Molded solid particles containing thermoplastic copolymer, method for producing same, and cosmetic containing same

Abstract

The purpose of the present invention is to provide: molded solid particles containing a thermoplastic copolymer having a silicon-containing organic group, which have excellent solubility in a cosmetically acceptable solvent and excellent handling workability, and which can be mass-produced by an industrial production process; molded solid particles containing a thermoplastic copolymer obtained by copolymerizing (a1) and (a2), in which (a1) is an unsaturated monomer having one radically polymerizable organic group and a silicon-containing organic group in the molecule, (a2) is an unsaturated monomer having one radically polymerizable organic group and one silicon-containing organic group in the molecule, and (a3) is an unsaturated monomer having one silicon-containing organic group in the molecule, and the use of the molded solid particles, and a method for producing the molded solid particles provided with a strand forming step and a cutting step. (a2) is an unsaturated monomer which is different from the component (a1) and has one radical polymerizable vinyl group in the molecule, and the long diameter of the particles is less than 10 mm.

Description

Technical Field

[0001] The present invention relates to molded solid particles of a thermoplastic copolymer having a silicon-containing organic group in the molecule, which have excellent solubility during use, and a method for producing the same. The present invention also relates to the use of the molded solid particles as a cosmetic raw material or a film-forming agent, and a cosmetic containing the molded solid particles. Background Art

[0002] It is well known that, for the purpose of improving the makeup persistence of cosmetics and improving water resistance and sebum resistance, copolymers having a silicon-containing organic group such as a carbosiloxane dendrimer structure are used in cosmetics (for example, Patent Document 1, etc.). These copolymers having a silicon-containing organic group are formed by radical copolymerization of an unsaturated monomer having a silicon-containing organic group such as a carbosiloxane dendrimer structure and other unsaturated monomers.

[0003] Generally, these copolymers having a silicon-containing organic group are used as a cosmetic raw material in the form of a solution or dispersion dissolved or uniformly dispersed in a soluble silicone-based solvent (volatile linear or cyclic dimethylpolysiloxane, etc.) or other organic solvents (for example, isododecane, etc.) (the above Patent Document 1, etc.). However, although the solvent as a carrier improves the handling workability of the copolymer, on the other hand, in terms of the formulation of cosmetics and the relationship with other additives, it sometimes limits the degree of freedom and diversity of formulation design. For example, organic solvents such as isododecane as a plasticizer sometimes deteriorate the usability of cosmetics mixed with the copolymer. In addition, solvents acceptable as carriers for cosmetic raw materials generally tend to have a low flash point, and careful safety management is required during transportation and handling.

[0004] On the other hand, it has been proposed to use a silicone acrylate copolymer in a solid form without containing a solvent as a carrier. For example, Patent Document 2 proposes removing the solvent from a commercially available silicone acrylate copolymer solution, crushing the obtained solid by hand, and then dissolving it in a plant-derived oil agent for cosmetics. However, this method is not suitable for industrial production processes, and the solubility of the solid crushed product in various oil agents is insufficient. Therefore, even in small amounts, it requires long-time and shear operations under heating conditions, and the handling workability as a cosmetic raw material is significantly deteriorated.

[0005] In addition, in Patent Document 1, it is also proposed to crush a solid silicone acrylate copolymer obtained by removing the solvent by a ball mill. However, since the silicone acrylate copolymer in Patent Document 1 has a low glass transition temperature and is soft, it has a tendency to aggregate during the crushing operation accompanied by frictional heat (for example, refer to Comparative Example 3 of the present application described later), and the handling workability as a cosmetic raw material is significantly deteriorated.

[0006] In contrast, Patent Document 3 proposes the following method: Emulsify a silicone methacrylate, and dry it with a spray dryer to obtain silicone methacrylate particles. Here, as a raw material of the silicone methacrylate, a crosslinkable monomer having two or more (meth)acryloyl groups in the molecule is used, and the obtained silicone methacrylate particles do not have thermoplasticity. Therefore, although aggregation of the particles shown in Patent Document 1 can be suppressed, since the obtained silicone methacrylate particles are not soluble in a solvent, they cannot be uniformly dispersed in a formulation as a cosmetic raw material.

[0007] As described above, molded particles of a copolymer having a silicon-containing organic group are not disclosed in any of the above-mentioned documents. The molded particles of the copolymer have good solubility in a solvent, can be uniformly dispersed in a formulation as a cosmetic raw material, can be mass-produced using an industrial production process, and have excellent handling workability as a cosmetic raw material.

[0008] Prior Art Documents

[0009] Patent Documents

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 2000-63225

[0011] Patent Document 2: Japanese Patent Application Laid-Open No. 2018-518505

[0012] Patent Document 3: Japanese Patent Application Laid-Open No. 2009-149880 Summary of the Invention

[0013] Problems to be Solved by the Invention

[0014] In view of the above problems and technical situation, an object of the present invention is to provide molded solid particles containing a thermoplastic copolymer having a silicon-containing organic group, which have excellent solubility and handling workability in a cosmetically acceptable solvent and can be mass-produced using an industrial production process. Another object of the present invention is to provide uses of the molded solid particles and a method for manufacturing the same.

[0015] Means for Solving the Problems

[0016] The inventors of the present invention have conducted in-depth research and found that the above problems can be solved by the following formed solid particles, thus completing the present invention. The formed solid particles contain a thermoplastic copolymer obtained by copolymerizing (a1) and (a2) (i.e., a copolymer having no crosslinked site in the molecule and containing a silicon-containing organic group). (a1) is an unsaturated monomer having one free-radically polymerizable organic group and a silicon-containing organic group in the molecule, and (a2) is an unsaturated monomer different from the (a1) component and having one radically polymerizable vinyl group in the molecule, and the major axis of the formed solid particles is less than 10 mm. In addition, it has been found that the above problems can be solved by using the formed solid particles as a cosmetic raw material, a cosmetic containing the formed solid particles, and a method for producing a cosmetic having a step of dissolving or dispersing the formed solid particles in a solvent acceptable for cosmetics, thus completing the present invention.

[0017] Similarly, the inventors of the present invention have found that the above problems can be solved by the method for producing the formed solid particles of the present invention, thus completing the present invention. The method for producing the formed solid particles includes: a step (I) of discharging the above thermoplastic copolymer from a die in a strand shape, and a step (II) of cutting the strand-shaped discharged product obtained by the step (I).

[0018] Effects of the Invention

[0019] According to the present invention, there can be provided formed solid particles containing a thermoplastic copolymer having a silicon-containing organic group, which have excellent solubility and handling workability in a solvent acceptable for cosmetics and can be mass-produced by an industrial production process.

[0020] In particular, the thermoplastic copolymer having a silicon-containing organic group of the present invention has no crosslinked portion in the molecule, so it has excellent solubility. On the other hand, since it does not restrict the solvent serving as a carrier, it has the advantages of not restricting the freedom and diversity of the formulation design of cosmetics when used as a cosmetic raw material. In addition, the formed solid particles of the present invention have the following advantages. Since they do not restrict the solvent, there is no worry about ignition caused by a flammable solvent. By designing a copolymer with an appropriate glass transition temperature point (Tg), the processability such as cutting is excellent, and the problem of aggregation can be avoided. It is possible to provide a cosmetic raw material or a film-forming agent (not limited to cosmetic use) that further improves handling workability, processability, and formulation stability in addition to good solubility.

[0021] Similarly, the method for manufacturing the shaped solid particles of the present invention has excellent mass productivity. By using an extruder equipped with a die head (including a single-screw or multi-screw extruder) and appropriate temperature management in the barrel during discharge, it can be applied to a continuous production process, and a manufacturing method can be provided that avoids problems such as agglomeration and processability in molding / cutting, and further improves quality and production stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is an overall view of the manufacturing apparatus used in the manufacture of the shaped solid particles of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0023] In this document, “(meth)acrylic acid” means including both acrylic acid and methacrylic acid. Similarly, “(meth)acrylate”, “(meth)acryloyloxy”, and “(meth)acrylamide” also each mean including two types, namely acrylate and methacrylate, acryloyloxy and methacryloyloxy, and acrylamide and methacrylamide, respectively. In this document, “cosmetic composition” and “cosmetic product” can be used interchangeably.

[0024] [Thermoplastic copolymer]

[0025] The shaped solid particles of the present invention contain a thermoplastic copolymer, which is obtained by copolymerizing the following components: Component (a1): An unsaturated monomer having one free-radically polymerizable organic group and a silicon-containing organic group in the molecule; and Component (a2): An unsaturated monomer different from Component (a1) and having one radically polymerizable vinyl group in the molecule. Here, both Component (a1) and Component (a2) are non-crosslinking monomers, and the resulting copolymer does not have a crosslinked structure in the molecule and has thermoplasticity. Therefore, the shaped solid particles of the present invention have good solubility (hereinafter sometimes referred to as “easy solubility”) in a solvent acceptable for cosmetics.

[0026] The silicon-containing organic group in Component (a1) is a functional group that imparts waterproofness to the entire copolymer and improves the makeup persistence of cosmetics, water resistance, sebum resistance, etc. when using the present shaped solid particles as a cosmetic raw material (especially a film-forming agent). Such a silicon-containing organic group is not particularly limited, but is preferably selected from at least one of a carbosiloxane dendrimer structure and a siloxane macromonomer structure having a chain-like polysiloxane structure.

[0027] As an example of the siloxane macromonomer structure, a chain-like organosiloxanyl group represented by the following structural formula can be exemplified:

[0028] [Chemical Formula 1]

[0029]

[0030] [Chemical Formula 2]

[0031]

[0032] (In the formula, R 11 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group, or a hydrogen atom, and at least one of R 11 is the monovalent hydrocarbon group. t is a number in the range of 2 to 10, and r is a number in the range of 1 to 500.)

[0033] As the carbosiloxane dendrimer structure, a silylalkyl having a siloxane dendrimer structure represented by the following formula (1) can be exemplified.

[0034] [Chemical Formula 3]

[0035]

[0036] {In the formula,

[0037] Z is a divalent organic group,

[0038] p is 0 or 1,

[0039] R 1 and R 2 are independently an alkyl group, an aryl group, or an aralkyl group having 1 to 10 carbon atoms,

[0040] When i = 1, L 1 is a silylalkyl represented by the following formula (2),

[0041] [Chemical Formula 4]

[0042]

[0043] (In the formula,

[0044] Z and p are as defined above,

[0045] R 1 and R 2 are as defined above,

[0046] i is an integer from 1 to 10 representing the total number of layers of the silylalkyl,

[0047] L i+1 is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, and the silylalkyl, provided that when i = c (c is an integer from 1 to 10 representing the layer of the silylalkyl), L i+1 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, and when i < c, L i+1is the silylalkyl group, a i is an integer from 0 to 3)

[0048] In addition, the carbosiloxane dendrimer structure is a highly branched chemical structure radially extending from a silicon atom, and i representing the total number of layers of the silylalkyl group represents the degree of branching. For example, when the total number of layers i is 1 and L i+1 is, for example, methyl, the carbosiloxane dendrimer structure means the following structure.

[0049] [Chemical formula 5]

[0050]

[0051] (In the formula, Z, p, R 1 and R 2 are the same as defined above, a 1 is an integer from 0 to 3)

[0052] Similarly, when the layer i is 2 and L i+1 is, for example, methyl, the carbosiloxane dendrimer structure means the following structure (provided that p = 1).

[0053] [Chemical formula 6]

[0054]

[0055] (In the formula, Z, R 1 and R 2 are the same as defined above, a 1 and a 2 are integers from 0 to 3)

[0056] Preferably, the a, a 1 and a 2 are 0, and the following structure is particularly preferred as the carbosiloxane dendrimer structure.

[0057] [Chemical formula 7]

[0058]

[0059] (In the formula, Z and R 2 are the same as defined above)

[0060] [Chemical formula 8]

[0061]

[0062] (In the formula, Z and R 2 are the same as defined above)

[0063] The unsaturated group-containing component (a1) is not limited as long as it has a free-radically polymerizable unsaturated bond in the molecule. For example, vinyl, allyl, (meth)acryloyl, etc. can be cited. In particular, preferably, the component (a1) is an acrylate monomer or methacrylate monomer having a silicon-containing organic group as described above. Among them, a particularly preferred unsaturated monomer is an unsaturated monomer in which the unsaturated group represented by the following structure is bonded to a silicon atom (Si) through -(Z)p- or -Z- in the above carbon-siloxane dendrimer structure, or an unsaturated monomer directly bonded to a silicon atom (Si).

[0064] [Chemical formula 9]

[0065]

[0066] (In the formula, R 4 is a hydrogen atom or a methyl group, and R 5 is an alkylene group having 1 to 10 carbon atoms.) Or

[0067] [Chemical formula 10]

[0068]

[0069] (In the formula, R 4 and R 5 are the same as defined above.) represents an acryloyl or methacryloyl group-containing organic group.

[0070] More specifically, as this component, unsaturated monomers containing silicon-containing organic groups represented by the following average composition formula are exemplified. These components can be used alone or in combination of two or more as the component (a1), and the resulting copolymer contains a silicon-containing organic group derived from the component (a1).

[0071] [Chemical formula 11]

[0072]

[0073] (That is,

[0074] [Chemical formula 12]

[0075]

[0076] (In the formula, Me is a methyl group))

[0077] [Chemical formula 13]

[0078]

[0079] [Chemical formula 14]

[0080]

[0081] [Chemical Formula 15]

[0082]

[0083] [Chemical Formula 16]

[0084]

[0085] [Chemical Formula 17]

[0086]

[0087] [Chemical Formula 18]

[0088]

[0089] [Chemical Formula 19]

[0090]

[0091] [Chemical Formula 20]

[0092]

[0093] [Chemical Formula 21]

[0094]

[0095] [Chemical Formula 22]

[0096]

[0097] [Chemical Formula 23]

[0098]

[0099] [Chemical Formula 24]

[0100]

[0101] [Chemical Formula 25]

[0102]

[0103] [Chemical Formula 26]

[0104]

[0105] (In the formula, "Si-" at the molecular end refers to "Si-CH 3 ")

[0106] [Chemical Formula 27]

[0107]

[0108] (In the formula, "Si-" at the end of the molecule refers to "Si-CH 3 ")

[0109] [Chemical formula 28]

[0110]

[0111] (In the formula, Me is methyl, n is a positive number, and Bu is butyl)

[0112] [Chemical formula 29]

[0113]

[0114] (In the formula, "Si-" at the end of the molecule refers to "Si-CH 3 ")

[0115] Component (a2) constituting the thermoplastic copolymer of the present invention is an unsaturated monomer different from component (a1), and it suffices to be a monomer having one radically polymerizable vinyl group in the molecule, and its type is not particularly limited. More specifically, it is a vinyl-based monomer having no organosilicon group such as a carbosiloxane dendrimer structure in the molecule and having one vinyl group in the molecule.

[0116] As such vinyl monomers, there are usually monomers that are starting materials for organic resins known as vinyl resins. Specifically, examples include: lower alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate; glycidyl (meth)acrylate; higher (meth)acrylates such as n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate; lower fatty acid vinyl esters such as vinyl acetate, vinyl propionate; higher fatty acid vinyl esters such as vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate; aromatic vinyl monomers such as styrene, vinyltoluene, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, vinylpyrrolidone; amide group-containing vinyl monomers such as (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, isobutoxymethoxy (meth)acrylamide, N,N-dimethyl (meth)acrylamide; hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate; fluorine-containing vinyl monomers such as 3,3,3-trifluoropropyl (meth)acrylate, perfluorobutylethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate; epoxy group-containing vinyl monomers such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate; carboxylic acid group-containing vinyl monomers such as (meth)acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid; ether bond-containing vinyl monomers such as tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol mono(meth)acrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether; unsaturated group-containing organosilicon compounds such as (meth)acryloxypropyltrimethoxysilane, (branched or linear) polydimethylsiloxane having a (meth)acryloyl group at one end, polydimethylsiloxane having a styryl group at one end; butadiene; vinyl chloride; vinylidene chloride; (meth)acrylonitrile; dibutyl fumarate; maleic anhydride; dodecyl succinic anhydride; glycidyl (meth)acrylate ether; alkali metal salts, ammonium salts, organic amine salts of free-radical polymerizable unsaturated carboxylic acids such as (meth)acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid; free-radical polymerizable unsaturated monomers having a sulfonic acid group such as styrenesulfonic acid and their alkali metal salts, ammonium salts, organic amine salts;Quaternary ammonium salts derived from (meth)acrylic acid such as 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, methacrylates of alcohols having a tertiary amino group such as diethylaminoethyl methacrylate, and their quaternary ammonium salts.

[0117] Furthermore, an organosilicon compound having a vinyl-based radically polymerizable unsaturated group and a hydrolyzable group can also be used. In this case, the film strength becomes hard and the durability of water resistance is improved, so it is preferred.

[0118] Similarly, an unsaturated monomer having at least one acidic group in the molecule or its salt can also be used. An unsaturated monomer or its salt having at least one acidic group in one molecule is a compound or its salt having a radically polymerizable vinyl group and at least one acidic group in one molecule. Examples of the acidic group include carboxylic acid, sulfonic acid, and phosphonic acid. Examples of these salts include alkali metal salts, alkaline earth metal salts, basic amino acid salts, ammonium salts, alkylammonium salts, alkylamine salts, alkanolamine salts. As specific examples, sodium salts, potassium salts, magnesium salts, calcium salts, L-arginine salts, L-histidine salts, L-lysine salts, ammonium salts, triethanolamine salts, aminomethylpropanediol salts, and their complex salts can be mentioned. Compounds having these acidic groups release protons (H + ) or combine with cation components in the solution to form salts at specific pH values in an aqueous solution, thereby changing the hydrophilic-hydrophobic properties of the compound. Similarly, compounds of salts having acidic groups also dissociate the salts at specific pH values and exhibit changes in the hydrophilic-hydrophobic properties of the compound. Therefore, by appropriately adding these compounds having acidic groups or their salts to cosmetic raw materials, they are easily rinsed during washing, and thus the effect of good cosmetic retention is achieved.

[0119] Similarly, for the purpose of improving the water resistance and the like of the thermoplastic copolymer containing a silicon-containing organic group of the present invention, an unsaturated monomer containing a fluorine-containing organic group such as a perfluoroalkyl group can be used. For example, vinyl-based monomers such as acrylic monomers or methacrylic monomers having a fluorine-containing organic group such as a perfluoroalkyl group.

[0120] The copolymer in the present invention is copolymerized from the above-mentioned component (a1) and component (a2). Preferably, the mass ratio during copolymerization is (a1):(a2) = 10:90 to 90:10. More preferably, the mass ratio during copolymerization is 20:80 to 85:15. Further preferably, the mass ratio during copolymerization is in the range of 30:70 to 60:40. In particular, preferably, the mass% of the above-mentioned component (a1) is 20% by mass or more and 30% by mass or more with respect to the total mass of component (a1) and component (a2). Particularly preferably, component (a1) is 20% by mass to 60% by mass in the total monomer units.

[0121] The thermoplastic copolymer containing a silicon-containing organic group in the present invention has a step of adding a polymerization initiator to a raw material composition containing the monomers to carry out a polymerization reaction. Subsequently, it may further have an optional step of contacting the obtained polymerization reaction product with a nickel catalyst or a palladium catalyst to carry out a hydrogenation reaction.

[0122] As the polymerization method used in the polymerization reaction, a radical polymerization method, an anionic polymerization method, a cationic polymerization method, a group transfer polymerization, an organometal-mediated radical polymerization method, or an atom transfer radical addition method is used, but the radical polymerization method is preferred. In this radical polymerization method, it can be carried out through at least one liquid-phase polymerization reaction selected from solution polymerization, suspension polymerization, microemulsion polymerization, and emulsion polymerization, and solution polymerization is preferably used. This solution polymerization is carried out by reacting a monomer composition containing the component (a1) and the component (a2) in a solvent at a temperature of 50 to 150 °C for 3 to 20 hours in the presence of a radical initiator. Examples of the solvent used during the polymerization reaction include aliphatic hydrocarbons such as hexane, octane, decane, cyclohexane, methylcyclohexane, and isoparaffin; aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone; esters such as methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate; alcohols such as methanol, ethanol, isopropyl alcohol, and butanol; and organosiloxane oligomers such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, and octamethyltrisiloxane. These solvents can be used alone or in combination of two or more. It should be noted that, as described later, the organic solvent used during the polymerization reaction is finally removed in the present invention during the process of forming molded solid particles.

[0123] As the radical initiator, generally, conventionally known compounds used in the radical polymerization method are used. Specifically, examples include azobis-based compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis(2,4-dimethylvaleronitrile); and organic peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, tert-amyl peroxyneopentanoate, tert-butyl peroxyneopentanoate, tert-hexyl peroxyneopentanoate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, bis(3,5,5-trimethylhexanoyl) peroxide, and diisopropyl peroxydicarbonate. This radical initiator can be used alone or in combination of two or more. Preferably, the usage amount of the radical initiator is in the range of 0.1 to 10 parts by weight based on 100 parts by weight in total of the above monomer composition.

[0124] In addition, a chain transfer agent can be added during polymerization. Specific examples of such chain transfer agents include mercapto compounds such as 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, polydimethylsiloxane having a mercaptopropyl group, and mercaptopropionic acid; halides such as dichloromethane, chloroform, carbon tetrachloride, butyl bromide, and 3-chloropropyltrimethoxysilane; secondary alcohols such as isopropyl alcohol and glycerol; sulfites such as sodium sulfite; sodium bisulfite; sodium dithionite; potassium metabisulfite; hydrogen peroxide; sodium bisulfite; sodium dithionite; potassium metabisulfite; hydrogen peroxide, etc.

[0125] The polymerization reactant can be contacted with a nickel catalyst or a palladium catalyst as a hydrogenation reaction catalyst. By contacting with such a catalyst, the vinyl groups of the unreacted monomers remaining in the polymerization reactant are saturated, and thus the irritation or odor when added to cosmetics can be reduced. Examples of the nickel catalyst include nickel / diatomaceous earth or Raney nickel catalyst, but are not necessarily limited thereto. Examples of the palladium catalyst include palladium compounds such as tetrakis(triphenylphosphine)palladium(0) and dichlorobis(triphenylphosphine)palladium(II), palladium on carbon, palladium hydroxide on carbon, and platinum oxide, etc., but are not necessarily limited thereto.

[0126] The temperature when the polymerization reactant is contacted with the nickel catalyst or the palladium catalyst is 50 to 200 °C, preferably 70 to 130 °C. The pressure is 1 to 1000 kg / cm 2 (absolute pressure), preferably 2 to 100 kg / cm 2 . The contact time is 1 to 15 hours, preferably 3 to 10 hours. The reaction can be carried out in a solvent. The solvent used for polymerization can be directly used, or solvent replacement can be performed. The solvents that can be used are the same as those described for the polymerization reaction.

[0127] [Properties of the copolymer]

[0128] The above-mentioned copolymer does not have a crosslinked structure in the molecule, so it has thermoplasticity and is easily soluble in solvents acceptable for cosmetics. In the present invention, a copolymer that does not have thermoplasticity and has a crosslinked structure in the molecule is generally insoluble or hardly soluble in solvents and cannot achieve the technical effects of the present invention. It should be noted that the formed solid particles using the copolymer of the present invention are preferably obtained by a continuous manufacturing method having a process of discharging while forming after the copolymer is melted. For example, they can be formed by discharging in a strand shape or using a droplet former. However, the manufacturing methods of these formed solid particles, especially the forming method, are not particularly limited, and of course, the optimal manufacturing conditions can be set according to the desired forming method and manufacturing apparatus. In addition, in the forming method, it includes cutting or pulverizing the discharged copolymer, and the forming process can be carried out at any time before cooling, during cooling, or after cooling.

[0129] In the copolymer of the present invention, the glass transition temperature (Tg) of the copolymer itself after removing the solvent is preferably in the range of 30 to 120 °C, more preferably in the range of 35 to 100 °C, and particularly preferably in the range of 40 to 90 °C. When the Tg of the copolymer exceeds the above upper limit, the solubility of the obtained formed solid particles in the solvent sometimes decreases. And, for example, since the hardness of the solid copolymer discharged in a strand shape increases, it is sometimes necessary to reheat after cooling for cutting, etc., and the industrial productivity decreases. On the other hand, if the Tg of the copolymer is lower than the above lower limit, especially in the case of applying it to the manufacturing process of formed solid particles having a process of discharging in a strand shape described later, the melt viscosity decreases sharply. In the case of forming into a strand shape, problems such as poor forming or deformation sometimes occur. In addition, if the Tg of the copolymer is low, the strand-shaped formed product discharged from the die head is too soft, and poor cutting is likely to occur. Sometimes it is necessary to adjust the cooling state to a temperature suitable for cutting for cutting, etc., and the industrial productivity decreases. Moreover, if the Tg of the copolymer is lower than the above lower limit, in the process of distilling off (removing) the solvent, the amount of residual solvent tends to increase, and there is residual solvent in the obtained formed solid particles, which sometimes impairs the suitability, performance, and usability as a cosmetic raw material. In addition, it sometimes causes quality problems such as stickiness, aggregation, and deformation on the surface of the formed solid particles.

[0130] From the viewpoint of its moldability, the melt viscosity of the copolymer of the present invention ranges from 0.1 to 10,000 Pa·s at the temperature at the time of discharge (for example, a temperature range of 35 to 220 °C can be cited as a temperature 5 to 100 °C higher than the above Tg).

[0131] The melt viscosity preferably ranges from 1 to 10,000 Pa·s, more preferably from 2.5 to 8,500 Pa·s, and particularly preferably from 5 to 7,000 Pa·s in the process of discharging in strands from the die head. It should be noted that if the temperature at the die head outlet is too high, it is easy to cause poor molding or deformation of the strand-shaped molded article.

[0132] In addition, in the process of discharging droplets with a droplet former, the melt viscosity preferably ranges from 0.1 to 100 Pa·s, more preferably from 0.5 to 80 Pa·s, and particularly preferably from 1 to 60 Pa·s. It should be noted that in the droplet former, if the melting temperature is too low, sometimes droplets are not discharged and it is easy to cause poor molding or deformation.

[0133] [Optional fillers and additives]

[0134] In the copolymer of the present invention, according to the use as a cosmetic raw material and the required properties, and within the range not impairing the technical effects of the present invention, any fillers and additives can be formulated, and molded solid particles containing these fillers and additives can also be formed. Specifically, one or more fillers selected from glass fiber, carbon fiber, glass cloth, calcium carbonate, mica, talc, etc. can be formulated, and one or more additives selected from strength improvers, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, plasticizers, foaming agents, nucleating agents, lubricants, antistatic agents, conductivity imparting agents, colorants (including pigments and dyes, etc.), compatibilizers, flame retardants, mildew-proof agents, low shrinkage agents, tackifiers, release agents, antifogging agents, bluing agents (colorants for the purpose of transparency), silane coupling agents, etc. can be formulated. It should be noted that these components are preferably uniformly mixed or kneaded with the copolymer of the present invention to form molded solid particles, these components can be added to the solution containing the copolymer of the present invention, or can be added to the molten copolymer while removing the solvent or after removing the solvent and kneaded. It should be noted that the above-mentioned fillers are insoluble in the solvents acceptable for cosmetics, but when formulated into the molded solid particles of the present invention in a state of being uniformly dispersed in the copolymer of the present invention, they have the following advantages: when the thermoplastic copolymer constituting the molded solid particles is dissolved in the solvent, the insoluble fillers carried by these copolymers can be uniformly dispersed in the cosmetic dosage form to form a preparation.

[0135] [Molded solid particles and their manufacturing method]

[0136] The shaped solid particles of the present invention are characterized by containing the above-mentioned thermoplastic copolymer and optional additives, and the major axis of the particles is less than 10 mm. The shape of the shaped solid particles is not particularly limited as long as it is formed into a certain shape, and it is preferably one or more forms selected from pellets, tablets, short fibers, and shaped granules. From the viewpoint of the manufacturing method described later, the forms of pellets and short fibers are particularly preferred. The major axis of the particle refers to the longest diameter of the particle. For example, in the case of being formed into a cubic shape, a cuboid shape, a cylindrical shape, a spherical shape, an oblong spherical shape, a hemispherical shape, or an amorphous crushed material, it can be any diameter including the diameter or length. In addition, in the case of containing a plurality of shaped solid particles, it can be the average value of the major axis determined by observation with an electron microscope or the setting of a granulator (cutting device).

[0137] However, from the viewpoint of the solubility of the shaped solid particles, the major axis (the average value of the major axis in the case of multiple particles) of the shaped solid particles of the present invention needs to be less than 10 mm. From the viewpoint of industrial productivity, it can be in the range of 0.1 to 9.5 mm, 0.5 to 9.0 mm, or 0.5 to 7.5 mm.

[0138] The content of the non-volatile components in the shaped solid particles of the present invention is preferably 97% by mass or more, and particularly preferably 98 to 100% by mass is the non-volatile component. It should be noted that the non-volatile components include the non-volatile components as optional fillers and additives. On the other hand, if a large amount of volatile components such as organic solvents or low-molecular-weight monomers used during synthesis remain in the shaped solid particles, in the obtained shaped solid particles (for example, the cut pellets obtained by the method described later), stickiness is likely to occur on the surface. Due to the aggregation or deformation of the shaped solid particles, it is easy to form uneven lumps, which sometimes cause poor appearance or quality, sometimes reduce the handling workability, and sometimes reduce the solubility in the solvents acceptable for cosmetics. In addition, if the amount of the remaining solvent is large, it sometimes causes ignition due to the volatile admixtures from the remaining solvent, or impairs the usability and quality of the obtained cosmetics.

[0139] The manufacturing method of the shaped solid particles involved in the present invention is not particularly limited. However, from the viewpoints of its quality and industrial productivity, a manufacturing method preferably having the following processes is adopted: Process (I) of discharging a thermoplastic copolymer from a die head in a strand shape; Process (II) of cutting the strand-shaped discharge obtained in the above Process (I). Similarly, as another manufacturing method of the shaped solid particles of the present invention, it may also be a manufacturing method having Process (III) of discharging a thermoplastic copolymer from a droplet former, and Process (IV) of cooling and solidifying the discharge obtained in Process (III). Hereinafter, this manufacturing method will be described in detail. It should be noted that this manufacturing method can be implemented in a batch mode or a continuous mode. However, from the viewpoints of productivity and quality control, it is preferably carried out continuously by using an extruder equipped with a die head and a cutting device described later.

[0140] Process (I) is a process of melting the thermoplastic copolymer of the present invention and discharging it from the hole part of the die head to form a strand-shaped discharge. The strand-shaped discharge is a solid or semi-solid of a thermoplastic copolymer in a planar or thin rod shape. Since it is at a high temperature during discharge, it is preferably cooled using a cooling tank such as a water bath or air cooling (including cooling transfer using a belt conveyor, etc.). The cooled wire material is preferably adjusted to a hardness that can be easily cut in the subsequent Process (II) of cutting the strand-shaped discharge. However, it is not necessarily required to form a wire material. In this case, it is cut in the subsequent Process (II) of cutting the discharge.

[0141] The thickness of the strand-shaped discharge is determined by the aperture of the die head. From the viewpoint of the solubility of the shaped solid particles obtained by this manufacturing method, the aperture of the die head needs to be less than 10 mm. In order to be able to easily cut in the subsequent Process (II) of cutting the strand-shaped discharge, the aperture of the die head is preferably in the range of 1.0 to 7.5 mm, and particularly preferably in the range of 3 to 7 mm. In addition, the number of strand-shaped discharges discharged from the die head is determined by the number of holes in the die head and is not particularly limited. However, from the viewpoint of production efficiency, the number of holes in the die head is preferably in the range of 2 to 50, 2 to 20, or 2 to 10. In the case where no wire material is formed, a die head aperture equivalent to this condition can also be used. In addition, for the purpose of improving the cooling efficiency or the convenience during use, the shape of the holes in the die head can be selected from any shape such as a circle, a polygon (including an asymmetric hole shape).

[0142] In step (I), the thermoplastic copolymer of the present invention is discharged from the orifice of the die in a molten state in which the solvent used in the polymerization reaction has been removed or reduced. At the time of discharge, within the range that does not impair the technical effects of the present invention, the above-mentioned filler or additive can be arbitrarily blended in the copolymer in advance. The steps of removing or reducing the solvent, melting, and discharging from the die orifice are not particularly limited, and one or more options selected from the following can be selected in step (I) according to the process, working environment, properties of the copolymer, or the type of the desired formed solid particles, etc.:

[0143] Option (a): Implement by an extruder having a die;

[0144] Option (b): Use a kettle (reactor) equipped with a decompression device or a thin-film evaporation device to perform a distillation removal operation for removing or reducing the solvent, and then set a die under the kettle or at the outlet of the evaporation device, and use a liquid feeding mechanism such as a gear pump to discharge the above-mentioned copolymer from the orifice of the die; and

[0145] Option (c): Arrange a liquid feeding mechanism such as a gear pump on the outlet side of the extruder,

[0146] Set a die at its outlet, and discharge the above-mentioned copolymer from the orifice of the die. In particular, in the manufacturing method of the present invention, it is particularly preferred to implement by an extruder having a die (that is, the above-mentioned option (a)). Since a strand-shaped discharge product composed of a copolymer can be continuously manufactured, it is suitable for a continuous manufacturing method with excellent industrial productivity. In addition, in the case where no wire material is formed, one or more options selected from the above options (a) to (c) can also be selected in step (I). Hereinafter, in the manufacturing method of the present invention, a single-screw or multi-screw extruder can be used as the extruder, and a multi-screw extruder is preferred, and a twin-screw extruder is particularly preferred. In addition, the specifications of the extruder and the ratio of the barrel length to the diameter (L / D) are not particularly limited, and the L / D value of the extruder can be in the range of 20 to 150, and can be in the range of 20 to 100.

[0147] Preferably, in the manufacturing method of the present invention, the thermoplastic copolymer is preferably supplied to an extruder having a die from a hopper or the like using a pump or the like in the form of a copolymer solution dissolved in at least one organic solvent (including the form of directly using the copolymer solution after synthesis). At this time, any filler and / or additive can be supplied to the extruder, and these components can be supplied from the same hopper together with the aforementioned copolymer solution, or can be supplied from different raw material inlets while adjusting the supply amount with a pump or the like. In particular, by adjusting the supply amount of a pump or the like, the composition of the formed solid particles obtained in the continuous manufacturing process can be kept constant.

[0148] The copolymer solution supplied to the extruder is subjected to a distillation removal operation in the extruder to remove or reduce an organic solvent that is a dispersion medium. This distillation removal operation is preferably continuously carried out by kneading with heating or under reduced pressure in the barrel part of the extruder. By the time it reaches the die provided at the exit of the extruder, volatile components such as the organic solvent are removed from the copolymer to the target level. Here, the conditions for the distillation removal operation in the barrel part of the extruder are not particularly limited. The set temperature of the barrel part is preferably set in the range from a temperature 60°C lower than the boiling point of the organic solvent to a temperature above the boiling point of all the organic solvents. It should be noted that in the case where there are multiple organic solvents in the copolymer solution, it can be set in the range from a temperature 60°C lower than the boiling point of the organic solvent with the lowest boiling point to a temperature above the boiling point of all the organic solvents. However, from the viewpoint of effectively removing the organic solvent, based on the boiling point of the organic solvent with the highest boiling point, it is particularly preferably set in the range from a temperature 30°C lower than this boiling point to a temperature 60°C higher. For example, when distilling off isododecane with a boiling point of 177°C from a copolymer solution dispersed only in isododecane, the set temperature of the barrel part can be set in the range from 117°C to above 177°C, preferably in the range from 147°C to 237°C. In particular, the set temperature inside the barrel is preferably a temperature difference of at least 60°C lower than the boiling point of the organic solvent. At a temperature lower than this temperature, sufficient distillation removal cannot be carried out, the amount of residual solvent increases, and as a result, the viscosity increases, and significant stickiness is likely to occur on the surface. Thus, sometimes strand formation cannot be carried out, or even if strand formation can be carried out, it cannot be cut with a cutting device having a rotary blade and / or a fixed blade. On the contrary, if the temperature inside the barrel is set too high, it is not only uneconomical, but the copolymer itself is liable to undergo chemical deterioration / decomposition due to overheating, or the melt viscosity becomes too high, and sometimes it cannot be formed into strands at the die exit.

[0149] Furthermore, from the viewpoint of effectively removing the organic solvent, this distillation removal operation is preferably carried out under reduced pressure conditions, and the desired degree of vacuum can be set. Based on atmospheric pressure (about 101 kPa), it can be set in the range from 0 to 90 kPa.

[0150] The copolymer from which the organic solvent has been distilled off in the barrel part (which may optionally contain other fillers or additives) reaches the die in the extruder while being heated and kneaded, and is discharged in strands. At this time, since the melt viscosity of the copolymer having thermoplasticity in the die is preferably in the range of 1 to 10,000 Pa·s, the die exit temperature of the extruder is particularly preferably set to a temperature 5 to 100 °C higher than the glass transition temperature (Tg) of the copolymer having thermoplasticity. By setting the die exit temperature within the above range, the copolymer after being kneaded and distilled off the organic solvent in the barrel part becomes a molten state having the above melt viscosity, and can be formed into strands without causing molding defects or die clogging, and can be cut after being arbitrarily cooled in subsequent processes. On the other hand, if the die exit temperature is too low, the cured copolymer causes clogging in the die, and sometimes a strand-shaped molded product cannot be obtained, or production becomes difficult. Conversely, if the die exit temperature is too high, the copolymer itself undergoes chemical deterioration or decomposition due to overheating, or sometimes the strand-shaped molded product from the die is easily melted and deformed, resulting in molding defects. It should be noted that it is not necessarily required to form a wire material. When discharging from the die without forming a wire material, the die exit temperature can be set in the same manner.

[0151] The strand-shaped discharge obtained in step (I) undergoes an optional cooling step such as a water bath, etc., and after adjusting to a hardness suitable for cutting, it is cut in this cutting step (II) to have a major axis of less than 10 mm. The cutting step of the strand-shaped discharge is preferably carried out by one or more cutting devices selected from a rotary blade and a fixed blade. It should be noted that this cutting step is industrially suitable to be carried out by a cutting device called a granulator, and the strand-shaped discharge is cut into uniform pellets with a major axis of less than 10 mm, that is, in the form of formed solid particles. It should be noted that by using a cutting device other than a granulator and any further granulation / molding device, sheets, short fibers, and formed granules with a major axis of less than 10 mm can also be formed.

[0152] It should be noted that when no wire material is formed in step (I), it can be cut immediately after discharging from the die. Furthermore, at this time, it can be cut in a molten state without going through a cooling step, or it can also be cut in a semi-solid state during cooling to obtain formed granules. For example, as a device for cutting immediately after discharging from the die without going through a cooling step, a well-known hot cutting granulator is applicable, and after cutting, it can be cooled by any method such as water cooling, air cooling, or belt cooling to obtain formed granules in a solid state. As a method for cutting in a semi-solid state during cooling immediately after discharging from the die, a well-known underwater cutting (alias: underwater granulator) is applicable.

[0153] In the appendix of this patent application Figure 1The figure shows a schematic diagram of an apparatus for manufacturing molded solid particles (pellets) composed of a copolymer particularly preferred in the present invention. That is, a thermoplastic copolymer solution of the present invention (for example, a solution obtained by dispersing or dissolving a silicone acrylate copolymer having a carbosiloxane dendritic polymer structure obtained by a synthesis reaction in isododecane or the like) charged into a hopper is fed by a pump into an extruder. In the barrel portion of the extruder, the temperature of the copolymer solution is adjusted, and it is kneaded under reduced pressure conditions, and volatile components such as organic solvents are distilled off, and it reaches the die of the extruder in a heated and molten state and is discharged in a strand form from the temperature-adjusted die hole (= step (I)). Next, the molten copolymer discharged in a strand form is cooled in a cooling tank serving as a water bath and solidified to a hardness suitable for cutting. Finally, the solidified strand-shaped copolymer reaches a cutting device serving as a granulator and is cut into a form of uniform pellets, i.e., molded solid particles, having a major axis of less than 10 mm (= step (II)) and recovered.

[0154] Step (III) is a step of melting the thermoplastic copolymer of the present invention and discharging it from a droplet former to form droplets in a molten state. As a method for granulating and molding a resin in a molten state, a melt granulation device is known, and there is no particular limitation, and a known steel belt granulator (alias: paste crusher, belt granulator, belt conveyor granulator, etc.), a known spray cooling device (alias: tower granulator, spray granulation device, etc.) can be used. For example, as a steel belt granulator, a device disclosed in Japanese Patent Laid-Open No. 60-212166 can be used, and as a spray cooling device, a spray cooling device or a cooling granulation method disclosed in Japanese Patent Laid-Open No. 61-245832 or the like can be used. Depending on the cooling method, a spray freezing device can also be used, and furthermore, it is not limited thereto.

[0155] It should be noted that this copolymer can be directly molded / re-molded using a spray granulation device such as a spray dryer, or after dissolving the above-mentioned molded solid particles in a solvent or the like.

[0156] [Post-treatment or re-molding operation]

[0157] The molded solid particles according to the present invention are manufactured by the above method, but depending on process requirements, or quality or specification requirements, the molded solid particles of the copolymer after coarse pulverization can be arbitrarily pulverized again (including for the purpose of obtaining molded pulverized particles with a smaller particle size) or melted and re-molded into a sheet form, granular form, strip form, etc. For the purpose of removing residual solvents or residual monomers, etc., the molded solid particles of the copolymer can be passed through the same or different processes again (representatively, a step of charging again into a hopper and performing a melt-kneading operation using an extruder, etc.), discharged in a strand form from the temperature-adjusted die hole, and pelletized by a method such as cutting.

[0158] When manufacturing the molded solid particles involved in the present invention, without forming a wire material, it can be cut immediately after being discharged from the die. Furthermore, at this time, it can be cut in a molten state without going through a cooling process, or it can also be cut in a semi-solid state during cooling to obtain molded particles. In addition, the obtained molded solid particles of the present copolymer can be directly or after coarse pulverization and fine pulverization, arbitrarily classified according to process requirements or quality or specification requirements (typically a screening device equipped with a wire mesh or an air classification device (weight classification device, inertial classification device, centrifugal force utilization classification device)). However, their post-treatment and re-molding processes are not limited. In the manufacturing method of the present invention, other raw materials can be arbitrarily mixed. Furthermore, it can also be formed into strips, granules, flakes, etc. by stamping molding, etc. In addition, in order to prevent agglomeration, etc., it can also be mixed with powdered silica, etc. to form a molded solid particle form with silica particles, etc. on the surface.

[0159] [Use of Molded Solid Particles: Cosmetics and Manufacturing Method of Cosmetics]

[0160] The molded solid particles of the present invention are molded solid particles composed of a copolymer having a silicon-containing organic group in the molecule and having thermoplasticity. Since they are easily soluble in a solvent acceptable for cosmetics, they can be used for the uses where this copolymer has been used in the past without particular limitation.

[0161] Specifically, the molded solid particles of the present invention can preferably be used as cosmetic raw materials, and as the copolymer itself, it has the same properties such as water resistance, detergency, and moldability as the known acrylic silicone dendrimer copolymer. Therefore, for example, in a known formulation such as the vinyl-based polymer having a carbosiloxane dendrimer structure in the side chain described in Japanese Patent No. 4009382 (Japanese Patent Laid-Open No. 2000-063225), etc., it can be used to replace a part or all of them. That is, in a cosmetic formulation containing a known vinyl-based polymer having a carbosiloxane dendrimer structure in the side chain, by using the molded solid particles composed of the copolymer of the present invention or a solution obtained by dissolving or dispersing the molded solid particles in a solvent acceptable for cosmetics to replace the corresponding vinyl-based polymer to design or prepare a cosmetic formulation, which is clearly pointed out by the applicant in this article.

[0162] Similarly, in known formulations proposed for commercially available products of vinyl polymers having a carbosiloxane dendrimer structure in the side chain, the copolymer of the present invention can be used to replace part or all of them. For example, as commercially available products, FA 4001CM Silicone Acrylate, FA 4002ID Silicone Acrylate, DOWSIL(TM) FA 4003DM Silicone Acrylate, etc. manufactured by Dow Toray Co., Ltd. can be cited. Cosmetic formulations using these are known in most products, patents, formulation samples provided by DOW SILICONE CORPORATION, public information in IP.com, etc. However, the formed solid particles composed of the copolymer of the present invention or a solution obtained by dissolving or dispersing the formed solid particles in a solvent acceptable to cosmetics can be used by unrestrictedly replacing part or all of the vinyl polymers having a carbosiloxane dendrimer structure in the side chain, and this is preferred.

[0163] In the case of replacing the vinyl polymer having a carbosiloxane dendrimer structure in the side chain in a known cosmetic formulation with the formed solid particles composed of the copolymer of the present invention, through the usual formulation procedures of those skilled in the art, it is only necessary to simply replace the corresponding material in the cosmetic formulation with the formed solid particles composed of the copolymer. Using a known formulation and without impairing the performance and characteristics of the cosmetic, since it is a solid raw material, the handling workability is more excellent, and it does not contain a solvent. Since it has good solubility in a solvent acceptable to cosmetics, there is a practical benefit in providing a cosmetic with an easy manufacturing process, excellent freedom in formulation design, and good usability.

[0164] It should be noted that cosmetics containing the formed solid particles composed of the copolymer of the present invention are particularly preferably prepared through a manufacturing process including a step of dissolving or dispersing the formed solid particles of the present invention in a solvent acceptable to cosmetics containing the above solvent.

[0165] In addition to the above-mentioned copolymers, the cosmetics of the present invention containing molded solid particles may contain various cosmetic raw materials. Other cosmetic raw materials are not particularly limited, and preferred examples thereof include cosmetics containing at least one selected from the group consisting of (B) water, (C) alcohol, (D) oil agent, (E) powder or coloring agent, (F) surfactant, (G) oil-soluble gelling agent, (H) organically modified clay mineral, (I) silicone resin, (J) silicone rubber, (K) silicone elastomer, (L) organically modified silicon, (M) ultraviolet ray-preventing component, (N) water-soluble polymer, and (O) alkyl-modified silicone resin wax. It should be noted that the molded solid particles of the present invention are dissolved or dispersed in one or more (C) alcohols and / or (D) oil agents which are solvents acceptable as cosmetics, and are formulated into cosmetics in the form of a copolymer composition containing the copolymer and such a dispersion medium.

[0166] Within the range that does not interfere with the effects of the present invention, other components used in conventional cosmetics may be added to the cosmetics of the present invention: organic resins, moisturizers, preservatives, antibacterial agents, fragrances, salts, antioxidants, pH regulators, chelating agents, refreshing agents, anti-inflammatory agents, skin beautifying components (whitening agents, cell activators, skin roughness improvers, blood circulation promoters, skin astringents, anti-seborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, clathrates, etc. These specific examples are the same as those specifically disclosed in paragraphs 0100 to 0113 of Japanese Patent Application Laid-Open No. 2011-149017, etc., but are not limited thereto.

[0167] The cosmetics of the present invention may be formulated with natural plant extract components, seaweed extract components, and crude drug components according to their purposes. Two or more such components may be formulated. These specific examples are the same as those specifically disclosed in paragraph 0115 of Japanese Patent Application Laid-Open No. 2011-149017, etc., but are not limited thereto.

[0168] Solvents such as light isoparaffin, ethers, LPG, N-methylpyrrolidone, and next-generation chlorofluorocarbons may also be formulated in the cosmetics of the present invention according to their purposes.

[0169] [Types and Preparations of Cosmetics]

[0170] Moreover, the types and preparation forms of the cosmetics are not particularly limited and may be skin cosmetics such as skin care products, antiperspirant products, deodorant products, makeup products, and ultraviolet protection products; hair cosmetics such as eyelash cosmetics, hair cleansing products, hair styling products, hair dyeing products, hair nourishing products, hair care products, hair conditioners, and hair treatment products; and bath cosmetics. Moreover, the form is not particularly limited, but may be any of a solution, emulsion, paste, solid, semi-solid, paste, gel, powder, multi-layer, mousse, water-in-oil or oil-in-water emulsified composition (emulsion composition).

[0171] Among them, external preparations are substances applicable to the skin, nails, hair, etc. of the human body. For example, they can be formulated with pharmaceutically active ingredients for the treatment of various diseases. Cosmetics are also substances applicable to the skin, nails, hair, etc. of the human body, but are also substances for cosmetic purposes. Even when used as an "external preparation", they may actually be used in the same dosage and amount as cosmetics. Therefore, in the cosmetics of the present invention, these external preparations are also described as substances included as cosmetics. One example includes antiperspirants, skin cleansers, topical skin preparations, hair cleansers, topical hair preparations, etc. When listing the uses of the external preparation drugs, examples include hair growth agents, hair nourishing agents, analgesics, bactericides, anti-inflammatory agents, refreshing agents, and skin anti-aging agents, but are not limited thereto.

[0172] Film-forming / hair touch effect

[0173] The cosmetics of the present invention contain the above copolymer, and thus can form a film with excellent waterproof performance, excellent persistence, and sebum durability on the skin or hair. In particular, the molded solid particles composed of the copolymer of the present invention do not contain organic solvents and are easily soluble in solvents acceptable for cosmetics. Therefore, the degree of freedom in formulation design is high, and a film with excellent water resistance and sebum resistance can be formed on the skin or hair, and cosmetics providing these functional films can be designed.

[0174] The described skin cosmetics can be used on the scalp, face (including lips, eyebrows, cheeks), fingers, nails, and any part of the whole body. Specific examples include: skin cleansing products such as facial cleansing gels, facial cleansing creams, facial cleansing foams, facial washes, eye makeup removers, facial washes, liquid soaps (body washes), hand sanitizers, gel soaps, shaving creams, nail polish removers, acne cosmetics, etc.; skin care products such as skin creams, scalp repair conditioners, skin lotions, milk body lotions, emulsions, facial masks, talcum powders, serums, shaving lotions, massage liquids, etc.; makeup products such as foundations, liquid foundations, oily foundations, makeup base liquids, white powders, face powders, blushes, lipsticks, rouges, lip glosses, eye creams, mascaras, eyebrow pencils, eyebrow cosmetics, etc.; antiperspirants such as deodorants; and anti-ultraviolet products such as sunscreen agents, tanning agents (sunless tanning agents).

[0175] Examples of the described hair cosmetics include hair cleansing agents such as shampoos, 2-in-1 hair products; hair styling products such as hair waxes, hair curl retainers, styling agents, hair creams, hair gels, hair liquids, etc.; hair coloring products such as hair dyes, hair coloring sprays, hair dyes, hair coloring sticks, etc.; hair nourishing products such as hair conditioners, hair treatment serums, hair masks, etc.; hair washing or hair care products such as hair oils, hair rinses, repair liquids, hair conditioners, repair conditioners, etc. And, the described bath cosmetics can include foam baths.

[0176] [Other uses]

[0177] The formed solid particles of the present invention can also be formulated into various external preparations, coatings, coating agents, defoaming agents, deodorants, and other uses other than cosmetics. In this case, it is particularly preferred that the formed solid particles exhibit their handling workability and solubility, and as a solid raw material with low flammability, advantages in handling such as transportation can be ensured, and they can be dissolved in a desired solvent and uniformly formulated into the final product.

[0178] [Use as a film-forming agent]

[0179] The formed solid particles of the present invention exhibit their handling workability and solubility, and as a film-forming agent, can also be used in applications other than cosmetics. That is, as long as applications require waterproofing effects, oil-proofing effects, integrity, strength, and abrasion resistance on the film, they can be used regardless of the field. In particular, they can also be used as waterproofing effect imparting agents for coating compositions and fibers, treatment agents for inorganic materials / organic materials, etc. And, as needed, the film-forming agent of the present invention can be used in an aqueous environment, so it is easy to handle.

[0180] Specifically, the film-forming agent of the present invention can be processed as a solid raw material and has good solubility in solvents. Therefore, its formulation stability is excellent, and it does not impair the film-forming property and the sense of use. Therefore, it can also be appropriately used as a film-forming agent for industrial applications such as fiber treatment agents or cotton / canvas treatment agents.

[0181] Examples

[0182] Hereinafter, the present invention will be further described in detail by way of examples, but the present invention is not limited to these examples.

[0183] Each characteristic in the examples and the like was measured by the following methods.

[0184] [Method for measuring the glass transition temperature (Tg) of the copolymer]

[0185] The solvent dispersion solution of each copolymer was infiltrated into a rectangular filter paper (size: 1×5 cm) cut and grown and dried, and used as a sample. Using a dynamic viscoelasticity device MCR302 manufactured by Anton Paar, the filter paper as a sample was tested under the conditions of shear mode, scanning conditions, heating rate of 3 °C / minute, vibration frequency of 1 Hz, and strain of 0.1%. First, the filter paper before impregnation was measured, and after confirming that no peaks such as transitions were particularly observed within the measurement range, the impregnated sample was measured, the tanδ at each temperature was measured, and the temperature at the peak top was taken as the glass transition temperature (Tg) of each copolymer.

[0186] [Method for measuring the non-volatile content (NVC) of the molded solid particles (granules) composed of the copolymer]

[0187] 1 g of each molded solid particle (pellet) was collected in an aluminum dish, and the weight after standing in an oven at 150 °C for 1 hour was measured, and the non-volatile content (NVC) was calculated according to the following formula.

[0188] NVC (%) = (weight before heating - weight after heating) × 100 / weight before heating [Measurement of melt viscosity]

[0189] Unless otherwise specified, the melt viscosity in the experimental examples was measured under a pressure condition of 2.452 MPa by the CFT-EX series of Shimadzu Corporation (unit of melt viscosity: Pa·s).

[0190] [Pelletizing process]

[0191] The pelletizing process and processing device in this experimental example (common to examples / comparative examples) are as Figure 1 shown, and are composed of a hopper, a liquid supply pipeline (including a liquid supply pump), a twin-screw extruder, a strand die, a water bath (cooling tank), and a connection of a granulator. Here, the L / D ratio (length to diameter ratio) of the twin-screw extruder is 53, and the die has three circular discharge holes with a diameter of 5 mm. The water bath is arranged between the strand die and the granulator having a cutting device (strand pelletizer), and the strand-shaped copolymer discharged in a molten state is cooled / solidified by the water bath and then cut by the granulator.

[0192] [Preparation of Thermoplastic Vinyl Copolymer Solutions No. 1 to No. 3 with a Carbon-Siloxane Dendrimer Structure in the Molecule]

[0193] As shown in Table 1, in the examples / comparative examples, the following copolymer solutions No. 1 to No. 3 were used. It should be noted that the copolymer concentration (= non-volatile component) in each solution was uniformly 40% by mass.

[0194] Copolymer Solution No. 1: DOWSIL(TM) FA 4002ID (manufactured by Dow Toray Co., Ltd., commercially available product: a dilution diluted to 40% by mass with isododecane (ID))

[0195] Copolymer Solution No. 2: DOWSIL(TM) FA 4004ID (manufactured by Dow Toray Co., Ltd., commercially available product: a dilution diluted to 40% by mass with isododecane (ID))

[0196] Copolymer Solution No. 3: A dilution diluted to 40% by mass with isopropyl alcohol (IPA) of the copolymer obtained from the following Synthesis Example 1

[0197] [Synthesis Example 1: Copolymer Solution No. 3]

[0198] In a 50-liter flask equipped with a stirring device, a thermometer, and a reflux tube, 11.62 kg of isopropyl alcohol (IPA) was charged, degassed thoroughly by nitrogen bubbling, and heated to 80°C. A mixture of 7.7 kg of methyl methacrylate, 0.7 kg of n-butyl acrylate, 5.6 kg of a monomer having a carbon-siloxane dendrimer structure represented by the following formula:

[0199] [Chemical Formula 30]

[0200]

[0201] and a mixture of 1.12 kg of 2,2'-azobis-2-methylbutyronitrile (manufactured by Fujifilm Wako Pure Chemical Corporation) and 7.42 kg of IPA were added dropwise at a constant rate over 2 hours, and finally the charging line was rinsed with 1.96 kg of IPA. After all the additions, the mixture was heated and stirred in a nitrogen atmosphere for 6 hours. The conversion rate of the polymerization was 96% as analyzed by liquid chromatography. The resulting Copolymer Solution No. 3 was a slightly yellow transparent liquid, and the viscosity measured with a rotational viscometer at room temperature was 116 mPa·s, and the copolymer concentration (= non-volatile component) was 40.0% by mass.

[0202] [Comparative Example 1]

[0203] In the pelleting process of this experimental example, 20 kg of copolymer solution No. 2 (8 kg in terms of non-volatile solid content) was continuously supplied into a twin-screw extruder at a supply rate of 5 kg / hr (= extrusion rate of 2 kg / hr). The maximum temperature inside the barrel was set at 200 °C, the temperature of the distillation section barrel near the die head was set at 100 °C, and the vacuum degree in the distillation section was set at 70 kPa. The rotational speed of the extruder was fixed at 101 rpm. After removing the solvent and volatile components inside the extruder (barrel section), the molten thermoplastic copolymer was discharged from the die head and passed through a water bath with a water temperature of 25 °C. However, since the discharged strand was very soft and thin and broke quickly, solid molded particles with a length-to-diameter ratio of less than 10 mm could not be obtained. The non-volatile component (NVC) of these poorly molded products was measured, and the result was 88.1 mass%, indicating that the organic solvent could not be sufficiently removed. Additionally, the measured Tg of the copolymer in copolymer solution No. 2 itself was 40.5 °C, which was relatively low. In the case of containing a large amount of organic solvent as described above, it was found that being too soft was also a cause of poor molding for molding / cutting into strands.

[0204] [Comparative Example 2]

[0205] In the pelleting process of this experimental example, 20 kg of copolymer solution No. 1 (8 kg in terms of non-volatile solid content) was continuously supplied into a twin-screw extruder at a supply rate of 5 kg / hr (= extrusion rate of 2 kg / hr). The maximum temperature inside the barrel was set at 200 °C, the temperature of the distillation section barrel near the die head was set at 100 °C, and the vacuum degree in the distillation section was set at 70 kPa. The rotational speed of the extruder was fixed at 101 rpm. After removing the solvent and volatile components inside the extruder (barrel section), the molten thermoplastic copolymer was extruded from the die head and passed through a water bath with a water temperature of 25 °C, thereby solidifying it. An attempt was made to cut the solidified strand with a granulator. Due to the stickiness on the surface of the strand, slight adhesion and winding of the strand on the conveyor roller were observed. Furthermore, in the granulator, since the strand itself softened and could not be cut, solid molded particles with a length-to-diameter ratio of less than 10 mm could not be obtained. The non-volatile component (NVC) of these poorly molded products was measured, and the result was 90 mass%, indicating that insufficient removal of the organic solvent was the cause of poor molding.

[0206] [Example 1]

[0207] In the pelletizing process of this experimental example, 20 kg of copolymer solution No. 1 (8 kg in terms of non-volatile solid content) was continuously supplied into the twin-screw extruder at a supply rate of 5 kg / hr (extrusion rate = 2 kg / hr). The maximum temperature in the barrel was set at 200 °C, the temperature of the barrel in the distillation section near the die head was set at 150 °C, and the vacuum degree in the distillation section was set at 70 kPa. The rotation speed of the extruder was fixed at 101 rpm. After removing the solvent and volatile components in the extruder (barrel section), the molten thermoplastic copolymer was extruded from the die head and passed through a water bath with a water temperature of 25 °C, thereby solidifying it. The solidified strands could be easily cut by a granulator and formed into a uniform shape, and solid particles (pellets) with a diameter of 4 mm and a length of 3 - 5 mm could be obtained. It should be noted that the difference from Comparative Example 2 is that in Example 1, by raising the temperature in the barrel, the organic solvent was sufficiently removed from the copolymer, and the non-volatile component (NVC) of the obtained solid particles was 99.4 mass% (refer to Table 1).

[0208] [Example 2]

[0209] Except for replacing copolymer solution No. 1 with an equal amount of copolymer solution No. 2, it was formed into a uniform shape in the same manner as in Example 1, and solid particles (pellets) with a diameter of 4 mm and a length of 3 - 5 mm could be obtained. The non-volatile component (NVC) of the obtained solid particles was 97.7 mass% (refer to Table 1).

[0210] [Example 3]

[0211] Except for replacing copolymer solution No. 1 with an equal amount of copolymer solution No. 3 and setting the temperature of the barrel in the distillation section near the die head at 100 °C, it was formed into a uniform shape in the same manner as in Example 1, and solid particles (pellets) with a diameter of 4 mm and a length of 3 - 5 mm could be obtained. The non-volatile component (NVC) of the obtained solid particles was 99.0 mass% (refer to Table 1).

[0212] Hereinafter, Table 1 summarizes the process conditions and results in Examples 1 - 3 and Comparative Examples 1 and 2. In the pelletizing process of this experimental example, it is important to sufficiently remove the organic solvent from the copolymer to avoid poor molding. In terms of the process, the barrel section of the distillation section as the solvent can be set at a high temperature, and methods such as using a low-boiling solvent (such as IPA) that is easily removed by distillation and setting the barrel section at a temperature consistent with the boiling point of the solvent can be adopted.

[0213] [Table 1]

[0214]

[0215]

[0216] [Examples 4-1 to 4-3: Evaluation of the Solubility of Pills Formed from Copolymers]

[0217] Evaluate the solubility of the pills composed of the respective copolymers obtained in Examples 1 to 3 in solvents acceptable as cosmetics (including oil agents, organic solvents, and liquid ultraviolet protection components). Specifically, add 0.5 g of each pill and 2 g of a specified solvent (oil, organic solvent) to a 20 cc vial, and leave it standing in an oven heated to 50°C for 30 minutes to confirm whether it dissolves uniformly.

[0218] As a result, for all of the following solvents, the pills of this example dissolved uniformly just by standing under the above conditions, confirming the solubility in a variety of solvents.

[0219] Evaluated solvents :

[0220] ethanol,

[0221] (decamethylcyclopentasiloxane) (DOWSIL(TM) SH 245 Fluid),

[0222] polydimethylsiloxane (DOWSIL(TM) SH 200C Fluid 2cs),

[0223] octylmethylpolysiloxane (DOWSIL(TM) FZ-3196 Fluid),

[0224] phenyltrimethylsiloxane (DOWSIL(TM) SH 556 Fluid),

[0225] isododecane (PUROLAN IDD, LANXESS Distribution GmbH),

[0226] undecane and tridecane (Cetiol(R) Ultimate, BASF Japan),

[0227] triglyceride of caprylic acid / capric acid (FineNeo-MCT, Nippon Fine Chemical),

[0228] ethylhexyl methoxycinnamate (Uvinul(R) MC 80, BASF),

[0229] butyl acetate (FUJIFILM Wako Pure Chemical Corporation)

[0230] From the above results, it can be seen that the molded solid particles (such as pellets) of the present invention, which are composed of a thermoplastic copolymer having a silicon-containing organic group in the molecule, are easily soluble in various liquid solvents for cosmetics. Therefore, the processing workability, the degree of freedom in formulation design, and the blending stability are excellent. Moreover, since they are molded solid particles without organic solvents, the possibility of fire and the safety problems related to transportation and storage are less. Also, after blending, they do not impair the reduction in the feeling of use or the touch from organic solvents. Furthermore, when formulating cosmetic raw materials, they can be dispersed or dissolved in an oil agent different from the diluent of commercially available acrylic silicone products. Even for the same oil agent, they can be formulated at a higher concentration than commercially available products, etc. It is strongly expected that the design and feeling of use of cosmetic formulations that cannot be achieved by existing products can be realized.

[0231] Symbol Explanation

[0232] 1: Hopper

[0233] 2: Insertion Pump

[0234] 3: Twin-Screw Extruder

[0235] 4: Strand Die

[0236] 5: Copolymer (material) discharged in strands

[0237] 6: Cooling Tank (Water-Cooled)

[0238] 7: Cutting Device for Pelletizing (Granulation Machine Device)

[0239] 8: Molded Solid Particles of Copolymer Molded into Pellets

[0240] Note: "Vac. and condense" in the figure refers to the distillation section in the barrel part of the twin-screw extruder that removes the solvent from the copolymer solution and concentrates the solid components.

Claims

1. A shaped solid particle, characterized in that, the shaped solid particle is composed of a copolymer having thermoplasticity, and the major axis of its particle is less than 10 mm. The copolymer is formed by copolymerizing (a1) and (a2). The (a1) is an unsaturated monomer having a radically polymerizable organic group and a silicon-containing organic group in the molecule, (a2) is different from the component (a1), and is an unsaturated monomer having a radically polymerizable vinyl group in the molecule.

2. The shaped solid particle according to claim 1, characterized in that, the shaped solid particle is one or more forms selected from pellets, tablets, short fibers, and shaped granules.

3. The shaped solid particle according to claim 1, characterized in that, the shaped solid particle has a glass transition temperature (Tg) of the copolymer having thermoplasticity in the range of 30°C to 120°C.

4. The shaped solid particle according to claim 1, characterized in that, the shaped solid particle has a silicon-containing organic group in the molecule of the copolymer having thermoplasticity, and the silicon-containing organic group has at least one structure selected from a carbosiloxane dendrimer structure and a siloxane macromonomer structure.

5. The shaped solid particle according to claim 1, characterized in that, (at least a part of the component (a1) is represented by the following formula (in the formula, Me is methyl), and is an unsaturated monomer containing a carbosiloxane dendrimer structure.

6. Use of the shaped solid particle according to any one of claims 1 to 5 as a cosmetic raw material.

7. Use of the shaped solid particle according to any one of claims 1 to 5 as a film-forming agent.

8. A cosmetic, characterized in that, the cosmetic contains the shaped solid particle according to any one of claims 1 to 5.

9. A method for manufacturing a cosmetic, characterized in that, the method for manufacturing a cosmetic has a step of dissolving or dispersing the shaped solid particle according to any one of claims 1 to 5 in a solvent acceptable for cosmetics.

10. A method for manufacturing a shaped solid particle, which manufactures the shaped solid particle according to any one of claims 1 to 5, characterized in that, it has a step of shaping and discharging a copolymer having thermoplasticity.

11. The method for manufacturing a shaped solid particle according to claim 10, characterized in that, the outlet temperature at the time of discharge is set so that the melt viscosity of the copolymer having thermoplasticity is in the range of 0.1 Pa·s to 10,000 Pa·s.

12. The method for manufacturing a shaped solid particle according to claim 10, characterized in that, the method for manufacturing the shaped solid particle is a continuous manufacturing method.

13. The method for manufacturing a shaped solid particle according to claim 10, characterized in that, the method for manufacturing the shaped solid particle has: step (I), which discharges the copolymer having thermoplasticity from a die in a strand shape; and step (II), which cuts the strand-shaped discharge obtained in step (I).

14. The method for manufacturing a shaped solid particle according to claim 13, characterized in that, Step (I) of discharging the thermoplastic copolymer in strands from the die is carried out by a single-screw or multi-screw extruder equipped with a die.

15. The method for manufacturing shaped solid particles according to claim 14, wherein: in step (I) of discharging the thermoplastic copolymer in strands from the die by a single-screw or multi-screw extruder equipped with a die, the thermoplastic copolymer is in the form of a copolymer solution dissolved in at least one organic solvent, and the temperature setting of the extruder simultaneously satisfies the following conditions: i) The outlet temperature of the die of the extruder is set to be 5 °C to 100 °C higher than the glass transition temperature (Tg) of the thermoplastic copolymer; ii) In order to carry out the operation of distilling off the organic solvent from the copolymer solution, the set temperature of the barrel part in the extruder is set in the temperature range from 60 °C lower than the boiling point of the organic solvent (in the case of multiple organic solvents, the lowest boiling point) to above the boiling point of all the organic solvents.

16. The method for manufacturing shaped solid particles according to claim 13, wherein: step (II) of cutting the strand discharge obtained in step (I) is carried out by one or more cutting devices selected from rotary blades and fixed blades.

17. The method for manufacturing shaped solid particles according to claim 10, wherein: the method for manufacturing the shaped solid particles comprises: step (III) of discharging the thermoplastic copolymer from a droplet former; and step (IV) of cooling and solidifying the discharge of step (III).

18. The method for manufacturing shaped solid particles according to claim 17, wherein: step (III) of discharging the thermoplastic copolymer from the droplet former and step (IV) of cooling and solidifying the discharge of step (III) are carried out by a melt granulation device.

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