Patent Application
20250057753
The present invention relates to surface-coated inorganic particles, a surface modifier, a cosmetic product, a surface modification method, and a method for producing the surface-coated inorganic particles.
Cosmetic products such as cosmetics, skin care products, toiletry products, and perfumes are sometimes blended with synthetic polymer fine particles from the viewpoint of improving the texture.
Here, the synthetic polymer fine particles are difficult to decompose in the natural environment and may adversely affect the ecosystem, so that texture-improving particles that can be an alternative to synthetic polymer fine particles are needed.
Examples of such texture-improving particles blended with cosmetic products include inorganic particles, the surface of which is coated with a silicone compound. Examples of techniques relating to such surface-coated inorganic particles include those described in JP H09-301826 A (Patent Literature 1) and WO2020/230650 (Patent Literature 2).
Patent Literature 1 describes inorganic particles, the surface of which is coated with a poly(N-acyl alkylene imine)-modified silicone.
Patent Literature 2 describes a composite surface-treated inorganic powder in which the surface of a base powder mainly composed of an inorganic material has been surface-treated with a cationic surfactant and an amino-modified silicone.
The present invention relates to the following [1] to [5].
There is a demand for texture-improving particles having a good texture and being suitable as alternative materials to synthetic polymer fine particles.
One embodiment of the present invention relates to providing surface-coated inorganic particles, a surface modifier, and a cosmetic product having a good texture and being suitable as alternative materials to synthetic polymer fine particles, and a surface modification method using the surface-coated inorganic particles, the surface modifier, or the cosmetic product.
Further, one embodiment of the present invention relates to providing a method for producing surface-coated inorganic particles having a good texture and being suitable as alternative materials to synthetic polymer fine particles.
Accordingly, one embodiment of the present invention can provide the surface-coated inorganic particles, a surface modifier, and a cosmetic product having a good texture and being suitable as alternative materials to synthetic polymer fine particles, and a surface modification method using the surface-coated inorganic particles, the surface modifier, or the cosmetic product.
Further, one embodiment of the present invention can provide a method for producing surface-coated inorganic particles having a good texture and being suitable as alternative materials to synthetic polymer fine particles.
The surface-coated inorganic particles of to the present invention is surface-coated inorganic particles, in which a portion or all of the surface of inorganic particles (A) is coated with a surface treatment agent (B), wherein
The surface-coated inorganic particles of the present invention have a good texture. Therefore, the surface-coated inorganic particles of the present invention can improve the texture of a cosmetic product by blending them in the cosmetic product or using them as the cosmetic product. Furthermore, the use of the surface-coated inorganic particles of the present invention as a surface modifier can modify the surface of skin, hair, nails, etc., to have a good texture.
Moreover, the surface-coated inorganic particles of the present invention comprise the inorganic particles (A) that do not correspond to synthetic polymer fine particles as core particles, wherein the inorganic particles (A) are coated with the surface treatment agent (B) comprising at least one selected from the group consisting of the modified silicone (b1) liquid at 25° C.′ and the water-soluble cationic polymer (b2), so that the surface-coated inorganic particles are environmentally friendly and are suitable as alternative materials to synthetic polymer fine particles.
As used herein, the expression “a portion or all of the surface of the inorganic particles (A) is coated with the surface treatment agent (B)” means a state such that the surface treatment agent (B) is adsorbed to at least a portion of the surface of the inorganic particles (A) via intermolecular force or ionic bond. The term “adsorption” as used herein does not include a mode in which the inorganic particles (A) and the surface treatment agent (B) are covalently bonded.
Whether or not the surface treatment agent (B) is adsorbed to at least a portion of the surface of the inorganic particles (A) is determined by a known method. For example, when the amount of the surface treatment agent (B) adsorbed to 100 parts by mass of the inorganic particles (A), which is calculated by “measurement of the amount of the surface treatment agent adsorbed to the inorganic particles” described in Examples, is greater than 0 part by mass, preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, it is determined that the surface treatment agent (B) is adsorbed to the surface of the inorganic particles (A).
As used herein, the term “texture” refers to the smoothness and no creakiness of particles when the particles are applied to skin, hair, nails, etc. The smoother and less creakiness, the better the texture. The term “smoothness” refers to a smooth, non-powdery texture, and “creakiness” refers to a feel of catching when a finger touches and moves over the skin, hair, nails, etc.
Moreover, as used herein, the term “liquid at 25° C.” refers to a state of having fluidity in a bulk state under an environment of 1 atm and 25° C.
The reason why the surface-coated inorganic particles of the present invention have a good texture is not clear, but is because the inorganic particles (A) comprising silica particles or silicate mineral particles are coated with the surface treatment agent (B) comprising at least one selected from the group consisting of a modified silicone (b1) and a water-soluble cationic polymer (b2) having excellent lubricity, so that the dynamic friction force and the amplitude of the dynamic friction force can be effectively reduced while maintaining the appropriate hardness of the inorganic particles (A).
The content of the synthetic polymer that is solid at 25° C., and water-insoluble in the surface-coated inorganic particles of the present invention is preferably less than 1% by mass, more preferably less than 0.5% by mass, further preferably less than 0.1% by mass, and further preferably less than 0.01% by mass from the viewpoint of further improving the environmental compatibility, and the surface-coated inorganic particles of the present invention are preferably substantially free of the synthetic polymer. As used herein, the expression “substantially free of the synthetic polymer” means that the synthetic polymer is not intentionally added, but this does not exclude the presence of a small amount of the synthetic polymer as an impurity.
As used herein, the term “water-insoluble synthetic polymer” refers to a synthetic polymer the dissolution amount of which is 2 g or less when 10 g of the synthetic polymer is mixed with 1,000 mL of water with pH 7 at 20° C. in accordance with the OECD guideline 120 followed by 24 hours of stirring.
Moreover, the term “solid at 25° C.” refers to a state of not having fluidity in a bulk state under an environment of 1 atm and 25° C.
The volume median particle size (D50) of the surface-coated inorganic particles described in the present invention is preferably more than 1 μm, more preferably more than 2 μm, and further preferably more than 3 μm, and, preferably 30 μm or less, more preferably 20 μm or less, further preferably 15 μm or less, and further preferably 12 μm or less from the viewpoint of further improving the texture.
Here, the volume median particle size (D50) described in the present invention is a 50% median diameter measured by a laser diffraction/scattering method using a particle size distribution analyzer, and can specifically be measured by a method described in Examples.
In the surface-coated inorganic particles of the present invention, the surface treatment agent (B) is preferably adsorbed to the surface of the inorganic particles (A) via intermolecular force or ionic bond, from the viewpoint of further improving the texture.
In the present specification, the presence or absence of adsorption due to intermolecular force or ionic bond between the inorganic particles (A) and the surface treatment agent (B) can be confirmed by a known method, for example, based on a change in the amount adsorbed after washing of the surface-coated inorganic particles with a solvent in which the surface treatment agent (B) is soluble, and can be confirmed specifically by a method described in Examples.
Each component constituting the surface-coated inorganic particles and the method for producing the surface-coated inorganic particles of the present invention will be described in order below.
The inorganic particles (A) comprise silica particles or silicate mineral particles. From the viewpoint of further improving the texture of the surface-coated inorganic particles, the inorganic particles (A) more preferably comprise at least one of particles selected from the group consisting of silica particles, talc particles and mica particles, and further preferably comprise at least one of particles selected from the group consisting of silica particles and mica particles. From the viewpoint of further suppressing the stickiness upon drying, the inorganic particles (A) further preferably comprise silica particles, and further preferably comprise porous silica particles.
The silicate mineral particles preferably comprise at least one selected from the group consisting of talc particles, mica particles, sericite particles, smectite particles, montmorillonite particles, bentonite particles and kaolin particles, more preferably comprise at least one selected from the group consisting of tale particles and mica particles, and further preferably comprise mica particles, from the viewpoint of further improving the texture of the surface-coated inorganic particles.
When the inorganic particles (A) comprise porous silica particles, the specific surface area of the porous silica particles is preferably 5 m2/g or more, and more preferably 10 m2/g or more, and, preferably 1,000 m2/g or less, and more preferably 900 m2/g or less from the viewpoint of suppressing the disintegration of the porous silica particles and further improving the texture of the surface-coated inorganic particles. The specific surface area is a BET specific surface area measured according to JIS Z 8830:2013.
When the inorganic particles (A) comprise porous silica particles, the pore volume of the porous silica particles is preferably 0.1 mL/g or more, more preferably 0.3 mL/g or more, and further preferably 0.5 mL/g or more, and, preferably 5 mL/g or less, more preferably 3 mL/g or less, and further preferably 2 mL/g or less from the viewpoint of suppressing the disintegration of the porous silica particles and further improving the texture of the surface-coated inorganic particles. In addition, from the viewpoint of no creakiness, it is preferably 0.3 mL/g or more, more preferably 0.5 mL/g or more, and further preferably 0.7 mL/g or more, and, preferably 5 mL/g or less, more preferably 3 mL/g or less, further preferably 2 mL/g or less, and further preferably 1.5 mL/g or less.
The pore volume can be measured by a gas adsorption method. Examples of the gas adsorption method include JIS Z 8831-2:2010 (Pore size distribution and porosity of solid materials-Part 2: Analysis of mesopores and macropores by gas adsorption), and JIS Z 8831-3:2010 (Pore size distribution and porosity of solid materials-Part 3: Analysis of micropores by gas adsorption).
The content of at least one of particles selected from the group consisting of silica particles and silicate mineral particles in the inorganic particles (A) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, and preferably 100% by mass or less from the viewpoint of further improving the texture of the surface-coated inorganic particles.
Examples of the shape of the inorganic particles (A) include spherical, plate-like, flaky, and irregular shapes. Among these, from the viewpoint of further improving the texture of the surface-coated inorganic particles, the inorganic particles (A) are preferably spherical, plate-like or flaky particles, and more preferably spherical or flaky particles.
More specifically, when the inorganic particles (A) are silica particles, they are more preferably spherical, and when the inorganic particles (A) are silicate mineral particles, they are more preferably flaky.
The volume median particle size (D50) of the inorganic particles (A) is preferably 1 μm or more, more preferably 2 μm or more, and further preferably 3 μm or more, and, preferably 30 μm or less, more preferably 20 μm or less, further preferably 15 μm or less, and further preferably 12 μm or less, from the viewpoint of further improving the texture of the surface-coated inorganic particles.
The surface treatment agent (B) comprises at least one selected from the group consisting of a modified silicone (b1) liquid at 25° C., and water-soluble cationic polymer (b2), and comprises more preferably the modified silicone (b1) liquid at 25° C., from the viewpoint of further suppressing stickiness upon drying.
The surface treatment agent (B) comprises preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, and preferably 100% by mass or less of at least one selected from the group consisting of the modified silicone (b1) and the water-soluble cationic polymer (b2), from the viewpoint of further improving the texture and environmental compatibility of the surface-coated inorganic particles.
The modified silicone (b1) liquid at 25° C., comprises at least one selected from the group consisting of a polyether-modified silicone, a polyglycerin-modified silicone, a branched polyglycerol-modified silicone, and an alkyl glyceryl ether-modified silicone, from the viewpoint of improving the texture of the surface-coated inorganic particles.
The HLB (hydrophilic-lipophilic balance) of the modified silicone (b1) is preferably 1.0 or more, more preferably 2.0 or more, and further preferably 2.5 or more, and, preferably 20.0 or less, more preferably 18.0 or less, further preferably 16.0 or less, further preferably 15.5 or less, further preferably 15.0 or less, further preferably 10.0 or less, further preferably 5.0 or less, further preferably 4.0 or less, and further preferably 3.5 or less from the viewpoint of improving the texture of the surface-coated inorganic particles.
Here, the HLB value is a value that represents the affinity of the modified silicone (b1) for water and oil, and can be found from the following formula according to the Griffin method.
HLB=20×[(molecular weight of hydrophilic group contained in modified silicone (b1))/(molecular weight of modified silicone (b1))]
Examples of the hydrophilic group include a hydroxy group and an ethyleneoxy group.
The viscosity of the modified silicone (b1) at 25° C. is preferably 50 mPa·s or more, more preferably 100 mPa·s or more, further preferably 200 mPa·s or more, and further preferably 400 mPa·s or more, and, preferably 500.000 mPa·s or less, more preferably 100,000 mPa·s or less, and further preferably 80,000 mPa·s or less.
The above viscosity can be measured at 25° C. using a Brookfield viscometer based on JIS Z8803:2011 “Methods for viscosity measurement of liquid”.
The polyether-modified silicone has a structure in which the side chains and/or terminal hydrocarbon groups of silicone oil are substituted with polyether groups.
The polyether group of the polyether-modified silicone is preferably a polyethyleneoxy group, a polypropyleneoxy group, or a polyalkyleneoxy group formed of an ethyleneoxy group (EO) and a propyleneoxy group (trimethyleneoxy group or propane-1,2-divloxy group, PO) added in a block form or randomly, and is more preferably a polyethyleneoxy group. As the polyether-modified silicone, a compound formed of a polyether group grafted to the silicone main chain, a compound formed of a silicone and a polyether group bonded in a block form, or the like can be used.
The viscosity of the polyether-modified silicone at 25° C. is preferably 50 mPa·s or more, more preferably 100 mPa·s or more, further preferably 150 mPa·s or more, further preferably 400 mPa·s or more, further preferably 450 mPa·s or more, further preferably 500 mPa·s or more, and further preferably 540 mPa·s or more, and, preferably 3,000 mPa·s or less, more preferably 2,000 mPa·s or less, further preferably 1.000 mPa·s or less, further preferably 750 mPa·s or less, and further preferably 600 mPa·s or less from the viewpoint of improving the texture of the surface-coated inorganic particles.
The above viscosity can be measured at 25° C. using a Brookfield viscometer based on JIS Z8803:2011 “Methods for viscosity measurement of liquid”.
Specific examples of the polyether-modified silicone include PEG-3 dimethicone, PEG-9 dimethicone. PEG-9 methyl ether dimethicone, PEG-10 dimethicone. PEG-11 methyl ether dimethicone, PEG-12 dimethicone, PEG/PPG-20/22 butyl ether dimethicone, PEG-32 methyl ether dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 poly dimethylsiloxyethyl dimethicone, cetyl PEG/PPG-10/1 dimethicone, PEG/PPG-30/10 dimethicone, and a linear polyether-modified silicone in which dimethyl silicone units and polyether units are alternately copolymerized.
Examples of a commercially available polyether-modified silicone include KF series by Shin-Etsu Chemical Co., Ltd. (for example, KF-6004, KF-6011. KF-6012, KF-6013, KF-6015, KF-6016, KF-6017, KF-6028, KF-6038, KF-6043, and KF-6048), and DOWSIL series manufactured by Dow Chemical Japan Ltd. (BY25-339, SH3775M, and FZ-2203).
The polyglycerin-modified silicone refers to a silicone having a monovalent polyglyceryl group in its structure, and examples thereof include polyglyceryl-3 disiloxane dimethicone, polyglyceryl-3 poly dimethylsiloxyethyl dimethicone, and lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone. Here, in the present specification, a branched polyglycerol-modified silicone is excluded from examples of the polyglycerin-modified silicone.
Examples of a commercially available polyglycerin-modified silicone include KF series manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KF-6100, KF-6104, KF-6106, and KF-6105).
The viscosity of the polyglycerin-modified silicone at 25° C. is preferably 500 mPa·s or more, more preferably 1,000 mPa·s or more, further preferably 2.000 mPa·s or more, and further preferably 3.000 mPa·s or more, and, preferably 20.000 mPa·s or less, more preferably 10.000 mPa·s or less, further preferably 5,000 mPa·s or less, and further preferably 4,000 mPa·s or less, from the viewpoint of improving the texture of the surface-coated inorganic particles.
The above viscosity can be measured at 25° C. using a Brookfield viscometer based on JIS Z8803:2011 “Methods for viscosity measurement of liquid”.
An example of the branched polyglycerol-modified silicone is a compound represented by the following formula (1) having a structure in which branched polyglycerol chains are bonded to both ends of dimethylpolysiloxane via linking groups each containing an oxyphenylene group.
In formula (1), each R12 independently represents a branched polyglycerol chain, and “m” represents an integer of 0 or more and 10,000 or less.
In formula (1), the binding mode of an oxygen atom and a trimethylene group (—C3H6—) in each phenylene group portion is not particularly limited, and may be ortho-, meta- or para-position. Further, “m” represents an integer of 0 or more and 10,000 or less, and preferably 1 or more and 300 or less. R12 represents a branched polyglycerol chain, is composed of glycerol units represented by the following structural formulas (2) to (5), and has at least one glycerol unit having a branched structure represented by structural formula (2), and the end is a glycerol unit represented by structural formula (5). The average total number of bonds of glycerol units in the branched polyglycerol chain is 3 or more and 200 or less, and preferably 3 or more and 30 or less.
The viscosity of the branched polyglycerol-modified silicone at 25° C. is preferably 10,000 mPa·s or more, more preferably 20,000 mPa·s or more, further preferably 40,000 mPa·s or more, further preferably 60,000 mPa·s or more, and further preferably 70,000 mPa·s or more, and, preferably 500,000 mPa·s or less, more preferably 100,000 mPa·s or less, and further preferably 80.000 mPa·s or less, from the viewpoint of improving the texture of the surface-coated inorganic particles.
The above viscosity can be measured at 25° C. using a Brookfield viscometer based on JIS Z8803:2011 “Methods for viscosity measurement of liquid”.
The branched polyglycerol-modified silicone represented by formula (1) can be produced by the method described in JP 2004-339244 A, which involves adding 2,3-epoxy-1-propanol to a modified silicone having phenyl groups substituted with hydroxy groups at both ends in the presence of an acidic or basic catalyst to perform graft polymerization for production, or other generally known methods.
Examples of a commercially available branched polyglycerol-modified silicone include SOFCARE GS-G (manufactured by Kao Corporation).
Examples of the alkyl glyceryl ether-modified silicone include the one represented by the following formula (6).
In formula (6), “Q” represents a divalent hydrocarbon group having 3 or more and 20 or less carbon atoms, R1 to R9 may be the same or different, and each represent a hydrogen atom, a linear or branched hydrocarbon group having 1 or more and 32 or less carbon atoms, or a phenyl group, R10 and R11 may be the same or different, and each represent a hydrogen atom or a linear or branched hydrocarbon group having 1 or more and 32 or less carbon atoms, multiple R10 and R11 in the same molecule may be different from each other. Further, “p” represents a number of 1 or more and 500 or less, and “q” represents a number of 1 or more and 50 or less. In addition, “p” and “q” represent preferably numbers such that the content of the alkyl glyceryl ether group [-Q-OCH2—CH(OR10)—CH2(OR11)] in the molecule is 1% by mass or more and 50% by mass or less.
In formula (6), the divalent hydrocarbon group represented by “Q” having 3 or more and 20 or less carbon atoms is preferably a linear or branched alkylene group having 3 or more and 20 or less carbon atoms. More specific examples thereof include: linear alkylene groups such as trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene and octadecamethylene; and branched alkylene groups such as propylene, 2-methyltrimethylene, 2-methyltetramethylene, 2-methylpentamethylene and 3-methylpentamethylene.
Examples of the linear or branched hydrocarbon group having 1 or more and 32 or less carbon atoms in the definitions of R1 to R11 include: linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, doeicosyl, tetraeicosyl, hexacicosyl, octaeicosyl, and triacontyl; and branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, neopentyl, 1-ethylpropyl, and 1-heptyldecyl. In the present specification. R1 to R9 are preferably linear or branched alkyl groups each having 1 or more and 25 or less carbon atoms (some of which may be hydrogen atoms), and are more preferably linear or branched alkyl groups each having 1 or more and 22 or less carbon atoms (some of which may be hydrogen atoms). In addition, R10 and R11 are preferably hydrogen atoms or alkyl groups each having 1 or more and 5 or less carbon atoms, and further preferably hydrogen atoms.
Furthermore. “p” and “q” are preferably numbers such that the content of the alkyl glyceryl ether group [-Q-OCH2—CH(OR10)—CH2(OR11)] is 1% by mass or more and 50% by mass or less, more preferably numbers such that the content is 5% by mass or more and 40% by mass or less, and further preferably numbers such that the content is 10% by mass or more and 30% by mass or less. Specifically. “p” is in the range of 1 or more and 500 or less, preferably in the range of 10 or more and 30 or less, and “q” is in the range of 1 or more and 50 or less, and preferably in the range of 1 or more and 30 or less in terms of the availability of the raw material organopolysiloxane, the operability during production, etc.
The viscosity of the alkyl glyceryl ether-modified silicone at 25° C. is preferably 1,000 mPa·s or more, more preferably 2,000 mPa·s or more, further preferably 3,000 mPa·s or more, further preferably 4,000 mPa·s or more, further preferably 5,000 mPa·s or more, and further preferably 6,000 mPa·s or more, and, preferably 20,000 mPa·s or less, more preferably 10.000 mPa·s or less, further preferably 8.000 mPa·s or less, and further preferably 7,000 mPa·s or less from the viewpoint of improving the texture of the surface-coated inorganic particles. The above viscosity can be measured at 25° C. using a Brookfield viscometer based on JIS Z8803:2011 “Methods for viscosity measurement of liquid”.
Such an alkyl glyceryl ether-modified silicone can be produced according to the methods described in JP H4-134013 A and JP 2005-194523 A that involve reacting organohydrogenpolysiloxane having at least one silicon-hydrogen bond with a corresponding alkenyl glyceryl ether.
Examples of a commercially available alkyl glyceryl ether-modified silicone include SI-UGE and SOFCARE RS-U (manufactured by Kao Corporation).
These modified silicones (b1) may be used alone or in combination of two or more.
The water-soluble cationic polymer (b2) preferably comprises at least one selected from the group consisting of a cationic polymer having a cellulose backbone, a cationic vinyl-based polymer, chitin compounds/chitosan compounds, and halogenated hexadimethrine, more preferably comprises at least one selected from the group consisting of a cationic polymer having a cellulose backbone, a cationic vinyl-based polymer, chitin compounds/chitosan compounds, hexadimethrine bromide and hexadimethrine chloride, preferably comprises at least one selected from the group consisting of a cationic polymer having a cellulose backbone, a cationic vinyl-based polymer and chitin compounds/chitosan compounds, and further preferably comprises at least one selected from the group consisting of a cationic polymer having a cellulose backbone and a cationic vinyl-based polymer, and further preferably comprises a cationic vinyl-based polymer from the viewpoint of further improving the texture and environmental compatibility of the surface-coated inorganic particles.
As used herein, the term “water-soluble polymer” refers to a polymer, the dissolution amount of which is more than 2 g when 10 g of the polymer is mixed with 1,000 ml of water with pH 7 at 20° C., and then the mixture is left to stand for 24 hours.
The water-soluble cationic polymer (b2) preferably has a basic group such as primary to tertiary amino groups, a quaternary ammonium group, and a hydrazino group, more preferably a tertiary amino group, or a quaternary ammonium group. As the basic group, those neutralized with acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, maleic acid, fumaric acid, citric acid, tartaric acid, adipic acid and lactic acid are included.
In the present specification, water-soluble cationic silicones such as water-soluble amino-modified silicones are excluded from examples of the water-soluble cationic polymer (b2).
The weight-average molecular weight Mw of the water-soluble cationic polymer (b2) is preferably 3,000 or more, more preferably 5,000 or more, further preferably 15,000 or more, further preferably 50,000 or more, and further preferably 100,000 or more from the viewpoint of improving the texture of the surface-coated inorganic particles. Also, the Mw is preferably 5 million or less, more preferably 3 million or less, and further preferably 2 million or less.
The weight average molecular weight Mw can be measured by a gel permeation chromatography (GPC) method using polyethylene glycol as a standard substance. For example, the weight-average molecular weight Mw of the cationized hydroxyethyl cellulose, which is the water-soluble cationic polymer (b2), is determined by performing GPC measurement under the following conditions.
As used herein, the term “cationic polymer having a cellulose backbone” refers to a polymer that has cationic groups and a cellulose backbone, and is a cation positively charged as a whole. In addition, the cationic group refers to a cationic group or a group that can be ionized to become a cationic group, and examples thereof include a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group.
Examples of the cationic polymer having a cellulose backbone include cationized cellulose and cationized cellulose derivatives, and specific examples thereof include cationized cellulose, cationized hydroxyethyl cellulose, cationized hydroxypropyl cellulose, and cationized carboxymethyl cellulose.
The cationic polymer having a cellulose backbone is preferably cationized hydroxyethyl cellulose, and more preferably a polymeric quaternary ammonium salt (INCI name: Polyquaternium-10) obtained by addition of glycidyltrimethylammonium chloride with hydroxyethyl cellulose.
Examples of the cationic vinyl-based polymer include vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer diethyl sulfate, vinylpyrrolidone/dimethylaminopropyl methacrylamide/lauryldimethylaminopropyl methacrylamide copolymer, vinylpyrrolidone/N,N-dimethylaminoethyl methacrylate/alkyl acrylate/tripropylene glycol diacrylate copolymer, polydimethylmethylenepiperidinium chloride, dimethyldiallylammonium chloride/acrylamide copolymer, trimethylammoniopropylacrylamide chloride/dimethylacrylamide copolymer, alkylacrylamide/acrylate/alkylaminoalkylacrylamide/polyethylene glycol methacrylate copolymer, t-butylacrylamide/dimethylacrylamide/dimethylaminopropylacrylamide/methoxypolyethylene glycol methacrylate copolymer, vinylpyrrolidone/N,N-dimethylaminoethyl methacrylate copolymer diethyl sulfate, vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer, N,N-dimethylaminoethyl methacrylate diethyl sulfate/N,N-dimethylacrylamide/polyethylene glycol dimethacrylate copolymer, ammonium-modified hydroxyethyl cellulose, and acrylamide/DMAPA acrylate/methoxy PEG methacrylate copolymer. Among these, a tertiary amino group-containing (meth)acrylic polymer is preferable, and an acrylamide/DMAPA acrylate/methoxy PEG methacrylate copolymer is far preferable.
Examples of chitin compounds/chitosan compounds include chitin/chitosan derivatives such as hydroxypropylchitosan, carboxymethylchitin and carboxymethylchitosan, and chitin and chitosan, with chitosan being preferred.
These water-soluble cationic polymers (b2) may be used alone or in combination of two or more.
The surface treatment agent (B) may comprise a surface treatment agent other than the modified silicone (b1) and the water-soluble cationic polymer (b2). Examples of the surface treatment agent other than the modified silicone (b1) and the water-soluble cationic polymer (b2) include surface treatment agents applied to cosmetic particles.
The content of at least one selected from the group consisting of the modified silicone (b1) liquid at 25° C., and the water-soluble cationic polymer (b2) in the surface treatment agent (B) is, from the viewpoint of further improving the texture of the surface-coated inorganic particles, and, from the viewpoint of further improving the environmental compatibility, preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, and further preferably 95% by mass or more, and preferably 100% by mass or less.
The content of the synthetic polymer that is solid at 25° C.′ and water-insoluble in the surface treatment agent (B) is preferably less than 10% by mass, more preferably less than 5% by mass, further preferably less than 1% by mass, further preferably less than 0.1% by mass, and further preferably less than 0.01% by mass, and the surface treatment agent (B) is preferably substantially free of the synthetic polymer from the viewpoint of further improving the environmental compatibility.
In the surface-coated inorganic particles of the present invention, the amount of the surface treatment agent (B) adsorbed to the inorganic particles (A) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 0.7 parts by mass or more, further preferably 0.9 parts by mass or more, further preferably 1.0 part by mass or more, further preferably 1.5 parts by mass parts or more, further preferably 2.0 parts by mass or more, further preferably 2.5 parts by mass or more, and, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 15 parts by mass or less, further preferably 13 parts by mass or less, further preferably 10 parts by mass or less, and further preferably 8 parts by mass or less with respect to 100 parts by mass of the inorganic particles (A) from the viewpoint of further improving the texture.
The amount of the surface treatment agent (B) adsorbed can be measured by a method described in Examples.
The surface-coated inorganic particles of the present invention can be obtained by coating the inorganic particles (A) with the surface treatment agent (B).
Specifically, the method for producing surface-coated inorganic particles preferably comprises, a step of mixing inorganic particles (A) with a surface treatment agent solution comprising the surface treatment agent (B) and a solvent from the viewpoint of coating the inorganic particles (A) with the surface treatment agent (B), and more preferably comprises a step of mixing an inorganic particle dispersion liquid comprising the inorganic particles (A) and solvent A with a surface treatment agent solution comprising the surface treatment agent (B) and solvent B.
Water or an organic solvent can be used as the solvent. Although the organic solvent is not particularly limited, alcohols such as methanol, ethanol. I-propanol and 2-propanol can be used as an organic solvent. Among the alcohols, at least one selected from the group consisting of ethanol and 2-propanol is preferable, and ethanol is further preferable.
The above solvent A and solvent B may be the same or different from each other as long as they have compatibility with each other.
Solvent A to be used in the inorganic particle dispersion liquid is preferably at least one selected from the group consisting of water and ethanol from the viewpoint of dispersibility of the inorganic particles (A).
When the surface treatment agent (B) comprises the modified silicone (b1), a solvent to be used in the surface treatment agent solution is preferably an organic solvent from the viewpoint of solubility of the modified silicone (b1), and is more preferably ethanol from the viewpoint of compatibility with solvent A.
When the surface treatment agent (B) comprises the water-soluble cationic polymer (b2), a solvent to be used in the surface treatment agent solution is preferably at least one selected from the group consisting of water and ethanol from the viewpoint of solubility of the water-soluble cationic polymer (b2), and is more preferably water. From the viewpoint of improving the solubility of the water-soluble cationic polymer (b2), an organic acid such as lactic acid may be further added to the surface treatment agent solution.
When the inorganic particle dispersion liquid is used, the concentration of the inorganic particles (A) in the inorganic particle dispersion liquid is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, and, preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and further preferably 10% by mass or less from the viewpoint of efficient adsorption of the surface treatment agent (B) onto the surface of the inorganic particles (A).
When the surface treatment agent solution is used, the concentration of the surface treatment agent (B) in the surface treatment agent solution is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, and, preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and further preferably 10% by mass or less from the viewpoint of efficient adsorption of the surface treatment agent (B) onto the surface of the inorganic particles (A).
The temperature, at which the inorganic particles (A) or the inorganic particle dispersion liquid is mixed with the surface treatment agent solution, is preferably 5° C., or higher, and more preferably 10° C., or higher from the viewpoint of efficient adsorption of the surface treatment agent (B) onto the surface of the inorganic particles (A), and the temperature is preferably 70° C., or lower, and more preferably 50° C., or lower from the viewpoint of suppressing volatilization of the solvent.
Further, the mixing time for mixing the inorganic particles (A) or the inorganic particle dispersion liquid with the surface treatment agent solution is preferably 5 minutes or longer, and more preferably 10 minutes or longer from the viewpoint of sufficient adsorption of the surface treatment agent (B) onto the surface of the inorganic particles (A), and the mixing time is preferably 12 hours or shorter, and more preferably 6 hours or shorter from the viewpoint of production efficiency.
In the step of mixing the inorganic particles (A) or the inorganic particle dispersion liquid with the surface treatment agent solution, a known stirring device can be used.
The mixture obtained by the above steps is separated using a known method such as centrifugation, filtration, decantation, and drying, so that the surface-coated inorganic particles can be recovered, for example.
The obtained surface-coated inorganic particles may be classified using a sieve or the like in order to adjust the particle size.
The surface-coated inorganic particles of the present invention can be applied to a surface modifier.
Specifically, the surface modifier of the present invention comprises the surface-coated inorganic particles of the present invention.
As used herein, the term “surface modifier” refers to an agent capable of improving the texture of the surface of skin, hair, nails and the like.
The content of the surface-coated inorganic particles of the present invention in the surface modifier of the present invention is not particularly limited because it can be appropriately set according to the type of the surface modifier, but is, for example, 0.1% by mass or more, and preferably 1% by mass or more, and is, for example, 50% by mass or less, preferably 30% by mass or less, and more preferably 10% by mass or less.
The surface modifier of the present invention can adequately comprise optional components that are used according to the type of the surface modifier, as long as they do not impair the effects of the present invention. Examples of optional components other than the surface-coated inorganic particles of the present invention include ultraviolet absorbers, oils, surfactants, water-soluble polymers, thickeners, neutralizers, propellants, pH adjusters, antiseptics, anti-inflammatory agents, preservatives, coloring agents, chelating agents, whitening agents, blood circulation promoters, cooling agents, antiperspirants, insect repellents, physiologically active ingredients, salts, moisturizers, antioxidants, flavors, and plant extracts.
Examples of the form of the surface modifier of the present invention include liquid, milky lotion, cream, paste, gel, wax, and solid forms. The surface modifier of the present invention can also be applied to sheet agents, spray agents, and mousse agents, for example. The surface modifier of the present invention can be applied to, for example, skin (including lips), hair, nails, etc., and can be used preferably by applying the surface modifier.
The content of the synthetic polymer fine particles in the surface modifier of the present invention is preferably less than 0.01% by mass, more preferably less than 0.005% by mass, and further preferably less than 0.001% by mass from the viewpoint of further improving the environmental compatibility.
As used herein, the term “synthetic polymer fine particles” refers to fine particles comprising a 1% by mass or more of synthetic polymer that is solid at 25° C., and water-insoluble and having a volume median particle size (D50) of 0.1 μm or more and 5 mm or less.
The method for producing the surface modifier of the present invention is not particularly limited, and the surface modifier can be produced by stirring and mixing each component using a known device, for example.
The surface-coated inorganic particles of the present invention can be blended with or applied to various cosmetic products.
Specifically, the cosmetic product of the present invention comprises the surface-coated inorganic particles of the present invention.
The content of the surface-coated inorganic particles of the present invention in the cosmetic product of the present invention is not particularly limited because it can be appropriately set according to the type of the cosmetic product, and is, for example, 0.1% by mass or more, and preferably 1% by mass or more, and, for example, 50% by mass or less, and preferably 30% by mass or less.
As used herein, the term “cosmetic product” refers to a product that comes into direct contact with a human body, such as cosmetics, skin care products, toiletry products, and perfumes.
The cosmetic product of the present invention can adequately contain optional components that are used according to the type of the cosmetic product within a range that does not impair the effects of the present invention. Examples of the optional components other than the surface-coated inorganic particles of the present invention include ultraviolet absorbers, oils, surfactants, water-soluble polymers, thickeners, neutralizers, propellants, pH adjusters, fungicides, anti-inflammatory agents, preservatives, coloring agents, chelating agents, whitening agents, blood circulation promoters, cooling agents, antiperspirants, insect repellents, physiologically active ingredients, salts, moisturizers, antioxidants, flavors, and plant extracts.
Examples of the form of the cosmetic product of the present invention include liquid, milky lotion, cream, paste, gel, wax, and solid forms. The cosmetic product of the present invention can also be applied to sheets, sprays, and mousses, for example.
The cosmetic product of the present invention can be applied to, for example, skin (including lips), hair, and nails, and can be used preferably by applying the cosmetic product.
The content of the synthetic polymer fine particles in the cosmetic product of the present invention is preferably less than 0.01% by mass, more preferably less than 0.005% by mass, and further preferably less than 0.001% by mass from the viewpoint of further improving the environmental compatibility.
The method for producing the cosmetic product of the present invention is not particularly limited. For example, the cosmetic product can be produced by stirring and mixing each component using a known device.
The surface modification method of the present invention comprises a step of applying the surface-coated inorganic particles of the present invention, the surface modifier of the present invention, or the cosmetic product of the present invention to a surface of object.
Examples of the surface of object include skin, hair, and nails, and preferably skin.
Examples of the method for applying the surface-coated inorganic particles, the surface modifier, or the cosmetic product of the present invention to the surface of object include a method of applying, spraying, or letting it to run over the surface of object, and a method of immersing an object in the surface-coated inorganic particles, the surface modifier, or the cosmetic product of the present invention.
The present invention will be described below with reference to examples, but the present invention is not limited to the scope of the examples. In Examples and Comparative Examples, various measurements and evaluations were performed by the following methods.
The amount of a surface treatment agent adsorbed was found by subjecting samples to thermogravimetry·differential thermal analysis (TG-DTA) using a thermal analyzer manufactured by Rigaku Corporation (Thermo plus EVO2 TG-DTA8122). The measurement conditions were as follows.
From the obtained TG-DTA curve, the amount of the surface treatment agent adsorbed to 100 parts by mass of the inorganic particles was calculated from the following formula. Here, the amount of the surface treatment agent adsorbed to the surface-coated inorganic particles was defined as x % by mass (the total amount of the surface-coated inorganic particles is assumed to be 100% by mass).
Amount (parts by mass) of surface treatment agent adsorbed to 100 parts by mass of inorganic particles=x/(100−x)×100.
x is calculated from the following formula.
The particle size distribution of the inorganic particles and the same of the surface-coated inorganic particles were each measured using a laser diffraction/scattering particle size distribution analyzer LA-960 manufactured by HORIBA, Ltd. Distilled water was added to measurement cells so that aqueous solutions of the inorganic particles and the surface-coated inorganic particles had the appropriate range of absorbance. Then the volume median particle size (D50) of the inorganic particles and the same of the surface-coated inorganic particles were each calculated from the obtained particle size distribution.
Under an environment of a temperature of 20° C.-25° C., and humidity of 25% RH to 40% RH, 0.2 g of particles obtained in Examples and Comparative Examples was applied evenly to the inside of the forearm using a finger, the applied product was rubbed with a finger to evaluate no creakiness and smoothness, severally, and then the results were scored according to the following criteria.
Three expert panelists evaluated each sample shown in the table below by comparing each texture of “no creakiness” and “smoothness” with those of a reference sample (lauryl methacrylate ethylene glycol dimethacrylate·sodium methacrylate copolymer particles, volume median particle size (D50): 2 μm, produced according to Example 1 of JP 2006-8980 A). The samples evaluated to be equivalent to the reference sample, and felt to be very good in terms of “no creakiness” and “smoothness” were scored “5”. Those evaluated to be somewhat inferior to the reference sample, but felt to be good in terms of “no creakiness” and “smoothness” were scored “4”. Those evaluated to be inferior to the reference sample, but felt to be normal in terms of “no creakiness” and “smoothness” were scored “3”. Those evaluated to be inferior to the reference sample and felt to be poor in terms of “no creakiness” and “smoothness” were scored “2”. Those evaluated to be extremely inferior to the reference sample, and felt to be very poor in terms of “no creakiness” and “smoothness” were scored “1”. The average values of scores scored by panelists were employed. In addition, each panelist scored in increments of 0.5 including the intermediate score.
Here, the lauryl methacrylate ethylene glycol dimethacrylate sodium methacrylate copolymer particles correspond to polymer particles generally used as texture-improving particles.
Under an environment of a temperature of 20° C., to 25° C., and humidity of 25% RH to 40% RH, 0.2 g of particles each obtained in Examples and Comparative Examples was applied evenly to the inside of the forearm using a finger, and then the entire applied area was rubbed with a finger 10 times. Thereafter, the applied product was rubbed with a finger to evaluate no creakiness and smoothness, severally, and then the results were scored according to the same criteria as in (3-1) above.
Under an environment of a temperature of 20° C.′ to 25° C., and humidity of 25% RH to 40% RH, 0.1 mL of a 5 mass % water/ethanol dispersion (particles/water/ethanol=5/70/25 (mass ratio)) of particles each obtained in Examples and Comparative Examples was applied to the inside of the forearm in such a manner that the applied area had a diameter of about 5 cm, and then spread across the area for 10 seconds, so as to evaluate stickiness upon drying, and then the results were scored according to the following criteria.
Three expert panelists evaluated each sample shown in the tables below by comparing each “stickiness upon drying” with that of a reference sample (lauryl methacrylate·ethylene glycol dimethacrylate·sodium methacrylate copolymer particles, volume median particle size (D50): 2 μm, produced according to Example 1 of JP 2006-8980 A). The samples evaluated to be equivalent to the reference sample, and felt to be very good in terms of “stickiness upon drying” were scored “5”. Those evaluated to be somewhat inferior to the reference sample, but felt to be good in terms of “stickiness upon drying” were scored “4”. Those evaluated to be inferior to the reference sample, but felt to be normal in terms of “stickiness upon drying” were scored “3”. Those evaluated to be inferior to the reference sample and felt to be poor in terms of “stickiness upon drying” were scored “2”. Those evaluated to be extremely inferior to the reference sample, and felt to be very poor in terms of “stickiness upon drying” were scored “1”. The average values of scores scored by the panelists were employed. In addition, each panelist scored in increments of 0.5 including the intermediate score.
To a 500 ml beaker, 2 g of a surface treatment agent, polyether-modified silicone 1 (PEG-10 dimethicone, Shin-Etsu Chemical Co., Ltd. “KF-6017”. HLB: 4.5, viscosity at 25° C.: 490 mPa·s) and 98 g of ethanol were added, thereby preparing a polyether-modified silicone solution.
To a separately prepared 500 ml beaker, 2 g of inorganic particles, silica 1 (porous silica particles, “HCS 160M5” manufactured by JGC Catalysts and Chemicals Ltd., volume median particle size (D50): 5 μm, pore volume: 0.7 mL/g) and 98 g of ethanol were added, and then the mixture was treated with an ultrasonic homogenizer (ULTRASONIC HOMOGENIZER US-600E, manufactured by NISSEI Corporation) at 200 W for 5 minutes, thereby preparing a particle dispersion.
The polyether-modified silicone solution was added to the obtained particle dispersion, and then the mixture was stirred with a magnetic stirrer at room temperature and 600 rpm for 1 hour. The resulting mixture was separated into particles (dispersoid) and a solution (dispersion medium) by centrifuging at 3,000 rpm for 30 minutes using a centrifuge (HITACHI, CR21G III). After removing the supernatant, the precipitate was dried under reduced pressure at 50° C., overnight to obtain surface-coated inorganic particles. Each evaluation was performed on the obtained surface-coated inorganic particles. The results are shown in the tables below.
Surface-coated inorganic particles were obtained respectively in the same manner as in Example 1, except that the types of inorganic particles and surface treatment agents were changed to those shown in the tables below. Each evaluation was performed on the obtained surface-coated inorganic particles. The results are shown in the tables below.
Surface-coated inorganic particles were obtained respectively in the same manner as in Example 1, except that the types of inorganic particles and surface treatment agents were changed to those shown in the tables below, and “98 g of ethanol” was changed to “98 g of water”. Each evaluation was performed on the obtained surface-coated inorganic particles. The results are shown in the tables below.
Except that the types of inorganic particles and surface treatment agents were changed to those shown in the tables below, “98 g of ethanol” was changed to “98 g of water”, and 40 mg of 90% lactic acid (product name: Musashino Lactic Acid 90, manufactured by Musashino Chemical Laboratory, Ltd.) was added to the obtained cationic vinyl-based polymer 1 solution, surface-coated inorganic particles were obtained respectively in the same manner as in Example 1. Each evaluation was performed on the obtained surface-coated inorganic particles. The results are shown in the tables below.
Surface-coated inorganic particles were obtained respectively in the same manner as in Example 1, except that the mixing amount of the surface treatment agent was changed so that the amount of the surface treatment agent adsorbed was a value shown in tables below. Each evaluation was performed on the obtained surface-coated inorganic particles. The results are shown in the tables below.
Inorganic particles were obtained in the same manner as in Example 1, except that 2 g of ethanol was used instead of “2 g of polyether-modified silicone”. Each evaluation was performed on the obtained inorganic particles. The results are shown in the tables below.
The ingredients listed in the tables are as follows.
A four-necked flask equipped with a reflux condenser, a liquid feeder, a thermometer, a nitrogen gas inlet tube and a stirrer was heated to 50° C. in an oil bath. A monomer solution was obtained by dissolving 100 parts by mass of monomers (mass ratio of monomers: N-tert-butylacrylamide/N,N-dimethylacrylamide/methoxypolyethylene glycol monomethacrylate/N-(3-dimethylaminopropyl) acrylamide=55/23/20/2) was dissolved in 75 parts by mass of ethanol. Further, a 0.2 mol % initiator (V-65B) with respect to the monomers was dissolved in ethanol so that the concentration was 5% by mass to obtain an initiator solution. The resulting monomer solution and the initiator solution were simultaneously added drop by drop to the flask over 130 minutes under a nitrogen atmosphere, maintained at 50° C., for 130 minutes, and then further maintained at 80° C., for 120 minutes for reaction. After polymerization, the ethanol solution of the polymer was poured into n-hexane for reprecipitation and purification, and then vacuum-dried at 80° C., thereby giving a cationic vinyl-based polymer 1 in a solid state.
The above tables demonstrate that the surface-coated inorganic particles of Examples are excellent in smoothness, no creakiness, and persistence of texture, and have a good texture. In addition, the surface-coated inorganic particles of Examples comprise inorganic particles that do not correspond to synthetic polymer fine particles as core particles, and the surface treatment agent does not comprise any synthetic polymer that is solid at 25° C., and insoluble in water. Therefore, the surface-coated particles are found to be environmentally friendly and suitable as an alternative material to synthetic polymer fine particles.
According to one embodiment of the present invention, surface-coated inorganic particles, a surface modifier, and a cosmetic product, which have a good texture and are suitable as alternative materials to synthetic polymer fine particles, and a surface modification method using the surface-coated inorganic particles, the surface modifier, or the cosmetic product can be provided.
Furthermore, one embodiment of the present invention can provide a method for producing surface-coated inorganic particles having a good texture and being suitable as alternative materials to synthetic polymer fine particles.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-212978 | Dec 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/046868 | 12/20/2022 | WO |
