution used in the spray-drying step is preferably an aqueous solution consisting of the polysaccharide and water, more preferably an aqueous solution consisting of the polysaccharide and ion-exchanged water.

The solution used in the spray drying process preferably does not contain polyhydric alcohols such as polyethylene glycol, polyvinyl alcohol, erythritol and the like.

The polysaccharide content is preferably 0.5 to 20 parts by mass, more preferably 0.75 to 15 parts by mass, and still more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the solution containing the polysaccharide. be.

In the spray drying step, spray drying is performed to obtain a precursor from a solution containing polysaccharides. The form of the precursor is preferably powder.

In the spray-drying step, a solution containing a polysaccharide is usually sprayed and dried using a spray dryer such as a spray dryer. The size and shape of the resulting precursor are adjusted by appropriately adjusting the feed rate, inlet temperature, outlet temperature, residence time, atomizer rotation speed, spray pressure, etc. of the polysaccharide-containing solution in the spray dryer. It is possible.

In the spray drying step, the lower limit of the inlet temperature (the temperature of the inlet where the solution containing the polysaccharide is introduced into the spray dryer) is preferably 80°C, more preferably 90°C, even more preferably 100°C, and particularly preferably is 110°C. In the spray-drying process, the upper inlet temperature is preferably 250°C, more preferably 240°C, even more preferably 230°C, particularly preferably 220°C.

In the spray-drying step, the lower limit of the outlet temperature (the temperature of the outlet where the polysaccharide-containing solution is spray-dried and discharged as a precursor) is preferably 40°C, more preferably 45°C, and even more preferably 50°C. , particularly preferably 55°C. In the spray-drying process, the upper outlet temperature is preferably 140°C, more preferably 130°C, even more preferably 120°C, particularly preferably 110°C.

In the spray-drying process, the residence time (the time during which the polysaccharide-containing solution is subjected to spray-drying) is preferably 0.5 seconds to 2 seconds.

(Heat treatment process)
The heat treatment step is a step of heating the precursor obtained in the spray drying step to obtain polysaccharide-containing particles. By heating the precursor, the polysaccharides are crosslinked to obtain polysaccharide-containing particles.

In the heat treatment step, the precursor is usually heated using a device such as a constant temperature bath.

By adjusting the heating temperature and heating time in the heat treatment step, the polysaccharides can be sufficiently crosslinked, and polysaccharide-containing particles having excellent light scattering properties can be produced.

In the heat treatment step, the precursor obtained in the spray drying step is preferably heated at a temperature of 60 to 300° C. for 1 hour or more, more preferably at a temperature of 60 to 300° C. for 1 hour or more and 20 hours or less. preferable.

In the heat treatment step, polysaccharides can be crosslinked by heating at a low temperature of 160° C. or lower for a long time, or by heating at a high temperature of 200° C. or higher for a short time. When the temperature is low, heating is preferably performed at 60 to 160° C. for 6 to 20 hours, more preferably at 80 to 150° C. for more than 3 to 20 hours. In the case of high temperature, it is preferable to heat at 200 to 300° C. for 1 hour or more and 3 hours or less.

The production method of the present invention preferably does not include a step of adding a cross-linking agent (organic cross-linking agents such as divinyl compounds and bisepoxides; ionic cross-linking agents such as calcium chloride and other divalent metal salts).

3. Uses of Polysaccharide-Containing Particles The polysaccharide-containing particles of the present invention are used as additives for topical preparations such as topical medicines and cosmetics; additives for coating materials such as matting agents for paints and powder coatings; automotive materials and building materials. additives for resin compositions such as; additives for antiblocking agents; or additives for light diffusion films.

The polysaccharide-containing particles of the present invention can be more suitably used as an additive for external preparations such as topical medicines and cosmetics. The polysaccharide-containing particles of the present invention can be used particularly preferably as an additive for cosmetics.

(External agent)
Embodiments of external preparations containing the polysaccharide-containing particles of the present invention are exemplified below. In this aspect, the external preparation contains the polysaccharide-containing particles of the present invention. The external preparation of the present invention can make pores, spots, wrinkles, etc. less noticeable by being applied to the skin.

In this aspect, the content of the polysaccharide-containing particles of the present invention in the external preparation can be appropriately set according to the type of the external preparation, preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably It is 5% by mass or more, preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

In this aspect, the external preparation can be used, for example, as an external drug or cosmetic. Examples of external medicines include creams, ointments, emulsions, and the like. Cosmetics include, for example, soaps, body shampoos, facial cleansing creams, scrub facial cleansers, cleaning cosmetics such as toothpastes; powders, face powders (loose powders, pressed powders, etc.), foundations (powder foundations, liquid foundations, emulsified foundation, etc.), lipstick, lip balm, blush, eyebrow cosmetics (eye shadow, eyeliner, mascara, etc.), makeup cosmetics such as nail polish; lotions such as pre-shave lotion and body lotion; body powder such as body powder and baby powder Skin care agents such as lotions, creams, milky lotions (cosmetic milky lotions); Antiperspirants (liquid antiperspirants, solid antiperspirants, cream antiperspirants, etc.), packs, hair washing cosmetics, dyes Examples include hair preparations, hair styling preparations, fragrant cosmetics, bath agents, sunscreen products, suntan products, shaving creams, and the like.

In this aspect, the cosmetic composition may contain a commonly used main ingredient or additive depending on the purpose, as long as the effect of the present invention is not impaired. Examples of such base agents or additives include water, lower alcohols (alcohols having 5 or less carbon atoms), oils and waxes, hydrocarbons, higher fatty acids, higher alcohols, sterols, fatty acid esters, metallic soaps, moisturizers, Surfactants, polymer compounds, raw materials for coloring materials, fragrances, clay minerals, antiseptic/bactericidal agents, anti-inflammatory agents, antioxidants, ultraviolet absorbers, organic-inorganic composite particles, pH adjusters (triethanolamine, etc.), Examples include specially formulated additives and active pharmaceutical ingredients.

Examples of the fats and waxes include avocado oil, almond oil, olive oil, cacao butter, beef tallow, sesame butter, wheat germ oil, safflower oil, shea butter, turtle oil, camellia oil, persic oil, castor oil, grape oil, Macadamia nut oil, mink oil, egg yolk oil, Japanese wax, coconut oil, rosehip oil, hydrogenated oil, silicone oil, orange roughy oil, carnauba wax, candelilla wax, whale wax, jojoba oil, montan wax, beeswax, lanolin, etc. .

Examples of the hydrocarbon include liquid paraffin, petrolatum, paraffin, ceresin, microcrystalline wax, squalane and the like.

Examples of the higher fatty acids include fatty acids having 11 or more carbon atoms, such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid, oxystearic acid, linoleic acid, lanolin fatty acid, and synthetic fatty acids. mentioned.

Examples of the higher alcohols include lauryl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyldecanol, octyldecanol, isostearyl alcohol, jojoba alcohol, Alcohols having 6 or more carbon atoms such as decyltetradecanol can be mentioned.

Examples of the sterol include cholesterol, dihydrocholesterol, phytocholesterol and the like.

Examples of the fatty acid ester include linoleic acid esters such as ethyl linoleate; lanolin fatty acid esters such as isopropyl lanolin fatty acid; lauric acid esters such as hexyl laurate; isopropyl myristate, myristyl myristate, cetyl myristate, and octyl myristate. myristate esters such as dodecyl; oleate esters such as decyl oleate and octyldodecyl oleate; dimethyloctanoate esters such as hexyldecyl dimethyloctanoate; Palmitate esters such as decyl palmitate; glyceryl trimyristate, tri(caprylic/capric acid) glyceryl, propylene glycol dioleate, glyceryl triisostearate, glyceryl triisooctanoate, cetyl lactate, myristyl lactate, diisostearyl malate, Cyclic alcohol fatty acid esters such as cholesteryl isostearate and cholesteryl 12-hydroxystearate.

Examples of the metal soap include zinc laurate, zinc myristate, magnesium myristate, zinc palmitate, zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, and zinc undecylenate.

Examples of the moisturizing agent include glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, sodium dl-pyrrolidonecarboxylate, sodium lactate, sorbitol, sodium hyaluronate, polyglycerin, xylitol, and maltitol. .

Examples of the surfactant include anionic surfactants such as higher fatty acid soaps, higher alcohol sulfates, N-acylglutamates, and phosphate ester salts; cationic surfactants such as amine salts and quaternary ammonium salts. Amphoteric surfactants such as betaine type, amino acid type, imidazoline type and lecithin; Ionic surfactants can be mentioned.

Examples of the polymer compound include natural polymer compounds such as gum arabic, tragacanth gum, guar gum, locust bean gum, karaya gum, irismos, quince seed, gelatin, shellac, rosin, casein; sodium carboxymethylcellulose, hydroxyethylcellulose, methylcellulose. , Ethyl cellulose, sodium alginate, ester gum, nitrocellulose, hydroxypropyl cellulose, semi-synthetic polymer compounds such as crystalline cellulose; polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether, polyamide resin, silicone oil , nylon particles, poly(meth)acrylate particles (eg, polymethyl methacrylate particles), polystyrene particles, silicone particles, urethane particles, polyethylene particles, silica particles, and other synthetic high molecular compounds.

Examples of raw materials for the coloring material include iron oxide (red iron oxide, yellow iron oxide, black iron oxide, etc.), ultramarine blue, konjo, chromium oxide, chromium hydroxide, carbon black, manganese violet, titanium oxide, zinc oxide, and talc. , kaolin, calcium carbonate, magnesium carbonate, mica, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, hydroxyapatite, ceramic powder, etc. and inorganic pigments such as azo, nitro, nitroso, xanthene, quinoline, anthraquinoline, indigo, triphenylmethane, phthalocyanine, and pyrene tar dyes.

It should be noted that powder raw materials such as the powder raw materials of the polymer compounds and the coloring material raw materials described above may be subjected to a surface treatment in advance. As the surface treatment method, known surface treatment techniques can be used. For example, oil agent treatment with hydrocarbon oil, ester oil, lanolin, etc., silicone treatment with dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, etc. Fluorine compound treatment with perfluoroalkyl group-containing esters, perfluoroalkylsilanes, perfluoropolyethers and polymers having perfluoroalkyl groups, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. treatment with a silane coupling agent, treatment with a titanium coupling agent such as isopropyl triisostearoyl titanate or isopropyl tris(dioctylpyrophosphate) titanate, metal soap treatment, amino acid treatment with acylglutamic acid, etc., lecithin treatment with hydrogenated egg yolk lecithin, etc., collagen Treatment methods include treatment, polyethylene treatment, moisture retention treatment, inorganic compound treatment, mechanochemical treatment, and the like.

Examples of the clay minerals include components having several functions such as extenders and adsorbents, such as talc, mica, sericite, titanium sericite (serisite coated with titanium oxide), and muscovite. , VEEGUM (registered trademark) manufactured by Vanderbilt, and the like.

Examples of the perfume include anisaldehyde, benzyl acetate, geraniol and the like.

Examples of the antiseptic/bactericidal agent include methyl paraben, ethyl paraben, propyl paraben, benzalkonium, and benzethonium.

Examples of the antioxidant include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, and tocopherol.

Examples of the ultraviolet absorber include inorganic absorbents such as microparticle titanium oxide, microparticle zinc oxide, microparticle cerium oxide, microparticle iron oxide, microparticle zirconium oxide, benzoic acid, para-aminobenzoic acid, anthranilic acid, salicylic acid, Organic absorbents such as cinnamic acid, benzophenone, and dibenzoylmethane are included.

Examples of the above-mentioned specially compounded additives include hormones such as estradiol, estrone, ethinyl estradiol, cortisone, hydrocortisone and prednisone; vitamins such as vitamin A, vitamin B, vitamin C and vitamin E; citric acid, tartaric acid, lactic acid; Skin astringent agents such as aluminum chloride, aluminum/potassium sulfate, allantoin chlorohydroxyaluminium, zinc paraphenolsulfonate, zinc sulfate, cantharis tincture, capsicum tincture, ginger tincture, juniper extract, garlic extract, hinokitiol, carpronium chloride .

(Coating agent)
Embodiments of the coating agent containing the polysaccharide-containing particles of the present invention are exemplified below. In this aspect, the coating agent contains the polysaccharide-containing particles of the present invention. In this embodiment, the content of the polysaccharide-containing particles of the present invention in the coating agent can be appropriately set according to the type of coating agent, preferably 1 to 90% by mass, more preferably 3 to 80% by mass.

In this aspect, the coating material can contain a binder resin, an ultraviolet curable resin, and a solvent as necessary. Examples of binder resins include acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, amorphous polyolefin resins, and the like. These resins can be used alone or in combination of two or more.

As the UV-curable resin, a polyfunctional (meth)acrylate resin is preferable, and a polyhydric alcohol polyfunctional (meth)acrylate resin having 3 or more (meth)acryloyl groups in one molecule is more preferable. Specific examples of polyhydric alcohol polyfunctional (meth)acrylate resins having 3 or more (meth)acryloyl groups in one molecule include trimethylolpropane tri(meth)acrylate and trimethylolethane tri(meth)acrylate. , 1,2,4-cyclohexanetetra(meth)acrylate, pentaglycerol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol triacrylate, tripentaerythritol hexaacrylate and the like. These resins can be used alone or in combination of two or more.

When an ultraviolet curable resin is used, a photopolymerization initiator is added to the ultraviolet curable resin to form a binder resin. Photopolymerization initiators include, for example, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, α-hydroxyalkylphenones, α-aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, peroxides (described in JP-A-2001-139663, etc.), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, onium salts, borate salts, active halogen compounds, α-acyloximes Ester etc. are mentioned. These photopolymerization initiators may be used alone or in combination of two or more.

Examples of the solvent include, for oil-based paints, hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; dioxane and ethylene glycol. Examples include ether-based solvents such as diethyl ether and ethylene glycol monobutyl ether, and water-based paints include water and alcohols. These solvents can be used alone or in combination of two or more.

In this embodiment, the coating material may optionally include known coating surface modifiers, fluidity modifiers, ultraviolet absorbers, light stabilizers, curing catalysts, extender pigments, coloring pigments, metallic pigments, mica powder pigments, A dye or the like may be included.

In this embodiment, the coating film forming method using the coating material includes, for example, known coating film forming methods such as a spray coating method, a roll coating method, and a brush coating method. The coating material may be diluted with a diluent to adjust viscosity as needed. Examples of diluents include aromatic compound solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as dioxane and ethylene glycol diethyl ether; Water such as natural water, purified water, distilled water, ion-exchanged water, and pure water; alcoholic solvents such as methanol, ethanol, and isopropyl alcohol; These diluents can be used alone or in combination of two or more.

In addition, a coating film is prepared by applying it to an arbitrary coating surface such as a base material, and after drying this coating film, the coating film is cured as necessary to form a cross-coated film. can do. The coating film using the coating material is used by coating various substrates, and is not particularly limited to metals, wood, glass, plastics, and the like. It can also be used by coating it on a transparent substrate such as polyethylene terephthalate (PET), polycarbonate (PC), acrylic resin, or the like.

(resin composition)
Embodiments of the resin composition containing the polysaccharide-containing particles of the present invention are exemplified below. In this aspect, the resin composition contains a base resin and the polysaccharide-containing particles of the present invention. Examples of base resins include polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, poly(ethylene succinate/terephthalate), and poly(butylene succinate/terephthalate). , poly(butylene adipate terephthalate), poly(ε-caprolactone), poly(β-propiolactone), polyamide 4, poly(3-hydroxybutyrate), poly(3-hydroxyvalerate), Poly(3-hydroxycaprolate), poly(3-hydroxyheptanoate), poly(3-hydroxyoctanoate), poly(3-hydroxybutyrate/3-hydroxyhexanoate), poly Biodegradable resins such as (3-hydroxybutyrate/3-hydroxyvalerate), starch-based resins, cellulose-based resins, glucosamine-based resins; polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide 6, polyamide 66, polyamide 12, ABS resin (acrylonitrile-butadiene-styrene copolymer resin), AS resin (acrylonitrile-styrene copolymer resin), polyethylene, polypropylene, polyacetal, polyamideimide, polyethersulfone, polyimide, polyphenylene oxide, polyphenylene sulphide, polystyrene, thermoplastic Polyurethane elastomer, thermoplastic polyester elastomer, thermoplastic polyamide elastomer, polyvinyl chloride, polyvinylidene fluoride, ethylene tetrafluoroethylene copolymer (ETFE resin), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA resin), polyether ketone, etc. of thermoplastic resins. These base resins can be used alone or in combination of two or more.

In this aspect, the content of the polysaccharide-containing particles of the present invention in the resin composition is preferably 0.1 to 70% by mass based on the total mass of the base resin and the polysaccharide-containing particles of the present invention. Yes, more preferably 0.5 to 50% by mass, still more preferably 1 to 30% by mass.

In this aspect, the resin composition may contain known additives as necessary. Additives include reinforcing fibers such as glass fiber and carbon fiber, flame retardants, fluidity modifiers, ultraviolet absorbers, heat stabilizers, light stabilizers, lubricants, extender pigments, coloring pigments, metal pigments, and dyes. be able to.

In this embodiment, the method for producing the resin composition is not particularly limited, and the base resin and the polysaccharide-containing particles of the present invention may be mixed by a conventionally widely known method such as a mechanical pulverization and mixing method. can be manufactured by In the mechanical pulverization and mixing method, for example, the base resin and the polysaccharide-containing particles of the present invention are mixed and stirred using a device such as a Henschel mixer, a V-type mixer, a Turbula mixer, a hybridizer, or a rocking mixer. Thereby, a resin composition can be produced.

In this embodiment, the method for forming the molded article using the resin composition is not particularly limited, and any known method can be used. For example, the base resin and the polysaccharide-containing particles of the present invention are mixed in a mixer and kneaded in a melt kneader such as an extruder to obtain pellets made of a resin composition, and then the pellets are extruded and injected. Molded articles of any shape suitable for automotive materials, building materials, packaging materials, etc., can be obtained by molding by blow molding or the like.

(Anti-blocking agent)
Embodiments of the antiblocking agent containing the polysaccharide-containing particles of the present invention are exemplified below. The polysaccharide-containing particles of the present invention impart irregularities to the surface of the resin film in order to prevent the surfaces of the resin film from coming into contact with each other and not being peeled off (blocking) when the resin film is wound. It can be used as an anti-blocking agent.

In this embodiment, the antiblocking agent may contain, if necessary, known antioxidants, fluidity modifiers, light stabilizers, color pigments, etc., in addition to the polysaccharide-containing particles of the present invention.

In this aspect, the content of the polysaccharide-containing particles of the present invention in the antiblocking agent is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass. is.

In this embodiment, the resin constituting the resin film to which an antiblocking agent can be used includes, for example, polylactic acid, polyglycolic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, poly(ethylene succinate), terephthalate), poly(butylene succinate/terephthalate), poly(butylene adipate/terephthalate), poly(ε-caprolactone), poly(β-propiolactone), polyamide 4, poly(3-hydroxybutyrate) ), poly (3-hydroxyvalerate), poly (3-hydroxycaprolate), poly (3-hydroxyheptanoate), poly (3-hydroxyoctanoate), poly (3- hydroxybutyrate/3-hydroxyhexanoate), poly(3-hydroxybutyrate/3-hydroxyvalerate), starch-based resins, cellulose-based resins, glucosamine-based resins, and other biodegradable resins; polyester resins such as phthalates; polyolefin resins such as polyethylene resins and polypropylene resins; (meth)acrylic resins, polystyrene resins, polyethersulfone resins, polyurethane resins, polycarbonate resins, polysulfone resins, Polyether-based resins, polymethylpentene-based resins, polyetherketone-based resins, (meth)acrylonitrile-based resins, norbornene-based resins, amorphous polyolefin-based resins, polyamide resins, polyimide resins, triacetyl cellulose resins, and the like. These resins can be used alone or in combination of two or more.

In this aspect, the content of the polysaccharide-containing particles of the present invention in the resin film is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.01% to 5% by mass. 01 to 3% by mass, particularly preferably 0.01 to 1% by mass.

(light diffusion film)
Embodiments of the light diffusion film containing the polysaccharide-containing particles of the present invention are illustrated below. In this aspect, the light diffusing film comprises the polysaccharide-containing particles of the invention. In this aspect, the content of the polysaccharide-containing particles of the present invention in the light diffusion film can be appropriately set according to the type of the light diffusion film, preferably 1 to 90% by mass, more preferably 3 to 80% by mass. be.

In this embodiment, the light diffusing film is prepared by, for example, mixing the polysaccharide-containing particles of the present invention, a binder resin, a diluent, etc. by a known method to prepare a dispersion, which is then used as a base film by a known method. It can be manufactured by coating and drying on the surface.

In this embodiment, the substrate used for producing the light diffusion film includes, for example, glass; plastic sheets and films made of polycarbonate (PC), acrylic resin, polyethylene terephthalate (PET), triacetyl cellulose (TAC), etc.; Examples include plastic lenses and plastic panels.

In this embodiment, examples of the binder resin used for producing the light diffusion film include acrylic resins, alkyd resins, polyester resins, polyurethane resins, chlorinated polyolefin resins, amorphous polyolefin resins, and the like. These resins can be used alone or in combination of two or more.

In this embodiment, diluents used in the production of the light diffusion film include aromatic compounds such as toluene and xylene; ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone; ester compounds such as ethyl acetate and butyl acetate. ether compounds such as dioxane and ethylene glycol diethyl ether; water such as natural water, purified water, distilled water, ion-exchanged water and pure water; alcohols such as methanol, ethanol and isopropyl alcohol. These diluents can be used alone or in combination of two or more.

EXAMPLES The present invention will be described in more detail below based on Examples, but the present invention is not limited to the aspects of these Examples. First, the measurement method and evaluation method in the section of Examples will be described. In the measurement method and the evaluation method, the particles or powder obtained in each example and each comparative example are simply referred to as "particles to be measured".

(Observation of surface shape)
A conductive tape was attached to the sample stage, and the particles to be measured were mounted thereon. Surface treatment (40 mA, 180 seconds) was performed using a JEOL Ltd. "Auto Fine Coater JFC-1300" sputtering device. Next, using a secondary electron detector of a "SU1510" scanning electron microscope manufactured by Hitachi High-Technologies Corporation, the surface shape of the surface-treated particles to be measured was photographed and evaluated according to the following evaluation criteria.
A: The particles to be measured were non-spherical, and had crater-like depressions on the surface.
B: The particles to be measured were spherical and did not have crater-like depressions on the surface.

(Measurement of circularity and measurement of aspect ratio)
The circularity of the particles to be measured was measured using a flow type particle image analyzer (trade name “FPIA (registered trademark)-3000S” manufactured by Sysmex Corporation). As a specific measurement method, 0.2 g of the particles to be measured was added to 20 ml of a 0.25% sodium dodecylbenzenesulfonate aqueous solution, and an ultrasonic dispersing machine "BRANSON SONIFIER 450" manufactured by BRANSON was used as a dispersing machine (output 400 W, frequency of 20 kHz) was applied for 5 minutes to disperse the particles to be measured in the surfactant aqueous solution to prepare a dispersion liquid for measurement.

For the measurement, the flow type particle image analyzer equipped with a standard objective lens (10x) was used. Sysmex Corporation) was used.

The measurement dispersion liquid prepared according to the above procedure was introduced into the flow type particle image analyzer and measured under the following measurement conditions. In the measurement, a suspension of standard polymer particles (for example, "5200A" (standard polystyrene particles diluted with ion-exchanged water) manufactured by ThermoFisher Scientific) was used before the start of the measurement, and the flow type particle image analyzer was used. performed automatic focus adjustment.
<Measurement conditions for circularity and aspect ratio>
・Measurement mode: HPF mode ・Measurement range of maximum diameter of particles: 0.996 μm to 200 μm
Measurement range of particle circularity: 0.5 to 1.0
・ Measurement range of aspect ratio of particles: 0 to 1.00
・Measured number of particles: 1000

The circularity is a value obtained by dividing the perimeter calculated from the diameter of a perfect circle having the same projected area as the image of the particle to be measured by the perimeter of the image of the particle to be measured.

The aspect ratio is obtained by dividing the maximum vertical length of a particle to be measured by the maximum length of the particle. The maximum length of the particle to be measured is the maximum length at two points on the contour of the particle image. The maximum vertical length of the particle to be measured is the shortest length vertically connecting two straight lines parallel to the maximum length when an image is sandwiched between the two straight lines.

(Measurement of volume average particle size)
The volume average particle size of the particles to be measured was measured with a Coulter Multisizer ^TM 3 (measuring device manufactured by Beckman Coulter, Inc.). Measurements were performed with an aperture calibrated according to the Multisizer ^™ 3 User's Manual published by Beckman Coulter, Inc. The aperture used for measurement was appropriately selected depending on the size of the particles to be measured. Current (aperture current) and Gain (gain) were appropriately set according to the size of the selected aperture. For example, if an aperture with a size of 50 μm was selected, Current was set to −800 and Gain was set to 4.

As a sample, 0.1 g of the particles to be measured was added to 10 ml of deionized water using a touch mixer (manufactured by Yamato Scientific Co., Ltd., "TOUCHMIXER MT-31") and an ultrasonic cleaner (manufactured by Vervoclear Co., Ltd., "ULTRASONIC CLEANER VS-150") and used as a dispersion. During the measurement, the inside of the beaker was gently stirred to the extent that air bubbles were not introduced, and the measurement was terminated when 100,000 particles were measured. The volume average particle diameter of the particles to be measured was the arithmetic mean of the volume-based particle size distribution of 100,000 particles.

(Measurement of swelling degree)
After dispersing 0.25 g of the particles to be measured in 2.5 g of deionized water, centrifugation (2500 rpm, 20 minutes, 20° C.) using a high-speed cooling centrifuge (manufactured by HITACHI, product name “CR21N”). After gently removing the supernatant, the weight of the swollen particles to be measured was measured. The degree of swelling is obtained by dividing the value obtained by subtracting the initial weight of the particles to be measured (0.25 g) from the weight of the swollen particles to be measured by the initial weight of the particles to be measured (0.25 g). Calculated. The calculated degree of swelling was evaluated according to the following evaluation criteria.
○: less than 5.0 △: 5.0 or more and less than 10.0 ×: 10.0 or more

(Measurement of light scattering index)
(i) Measurement of Reflected Light Intensity Distribution Scattering properties of light reflected by the surface of the particle to be measured were evaluated by the method shown below. Black drawing paper PI-N86D (manufactured by Maruai Co., Ltd.) was pasted on a soda glass (“Azlab Slide Glass” manufactured by AS ONE Co., Ltd.) using Nicetak (registered trademark) NW-10S (manufactured by Nichiban Co., Ltd.). . Next, Nystak (registered trademark) NW-10S is attached to the above-mentioned black drawing paper, and after pressing the particles to be measured on it, excess particles are removed with an air gun adjusted to a pressure of 0.2 MPa. rice field. The test piece thus obtained was used as a test piece for measuring the distribution of reflected light intensity. The reflection light intensity distribution was measured using a three-dimensional photometer (“GC-500L” manufactured by Nippon Denshoku Industries Co., Ltd.).

Light is incident on the test piece from a light source at an angle of −45° with respect to the normal line (0°) of the obtained test piece, and the light intensity distribution at the reflection angle of −90° to +90° of the reflected light is measured. Measured with a three-dimensional photometer. During the measurement, the position of the test piece was adjusted so that all the incident light was incident on the black portion of the test piece.

(ii) Calculation of reflected light intensity at 0° with respect to reflected light intensity 100 at +45° Reflected light at reflection angle +45° The reflected light intensity at a reflection angle of 0° was obtained when the intensity was defined as 100. When the reflected light intensity at a reflection angle of +45° is taken as 100, the closer the reflected light intensity at a reflection angle of 0° approaches 100, the greater the soft focus effect when the particles are blended in the cosmetic.

The light scattering index was calculated by the following formula.
Light scattering index = (scattered light intensity at 0°)/(scattered light intensity at 45°)
It can be said that the closer the light scattering index is to 1.0, the higher the angle-independent light scattering properties. The calculated light scattering index was evaluated according to the following evaluation criteria.
○: 0.75 or more △: 0.55 or more and less than 0.75 ×: less than 0.55

(Method for evaluating robustness)
The toughness (elastic modulus) of the particles to be measured was measured using a microcompression tester (trade name “MCT-210” manufactured by Shimadzu Corporation) under the following measurement conditions.
<Conditions for measurement of toughness (elastic modulus)>
Test temperature and humidity: Room temperature (20°C), relative humidity 65%
Upper pressure indenter: Flat indenter with a diameter of 50 μm (material: diamond)
Lower pressure plate: SKS flat plate Test type: Compression test (MODE 1)
Maximum test load: 9.81mN
Load speed: 0.732mN/sec
Displacement full scale: 20 μm

First, the particles to be measured are added to ethanol, and an ultrasonic cleaner manufactured by Vervoclear Co., Ltd. is used as a dispersing machine (“ULTRASONIC CLEANER VS-150” manufactured by Vervoclear Co., Ltd.). The particles were dispersed in an aqueous surfactant solution to prepare a dispersion for measurement. The prepared dispersion was applied to a mirror-finished steel sample stage and dried to prepare a measurement sample.

Then, in an environment of room temperature 20 ° C. and relative humidity 65%, an optical microscope equipped with MCT-210 selects and selects one independent fine particle (a state in which no other particles exist within a range of at least 50 μm in diameter). The long diameter of the particles was measured with a particle size measurement cursor mounted on the MCT-210. The selected particles were fine particles with a major diameter within the range of 6 μm to 12 μm, and particles outside this range were not used for measurement of compressive strength.

Next, by lowering the test indenter on the selected particles at the following loading speed, a load is gradually applied to the particles up to a maximum load of 9.81 mN. was taken as a 10% test force, and the toughness (elastic modulus) was determined by the following formula.

<Calculation formula for robustness (modulus of elasticity)>
The toughness (elastic modulus) of the particles to be measured is calculated from the long diameter of the particle measured one by one with an optical microscope, the cross-sectional area calculated from the long diameter of the particle by regarding the cross section of the particle as a circle, and the microcompression tester. It was calculated from % test force and compression displacement by the following formula.
Robustness (elastic modulus) = σ ÷ ε = (P ÷ A) ÷ (λ ÷ L)
σ: Normal stress (mN/μm ² )
P: 10% test force (mN)
A: Particle cross-sectional area (μm ² )
ε: Strain (no unit)
λ: compression displacement (μm)
L: Particle long diameter (μm)

The calculated toughness (elastic modulus) was evaluated according to the following evaluation criteria.
○: 130 MPa or more △: 110 MPa or more and less than 130 MPa ×: less than 110 MPa

(Example 1)
Into a container, 2 g of carboxymethylcellulose ammonium (NH ₄ CMC, product name "NA-3L" manufactured by Nichirin Chemical Industry Co., Ltd.) as a polysaccharide and 98 g of ion-exchanged water were added and dissolved by stirring to prepare an aqueous solution. . The aqueous solution was spray-dried using a spray dryer (manufactured by Nihon Buchi Co., Ltd., product name "Mini Spray Dryer B-290") under the following apparatus conditions to obtain powder.
<Equipment conditions>
・Supply rate of aqueous solution: 40 mL/min
・Air volume: 8 m ³ /min
- Inlet temperature (temperature at the inlet where the aqueous solution is introduced into the device): 185°C
- Outlet temperature (outlet temperature at which aqueous solution is spray-dried and discharged as powder): 102°C
・Residence time: 2 seconds ・Nozzle: 2-fluid nozzle

The obtained powder was heated at 110° C. for 16 hours using a constant temperature bath (product name “DRM420DD” manufactured by Advantech Toyo Co., Ltd.) to obtain polysaccharide-containing particles.

A SEM photograph of the obtained particles is shown in FIG. As shown in FIG. 1, the polysaccharide-containing particles obtained in Example 1 were found to be non-spherical and to have crater-like depressions on the surface.

(Example 2)
Preparation of an aqueous solution, spray drying and heat treatment were performed in the same manner as in Example 1, except that the inlet temperature during spray drying was 120° C. and the outlet temperature was 60° C., to obtain polysaccharide-containing particles.

A SEM photograph of the obtained particles is shown in FIG. As shown in FIG. 2, the polysaccharide-containing particles obtained in Example 2 were found to be non-spherical and to have crater-like depressions on the surface.

(Comparative example 1)
In a container, 2 g of carboxymethyl cellulose ammonium (NH ₄ CMC, product name "NA-3L" manufactured by Nichirin Chemical Industry Co., Ltd.) as a polysaccharide and polyethylene glycol (PEG, manufactured by NOF Corporation, weight average molecular weight) as a polyhydric alcohol 20000) and 96 g of ion-exchanged water were added and dissolved by stirring to prepare an aqueous solution.

Subsequently, by the same method as in Example 2, powder was obtained by spray-drying the prepared aqueous solution. In Comparative Example 1, the obtained powder was not subjected to heat treatment.

A SEM photograph of the obtained powder is shown in FIG. As shown in FIG. 3, it was found that the powder obtained in Comparative Example 1 was spherical and had no crater-like depressions on the surface.

(Comparative example 2)
An aqueous solution was prepared in the same manner as in Comparative Example 1, except that 2 g of polyvinyl alcohol (PVA, product name "Gosenol (registered trademark) GL-05" manufactured by Mitsubishi Chemical Corporation) was used as the polyhydric alcohol. Next, by the same method as in Example 1, the prepared aqueous solution was spray-dried to obtain powder. In Comparative Example 2, the obtained powder was not heat-treated.

A SEM photograph of the obtained powder is shown in FIG. As shown in FIG. 4, it was found that the powder obtained in Comparative Example 2 was spherical and had no crater-like depressions on the surface.

(Comparative Example 3)
An aqueous solution was prepared in the same manner as in Comparative Example 1, except that 2 g of erythritol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the polyhydric alcohol. Then, powder was obtained by spray drying the prepared aqueous solution in the same manner as in Example 1 except that the inlet temperature during spray drying was 220 ° C. and the outlet temperature was 120 ° C. . In Comparative Example 3, the obtained powder was not heat-treated.

A SEM photograph of the obtained powder is shown in FIG. As shown in FIG. 5, it was found that the powder obtained in Comparative Example 3 was spherical and did not have crater-like depressions on the surface.

(Comparative Example 4)
Cellulose acetate particles (product name “BELLOCEA (registered trademark)” manufactured by Daicel Corporation) were used as polysaccharides. In Comparative Example 4, the cellulose acetate particles were not spray dried and heat treated. In Comparative Example 4, the cellulose acetate particles were used only for observing the surface shape and evaluating the physical properties. "-" is indicated.

A SEM photograph of the particles is shown in FIG. As shown in FIG. 6, it was found that the particles of Comparative Example 4 were spherical and did not have crater-shaped depressions on the surface.

Table 1 shows the composition of Examples 1-2 and Comparative Examples 1-4, the conditions of spray drying, the presence or absence of heat treatment, the physical properties, and the evaluation items.

In the items of circularity and aspect ratio in Table 1, "cannot be measured" means that the powder dissolved in the solution for measurement, and the measurement test of circularity and aspect ratio could not be carried out.

In the item of volume average particle size in Table 1, "cannot be measured" means that the powder dissolved in the solution for measurement, and the volume average particle size measurement test could not be performed.

(Discussion)
The degree of swelling of Examples 1-2 was less than 1/4 of the degree of swelling of Comparative Examples 1-3. The reason why there is such a difference in the degree of swelling is that the polysaccharide-containing particles obtained in Examples 1 and 2 have a structure in which the polysaccharides are crosslinked by hydrogen bonding due to the heat treatment. It is speculated that Furthermore, from the results of the light scattering index, unlike the powders or particles obtained in Comparative Examples 1 to 4, the polysaccharide-containing particles obtained in Examples 1 to 2 have good light scattering properties. It was shown that it can be suitably used for cosmetics and the like.

(Comparative Example 5)
An aqueous medium prepared by dispersing 15 parts by weight of magnesium pyrophosphate in 1000 parts by weight of deionized water was added to a 2 L polymerization vessel equipped with a stirrer and a thermometer, and 0.02 parts by weight of sodium lauryl sulfate was added. 260 parts by weight of previously prepared methyl methacrylate (MMA) (monofunctional vinyl monomer), 40 parts by weight of ethylene glycol dimethacrylate (EDGMA) (polyfunctional vinyl monomer), 40 parts by weight of methacrylic modified silicone oil (methacrylic A mixture of a modified silicone oil-based vinyl monomer, manufactured by Shin-Etsu Chemical Co., Ltd., product name "X-22-174DX") and 0.9 parts by weight of azobisisobutyronitrile (polymerization initiator) was placed in a polymerization vessel. Added to Next, the mixed liquid was dispersed in an aqueous medium with a stirrer (trade name “TK Homomixer” manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare a suspension having a droplet diameter of about 10 μm. While stirring with a stirrer, the suspension was heated to 65° C. and polymerized for 6 hours, then heated to 100° C., heated at 100° C. for 2 hours, and cooled to room temperature (about 20° C.). The resulting suspension was filtered, washed and dried to obtain particles. A SEM photograph of the obtained particles is shown in FIG.

(Comparative Example 6)
After adding 128 g of ion-exchanged water to 50 g of bamboo-derived cellulose nanofiber (CNF, product name “nanoforest (registered trademark)” manufactured by Chuetsu Pulp Industry Co., Ltd.) with a solid content of 5% by mass, stir with a mechanical stirrer, Dispersed cellulose nanofibers. An aqueous solution for spray drying was prepared by dispersing this dispersion liquid for 5 minutes while stirring with an ultrasonic homogenizer (manufactured by BRANSON, model SONIFIER450). Powder was obtained by spray-drying the prepared aqueous solution in the same manner as in Example 1 except that the inlet temperature was 180°C and the outlet temperature was 110°C. The obtained powder was heated at 110° C. for 16 hours in the same manner as in Example 1 to obtain particles. A SEM photograph of the obtained particles is shown in FIG.

Table 2 shows the composition of Examples 1 and 2 and Comparative Examples 5 and 6, the conditions of spray drying, the presence or absence of heat treatment, and the evaluation items. In addition, "unmeasured" in Table 2 means that no measurement was performed.

In the item of degree of swelling in Table 2, "impossible to measure" means that the particles of Comparative Example 5 floated in water, and the measurement test of degree of swelling could not be carried out.

(Discussion)
The degree of swelling of Examples 1 and 2 was less than half the degree of swelling of Comparative Example 6. The reason why there is such a difference in the degree of swelling is that the polysaccharide-containing particles obtained in Examples 1 and 2 have a structure in which the polysaccharides are crosslinked by hydrogen bonding due to the heat treatment. It is speculated that Furthermore, the toughness of Examples 1 and 2 was about 1.7 times the toughness of Comparative Example 6, which was excellent. The reason why there was such a difference in toughness is that the particles of Comparative Example 6 are particles in which cellulose fibers are aggregated and have a heterogeneous internal structure, while the polysaccharide-containing particles obtained in Examples 1 and 2 It is presumed that the particles have a uniform structure inside the particles and a structure in which the polysaccharides are crosslinked by hydrogen bonding.

Claims (15)

A polysaccharide-containing particle having at least one crater-shaped recess on its surface. 2. The polysaccharide-containing particles according to claim 1, having a circularity of 0.70 or more and 0.97 or less. 3. The polysaccharide-containing particles according to claim 1, having an aspect ratio of 0.60 or more and 0.85 or less. The polysaccharide-containing particles according to any one of claims 1 to 3, wherein the polysaccharide has a crosslinked structure. The polysaccharide-containing particles according to any one of claims 1 to 4, wherein the polysaccharide is a cellulose derivative. The polysaccharide-containing particles according to any one of claims 1 to 5, having a volume average particle size of 0.1 µm to 100 µm. The polysaccharide-containing particles according to any one of claims 1 to 6, having a light scattering index of 0.6 to 1.0. The polysaccharide-containing particles according to any one of claims 1 to 7, having a swelling degree of 1.0 to 5.0. A method for producing the polysaccharide-containing particles according to any one of claims 1 to 8,
a spray-drying step of spray-drying a solution containing a polysaccharide to obtain a precursor;
A method for producing polysaccharide-containing particles, comprising a heat treatment step of heating the precursor obtained in the spray drying step to obtain polysaccharide-containing particles. The method for producing polysaccharide-containing particles according to claim 9, wherein in the heat treatment step, the precursor obtained in the spray drying step is heated at a temperature of 60 to 300° C. for 1 hour or longer. An external preparation comprising the polysaccharide-containing particles according to any one of claims 1 to 8. A coating material comprising the polysaccharide-containing particles according to any one of claims 1-8. A resin composition comprising the polysaccharide-containing particles according to any one of claims 1 to 8. An antiblocking agent comprising the polysaccharide-containing particles according to any one of claims 1 to 8. A light diffusion film comprising the polysaccharide-containing particles according to any one of claims 1 to 8.

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