WO2023120690A1 - 反応性基含有ポリカプロラクトン化合物、それを用いる新規シリコーンエラストマー粒子および化粧料組成物その他の用途 - Google Patents

反応性基含有ポリカプロラクトン化合物、それを用いる新規シリコーンエラストマー粒子および化粧料組成物その他の用途 Download PDF

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WO2023120690A1
WO2023120690A1 PCT/JP2022/047560 JP2022047560W WO2023120690A1 WO 2023120690 A1 WO2023120690 A1 WO 2023120690A1 JP 2022047560 W JP2022047560 W JP 2022047560W WO 2023120690 A1 WO2023120690 A1 WO 2023120690A1
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silicone elastomer
elastomer particles
group
silicone
particles
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English (en)
French (fr)
Japanese (ja)
Inventor
常仁 杉浦
万里 脇田
裕子 谷口
立易 談
康枝 神崎
敬 永山
洋 瀬戸口
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Dow Toray Co Ltd
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Dow Toray Co Ltd
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Priority to CN202280085502.1A priority Critical patent/CN118434709A/zh
Priority to US18/723,425 priority patent/US20250057754A1/en
Priority to KR1020247024422A priority patent/KR20240130102A/ko
Priority to JP2023569564A priority patent/JPWO2023120690A1/ja
Priority to EP22911392.3A priority patent/EP4455121A4/en
Publication of WO2023120690A1 publication Critical patent/WO2023120690A1/ja
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Definitions

  • the present invention provides reactive group-containing polycaprolactone compounds useful as raw materials for synthetic reactions selected from radical polymerization and hydrosilylation reactions, and methods for producing them. Furthermore, the present invention relates to novel silicone elastomer particles that have a cross-linked structure between silicon atoms derived from the reactive group polycaprolactone compound and that can impart excellent texture and feel to cosmetics. In addition, since the new silicone elastomer particles have a crosslinked structure that is active for biodegradability, the primary particles are disintegrated with the generation of non-crosslinked siloxane molecules due to decomposition reactions by microorganisms in the natural world. properties are expected, and behavior as biodegradable silicone elastomer particles is expected. Furthermore, the present invention relates to cosmetic raw materials, cosmetic compositions, organic resin additives and other uses containing the silicone elastomer particles, and methods for producing the silicone elastomer particles.
  • Silicone elastomer particles are obtained by curing addition reaction-curable silicone compositions or condensation reaction-curable silicone compositions, and their particle size and oil absorbency vary depending on the manufacturing method. It is widely used as a drug.
  • silicone particles having excellent dispersibility, high lipophilicity, and excellent storage stability have a low content of silicon-bonded hydrogen atoms per unit mass described in Patent Document 1, and hexenyl group proposed silicone particles containing an alkylene group having 4 to 20 carbon atoms obtained by curing a crosslinkable composition for forming silicone particles containing an alkenyl group having 4 to 20 carbon atoms.
  • conventional silicone elastomer particles are formed through a cross-linking reaction of organopolysiloxane raw materials by a hydrosilylation reaction or the like, but the cross-linked structure is chemically stable. If it is released into the environment, it cannot be denied the possibility that it will continue to remain in the natural world without being decomposed for at least a short period of time, just like so-called microplastics.
  • the present applicants have proposed a silicone elastomer having a structure crosslinked by divalent organic groups having a partial structure formed by radical polymerization of vinyl acetate described in Patent Document 2. Suggest particles.
  • the silicone elastomer particles can be expected to have a high degree of biodegradability, and compared to conventional silicone elastomer particles, their aggregation over time is suppressed, giving a smaller average secondary particle size.
  • silicone elastomer particles that are expected to have a high degree of biodegradability and that can impart a texture equivalent to or better than that of existing silicone elastomer particles when used as a raw material for cosmetics.
  • Patent Document 3 discloses an (AB)n-type block copolymer containing a polycaprolactone structure and a polysiloxane structure.
  • Non-Patent Documents 1 to 3 disclose that a polycaprolactone compound having a polyol terminal structure is reacted with butyroyl chloride or the like. and all of its terminal structures are (meth)acrylic terminal groups, and are capable of forming silicone elastomer particles by a cross-linking reaction between polysiloxane structures or a radical polymerization reaction with a (meth)acrylic group-containing organopolysiloxane. , do not disclose a (meth)acrylic-modified polycaprolactone compound of a specific structure.
  • the present invention has been made to solve the above problems, and when blended in a cosmetic composition or the like, it is possible to achieve a feel and feeling of use equal to or greater than that of conventional silicone elastomer particles, and biodegradability.
  • the present invention provides silicone elastomer particles having a crosslinked structure active against , a reactive group-containing polycaprolactone compound having a specific structure useful as a raw material for the synthesis reaction thereof, and methods for producing them.
  • a further object of the present invention is to provide a raw material for cosmetics, an organic resin additive, and other uses that are excellent in feeling of use, etc., by using the silicone elastomer particles.
  • Another object of the present invention is to provide a cosmetic composition containing the silicone elastomer particles and having an excellent feeling of use.
  • the present invention can be expected to have biodegradability in addition to performance equal to or greater than that of conventional silicone elastomer particles.
  • n is a number ranging from 1 to 5
  • R 1 is a carbonyl group or a divalent linkage containing one carbonyl group a reactive group-containing polycaprolactone compound having two or more modified polycaprolactone structures having a (meth)acrylic end group and an alkenyl end group ⁇ represented by R 2 is a hydrogen atom or a methyl group
  • the above-mentioned reactive group means one or more reactive functional groups selected from (meth)acrylic modifying groups and alkenyl modifying groups having radical polymerizability or hydrosilylation reactivity, in other words, Accordingly, the reactive group-containing polycaprolactone compounds according to the present invention include both (meth)acrylic-modified polycaprolactone compounds and alkenyl-modified polycaprolactone compounds.
  • the silicone elastomer particles obtained by using the reactive group-containing polycaprolactone compound according to the present invention as a raw material can realize a touch and feel equal to or greater than those of conventional silicone elastomer particles when blended into a cosmetic composition or the like.
  • silicone elastomer particles according to the present invention it is possible to provide cosmetic raw materials, organic resin additives, and other uses containing them.
  • a cosmetic composition containing the silicone elastomer particles according to the present invention can provide a cosmetic with excellent feeling of use.
  • the radical polymerization or hydrosilylation reaction of the reactive group-containing polycaprolactone compound of the present invention occurs between at least two silicon atoms constituting the polyorganosiloxane chain in the silicone elastomer particles. It has a structure crosslinked by a divalent organic group having a partial structure formed by the divalent organic group having the partial structure is active in a biodegradable reaction and biodegradable In a sexual environment, the crosslinked structure formed between silicon atoms in the silicone elastomer particles is at least partially cleaved, and the primary particles of the silicone elastomer particles are disintegrated with the generation of non-crosslinked polyorganosiloxane.
  • the silicone elastomer particles according to the present invention are expected to be biodegradable and can reduce risks to the global environment. It can be appealed that it is an eco-friendly material that can be used with a considerable sense of security.
  • Silicone elastomer particle No. 1 according to the present invention 1 (Example 5) observed with a digital microscope (device name: model number VH-6000 manufactured by Keyence). Silicone elastomer particle No. 1 according to the present invention. 3 (Example 7) was observed with a digital microscope (device name: Keyence model number VH-6000). 2 shows the enzymatic decomposition test results of silicone elastomer particles of Examples 8, 7 and 12 according to the present invention and an existing silicone elastomer product (comparative experiment).
  • (meth)acryl means “acryl or methacryl", and when expressed as "(meth)acrylic modification", the modifying group is an acrylic modifying group and a methacrylic modifying group. may be one or both of Similarly, the term “(meth)acryloxy” means “methacryloxy or acryloxy”, and “(meth)acryloxy group-containing organic group” is one or both of a methacryloxy group-containing organic group and an acryloxy group-containing organic group. means that
  • the reactive group-containing polycaprolactone compound according to the present invention is one or more compounds selected from (meth)acrylic-modified polycaprolactone compounds and alkenyl-modified polycaprolactone compounds, and is a reactive raw material for the novel silicone elastomer particles according to the present invention. designed as a divalent divalent having a specific partial structure between at least two silicon atoms constituting a polyorganosiloxane chain within the silicone elastomer particles by its radical polymerization reaction and hydrosilylation reaction to silicon-bonded hydrogen atoms It is a component that provides a structure crosslinked by organic groups.
  • the reactive group-containing polycaprolactone compound of the present invention has the following structural formula (1) in its molecule: (1) It is characterized by having two or more modified polycaprolactone structures having Since such a compound has two or more (meth)acrylic modifying groups or alkenyl modifying groups at its terminals, a hydrosilylation reaction or a radical polymerization reaction forms a crosslinked structure within the silicone elastomer particles to obtain silicone elastomer particles. When used as a raw material for cosmetics, it is expected that the crosslinked structure formed between the two silicon atoms will not impair the feeling of use or feel, and that the crosslinked structure will be biodegradable.
  • the reactive group-containing polycaprolactone compound according to the present invention is designed as a cross-linking agent between silicon atoms in silicone elastomer particles. has a relatively small number of repeating units, it has the advantage of not significantly impairing the touch and feeling of use derived from the organopolysiloxane main chain of the silicone elastomer particles.
  • R2 is a hydrogen atom or a methyl group, which gives an acrylic modifying group, a methacrylic modifying group and an alkenyl modifying group, respectively.
  • the reactive group-containing polycaprolactone compound of the present invention is a cross-linking agent between at least two silicon atoms, at least Must have two. Therefore, the (meth)reactive group-containing polycaprolactone compound of the present invention must have 2 or more of the above structures in its molecule, and may have 2 to 4 structures. This is because a polycaprolactone compound having a polyol (alcoholic) terminal hydroxyl group, which serves as a precursor of the structure, is relatively readily available as a reactive production raw material on an industrial scale.
  • the number of repeating units of caprolactone units in each structure is relatively small, and the sum of the number of repeating units of caprolactone units in the molecule is in the range of 2 to 20. is preferably in the range of 2.5 to 15, and may be in the range of 3.0 to 12.
  • the number of repeating units of the caprolactone unit in the reactive group-containing polycaprolactone compound molecule exceeds the above upper limit, the properties derived from the polycaprolactone structure are strongly reflected in the obtained silicone elastomer particles, and the feel and use of the cosmetic, etc. It may adversely affect your sense of well-being.
  • the reactive group-containing polycaprolactone compound of the present invention may be a compound represented by one or more structural formulas selected from the following structural formulas (1-1) to (1-5). .
  • Each compound has 2, 3 and 4 modified polycaprolactone structures represented by the following structural formula (1).
  • Structural formula (1-1) (1-1) Structural formula (1-2): (1-2) Structural formula (1-3): (1-3) Structural formula (1-4): (1-4) Structural formula (1-5): (1-5)
  • Ra is the same group as described above.
  • m and n are each independently a number ranging from 1 to 5, m+n is a number ranging from 2 to 20, and m+n is a number ranging from 2.5 to 15. and may be a number in the range of 3-10.
  • w, x, y, and z are each independently a number ranging from 1 to 5, x+y+z is a number ranging from 3 to 20, and w+x+y+z may be a number in the range of 4-20.
  • x+y+z may be a number in the range of 3-7 and w+x+y+z may be a number in the range of 4-10.
  • m and n are each independently a number ranging from 1 to 5, m+n is a number ranging from 2 to 20, and m+n is a number ranging from 2.5 to 15. and may be a number in the range of 3-10.
  • m and n are each independently a number ranging from 1 to 5, m+n is a number ranging from 2 to 20, and m+n is a number ranging from 2 to 15. and may be a number in the range of 2-10.
  • a+b may be a number in the range 1-500 and a+b may be a number in the range 2-350.
  • Such a reactive group-containing polycaprolactone compound is a precursor polycaprolactone compound having a polyol terminal structure, It can be obtained by reacting a (meth)acryloyl chloride compound and an alkenoyl chloride compound in the presence of a basic catalyst. It can be obtained by reacting in the presence of a catalyst.
  • the reactive group-containing polycaprolactone compound according to the present invention has the following structural formula (1′) in its molecule: (1') (Wherein, n is a number in the range of 1 to 5.)
  • a polycaprolactone compound having two or more polycaprolactone structures having a polyol terminal structure with Cl—C( ⁇ O)—R 1 —CR 2 ⁇ CH 2 (R 1 is a chemical bond between CH and C( ⁇ O) or a divalent organic group having 1 to 20 carbon atoms, and R 2 is (a hydrogen atom or a methyl group) can be obtained by reacting a (meth)acryloyl chloride compound and an alkenoyl chloride compound represented by a hydrogen atom or a methyl group in the presence of a basic catalyst; can be obtained by reacting below.
  • the reaction ratio of the polycaprolactone compound, the (meth)acryloyl chloride compound, the alkenoyl chloride compound, and the vinylsilazane is the amount (moles) of the polyol terminal structure (—OH) of the polycaprolactone compound to the (meth)acryloyl chloride compound. and the alkenoyl chloride compound and vinylsilazane are in an amount (number of moles) of 1 equivalent to a small excess.
  • the basic catalyst that can be used for the reaction is not particularly limited, but alkali metal salts such as inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate; It may be an amine compound such as triethylamine, pyridine, dimethylaminopyridine, or a nitrogen-containing heterocyclic compound.
  • alkali metal salts such as inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate; It may be an amine compound such as triethylamine, pyridine, dimethylaminopyridine, or a nitrogen-containing heterocyclic compound.
  • Usable acidic catalysts are not particularly limited, but may be trifluoromethanesulfonic acid, sulfuric acid, hydrochloric acid, and the like.
  • the reaction may be carried out in an organic solvent, and usable organic solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; formamide, acetamide, N-methyl-2-pyrrolidone (NMP), N, N - amides such as dimethylformamide, dimethylacetamide; halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, benzotrifluoride, hexafluoro-2-propanol; dimethyl sulfoxide (DMSO ), diethyl sulfoxide, sulfoxides such as benzylphenyl sulfoxide; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran (THF), dio
  • one or more polymerization inhibitors are present in the system.
  • the reaction conditions should be appropriately selected depending on the amount of synthesis, the reaction apparatus, etc., but the mixed solution containing the above polycaprolactone compound, basic catalyst and optional polymerization inhibitor is stirred under inert gas flow such as nitrogen. It is preferable to add the (meth)acryloyl chloride compound, the alkenoyl chloride compound and the vinylsilazane dropwise while adding the (meth)acryloyl chloride compound. After completion of the reaction, it is particularly preferable to separate the target reactive group-containing polycaprolactone compound and vinylsilazane and distill off the unnecessary organic solvent under reduced pressure for purification.
  • silicone elastomer particles The silicone elastomer particles of the present invention, particularly their uses including cosmetic raw materials, their production methods, and cosmetic compositions and organic resins (including paints and coating agents) containing them are described in detail below.
  • the silicone elastomer particles of the present invention at least two silicon atoms in the silicone elastomer particles are (i) a radical polymerization reaction of the (meth)acrylic-modified polycaprolactone compound, which is a reactive group-containing polycaprolactone compound; and (ii) the silicon atom of the alkenyl-modified polycaprolactone compound, which is a reactive group-containing polycaprolactone compound. It is characterized by having a structure crosslinked by one or more reactions selected from hydrosilylation reactions to bonded hydrogen atoms.
  • the silicone elastomer particles of the present invention are obtained by a cross-linking reaction selected from radical polymerization reaction and hydrosilylation reaction, and have the following structural characteristics.
  • [Hydrosilylation Reactive Silicone Elastomer Particles] Obtained by subjecting an organopolysiloxane ( organohydrogenpolysiloxane) having three or more silicon-bonded hydrogen atoms in the molecule to a hydrosilylation reaction with an alkenyl-modified polycaprolactone compound in the presence of a hydrosilylation reaction catalyst, At least two silicon-silicon spaces in the silicone elastomer particles have a crosslinked structure formed by a hydrosilylation reaction (addition reaction) between an alkenyl-terminal modified group of the alkenyl-modified polycaprolactone compound and a silicon-bonded hydrogen atom. characterized by
  • the silicone elastomer particles of the present invention are further — (R 12 SiO) n — (Wherein, R 1 is an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a halogen atom and having 1 to 20 carbon atoms, an aryl group having 6 to 22 carbon atoms or a hydroxyl group, and n is 1 to numbers in the range of 1000) It is preferable to further have a polyorganosiloxane structure represented by. This is a linear polysiloxane structure derived from component (A), which will be described later, and imparts appropriate hardness and flexibility to the silicone elastomer particles.
  • each R 1 is preferably a methyl group or a phenyl group, and n is preferably a number in the range of 50-800, more preferably in the range of 75-750.
  • the silicone elastomer particles according to the present invention are preferably obtained by curing cross-linkable silicone emulsified particles through a cross-linking reaction.
  • the silicone elastomer particles of the present invention are defined by their manufacturing process, (A) at least one reactive organopolysiloxane selected from the following components (a1) and (a2); (a1) organopolysiloxane having at least three (meth)acryloxy group-containing organic groups selected from methacryloxy group-containing organic groups and acryloxy group-containing organic groups in the molecule, and (a2) silicon in the molecule (B) an organopolysiloxane having at least three atom-bonded hydrogen atoms; (B) the reactive group-containing polycaprolactone compound (C); Crosslinkable silicone emulsified particles obtained by emulsifying in water a crosslinkable silicone composition capable of being crosslinked by one or more reactions selected from a polymerization reaction and a hydrosilylation reaction to form silicon-bonded hydrogen
  • silicone elastomer particles obtained through such a production process may further improve the appearance, spreadability, and feel of cosmetics, especially when used as raw materials for cosmetics.
  • problems of the present invention can be solved more favorably.
  • one of the preferred modes for realizing the technical effects of the present invention can and is suitable to be defined by the manufacturing process.
  • the silicone elastomer particles according to the present invention are not particularly limited in terms of their average primary particle diameter, but they impart a smooth feel and a comfortable feel to cosmetics, do not cause defects in appearance, etc., and are raw materials for cosmetics.
  • the average particle size measured by a laser diffraction scattering method is preferably in the range of 0.5 to 20 ⁇ m, more preferably in the range of 0.5 to 15 ⁇ m. more preferred.
  • the particle size of the silicone elastomer particles can be controlled according to the pulverization/classification process of the crosslinkable silicone emulsified particles and the obtained silicone elastomer particles.
  • Examples of the shape of the silicone elastomer particles according to the present invention include spherical, spherical, elliptical, and irregular shapes, with spherical and spherical shapes being particularly preferred.
  • Spherical silicone elastomer particles can be easily obtained by preparing an aqueous suspension, which will be described later, and drying it using a vacuum dryer, a hot air circulating oven, or a spray dryer.
  • the crosslinkable silicone composition used for forming the silicone elastomer particles when cured into a sheet, it has a hardness of 10 to 80 as measured by a JIS A hardness tester specified in JIS K6301. A range is preferred.
  • the JIS-A hardness of the rubber sheet measured by curing the crosslinkable silicone composition into a sheet is within the above range, the obtained silicone elastomer particles have sufficiently suppressed cohesion, flowability and dispersion.
  • JIS-A hardness it is possible to design to some extent the usability, feel, and handling workability when blended in cosmetics. or predictable, and can improve stress relaxation properties when incorporated into organic resins.
  • silicone elastomer particles according to the present invention are used as raw materials for cosmetics or stress relaxation agents for organic resins
  • silicone elastomer particles having a JIS-A hardness in the range of 30 to 80, particularly 50 to 80 are used. is particularly preferred.
  • the silicone elastomer particles of the present invention have a structure in which part or all of the surface is coated with one or more selected from organopolysiloxane resin, silica, and other silicone elastomer particles.
  • the coating may be expected to further reduce cohesiveness, control oil absorption, improve texture, and the like.
  • the silicone elastomer particles of the present invention may have a microporous mesoporous structure.
  • the silicone elastomer particles of the present invention may contain an oil that is liquid at 40°C.
  • the oil agent can be easily incorporated into the silicone elastomer particles by emulsifying them together in the crosslinkable silicone composition described below. improvement, etc. can be expected.
  • the silicone elastomer particles of the present invention have a C2-C20 silyl group formed by a hydrosilylation reaction involving a C2-C20 alkenyl group between at least two silicon atoms constituting the particles. It may further have a structure crosslinked by alkylene groups. These structures can be easily realized by using an alkenyl group-containing organopolysiloxane, an organohydrogenpolysiloxane, and a hydrosilylation-reactive catalyst in combination. In addition, for example, when an alkenyl group having 4 or more carbon atoms such as a hexenyl group is used, further reduction in cohesiveness, control of oil absorption, improvement in feel, etc. can be expected due to the coexistence of the silalkylene structure. There is however, when biodegradability is the main objective, the silicone elastomer particles of the present invention preferably do not substantially contain a structure containing a silalkylene group.
  • the silicone elastomer particles of the present invention are prepared by cross-linking a cross-linkable silicone composition containing the following components by one or more reactions selected from radical polymerization reactions and hydrosilylation reactions to silicon-bonded hydrogen atoms. It can be obtained by (curing).
  • A at least one reactive organopolysiloxane selected from the following components (a1) and (a2); (a1) organopolysiloxane having at least three (meth)acryloxy group-containing organic groups selected from methacryloxy group-containing organic groups and acryloxy group-containing organic groups in the molecule, and (a2) silicon in the molecule
  • B) Polycaprolactone compound containing reactive groups
  • C One or more curing agents selected from radical polymerization initiators and hydrosilylation reaction catalysts
  • the cross-linking (curing) reaction is one or more reactions selected from radical polymerization reaction and hydrosilylation reaction, and these reactions may proceed simultaneously, but from the viewpoint of reaction control, either one is selected. to form silicone elastomer particles. That is, the composition may be a composition comprising the following two reaction types and components.
  • [Radical polymerization reactive composition for forming silicone elastomer particles] (a1) organopolysiloxane having at least one (meth)acryloxy group-containing organic group selected from methacryloxy group-containing organic groups and acryloxy group-containing organic groups in the molecule, A crosslinkable silicone composition comprising (B1) the (meth)acrylic-modified polycaprolactone compound, which is a reactive group-containing polycaprolactone compound, and (c1) a radical polymerization initiator.
  • composition for forming hydrosilylation-reactive silicone elastomer particles (a2) an organopolysiloxane having at least three silicon-bonded hydrogen atoms in the molecule (B2) the above alkenyl-modified polycaprolactone compound which is a reactive group-containing polycaprolactone compound, and (c2) crosslinking containing a hydrosilylation reaction catalyst A reactive silicone composition.
  • Component (a1) is an organopolysiloxane having at least three (meth)acryloxy group-containing organic groups in the molecule, and its structure is not particularly limited, and may be linear, cyclic, network, or partially branched linear. Although it may be one or more types of structures selected from the shape, a straight-chain organopolysiloxane is particularly preferable.
  • the viscosity of the component (a) is preferably such that the crosslinkable composition can be dispersed in water. Specifically, at 25° C., it is preferably in the range of 20 to 100,000 mPa ⁇ s, particularly preferably in the range of 20 to 10,000 mPa ⁇ s.
  • the content of dimethylsiloxane units represented by the formula: -(CH 3 ) 2 SiO- in component (a1) is It is preferably a linear organopolysiloxane that accounts for 90 mol % or more of all siloxane units.
  • cyclic or chain organopolysiloxanes with a low degree of polymerization degree of polymerization: 3 to 20 are removed in advance by stripping or the like from component (a1).
  • the silicone elastomer particles according to the present invention when placed in a biodegradable environment, the silicone elastomer particles are disintegrated due to cleavage of the crosslinked structure. , easily decomposes into non-crosslinkable and linear organopolysiloxane, and has the advantage of easily reducing environmental load and environmental risk.
  • component (a1) Since component (a1) forms a crosslinked structure by radical reaction with component (B1), it must have at least three (meth)acryloxy group-containing organic groups in the molecule on average. If the molecule has an average of 2 or less (meth)acryloxy group-containing organic groups, a sufficient crosslinked structure may not be formed, and practical silicone elastomer particles may not be obtained.
  • R 2 is an alkylene group having 1 to 20 carbon atoms or a divalent
  • a linking group where p and q are numbers in the range of 1 to 20
  • R3 is a hydrogen atom or a methyl group.
  • the alkylene group represented by R 2 in the formula may industrially be an alkylene group having 2 to 10 carbon atoms, exemplified by a propylene group, a butylene group, a hexylene group and the like.
  • the divalent linking group represented by (CH 2 ) p -Si(CH 3 ) 2 -O-Si(CH 3 ) 2 -(CH 2 ) q is a divalent linking group having a siloxane converter structure. Industrially, a linking group in which p and q are each independently a number of 3 to 6 is exemplified.
  • Component (a1) is preferably a linear organopolysiloxane represented by the following structural formula.
  • each R 11 is independently an unsubstituted or halogen-substituted alkyl group having 1 to 20 carbon atoms (e.g., methyl group), an aryl group having 6 to 22 carbon atoms ( For example, a phenyl group, etc.) or a hydroxyl group, industrially preferably a methyl group or a phenyl group.
  • R a is the above-mentioned (meth)acryloxy group-containing organic group, and is particularly preferably the above-mentioned alkylene group or (meth)acryloxy group bonded to a silicon atom via a divalent linking group having a siloxane converter structure.
  • R is independently a group represented by R 11 or R a .
  • m is a number of 1 or more
  • n is a number of 1 or more.
  • component (a) contains at least three (meth)acryloxy group-containing organic groups represented by Ra in the molecule
  • R a the linear organopolysiloxane represented by the above structural formula
  • R a the linear organopolysiloxane represented by the above structural formula
  • It may be an organopolysiloxane having (meth)acryloxy group-containing organic groups, and containing at least three (meth)acryloxy group-containing organic groups in the molecule, and is preferred.
  • m+n is the degree of siloxane polymerization of the linear organopolysiloxane molecule excluding the terminal siloxane structure. is preferably in the range of 10-800, more preferably in the range of 20-600, and particularly preferably in the range of 30-500. Further, it is particularly preferable that the viscosity of the component (a) is 20 to 10,000 mPa ⁇ s at 25°C.
  • Component (a2) is an organopolysiloxane component that is crosslinked by component (B2) through a hydrosilylation reaction, and is characterized by having at least three silicon-bonded hydrogen atoms in the molecule.
  • the binding position in the inside is not particularly limited.
  • component (a2) examples include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl groups. is preferred.
  • the molecular structure of the component (a2) organohydrogenpolysiloxane is exemplified by any one of linear, branched, and branched cyclic or a combination of one or more thereof.
  • the number of silicon-bonded hydrogen atoms in one molecule is the average value of all molecules.
  • the component (a2) is a straight-chain organopolysiloxane (organohydrogenpolysiloxane)
  • the silicone elastomer particles according to the present invention when placed in a biodegradable environment, the crosslinked structure is cleaved to form a silicone elastomer.
  • the particles When the particles are pulverized, they easily decompose into non-crosslinked and straight-chain organopolysiloxanes, which has the advantage of easily reducing environmental load and environmental risks.
  • the viscosity of component (a2) at 25° C. is 1 to 1,000 mPa ⁇ s, preferably 5 to 500 mPa ⁇ s. This is because when the viscosity of component (b) at 25° C. is less than 1 mPa ⁇ s, component (a2) easily volatilizes from the crosslinkable composition containing it, and when it exceeds 1,000 mPa ⁇ s, the The curing time of the crosslinkable composition containing the component (a2) may be prolonged, or it may cause poor curing.
  • such component (a2) is not particularly limited, for example, a dimethylsiloxane/methylhydrogensiloxane copolymer having both ends trimethylsiloxy group-blocked, a dimethylsiloxane/methylhydrogensiloxane copolymer having both ends dimethylhydrogensiloxy group-blocked, Examples include a coalescence, dimethylhydrogensiloxy group-blocked dimethylpolysiloxane at both ends, methylhydrogenpolysiloxane blocked at both ends with trimethylsiloxy groups, cyclic methylhydrogenpolysiloxane, and cyclic methylhydrogensiloxane/dimethylsiloxane copolymer.
  • H/Alk which is the reaction ratio in () is in the range of 0.7 to 1.2.
  • the lower limit of H/Alk is preferably 0.80 or more, 0.85 or more, 0.90 or more, or 0.95 or more, and the upper limit is 1.15 or less, more preferably 1.10 or less. , 1.05 or less. If the upper limit of H/Alk exceeds the above value, unreacted silicon-bonded hydrogen atoms tend to remain after the reaction.
  • Component (B) is a reactive group-containing polycaprolactone compound (specifically, a compound selected from the aforementioned (meth)acrylic-modified polycaprolactone compound and alkenyl-modified polycaprolactone compound), and the silicone elastomer particles according to the present invention. and a radically polymerizable monomer (monomer) component that itself forms a polymer or copolymer structure by radical polymerization.
  • a reactive group-containing polycaprolactone compound specifically, a compound selected from the aforementioned (meth)acrylic-modified polycaprolactone compound and alkenyl-modified polycaprolactone compound
  • silicone elastomer particles according to the present invention.
  • a radically polymerizable monomer (monomer) component that itself forms a polymer or copolymer structure by radical polymerization.
  • the crosslinked portion does not significantly impair the texture and usability of the resulting silicone elastomer particles, and is active against biodegradation reactions,
  • the crosslinked structure formed between silicon atoms in the silicone elastomer particles is at least partially cleaved, and the primary particles of the silicone elastomer particles are disintegrated with the generation of non-crosslinked polyorganosiloxane.
  • the component (A) is a linear polyorganosiloxane as described above, the biodegradation reaction facilitates the disintegration of the silicone elastomer particles into linear polyorganosiloxane molecules, resulting in macroplastics.
  • the component (A) is a linear polyorganosiloxane as described above, the biodegradation reaction facilitates the disintegration of the silicone elastomer particles into linear polyorganosiloxane molecules, resulting in macroplastics.
  • it is not a solid powder with a minute particle size, but is decomposed to a minute liquid component, so it is difficult to cause problems of bioaccumulation in the food chain and accumulation/deposition in the environment, and it is safe for the global environment. Low impact or load is expected.
  • the amount of component (B) used must be selected as follows according to the type of component (A) and the cross-linking reaction for obtaining the silicone elastomer particles of the present invention.
  • the content of component (B1) relative to the content of (meth)acryloxy group-containing organic groups in component (a1) is preferably in the range of 0.5 to 30, preferably in the range of 1 to 20, more preferably in the range of 3 to 15, and particularly preferably in the range of 5 to 10.
  • the amount of the component (B) used is within the above range, a crosslinked structure derived from the (meth)acrylic-modified polycaprolactone compound having a moderate average length between the polyorganosiloxane structures can be obtained, so that the particles have a moderate hardness.
  • Component (C) is a curing agent, which is selected from (c1) radical polymerization initiators and (c2) hydrosilylation reaction catalysts depending on the selection of component (A) and the reaction system.
  • Component (c1) is a radical initiator, and is a component that accelerates the radical polymerization reaction or radical copolymerization reaction of the above components (a1) and (B1).
  • Conventionally known compounds are used, specifically, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), and 2,2'-azobis Azo compounds such as (2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, and tert-hexylperoxy- Examples include organic peroxides such as 2-ethylhexanoate; and persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate. These radical initiators may be used singly or in combination of two or more.
  • the amount of the radical initiator as component (c1) to be used is preferably in the range of 0.1 to 5 parts by mass per 100 parts by mass of the total of components (a1) and (B1).
  • the component (c1) is a water-soluble persulfate such as potassium persulfate
  • the crosslinkable silicone emulsified particles obtained by emulsifying the crosslinkable silicone composition by radical polymerization reaction in water are crosslinked in water. , it has the advantage of being extremely easy to add and react.
  • the timing of adding component (c1) to the crosslinkable composition can be selected according to the method of forming the silicone elastomer particles, and may be added in advance to the composition. may be supplied from different spray lines, added to one of them and mixed during spraying. It is preferable that the silicone elastomer particles in the present invention pass through an aqueous suspension formed through emulsification in water. You may add the containing emulsion to water.
  • a chain transfer agent may optionally be added during the polymerization reaction of the crosslinkable silicone composition.
  • the chain transfer agent include mercapto compounds such as 2-mercaptoethanol, butylmercaptan, n-dodecylmercaptan, 3-mercaptopropyltrimethoxysilane, and polydimethylsiloxane having a mercaptopropyl group; Halides such as carbon chloride, butyl bromide, and 3-chloropropyltrimethoxysilane are included.
  • a modified polycaprolactone compound having a (meth)acrylic terminal modification group and an alkenyl terminal modification group at one end in order to adjust the hardness of the particles during the polymerization reaction of the crosslinkable silicone composition.
  • a (meth)acrylic one end-modified product include Plaxel FM1 manufactured by Daicel Corporation.
  • Component (c2) is a hydrosilylation reaction catalyst, and is an addition reaction between a carbon-carbon double bond contained in a (meth)acrylic terminal group present in the crosslinkable composition and a silicon-bonded hydrogen atom ( hydrosilylation reaction).
  • a preferred hydrosilylation reaction catalyst is a hydrosilylation reaction catalyst containing a platinum-based metal, and specifically includes chloroplatinic acid, alcohol-modified chloroplatinic acid, an olefin complex of chloroplatinic acid, and a complex of chloroplatinic acid and ketones.
  • platinum-based catalysts include carbonyl complexes, methyl methacrylate resins containing these platinum-based catalysts, thermoplastic organic resin powders such as polycarbonate resins, polystyrene resins, and silicone resins.
  • a complex of chloroplatinic acid and divinyltetramethyldisiloxane a complex of chloroplatinic acid and tetramethyltetravinylcyclotetrasiloxane, a platinum divinyltetramethyldisiloxane complex, a platinum tetramethyltetravinylcyclotetrasiloxane complex, etc.
  • Platinum alkenylsiloxane complexes are preferably used.
  • non-platinum metal catalysts such as iron, ruthenium, and iron/cobalt may be used.
  • the amount of component (c2) added to the crosslinkable composition may be a catalytic amount, and usually, the amount of platinum-based metal contained in component (c2) is 1 to 1 with respect to the total mass of the crosslinkable composition.
  • An amount in the range of 1,000 ppm is preferred, and an amount in the range of 5 to 500 ppm is more preferred.
  • the amount of platinum metal in the silicone elastomer particles may be reduced by the method proposed by the present inventors in JP-A-2014-122316.
  • the timing of adding component (c2) to the crosslinkable composition can be selected according to the method of forming the silicone elastomer particles, and may be added to the composition in advance. may be supplied from different spray lines, added to one of them and mixed during spraying.
  • the oil-containing silicone elastomer particles of the present invention preferably pass through an aqueous suspension that is formed through emulsification in water. An emulsion containing the ingredients may be added to the water.
  • the above crosslinkable silicone composition may contain a curing retarder typified by a hydrosilylation reaction inhibitor.
  • a curing retarder typified by a hydrosilylation reaction inhibitor.
  • Such curing retarders are exemplified by acetylenic compounds, enyne compounds, organic nitrogen compounds, organic phosphorus compounds, and oxime compounds.
  • Specific compounds include 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, 2-phenyl-3 - butyn-2-ol, and alkyne alcohols such as 1-ethynyl-1-cyclohexanol (ETCH); 3-methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, enyne compounds such as 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 3-methyl-3-penten-1-yne, and 3,5-dimethyl-3-hexene-1-yne; 1-ethynyl- 1-trimethylsiloxycyclohexane, bis(2,2-dimethyl-3-butynoxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, 1,3,5,7-te
  • the crosslinkable silicone composition described above may contain one or more polymerization inhibitors from the standpoint of preventing unintended side reactions.
  • one or more selected from hindered phenol-based polymerization inhibitors, hydroquinone-based polymerization inhibitors, and catechol-based polymerization inhibitors may be included.
  • the amount used can be appropriately selected, but the total concentration of the polymerization inhibitor is preferably 50 ppm by mass or less, and 30 ppm by mass or less, relative to the sum of the components (A) to (C). is more preferable.
  • the crosslinkable silicone composition may contain components other than the above components within the range that does not impair the technical effects of the present invention.
  • aliphatic hydrocarbons such as n-hexane, cyclohexane and n-heptane
  • aromatic hydrocarbons such as toluene, xylene and mesitylene
  • ethers such as tetrahydrofuran and dipropyl ether
  • ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone.
  • Organic solvents such as phenolic, quinone, amine, phosphorus, phosphite, sulfur, or thioether antioxidants; triazole or benzophenone light stabilizers; phosphate esters, Flame retardants such as halogen-based, phosphorus-based, or antimony-based; one or more antistatic agents consisting of cationic surfactants, anionic surfactants, or nonionic surfactants; dyes; pigments, etc. be able to.
  • Organic solvents such as phenolic, quinone, amine, phosphorus, phosphite, sulfur, or thioether antioxidants; triazole or benzophenone light stabilizers; phosphate esters, Flame retardants such as halogen-based, phosphorus-based, or antimony-based; one or more antistatic agents consisting of cationic surfactants, anionic surfactants, or nonionic surfactants; dyes; pigments, etc. be able to.
  • the silicone elastomer particles of the present invention optionally have a structure in which (a) part or all of the surface is coated with one or more selected from organopolysiloxane resin, silica, and other silicone elastomer particles; (c) a structure containing an oil agent that is liquid at 40°C; and (d) a structure crosslinked by silalkylene groups having 2 to 20 carbon atoms, and any structure that provides these structures. Combinations of ingredients may also be used. Furthermore, in consideration of biodegradability, it may contain a biodegradable oil such as olive oil.
  • the hardness of silicone elastomer particles cannot be directly measured, the hardness can be indirectly measured by curing the crosslinkable silicone composition used to form the silicone elastomer particles.
  • the crosslinkable silicone composition can be cured into a sheet without being emulsified in water, and the hardness of the silicone elastomer sheet can be measured using a JIS A hardness tester specified in JIS K6301. is.
  • the hardness of the silicone elastomer according to the present invention varies depending on the type of crosslinkable silicone composition, the amount of components (a)/(b) used, and the crosslink density, but should be in the range of 10 to 80. is preferred. Other preferred hardnesses are as described above.
  • the crosslinkable silicone emulsified particles obtained by emulsifying the crosslinkable silicone composition used for forming the above silicone elastomer particles in water are cured in the presence of (C) a curing agent. and obtaining spherical silicone elastomer particles.
  • the silicone elastomer particles according to the present invention can be prepared using a production method including the following steps (I) and (II), and is preferred.
  • the crosslinkable silicone composition used to form the silicone elastomer particles can be uniformly mixed using a mechanical force such as a mixer.
  • a mechanical force such as a mixer.
  • silicone elastomer particles can be obtained by emulsifying and curing the crosslinkable silicone composition in an aqueous surfactant solution.
  • the particle size can be easily adjusted by adjusting the emulsion particle size.
  • surfactants include nonionic, anionic, cationic, betaine, and water-soluble polymers such as polyvinyl alcohol.
  • the particle size of the resulting silicone elastomer particles varies depending on the type and content of the surfactant.
  • the amount of the surfactant added is preferably in the range of 0.5 to 50 parts by weight per 100 parts by weight of the crosslinkable silicone composition.
  • an emulsifier to uniformly disperse the crosslinkable silicone composition in water in the form of crosslinkable silicone emulsified particles.
  • the emulsifier include a homomixer, a paddle mixer, a Henschel mixer, a homodisper, a colloid mill, a propeller stirrer, a homogenizer, an in-line continuous emulsifier, an ultrasonic emulsifier, and a vacuum kneader.
  • the aqueous dispersion of the crosslinkable silicone emulsified particles prepared by the above method is heated or allowed to stand at room temperature to cure the crosslinkable silicone emulsified particles in the aqueous dispersion, yielding silicone elastomer particles.
  • the heating temperature is preferably 100° C. or less, particularly preferably 10 to 95° C., from the viewpoint of hydrosilylation reactivity or radical polymerization reactivity.
  • Methods for heating the aqueous dispersion containing crosslinkable silicone emulsified particles include, for example, a method of directly heating the aqueous dispersion and a method of adding the aqueous dispersion to hot water.
  • the cross-linking reaction cures the liquid cross-linkable silicone emulsified particles in water to form an aqueous dispersion of silicone elastomer particles.
  • the obtained silicone elastomer particles of the present invention can be used as they are as an aqueous dispersion (aqueous suspension).
  • aqueous suspension aqueous suspension
  • it may be used in the form of this water-based suspension as a raw material for cosmetics, etc., and is preferred.
  • the silicone elastomer particles of the present invention can be easily and uniformly dispersed by blending as an aqueous dispersion containing the silicone elastomer particles of the present invention. performance and usability of
  • the silicone elastomer particles of the present invention can be isolated by removing water from the aqueous dispersion of silicone elastomer particles.
  • methods for removing water from the aqueous dispersion include drying using a vacuum dryer, a hot air circulation oven, and a spray dryer.
  • the heating/drying temperature of the spray dryer should be appropriately set based on the heat resistance of the silicone elastomer particles, the cross-linking temperature, and the like.
  • the silicone elastomer particles obtained in this manner can be recovered by a cyclone, bag filter or the like.
  • the dispersion may be concentrated by a method such as heat dehydration, filtration separation, centrifugation, or decantation, or if necessary, the dispersion may be washed with water.
  • the silicone elastomer particles of the present invention may be surface-treated as necessary, which may further improve the anti-agglomeration effect of the silicone elastomer particles of the present invention. Further, the surface may be treated with other known hydrophilic treatment agents or hydrophobic treatment agents.
  • the obtained silicone elastomer particles may be further coated with inorganic fine particles such as silica, silicone resins, etc. on part or all of their surfaces, as described above.
  • the obtained silicone elastomer particles may be crushed or pulverized using a mechanical force as necessary, and may be classified using a known technique.
  • the silicone elastomer particles of the present invention are useful as a raw material for cosmetics. Remarkably excellent handling workability, storage stability, and blending stability in systems.
  • the silicone elastomer particles of the present invention are superior to conventional silicone particles in terms of feel and touch upon use, have a high degree of freedom in formulation design, and when blended in cosmetics, absorb oily raw materials over time and increase. When applied to the skin or hair, it suppresses the oiliness and stickiness of cosmetics, imparts a smooth spread, a soft feel, and a moist feeling, and blends well with the skin.
  • the silicone elastomer particles of the present invention when used in combination with an ultraviolet protection ingredient, the silicone elastomer particles of the present invention have the UV protection effect without impairing the texture and usability of the cosmetic compared to other powders and existing silicone elastomer particles. can be improved.
  • the silicone elastomer particles of the present invention have performance equal to or greater than that of conventionally known silicone elastomer particles, and are active against biodegradation reactions, and in a biodegradable environment, the silicon atoms in the silicone elastomer particles The crosslinked structure formed between them is at least partially cleaved, and the primary particles of the silicone elastomer particles have the property of being crushed with the generation of polyorganosiloxane with a non-crosslinked structure. is a small material. Furthermore, it can be used in place of conventionally known silicone elastomer particles, and is extremely versatile.
  • the cosmetic composition containing the silicone elastomer particles of the present invention is not particularly limited in its type, but it can be used as cleansing cosmetics such as soaps, body shampoos, and facial cleansing creams; Basic cosmetics; Base makeup cosmetics such as face powder and foundation; Eyebrow cosmetics such as lipstick, blush, eye shadow, eyeliner and mascara; Makeup cosmetics such as manicure; Hair cosmetics such as hair tonics and hair dyes; aromatic cosmetics such as perfumes and eau de colognes; toothpaste; of special cosmetics are exemplified.
  • Examples of dosage forms of these cosmetic compositions include aqueous liquids, oily liquids, milky lotions, creams, foams, semisolids, solids, and powders.
  • these cosmetic compositions can also be used by spraying.
  • the content of the silicone elastomer particles is preferably in the range of 0.5 to 99.0% by mass, particularly 1.0 to 95% by mass. % is preferred. This is because if the content of the silicone elastomer particles exceeds the upper limit of the above range, the effect of the cosmetic is lost. This is because it becomes difficult to improve the usability of the product.
  • silicone elastomer particles of the present invention are disclosed in JP-A-07-316014, International Patent Publication WO2017/191798, JP-A-02-243612, JP-A-2011-105663, JP-A-2011-168634, JP-A-2011. -102354 and Japanese Patent Laid-Open No. 2014-122316, for cosmetic compositions containing silicone particles (silicone rubber powder, etc.) or silicone composite particles (in particular, formulation examples), these silicone-based particles can be used by replacing a part or all of, and the feeling of use and production efficiency of the cosmetic compositions proposed in these patent documents may be further improved.
  • examples of cosmetic compositions containing silicone particles (silicone rubber powder, etc.) or silicone composite particles that can be blended with the silicone elastomer particles of the present invention are not limited to the above.
  • a formulation may be designed in which part or all of the silicone particle component of is replaced with the silicone elastomer particles of the present invention by the general technique of those skilled in the art.
  • silicone elastomer particles of the present invention can be applied by replacing some or all of these silicone-based particles with respect to the uses and formulations of the cosmetic compositions disclosed in the above patent documents and the like, and Their use is included within the scope of the present invention.
  • the silicone elastomer particles of the present invention are prepared by selecting the same method and quantitative range as those disclosed in International Patent Publication WO2017/191798, and using a cosmetic medium (aqueous medium or oily medium), an oily medium (oil agent , including volatile oils), water, colorants, pigments, UV protection ingredients, alcohols, water-soluble polymers, film-forming agents, oils, oil-soluble gelling agents, organic modified clay minerals, surfactants, resins, Salts, moisturizers, preservatives, antibacterial agents, antioxidants, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, skin-beautifying ingredients (whitening agents, cell activators, rough skin improvers, blood circulation promoters, skin astringent and antiseborrheic agents), vitamins, amino acids, nucleic acids, hormones, clathrate compounds, etc., physiologically active substances, active pharmaceutical ingredients, fragrances and other optional ingredients may be used in combination, and is preferred.
  • a cosmetic medium aqueous medium or oily medium
  • the silicone elastomer particles of the present invention are equivalent or superior to conventionally known silicone particles, silsesquioxane-coated silicone composite particles, and oil-containing silicone particles. Because of its excellent properties, dispersibility and high oil absorption properties, (1) Cosmetic compositions and formulations containing an oily medium such as an oil agent (oily cosmetic raw materials) (2) Cosmetic compositions and formulations containing a lipophilic UV protection component (e.g., octyl paramethoxycinnamate, etc.) (3) ) It is possible to realize a particularly suitable appearance, feeling of use, etc. in cosmetic compositions and formulations containing inorganic powders such as colorants or pigments. These specific formulations will be described in further detail in the Examples and thereafter.
  • an oily medium such as an oil agent (oily cosmetic raw materials)
  • Cosmetic compositions and formulations containing a lipophilic UV protection component e.g., octyl paramethoxycinnamate, etc.
  • silicone elastomer particles of the present invention can be easily designed into water-based dispersions, water-based cosmetic compositions and formulations are also excellent in formulation design flexibility and blending stability, and have a favorable feeling of use. can be realized. These specific formulations will be described in further detail in the Examples and thereafter.
  • the cosmetic of the present invention can be easily produced by simply homogeneously mixing the above-described cosmetic raw material of the present invention with other cosmetic raw materials.
  • various mixing devices and kneading devices that are commonly used in the production of cosmetics can be used. Examples of such devices include homomixers, paddle mixers, Henschel mixers, homodispers, colloid mixers, propeller stirrers, homogenizers, in-line continuous emulsifiers, ultrasonic emulsifiers, and vacuum kneaders.
  • the silicone elastomer particles of the present invention have the properties described above, they are extremely useful as an additive for organic resins. Specifically, the silicone elastomer particles of the present invention are excellent in uniform dispersibility in organic resins and, if desired, in stress relaxation properties and the like. remarkably superior. In addition, members, coatings, or coatings made by curing organic resins containing the silicone elastomer particles have improved flexibility (including the softness of the coating layer), durability, and adhesion and conformability to substrates. Because of its excellent flexibility and thermal shock resistance, it is extremely useful as a highly functional organic resin, paint or coating agent for use in electronic materials.
  • Suitable examples of the organic resin containing the silicone elastomer particles of the present invention include curable organic resin compositions and thermoplastic resins.
  • curable resins are suitable for electronic materials such as semiconductor substrates. More specifically, curable organic resin compositions include phenol resins, formaldehyde resins, xylene resins, xylene-formaldehyde resins, ketone-formaldehyde resins, furan resins, urea resins, imide resins, melamine resins, alkyd resins, unsaturated Polyester resins, aniline resins, sulfone-amide resins, silicone resins, epoxy resins, copolymer resins of these resins are exemplified, and two or more of these curable resins can be combined.
  • the curable resin is preferably at least one selected from the group consisting of epoxy resins, phenol resins, imide resins, and silicone resins. Any compound containing a glycidyl group or an alicyclic epoxy group can be used as the epoxy resin.
  • epoxy resin dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphtholaralkyl type epoxy resin, polyvinylphenol type epoxy resin, diphenylmethane type epoxy resin, diphenylsulfone type epoxy resin, triphenolalkane type epoxy resin Resins, cresol-naphthol cocondensation type epoxy resins, bisphenylethylene type epoxy resins, fluorene type epoxy resins, stilbene type epoxy resins, spirocumaron type epoxy resins, norbornene type epoxy resins, terpene type epoxy resins, phenolcyclohexane type epoxy resins, halogens
  • modified epoxy resins imide group-containing epoxy resins, maleimide group-containing epoxy resins, allyl group-modified epoxy resins, and silicone-modified epoxy resins.
  • phenol resin polyvinylphenol type, phenol novolak type, naphthol type, terpene type, phenoldicyclopentadiene type, phenol aralkyl type, naphthol aralkyl type, triphenol alkane type, dicyclopentadiene type, cresol/naphthol Condensed type and xylene/naphthol co-condensed type are exemplified.
  • silicone resins include epoxy-modified silicone resins obtained by reacting epoxy resins with silanol groups or silicon-bonded alkoxy groups in silicone resins.
  • Examples of the curing mechanism of such a curable resin include a thermosetting type, a high-energy ray-curing type such as ultraviolet rays or radiation, a moisture-curing type, a condensation reaction-curing type, and an addition reaction-curing type.
  • the properties of such a curable resin at 25° C. are not limited, and may be liquid or solid that softens when heated.
  • the organic resin containing the silicone elastomer particles of the present invention may contain other optional components such as curing agents, curing accelerators, fillers, photosensitizers, higher fatty acid metal salts, ester waxes, and plasticizers. can be done.
  • the curing agent include organic acids such as carboxylic acids and sulfonic acids and their anhydrides; organic hydroxy compounds; organosilicon compounds having a silanol group, an alkoxy group, or a halogeno group; primary or secondary amino compounds; Two or more of these may be combined.
  • the curing accelerator includes tertiary amine compounds, organic metal compounds such as aluminum and zirconium; organic phosphorus compounds such as phosphine; other heterocyclic amine compounds, boron complex compounds, organic ammonium salts, organic sulfonium salts, Examples include organic peroxides and hydrosilylation catalysts.
  • examples of fillers include glass fiber, asbestos, alumina fiber, ceramic fiber containing alumina and silica, boron fiber, zirconia fiber, silicon carbide fiber, metal fiber, polyester fiber, aramid fiber, nylon fiber, and phenol fiber.
  • fibrous fillers such as natural animal and plant fibers; fused silica, precipitated silica, fumed silica, calcined silica, zinc oxide, calcined clay, carbon black, glass beads, alumina, talc, calcium carbonate, clay, aluminum hydroxide, Granular fillers such as barium sulfate, titanium dioxide, aluminum nitride, silicon carbide, magnesium oxide, beryllium oxide, kaolin, mica, and zirconia are exemplified, and two or more of these may be combined.
  • an epoxy resin it is particularly preferred to contain an amine curing agent.
  • the silicone elastomer particles of the present invention may be blended as additives in thermoplastic resins other than those described above, and may be used as modifiers of physical properties such as surface lubricants and stress relaxation agents, or optical properties such as light scattering agents. It can be used as a modifier.
  • the type of thermoplastic resin is not particularly limited, and may be polycarbonate resin, polyester resin, polyether resin, polylactic acid resin, polyethylene, polypropylene, polyolefin resin such as ethylene-propylene copolymer, polystyrene.
  • the silicone resin-coated silicone elastomer particles of the present invention can be uniformly dispersed in these thermoplastic resins (including masterbatch) by using a mixing device such as a twin-screw/single-screw extruder or a kneader mixer, and a film can be obtained. It may be used after being molded into a desired shape such as a shape.
  • the amount of the silicone elastomer particles of the present invention to be added can be appropriately selected according to the physical properties required for the organic resin. It may be in the range of 0.5 to 10 parts by mass. If the amount of the particles added is less than the above lower limit, performance such as stress relaxation properties for resins and the like may be insufficient, and the flexibility and thermal shock resistance of the obtained organic resin cured product may be reduced. This is because the subsequent thermal shock resistance tends to decrease. On the other hand, if the above upper limit is exceeded, the viscosity of the organic resin or paint/coating agent after blending may increase and handling workability may decrease, and the mechanical properties of the resulting cured organic resin tend to decrease. It is from.
  • silicone elastomer particles of the present invention when blended with an organic resin, they exhibit excellent stress relaxation effects.
  • a copper foil with a filler particle-containing resin layer for a printed wiring board having a resin layer containing the silicone elastomer particles of the present invention may be formed and used for copper clad laminates (CCL).
  • Paints and coating agents containing the silicone elastomer particles of the present invention are exemplified by room temperature curing type, room temperature drying type and heat curing type.
  • the amount of the silicone elastomer particles of the present invention to be added can be appropriately selected according to the physical properties required for the paint/coating agent. It is preferably in the range of 0.1 to 150 parts by mass, more preferably in the range of 0.1 to 100 parts by mass, particularly 0.1 to 50 parts by mass, based on 100 parts by mass of the solid content. Within the range of parts by mass, preferably within the range of 0.1 to 20 parts by mass. If the amount of the particles added is less than the above lower limit, performance such as matte properties, adhesion, and stress relaxation properties for the coating film may be insufficient. ⁇ The coating agent may thicken and the handling workability may decrease.
  • Paints and coating agents containing the silicone elastomer particles of the present invention include alcohols such as methanol and ethanol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate and cellosolve acetate; amide; olefins such as hexane, heptane, octane; organic solvents such as aromatic hydrocarbons such as toluene and xylene; known inorganic fillers such as reinforcing silica, organic fillers, curing accelerators, silane coupling agents, It may contain a pigment such as carbon black, a dye, an antioxidant, a thickener composed of a polymer compound, a flame retardant, and a weather resistance imparting agent.
  • a pigment such as carbon black, a dye, an antioxidant, a thickener composed of a polymer compound, a flame retardant, and a weather
  • the silicone elastomer particles of the present invention have a crosslinked structure formed between silicon atoms within the silicone elastomer particles in a biodegradable environment. is at least partially cleaved, and the primary particles of the silicone elastomer particles are expected to be biodegradable, with the generation of non-crosslinked polyorganosiloxane. For this reason, it can be used as an "eco-friendly" cosmetic raw material and industrial raw material with low environmental impact and low environmental risk in response to regulations such as microplastics. It can be expected that it will be able to appeal that it is an "eco-friendly" material with biodegradability.
  • Reactive group-containing polycaprolactone compound according to the present invention (specifically, a compound selected from the above-mentioned (meth)acrylic-modified polycaprolactone compound and alkenyl-modified polycaprolactone compound), silicone elastomer particles using the same as a raw material, and production thereof
  • a compound selected from the above-mentioned (meth)acrylic-modified polycaprolactone compound and alkenyl-modified polycaprolactone compound silicone elastomer particles using the same as a raw material, and production thereof
  • Viscosities in the examples are values at 25°C.
  • the properties of each silicone particle were measured as follows. Unless otherwise specified in the examples and the like, silicone particles are a general term for particles made of cured silicone (cured silicone particles), and do not include emulsions.
  • Examples 1 to 6 (meth)acrylic-modified polycaprolactone compound No. 1 to 3 and alkenyl-modified polycaprolactone compound Nos. Synthesis of 4 to 6]
  • Synthesis examples of (meth)acrylic-modified polycaprolactone compounds according to examples of the present invention are shown below by reacting a polycaprolactone compound having a polyol terminal structure with a specific (meth)acryloyl chloride compound. These components are the components used as raw materials for the silicone elastomer in Example 5 and subsequent examples, which will be described later.
  • Example 1 (Meth)acrylic-modified polycaprolactone compound No. 1]
  • Example 2 (Meth)acrylic-modified polycaprolactone compound No. 2] 17.92 parts by weight of chloroform, 10.27 parts by weight of triethylamine, 0.05 parts by weight of MEHQ, 9.02 parts by weight of acryloyl chloride, water
  • Example 4 alkenyl-modified polycaprolactone compound No. 4
  • a four-necked separable flask was charged with 27.36 parts by weight of trade name Placcel 305 (manufactured by Daicel Corporation, triol type polycaprolactone, molecular weight: 550), 27.36 parts by weight of chloroform, and 14.41 parts by weight of potassium carbonate.
  • 30.86 parts by weight of undecenoyl chloride was added dropwise while stirring at 200 rpm and N2 gassing. It was carried out while cooling in a water bath so that the heat generation did not exceed 30°C. After the dropwise addition was completed, the mixture was stirred for 24 hours, and the by-product was filtered.
  • Example 5 alkenyl-modified polycaprolactone compound No. 5
  • Placcel 210 manufactured by Daicel Corporation, diol type polycaprolactone, molecular weight: 1000
  • 42.35 parts by weight of vinylsilazane 0.02 parts by weight of trifluoromethanesulfonic acid was added dropwise while heating to 50° C., stirring, and N2 gassing. The reaction was carried out at 50°C for 4 hours.
  • 3.00 parts by weight of Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.: synthetic hydrotalcite) was added and stirred for 1 hour.
  • Example 6 alkenyl-modified polycaprolactone compound No. 6
  • 35.12 parts by weight of Pluronic L-31 manufactured by Adeka Co., Ltd., diol type polyoxyethylene-polyoxypropylene copolymer, molecular weight: about 1100
  • 49.70 parts by weight of chloroform were placed in a four-necked separable flask. , and 0.22 parts by weight of triazabicyclodecene were charged. 14.58 parts by weight of ⁇ -caprolactone was added dropwise with N2 bubbling. Stir at room temperature for 4 hours. After the reaction, 0.38 parts by weight of benzoic acid was added.
  • Examples 7 to 12 show production examples of silicone elastomer particles obtained using the above (meth)acrylic-modified polycaprolactone compound as a raw material.
  • Comparative Example 1 is a non-silicone polymer particle obtained using only a (meth)acrylic-modified polycaprolactone compound as a raw material.
  • Example 7 Silicone elastomer particle No. 1 (hydrosilylation reactive type)] (a2-1) component organohydrogenpolysiloxane and (b4) alkenyl-modified polycaprolactone compound No. 4 were uniformly mixed at room temperature at a mass ratio of 37:63. Next, this composition was dispersed in an aqueous solution of 0.5 parts by mass of polyoxyethylene alkyl (C12-14) ether and 30 parts by mass of pure water at 25° C., and was uniformly emulsified by a colloid mill. An emulsion was prepared by diluting with 526 parts by mass of water.
  • an isopropyl alcohol solution of chloroplatinic acid (in this composition, the amount of platinum metal is 10 ppm by mass) is added to the emulsion as an aqueous dispersion with polyoxyethylene alkyl (C12-14) ether and pure water. After stirring, this emulsion was allowed to stand at 50° C. for 4 hours to prepare a uniform aqueous suspension of elastomer particles. Next, this water-based suspension was filtered, and the residue was dried in an oven at 50° C. for 5 hours. got 1. The average primary and secondary particle sizes of the obtained silicone elastomer particles were 4.03 ⁇ m and 15.3 ⁇ m, respectively. An electron micrograph thereof is shown in FIG.
  • Example 8 Silicone elastomer particle no. 2 (radical polymerization type)] (a1-1) component methacrylic-modified silicone polymer and (b1) (meth)acrylic-modified polycaprolactone compound No. 1 were uniformly mixed at room temperature at a mass ratio of 30:70, and olive oil (manufactured by Summit Oil Co., Ltd.) was added in an amount of 20% of the total composition and mixed. Next, this composition was dispersed in an aqueous solution containing 0.27 parts by mass of Gohsenol EG-05C and 0.53 parts by mass of Gohsenol EG-18P in an aqueous solution of 46 parts by mass of pure water at 25°C.
  • Example 9 Silicone elastomer particle No. 3 (radical polymerization type)] (a1-1) component methacrylic-modified silicone polymer and (b2) (meth)acrylic-modified polycaprolactone compound No. 2 at a mass ratio of 30:70 at room temperature. Silicone elastomer particles No. 1 were prepared in the same manner as in Example 8 except for the above. got 3. The average primary and secondary particle sizes of the obtained silicone elastomer particles were 3.43 ⁇ m and 31.1 ⁇ m. An electron micrograph thereof is shown in FIG.
  • Example 10 Silicone elastomer particle No. 4 (radical polymerization type)] (a2-1) component methacrylic-modified silicone polymer and (b3) (meth)acrylic-modified polycaprolactone compound No. 3 were uniformly mixed at room temperature at a mass ratio of 30:70. Otherwise, the procedure of Example 8 was repeated to obtain silicone elastomer particles. The average primary and secondary particle sizes of the obtained silicone elastomer particles were 4.42 ⁇ m and 336 ⁇ m.
  • Example 11 Silicone elastomer particle No. 5 (hydrosilylation reactive type)] Organohydrogenpolysiloxane as component (a1-1) and (b5) alkenyl-modified polycaprolactone compound no. 5 were uniformly mixed at room temperature in a mass ratio of 18.7:81.3. Silicone elastomer particles No. 2 were obtained in the same manner as in Example 7 except for the above. Got 5. The average primary and secondary particle sizes of the obtained silicone elastomer particles were 3.73 ⁇ m and 18.5 ⁇ m.
  • Example 12 Silicone elastomer particle No. 6 (hydrosilylation reactive type)] Organohydrogenpolysiloxane as component (a1-1) and (b6) alkenyl-modified polycaprolactone compound No. 6 were uniformly mixed at room temperature at a mass ratio of 15:85. Silicone elastomer particles No. 2 were obtained in the same manner as in Example 7 except for the above. got 6. The average primary and secondary particle sizes of the obtained silicone elastomer particles were 0.95 ⁇ m and 30.2 ⁇ m.
  • Examples 9 and 10 Comparative Example 2
  • the feeling of use of loose powders containing silicone elastomer particles having the compositions shown in Table 3 below was comparatively evaluated by panelists. (tactile evaluation)
  • the smoothness of the samples applied to the inside of the forearms of 18 panelists was evaluated according to the criteria shown in Table 2 below.
  • the loose powder using the silicone elastomer particles of the present invention (Example 1, hydrosilylation-reactive type) has good slip properties, unlike the loose powder using other particles (Comparative Example 1). Then it was evaluated.
  • the water-in-oil type sunscreen agent using silicone elastomer particle No. 1 (Example 5) of the present invention uses Comparative Example 5 that does not contain elastomer particles and other particles (Comparative Example 4). Unlike conventional sunscreens, it spreads well, has a smooth and moist feeling, and was evaluated as being less squeaky. Furthermore, it was evaluated that it gave a better touch than the existing product (Comparative Example 5). In addition, Example 11 containing the silicone elastomer particles of the present invention was able to significantly improve the SPF value and PA value compared to sunscreens containing other particles without impairing the feeling of use. .
  • Type XIII lipase derived from bacteria of the genus Pseudomonas was mixed with 0.1 M phosphate buffered saline (pH 7.4) to prepare an enzyme solution of 8 U/mL. 1 mL of the resulting enzyme solution was added to each tube to prepare test specimens. The specimen was placed in an oven at 37°C and tested for up to 96 hours while exchanging the enzyme every 24 hours. After a given time, each sample was removed, rinsed with water, dried overnight, and then dried in a vacuum oven. The weight of the sample after absolute drying was measured, and the weight reduction rate was defined as the decomposition rate. The enzymatic degradation test (test time-degradation rate %) is shown in FIG.
  • Silicone elastomer particles Nos. 1 and 6 of Examples 7 and 12 have a crosslinked structure of polycaprolactone having alkenyl groups and organohydrogenpolysiloxane having hydrogen atoms bonded to silicon atoms in the presence of a hydrosilylation catalyst.
  • Silicone elastomer particle No. 2 of Example 8 has a structure crosslinked by (meth)acryl-modified siloxane and polycaprolactone having (meth)acryl-modified groups in the presence of a radical polymerization catalyst.
  • silicone elastomer particles according to these examples decreased in weight over time in the presence of the enzyme, and are therefore presumed to have degradability.
  • the silicone elastomer particles according to Examples 8 and 12 both exhibit a high decomposition rate exceeding 9% after 96 hours, and the silicone elastomer particles according to the Examples of the present application are biodegradable. It is highly expected.
  • the elastomer particles obtained by hydrosilylating alkenyl-modified siloxane and organohydrogenpolysiloxane do not have enzymatically decomposable groups like polyester, and no weight loss was observed even in the presence of enzymes. Presumably not biodegradable.
  • the decomposition rates of the silicone elastomer particles according to the examples and the existing silicone elastomer products after 96 hours show a clear and significant difference, and the silicone elastomer particles according to the present invention have performance equal to or higher than that of existing products. It is strongly suggested that in addition to the advantages in terms of touch and touch, high biodegradability, which has been difficult to achieve with existing silicone elastomer products, has been achieved.

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PCT/JP2022/047560 2021-12-24 2022-12-23 反応性基含有ポリカプロラクトン化合物、それを用いる新規シリコーンエラストマー粒子および化粧料組成物その他の用途 Ceased WO2023120690A1 (ja)

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US18/723,425 US20250057754A1 (en) 2021-12-24 2022-12-23 Reactive group-including polycaprolactone compound, novel silicone elastomer particles in which same is used, cosmetic composition, and other application
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US20250263521A1 (en) * 2022-09-09 2025-08-21 Dow Silicones Corporation ELASTOMER WITH C-O-Si LINKAGES BETWEEN POLYESTER BACKBONE AND CROSSLINKER

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US20250263521A1 (en) * 2022-09-09 2025-08-21 Dow Silicones Corporation ELASTOMER WITH C-O-Si LINKAGES BETWEEN POLYESTER BACKBONE AND CROSSLINKER
US12441846B2 (en) * 2022-09-09 2025-10-14 Dow Silicones Corporation Elastomer with C—O—Si linkages between polyester backbone and crosslinker
WO2025142785A1 (ja) * 2023-12-26 2025-07-03 ダウ・東レ株式会社 架橋部に親水性基を有する生分解性シリコーンエラストマー粒子および化粧料組成物その他の用途

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