Polycarbonate compound containing reactive group, novel silicone elastomer particles using same, cosmetic composition, and other uses

Abstract

Provided are: a polycarbonate compound containing a reactive group, which is capable of forming silicone elastomer particles by a hydrosilylation reaction and a radical polymerization reaction; and a method for producing the polycarbonate compound. Also provided are silicone elastomer particles using the compound as a starting material, uses thereof, and a method for producing the silicone elastomer particles. Provided are: a polycarbonate compound containing a reactive group; novel silicone elastomer particles which have a cross-linked structure between silicon atoms derived from the compound and which are capable of imparting excellent tactile sensation and use sensation to cosmetics; and uses of these. The reactive group-containing polycarbonate compound has two or more modified polycarbonate structures in the molecule represented by structural formula (1) (in the formula, x and y are each a number in the range of 0-18, n is a number in the range of 0-30, and Ra is a reactive group selected from the group consisting of a (meth) acryloyl terminal group and an alkenyl terminal group having 2-20 carbon atoms). # imgabs0 #

Description

Technical Field

[0001] The present invention provides a polycarbonate compound having a reactive group and a method for producing the same. The polycarbonate compound having a reactive group has a specific modified polycarbonate structure containing a reactive group selected from (meth)acryloyl end groups and alkenyl end groups in the molecule, and can form organosilicon elastomer particles through hydrosilylation reaction and radical polymerization reaction. Further, the present invention relates to a novel organosilicon elastomer particle having an inter-silicon atom crosslinked structure derived from the polycarbonate compound having a reactive group, and capable of imparting excellent touch and usability to cosmetics. In addition, since the novel organosilicon elastomer particle has an active crosslinked structure for biodegradability, in nature, through degradation reactions by microorganisms and the like, it can be expected that the primary particles are broken with the generation of non-crosslinked structure siloxane molecules, and its behavior as a biodegradable organosilicon elastomer particle can be expected. Further, the present invention also relates to a cosmetic raw material, a cosmetic composition, other uses of an organic resin additive containing the organosilicon elastomer particle, and a method for producing the organosilicon elastomer particle. Background Art

[0002] Organosilicon elastomer particles are obtained by curing a curable organosilicon composition through an addition reaction or a condensation reaction, and although their particle size and oil absorption vary depending on the production method, they are widely used as cosmetic raw materials or stress relievers for thermoplastic resins. For example, as organosilicon particles having excellent dispersibility, high lipophilicity, and excellent storage stability, the present applicant has proposed the organosilicon particles described in Patent Document 1. The content of hydrogen atoms bonded to silicon atoms per unit mass of the organosilicon particles is small, and the organosilicon particles containing an alkenyl having 4 to 20 carbon atoms such as hexenyl are formed by curing a crosslinkable composition, and contain an alkylene having 4 to 20 carbon atoms.

[0003] On the other hand, the present applicant has noticed an inherent problem in existing organosilicon elastomer particles. That is, although existing organosilicon elastomer particles are formed through a crosslinking reaction of an organopolysiloxane raw material based on a hydrosilylation reaction or the like, this crosslinked structure is chemically stable. Assuming that these organosilicon elastomer particles are released into the natural world, like so-called microplastics, it is undeniable that there is a possibility that they remain undegraded and continue to remain in the natural world at least for a short period of time. Therefore, in order to reduce the risk to the global environment, there may be a potential demand in the market for organosilicon elastomer particles having properties that can smoothly replace or substitute existing organosilicon elastomer particles and that can be expected to have a high degree of biodegradability.

[0004] In view of the potential market demand involved, the applicants in this case proposed silicone elastomer particles having a structure crosslinked by a divalent organic group having a partial structure formed by radical polymerization of vinyl acetate. These silicone elastomer particles can be expected to have a high degree of biodegradability, and compared with existing silicone elastomer particles, their coagulation over time is suppressed, a smaller average secondary particle size is imparted, and thus they have excellent dispersibility, successfully achieving excellent characteristics such as handling workability, storage stability, and formulation stability in the system as cosmetic raw materials and the like.

[0005] However, on the basis of being used as a cosmetic raw material, there is still a need for silicone elastomer particles that can impart a touch feeling equal to or further excellent than that of existing silicone elastomer particles and can be expected to have a high degree of biodegradability.

[0006] On the other hand, polycarbonate compounds are synthesized from dimethyl carbonate and diols having hydroxyl groups at both ends, and in addition to being a film-forming material, they are also expected to have properties as biodegradable raw materials. In addition, in Patent Document 3, although a (meth)acrylate functional group is introduced into the polycarbonate structure, there is neither description nor suggestion, nor disclosure of silicone elastomer particles having this polycarbonate structure.

[0007] On the other hand, Non-Patent Documents 1 to 2 disclose the reaction of a polycarbonate compound having a polyol terminal structure with acryloyl chloride or the like, but do not disclose a (meth)acryloyl group-modified polycarbonate compound having a specific structure that can form silicone elastomer particles through a crosslinking reaction between polysiloxane structures or a radical polymerization reaction with an organopolysiloxane containing a (meth)acryloyl group.

[0008] Prior Art Documents

[0009] Patent Documents

[0010] Patent Document 1: International Patent Publication WO2017 / 191798

[0011] Patent Document 2: International Patent Publication WO2022 / 138346

[0012] Patent Document 3: Japanese Unexamined Patent Publication No. 2006-70145

[0013] Non-Patent Documents

[0014] Non-Patent Document 1: Branching by reactive end groups. II. Synthesis, branching, and melt rheology of (meth)acrylate / p-t-butylphenol-coterminated bisphenol a polycarbonates (by M. J. Marks et al., Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 38, 2340-2351 (2000)

[0015] Non-Patent Document 2: Synthesis, crosslinking, and abrasion and weathering properties of (meth)acrylate-terminated bisphenol A polycarbonates (by M. J. Marks et al., Journal of Applied Polymer Science / Volume 73, Issue 5, P663-675) Summary of the Invention

[0016] Problems to be Solved by the Invention

[0017] The present invention is completed to solve the above problems, and provides an organosilicon elastomer particle, a polycarbonate compound containing reactive groups having a specific structure used as a raw material for its synthesis reaction, and a manufacturing method thereof. When the organosilicon elastomer particle is formulated into a cosmetic composition or the like, it can achieve a touch and usability equal to or better than those of existing organosilicon elastomer particles, and has an active crosslinked structure for biodegradability.

[0018] Furthermore, the object of the present invention is to provide a cosmetic raw material, an organic resin additive, and other uses with excellent usability by using the organosilicon elastomer particle. In addition, the object of the present invention is to provide a cosmetic composition containing the organosilicon elastomer particle and having excellent usability and the like.

[0019] Furthermore, the object of the present invention is to provide an organosilicon elastomer particle, its synthetic material, and uses thereof. The organosilicon elastomer particle not only has properties equal to or better than those of existing organosilicon elastomer particles, but also can be expected to have biodegradability, thus reducing the potential risk to the global environment, can be used continuously and stably industrially, and can promote an environmentally friendly material with biodegradability to demanders and general consumers who attach importance to the impact on the global environment.

[0020] Solution for solving problems

[0021] In order to solve the above problems, the present inventors conducted in-depth research and found that by having two or more in the molecule represented by the following structural formula (1):

[0022] [Chemical formula 1]

[0023]

[0024] {In the formula, x and y are numbers in the range of 0 to 18, n is a number in the range of 0 to 30, and Ra is -C(=O)-R 1 -CR 2 =CH2 (R 1 is a chemical bond between CH and C(=O) or a divalent organic group having 0 to 20 carbon atoms, and R 2 is a hydrogen atom or a methyl group)} a polycarbonate compound containing a reactive group having a modified polycarbonate structure and a raw material for its organosilicon elastomer particles can solve the above problems, and thus the present invention has been completed. It should be noted that the above reactive group refers to one or more reactive functional groups selected from (meth)acryloyl terminal groups and alkenyl terminal groups having radical polymerizability or hydrosilylation reactivity. In other words, the polycarbonate compound containing a reactive group involved in the present invention includes both (meth)acryloyl-modified polycarbonate compounds and alkenyl-modified polycarbonate compounds.

[0025] Similarly, the present inventors found that the above problems can be solved by organosilicon elastomer particles, a cosmetic raw material containing the organosilicon elastomer particles, an organic resin additive, a cosmetic, or an organic resin, and thus the present invention has been completed. The organosilicon elastomer particles have a structure in which at least two silicon atoms in the organosilicon elastomer particles are crosslinked by one or more reactions selected from the radical polymerization reaction and hydrosilylation reaction of the polycarbonate compound containing a reactive group. More specifically, it is selected from the radical polymerization reaction of (meth)acryloyl-modified polycarbonate compounds and the hydrosilylation reaction of alkenyl-modified polycarbonate compounds with hydrogen atoms bonded to silicon atoms.

[0026] Effects of the invention

[0027] The silicone elastomer particles obtained from the polycarbonate compound containing reactive groups involved in the present invention can achieve a touch and usability equal to or better than those of existing silicone elastomer particles when formulated into cosmetic compositions or the like. Further, by using the silicone elastomer particles involved in the present invention, a cosmetic raw material, an organic resin additive, and other uses containing the silicone elastomer particles can be provided. Further, a cosmetic composition containing the silicone elastomer particles involved in the present invention can provide a cosmetic having excellent usability and the like.

[0028] Further, the silicone elastomer particles involved in the present invention have a structure crosslinked by a divalent organic group, but the divalent organic group having this partial structure is active in biodegradation reactions, and is designed such that in a biodegradable environment, at least part of the crosslinked structure formed between silicon atoms in the silicone elastomer particles is broken, and the primary particles of the silicone elastomer particles have the property of being broken along with the generation of a polyorganosiloxane having a non-crosslinked structure. The divalent organic group has a partial structure formed between at least two silicon atoms constituting a polyorganosiloxane chain in the silicone elastomer particles by radical polymerization or hydrosilylation reaction of a polycarbonate compound containing reactive groups. Therefore, it is expected that the silicone elastomer particles involved in the present invention have biodegradability, and in addition to being able to reduce the risk to the global environment, they can also promote to those who pay attention to the impact on the global environment and general consumers that these are environmentally friendly materials that can be used with a considerable sense of security. Detailed Description

[0029] In the present specification, the term “(meth)acryloyl” means “acryloyl or methacryloyl”, and in the case of being expressed as “(meth)acryloyl-modified group”, it means that the modified group (including the terminal group) can be one or both of an acrylate-modified group and a methacryloyl-modified group. Similarly, the term “(meth)acryloyloxy” means “methacryloyloxy or acryloyloxy”, and “organic group containing (meth)acryloyloxy” means that it can be one or both of an organic group containing methacryloyloxy and an organic group containing acryloyloxy.

[0030] [Polycarbonate Compound Containing Reactive Groups]

[0031] Specifically, the polycarbonate compound containing a reactive group involved in the present invention is at least one compound selected from (meth)acryloyl-modified polycarbonate compounds and alkenyl-modified polycarbonate compounds, and is designed as a reactive raw material for the novel silicone elastomer particles involved in the present invention. Moreover, through its radical polymerization reaction and hydrosilylation reaction with a hydrogen atom bonded to a silicon atom, a structure is provided within the silicone elastomer particles in which at least two silicon atoms constituting the polyorganosiloxane chain are crosslinked by a divalent organic group having a specific partial structure.

[0032] Specifically, the polycarbonate compound containing a reactive group of the present invention is characterized in that it has two or more in the molecule represented by the following structural formula (1):

[0033] [Chemical formula 2]

[0034]

[0035] The modified polycarbonate structure shown. Since such a compound has two or more (meth)acryloyl-modified groups or alkenyl-modified groups at its terminals, a crosslinked structure is formed within the silicone elastomer particles through a hydrosilylation reaction or a radical polymerization reaction. When the obtained silicone elastomer particles are used as a cosmetic raw material, it is expected that the feel or touch during use will not be impaired, and the crosslinked structure formed between two silicon atoms has biodegradability.

[0036] Here, n in the formula is the number of repeating units of the carbonate unit {-O-C(=O)-O-CH2-(CH2)x-O-} in this structure, and can be a number in the range of 0 to 30, can be a number in the range of 0 to 15, or can also be a number in the range of 0 to 10. Additionally, the number of repeating units n can be essential and is a number in the range of 1 to 30, can be a number in the range of 1 to 15, or can also be a number in the range of 1 to 10. The (meth)acryloyl-modified polycarbonate compound and alkenyl-modified polycarbonate compound involved in the present invention are designed as crosslinking agents between silicon atoms in the silicone elastomer particles. Since the number of carbonate units in each structure is relatively small, even if the number of repeating units of the carbonate unit as the whole molecule is 0 or relatively small, it has the advantage of not significantly impairing the feel or use feel of the polyorganosiloxane main chain from the silicone elastomer particles.

[0037] Ra in the formula is a reactive group selected from (meth)acryloyl terminal groups or alkenyl terminal groups having 2 to 20 carbon atoms represented by -C(=O)-R 1 -CR 2 =CH2. Here, R 1is a chemical bond between CH and C(=O) or a divalent organic group having 0 to 20 carbon atoms, preferably a simple chemical bond such as "-C(=O)-CH=", or "-C(=O)-CmH2m-CH=" (where m is a number in the range of 1 to 20) of an alkylene group having 1 to 20 carbon atoms represented by CmH2m (it should be noted that when R 1 is a chemical bond between CH and C(=O), m is 0). In addition, R 2 is a hydrogen atom or a methyl group, providing an acrylic acid-modified group, a methacryloyl group, or an alkenyl group, respectively.

[0038] In the formula, x and y are each independently the number of methylene groups represented by CH2, which is a number in the range of 0 to 18, preferably a number in the range of 1 to 18, more preferably a number in the range of 1 to 10, and particularly preferably a number in the range of 1 to 5.

[0039] The polycarbonate compound having a reactive group of the present invention is a crosslinking agent between at least two silicon atoms, and thus needs to have at least two reactive groups selected from reactive (meth)acryloyl-modified groups and alkenyl-modified groups in the molecule. Therefore, the polycarbonate compound having a reactive group of the present invention must have two or more of the above structures in its molecule, and can have them in the range of 2 to 4. This is because, as a reactive production raw material on an industrial scale, a polycarbonate compound having a hydroxyl terminal and being polyol (alcoholic) and being a precursor of this structure is relatively easy to obtain.

[0040] In the polycarbonate compound having a reactive group of the present invention, in addition to the relatively small number of repeating units of the carbonate units in each of the above structures, the sum of the number of repeating units of the carbonate units in the molecule is preferably in the range of 2 to 20, and can be in the range of 2.5 to 15, or 3.0 to 12. If the number of repeating units of the carbonate units in the (meth)acryloyl-modified polycarbonate compound and the alkenyl-modified polycarbonate compound exceeds the above upper limit, the properties derived from the polycarbonate structure are strongly reflected in the obtained organosilicon elastomer particles, which may adversely affect the touch and usability of cosmetics and the like.

[0041] More specifically, the polycarbonate compound having a reactive group of the present invention may be a compound represented by the following structural formula (1-1).

[0042] From the following structural formula (1-1):

[0043] [Chemical formula 3]

[0044]

[0045] (In the formula, Ra is the same group as described above, and x, y, and n are the same numbers as described above)

[0046] as shown in

[0047] This polycarbonate compound containing a reactive group can be obtained by reacting a polycarbonate compound having a polyol terminal structure as a precursor with a (meth)acryloyl chloride compound and an enoyl chloride compound in the presence of a basic catalyst.

[0048] Specifically, the polycarbonate compound containing a reactive group according to the present invention can be obtained by using the following structural formula (1'):

[0049]

[0050] (In the formula, x, y, and n are the same numbers as described above)

[0051] the polycarbonate compound shown in

[0052] Cl-C(=O)-R 1 -CR 2 =CH2 (R 1 and R 2 are the same groups as described above) the (meth)acryloyl chloride compound or enoyl chloride compound shown in is reacted in the presence of a basic catalyst. Here, in the structural formula (1') representing the polycarbonate compound having a polyol terminal structure, n is preferably in the range of 1 to 15.

[0053] The reaction ratio of the polycarbonate compound having this polyol terminal structure with the (meth)acryloyl chloride compound and the enoyl chloride compound is such that, relative to the amount (moles) of the polyol terminal structure (-OH) of the polycarbonate compound, the (meth)acryloyl chloride compound and the enoyl chloride compound are in an amount of 1 equivalent to a slightly excessive amount (moles).

[0054] The basic catalyst that can be used in this reaction is not particularly limited, but it can be an alkali metal salt such as an inorganic base such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, etc.; an amine compound or a nitrogen-containing heterocyclic compound such as triethylamine, pyridine, dimethylaminopyridine, triazabicyclodecene, etc.

[0055] This reaction can be carried out in an organic solvent. Examples of the organic solvent that can be used include: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; amides such as formamide, acetamide, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide, dimethylacetamide; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, benzotrifluoride, hexafluoro-2-propanol; sulfoxides such as dimethyl sulfoxide (DMSO), diethyl sulfoxide, benzyl phenyl sulfoxide; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran (THF), dioxane, 1,2-dimethoxyethane, cyclopentyl methyl ether; esters such as ethyl acetate; nitriles such as acetonitrile, benzonitrile; aromatic hydrocarbons such as benzene, toluene, xylene, and mixtures of two or more of these.

[0056] In this reaction, in order to inhibit the further free radical polymerization reaction of the synthesized polycarbonate compound containing a reactive group, the system may contain one or more polymerization inhibitors. For example, it may contain one or more selected from hindered phenol polymerization inhibitors, hydroquinone polymerization inhibitors (representatively hydroquinone monomethyl ether, MEHQ, etc.), and catechol polymerization inhibitors.

[0057] The reaction conditions should be appropriately selected according to the synthesis amount, reaction apparatus, etc., but it is preferred to dropwise add the (meth)acryloyl chloride compound and the enoyl chloride compound while stirring the mixed solution containing the polycarbonate compound, the basic catalyst, and an optional polymerization inhibitor under the flow of an inert gas such as nitrogen. It should be noted that after the reaction is completed, it is particularly preferred to separate the target polycarbonate compound containing a reactive group by liquid separation and purify it by distilling off the unnecessary organic solvent under reduced pressure.

[0058] [Organosilicon elastomer particles]

[0059] Hereinafter, the organosilicon elastomer particles of the present invention, particularly their uses containing cosmetic raw materials, their manufacturing methods, and cosmetic compositions and organic resins (including coatings / coating agents) containing these, will be described in detail.

[0060] The organosilicon elastomer particles of the present invention are characterized in that they have a structure in which at least two silicon atoms in the organosilicon elastomer particles are crosslinked by one or more reactions selected from the free radical polymerization reaction of the polycarbonate compound containing a reactive group and the hydrosilylation reaction of a hydrogen atom bonded to a silicon atom.

[0061] More specifically, the organosilicon elastomer particles of the present invention are obtained by a crosslinking reaction selected from a free radical polymerization reaction and a hydrosilylation reaction, and each has the following structural characteristics.

[0062] [Free radical polymerization reaction type organosilicon elastomer particles]

[0063] It is characterized in that it is obtained by radical polymerization of an organopolysiloxane having a radical-reactive functional group in which three or more organic groups containing (meth)acryloyloxy bonded to a silicon atom in the molecule and the like in the presence of a radical polymerization initiator and the (meth)acryloyl-modified polycarbonate compound, and has a crosslinked structure formed by radical polymerization reaction of at least two silicon-silicon bonds in the organosilicon elastomer particles through the terminal (meth)acryloyl-modified group of the (meth)acryloyl-modified polycarbonate compound and the radical-reactive functional group of the silicon atom.

[0064] [Organosilicon elastomer particles of hydrosilylation reaction type]

[0065] It is characterized in that it is obtained by hydrosilylation reaction of an organopolysiloxane having three or more silicon atoms bonded to hydrogen atoms in the molecule (i.e., organohydrogenpolysiloxane) and the alkenyl-modified polycarbonate compound in the presence of a hydrosilylation reaction catalyst, and has a crosslinked structure formed by hydrosilylation reaction (addition reaction) of at least two silicon-silicon bonds in the organosilicon elastomer particles through the alkenyl-modified group of the alkenyl-modified polycarbonate compound and the silicon atom bonded to a hydrogen atom.

[0066] The organosilicon elastomer particles of the present invention further preferably have a

[0067] -(R2SiO) m -

[0068] (wherein R is an unsubstituted or halogen atom-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 22 carbon atoms or a hydroxyl group, and m is a number in the range of 1 to 1000)

[0069] shown polyorganosiloxane structure. This is the linear polyorganosiloxane structure from the following component (A), which imparts appropriate hardness and flexibility to the organosilicon elastomer particles.

[0070] Industrially, R is preferably independently methyl or phenyl, and m is preferably a number in the range of 50 to 800, more preferably a number in the range of 75 to 750.

[0071] The organosilicon elastomer particles of the present invention are preferably obtained by curing crosslinkable organosilicon emulsion particles through a crosslinking reaction. Particularly preferably, the organosilicon elastomer particles of the present invention are defined by their manufacturing process, and an organosilicon elastomer particle contains at least selected from:

[0072] (A) at least one reactive organopolysiloxane selected from the following component (a1) and component (a2):

[0073] (a1) An organopolysiloxane having at least three (meth)acryloyloxy-containing organic groups selected from among organic groups containing methacryloyloxy and organic groups containing acryloyloxy in the molecule; and

[0074] (a2) An organopolysiloxane having at least three silicon atoms bonded to hydrogen atoms in the molecule;

[0075] (B) A polycarbonate compound containing a reactive group

[0076] (C) A curing agent selected from among at least one of a free radical polymerization initiator and a hydrosilylation reaction catalyst, formed by subjecting crosslinkable reactive silicone emulsion particles to a crosslinking reaction in water, the crosslinkable reactive silicone emulsion particles being emulsified in water by a crosslinkable reactive silicone composition through at least one reaction selected from among a free radical polymerization reaction and a hydrosilylation reaction with a silicon atom bonded to a hydrogen atom.

[0077] In addition, the silicone elastomer particles obtained by this manufacturing process, particularly when used as a cosmetic raw material, can sometimes further improve the appearance, extensibility, and touch of cosmetics, and the particles obtained by this manufacturing method tend to be able to better solve the problems of the present invention. Thus, one of the preferred modes for achieving the technical effects of the present invention can be defined and appropriately determined by the manufacturing process.

[0078] Regarding the silicone elastomer particles of the present invention, there is no particular limitation on their average primary particle size, but they impart a smooth touch and a comfortable feeling of use to cosmetics and do not cause poor appearance or the like. From the viewpoints of storage stability and formulation stability as a cosmetic raw material, etc., the average primary particle size measured by the laser diffraction scattering method is preferably in the range of 0.5 to 20 μm, more preferably in the range of 0.5 to 15 μm. It should be noted that the particle size of the silicone elastomer particles can be controlled according to the crosslinkable reactive silicone emulsion particles and the crushing / grading process of the obtained silicone elastomer particles.

[0079] Examples of the shape of the silicone elastomer particles of the present invention include spherical, regular spherical, elliptical, and irregular shapes, and spherical and regular spherical shapes are particularly preferred. Produced in the form of an aqueous suspension described later, spherical silicone elastomer particles can be easily obtained by drying using a vacuum dryer, a hot air circulation oven, or a spray dryer.

[0080] In addition, in the present invention, when the crosslinkable reactive silicone composition for forming silicone elastomer particles is preferably cured into a sheet, as measured by a JIS A durometer specified in JIS K6301, it is preferably in the range of 10 to 80. If the JIS-A hardness of the rubber sheet measured by curing the crosslinkable reactive silicone composition into a sheet is within the above range, the cohesiveness of the obtained silicone elastomer particles is sufficiently suppressed, and it is easy to obtain particles with fluidity, dispersibility, dryness, smoothness, and a soft touch. Further, by selecting the above JIS-A hardness, the usability, touch, and operability in the case of being formulated into cosmetics can be designed or predicted to some extent. In addition, the stress relaxation property in the case of being formulated into an organic resin can be improved. When the silicone elastomer particles according to the present invention are used as a cosmetic raw material or a stress relaxant for an organic resin, it is particularly preferable to use the silicone elastomer particles having a JIS-A hardness in the range of 30 to 80, particularly 50 to 80.

[0081] Optionally, the silicone elastomer particles of the present invention may have a structure in which part or all of their surfaces are coated with one or more selected from organopolysiloxane resins, silica, and other silicone elastomer particles. Through this coating, further reduction of cohesiveness, control of oil absorption, improvement of touch, etc. can sometimes be expected.

[0082] Optionally, the silicone elastomer particles of the present invention may be a mesoporous structure having micropores.

[0083] Optionally, the silicone elastomer particles of the present invention may contain an oil agent that is liquid at 40°C. This oil agent can be easily contained in the silicone elastomer particles by emulsifying it together in the crosslinkable reactive silicone composition described below. By containing this oil agent, further reduction of cohesiveness, control of oil absorption, improvement of touch, etc. can be expected.

[0084] Optionally, the silicone elastomer particles of the present invention may further have a structure in which an alkylene group having 2 to 20 carbon atoms is crosslinked between at least two silicon atoms constituting the particles through a hydrosilylation reaction involving an alkenyl group having 2 to 20 carbon atoms. These structures can be easily achieved by using an organopolysiloxane containing an alkenyl group, an organohydrogenpolysiloxane, and a hydrosilylation reaction catalyst in combination. In addition, for example, by using an alkenyl group having 4 or more carbon atoms such as hexenyl, further reduction of cohesiveness, control of oil absorption, improvement of touch, etc. can sometimes be expected by simultaneously having this silalkylene structure. However, when the main purpose is biodegradability, the silicone elastomer particles of the present invention preferably substantially do not contain a structure containing a silalkylene group.

[0085] [Crosslinkable Reactive Silicone Composition for Forming Silicone Elastomer Particles]

[0086] More specifically, the silicone elastomer particles of the present invention can be obtained by crosslinking (curing) a crosslinkable silicone composition containing the following components through one or more reactions selected from a radical polymerization reaction and a hydrosilylation reaction of a hydrogen atom bonded to a silicon atom.

[0087] (A) At least one reactive organopolysiloxane selected from the following components (a1) and (a2):

[0088] (a1) An organopolysiloxane having at least three organic groups selected from organic groups containing methacryloxy groups and organic groups containing acryloxy groups in the molecule, and having at least one or more (meth)acryloxy-containing organic groups; and

[0089] (a2) An organopolysiloxane having at least three hydrogen atoms bonded to silicon atoms in the molecule;

[0090] (B) A polycarbonate compound containing a reactive group

[0091] (C) At least one curing agent selected from a radical polymerization initiator and a hydrosilylation reaction catalyst

[0092] It should be noted that the crosslinking (curing) reaction is one or more reactions selected from a radical polymerization reaction and a hydrosilylation reaction, and these reactions can be carried out simultaneously. However, from the viewpoint of reaction control, it is preferable to select any one to form the silicone elastomer particles. That is, the above composition can be a composition containing the following two reaction types and components.

[0093] [Composition for forming silicone elastomer particles of radical polymerization reaction type]

[0094] Containing (a1) an organopolysiloxane having at least three organic groups selected from organic groups containing methacryloxy groups and organic groups containing acryloxy groups in the molecule, and having at least one or more (meth)acryloxy-containing organic groups;

[0095] (B) The (meth)acryloyl-modified polycarbonate compound as a polycarbonate compound containing a reactive group; and

[0096] (c1) A radical polymerization initiator

[0097] A crosslinkable silicone composition.

[0098] [Composition for forming silicone elastomer particles of hydrosilylation reaction type]

[0099] (a2) An organopolysiloxane having at least three hydrogen atoms bonded to silicon atoms in the molecule;

[0101] (B) the alkenyl-modified polycarbonate compound as the polycarbonate compound having reactive groups; and

[0102] (c2) a hydrosilylation reaction catalyst

[0103] A crosslinkable organosilicon composition.

[0104] Component (a1) is an organopolysiloxane having at least three organic groups containing (meth)acryloyloxy in the molecule, and its structure is not particularly limited and may be one or more structures selected from linear, cyclic, network, and partially branched linear structures, and a linear organopolysiloxane is particularly preferred. In addition, the viscosity of component (a) is preferably such that the above crosslinkable composition can be dispersed in water. Specifically, at 25 °C, it is preferably in the range of 20 to 100,000 mPa·s, and particularly preferably in the range of 20 to 10,000 mPa·s.

[0105] From the viewpoints of the touch, dispersibility, and handling workability of the organosilicon elastomer particles, component (a1) is preferably a linear organopolysiloxane in which the content of dimethylsiloxane units represented by the formula: -(CH3)2SiO- is 80 mol% or more of all the siloxane units except the siloxane units at the molecular terminals. Similarly, from the viewpoint of improving the oil absorbency of the obtained organosilicon elastomer particles, etc., cyclic or linear organopolysiloxanes with a low degree of polymerization (degree of polymerization 3 to 20) can be removed from component (a1) in advance by stripping, etc.

[0106] Furthermore, when component (a1) is a linear organopolysiloxane, when the organosilicon elastomer particles of the present invention are placed in a biodegradable environment, when the organosilicon elastomer particles are broken due to the breakage of the crosslinked structure, they are easily decomposed into non-crosslinked and linear organopolysiloxanes, which has the advantages of being easy to reduce the environmental burden and environmental risk.

[0107] Since component (a1) forms a crosslinked structure through a radical reaction with component (B), it is necessary to have an average of at least three or more organic groups containing (meth)acryloyloxy in the molecule. When there are only two or less organic groups containing (meth)acryloyloxy on average in the molecule, a sufficient crosslinked structure cannot be formed, and sometimes practical organosilicon elastomer particles cannot be obtained.

[0108] More specifically, the organic group containing (meth)acryloyloxy is a (meth)acryloyloxy bonded to a silicon atom through a divalent organic group, and examples thereof include:

[0109] -R 2 -O-C(=O)-C(R 3)=CH2

[0110] {In the formula, R 2 is an alkylene group having 1 to 20 carbon atoms or

[0111] (CH2) p -Si(CH3)2-O-Si(CH3)2-(CH2) q shown divalent linking group (where p and q in the formula are numbers in the range of 1 to 20 respectively),

[0112] R 3 is a hydrogen atom or a methyl group.}

[0113] One or more functional groups shown.

[0114] In the formula, the alkylene group as R 2 can industrially be an alkylene group having 2 to 10 carbon atoms, and examples thereof include a propylene group, a butylene group, a hexylene group, etc. In addition, (CH2) p -Si(CH3)2-O-Si(CH3)2-(CH2) q shown divalent linking group is a divalent linking group having a siloxane converter structure, and industrially, examples thereof include linking groups where p and q are each independently a number from 3 to 6.

[0115] Preferably, the component (a1) is preferably a linear organopolysiloxane represented by the following structural formula.

[0116] [Chemical formula 5]

[0117]

[0118] In formula (1), R 11 are each independently an unsubstituted or halogen atom-substituted alkyl group having 1 to 20 carbon atoms (for example, a methyl group, etc.), an aryl group having 6 to 22 carbon atoms (for example, a phenyl group, etc.) or a hydroxyl group, and industrially preferably a methyl group or a phenyl group. R a is the above-mentioned organic group containing a (meth)acryloyloxy group, and particularly preferably a (meth)acryloyloxy group bonded to a silicon atom through the above-mentioned alkylene group or a divalent linking group having a siloxane converter structure. R is independently a group represented by R 11 or R a shown group. m is a number of 1 or more, and n is a number of 1 or more. Among them, since the component (a) contains at least three organic groups containing a (meth)acryloyloxy group represented by R a in the molecule, when m = 1, R must all be R a. That is, the linear organopolysiloxane represented by the above structural formula has an organic group containing (meth)acryloyloxy at any one of the single-terminal part and the side-chain part, only the side-chain part, both terminal parts and the side-chain part of its siloxane molecule, and can be an organopolysiloxane containing at least three organic groups containing (meth)acryloyloxy in the molecule, and is preferably a as described.

[0119] m + n is the siloxane polymerization degree of the linear organopolysiloxane molecule except for the terminal siloxane structure. From the viewpoints of the operation workability as a raw material, emulsifiability, and the fragmentation into fine linear siloxane molecules during biodegradation, m + n is preferably in the range of 10 to 800, more preferably in the range of 20 to 600, and particularly preferably in the range of 30 to 500. In addition, the viscosity of the component (a) is particularly preferably a value of 20 to 10,000 mPa·s at 25°C.

[0120] (a2) component is an organopolysiloxane component crosslinked with the component (B) by a hydrosilylation reaction, and is characterized in that it has at least three silicon atoms bonded to hydrogen atoms in the molecule, and there is no particular limitation on the bonding position of the hydrogen atoms in the molecule.

[0121] In addition to hydrogen atoms, examples of the organic groups bonded to silicon atoms contained in the component (a2) include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl, and methyl is preferred. In addition, examples of the molecular structure of the organohydropolysiloxane of the component (a2) include any one of linear, branched, and branched cyclic structures or a combination of one or more of these. It should be noted that the number of silicon-bonded hydrogen atoms in one molecule is the average value of all molecules.

[0122] In particular, when the component (a2) is a linear organopolysiloxane (organohydropolysiloxane), when the organosilicon elastomer particles involved in the present invention are placed in a biodegradable environment, when the organosilicon elastomer particles are broken due to the breakage of the crosslinked structure, it is easily decomposed into non-crosslinked and linear organopolysiloxanes, having the advantages of being easy to reduce the environmental burden and environmental risk.

[0123] The viscosity of component (a2) at 25°C is 1 to 1,000 mPa·s, preferably 5 to 500 mPa·s. If the viscosity of component (b) at 25°C is less than 1 mPa·s, component (a2) is likely to volatilize from the crosslinkable composition containing it. If it exceeds 1,000 mPa·s, the curing time of the crosslinkable composition containing such component (a2) will become longer, or sometimes it may cause poor curing. Such component (a2) is not particularly limited, and examples thereof include dimethylsiloxane / methylhydrogensiloxane copolymer capped with trimethylsilyloxy at both ends, dimethylsiloxane / methylhydrogensiloxane copolymer capped with dimethylhydrogensilyloxy at both ends, dimethylpolysiloxane capped with dimethylhydrogensilyloxy at both ends, methylhydrogenpolysiloxane capped with trimethylsilyloxy at both ends, cyclic methylhydrogenpolysiloxane, and cyclic methylhydrogensiloxane / dimethylsiloxane copolymer.

[0124] Here, the value of H / Alk, which is the molar ratio (i.e., the reaction ratio in the hydrosilylation reaction) of the carbon-carbon double bond (Alk) contained in the alkenyl terminal group in component (B) to the hydrogen atom content (H) of the silicon atom-bonded hydrogen atoms in component (a2), is preferably in the range of 0.7 to 1.2. The lower limit of the above H / Alk is preferably 0.80 or more, 0.85 or more, 0.90 or more, 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 atom-bonded hydrogen atoms are likely to remain after the reaction. Conversely, when the upper limit of H / Alk is less than the above value, unreacted component (B) and its (meth)acryloyl terminal group are likely to remain after the reaction. These are curing reactive groups, so when a large amount of them remains in the particles, it may sometimes cause a crosslinking reaction to occur between the particles over time. Regarding the obtained silicone elastomer particles containing the oil agent, it may sometimes cause reasons such as poor aggregation and dispersion, and furthermore, when reactive hydrogen atoms remain, flammable hydrogen gas may be generated over time. Particularly preferably, when the value of H / Alk is between 0.9 and 1.1, especially close to 1.0, the curing reactive groups are completely consumed and the crosslinking reaction ends, and the aggregation over time between the particles can be effectively inhibited.

[0125] (Component (B) is a polycarbonate compound containing reactive groups (specifically, the (meth)acryloyl-modified polycarbonate compound and the alkenyl-modified polycarbonate compound), which is a crosslinking agent for component (A) that imparts the characteristic crosslinked structure to the silicone elastomer particles of the present invention, and is a radically polymerizable monomer (monomer) component that forms a polymer or copolymer structure by free radical polymerization on its own. This crosslinked portion, whether it is a hydrosilylation reaction type or a free radical polymerization type, does not significantly impair the touch and usability of the obtained silicone elastomer particles, and is active in biodegradation reactions. In a biodegradable environment, at least part of the crosslinked structure formed between silicon atoms in the silicone elastomer particles breaks, and the primary particles of the silicone elastomer particles have the property of breaking along with the generation of polyorganosiloxane with a non-crosslinked structure. Here, when component (A) as described above is a linear polyorganosiloxane, due to the biodegradation reaction, the silicone elastomer particles are easily broken into linear polyorganosiloxane molecules and decomposed into fine liquid components, rather than being decomposed into solid powders with a small particle size like large particle plastics. Therefore, it is not easy to cause bioaccumulation through the food chain and the problem of accumulation / deposition in the environment, and it is expected to have a small impact or burden on the global environment.)

[0126] The amount of component (B) to be used needs to be selected as follows according to the type of component (A) and the crosslinking reaction for obtaining the silicone elastomer particles of the present invention.)

[0127] In the case of forming silicone elastomer particles by the free radical polymerization reaction of component (a1) and component (B), the molar ratio of the content of component (B) to the content of the (meth)acryloyloxy-containing organic group in component (a1) is preferably in the range of 0.5 to 50, more preferably in the range of 1 to 20, still more preferably in the range of 3 to 15, and particularly preferably in the range of 5 to 10. If the amount of component (B) is within the above range, a crosslinked structure derived from a (meth)acryloyl-modified polycarbonate compound with a moderate average length can be obtained between the polyorganosiloxane structures. Therefore, a moderate hardness, a low viscosity and a smooth surface state can be achieved in the particles, and their touch and usability can be improved. On the other hand, if the amount of component (B) is less than the above lower limit, the crosslinking may sometimes be insufficient. In addition, if the amount of component (B) exceeds the above upper limit, emulsion breakage and the like are likely to occur during the curing reaction, and sometimes silicone elastomer particles cannot be obtained.)

[0128] In the case of forming organosilicon elastomer particles by the hydrosilylation reaction of the component (a2) and the component (B), the amount of the component (B) is preferably designed such that the H / Alk value is within the above range, where H / Alk is the molar ratio of the carbon-carbon double bond (Alk) contained in its vinyl terminal group to the content (H) of the silicon atom-bonded hydrogen atoms of the component (a2) (= reaction ratio in the hydrosilylation reaction).

[0129] Component (C) is a curing agent and is selected from (c1) a radical polymerization initiator and (c2) a hydrosilylation reaction catalyst according to the selection of the component (A) and the reaction system.

[0130] (c1) Component is a radical initiator, which is a component that promotes the radical polymerization reaction or radical copolymerization reaction of the above (a1) component and (B) component. As the radical initiator, conventionally known compounds usually used in the radical polymerization method can be used. Specifically, examples include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobis(2,4-dimethylvaleronitrile); organic peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, and tert-hexyl peroxy-2-ethylhexanoate; and persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate. This radical initiator can be used alone or in combination of two or more.

[0131] Relative to a total of 100 parts by mass of the above (a1) component and (B) component, the amount of the radical initiator as the (c1) component is preferably in the range of 0.1 to 5 parts by mass. In particular, when the component (c1) is a water-soluble persulfate such as potassium persulfate, in the case where the crosslinkable organosilicon emulsion particles formed by emulsifying the crosslinkable organosilicon composition by a radical polymerization reaction undergo a crosslinking reaction in water, it has the advantage of being extremely easy to add and react. Further, at the end of the radical polymerization reaction, for the purpose of neutralizing the solution accompanied by the termination of the reaction and pH adjustment, it is particularly preferable to add aminomethylpropanediol or the like in the range of 0.1 to 5 parts by mass.

[0132] The timing of adding the (c1) component to the crosslinkable composition can be selected according to the method of forming the organosilicon elastomer particles. It can be added to the composition in advance, or it can be in a form where the (a1) component or (B) component is supplied from a different spray line and added to either of them and mixed in the spray. The organosilicon elastomer particles in the present invention are preferably formed via an aqueous suspension formed by emulsification in water. The component (c1) can also be added to the crosslinkable organosilicon composition in advance, or an emulsion containing the component (c1) can be added to water separately.

[0133] During the polymerization reaction of the above-mentioned crosslinkable reactive silicone composition, a chain transfer agent can be optionally added. Specific examples of the chain transfer agent include: mercapto compounds such as 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, and polydimethylsiloxane having mercaptopropyl groups; and halides such as dichloromethane, chloroform, carbon tetrachloride, butyl bromide, and 3-chloropropyltrimethoxysilane.

[0134] (c2) component is a hydrosilylation reaction catalyst, which is a catalyst for promoting the addition reaction (hydrosilylation reaction) of the carbon-carbon double bond contained in the alkenyl terminal group present in the above-mentioned crosslinkable composition and the hydrogen atom bonded to the silicon atom. Preferred hydrosilylation reaction catalysts are hydrosilylation reaction catalysts containing platinum group metals. Specifically, examples thereof include: chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, complexes of chloroplatinic acid and ketones, complexes of chloroplatinic acid and vinylsiloxanes, platinum tetrachloride, platinum fine powder, substances obtained by supporting solid platinum on alumina or silica carriers, platinum black, olefin complexes of platinum, vinylsiloxane complexes of platinum, carbonyl complexes of platinum, and platinum group catalysts in the form of thermoplastic organic resin powders such as methyl methacrylate resins, polycarbonate resins, polystyrene resins, and silicone resins containing these platinum group catalysts. In particular, platinum vinylsiloxane complexes such as complexes of chloroplatinic acid and divinyltetramethyldisiloxane, complexes of chloroplatinic acid and tetramethyltetravinylcyclotetrasiloxane, platinum divinyltetramethyldisiloxane complex, and platinum tetramethyltetravinylcyclotetrasiloxane complex can be preferably used. It should be noted that as catalysts for promoting the hydrosilylation reaction, non-platinum group metal catalysts such as iron, ruthenium, and iron / cobalt can be used.

[0135] (c2) component can be added in an amount as long as it is a catalytic amount in the crosslinkable composition. Generally, relative to the total mass of the above-mentioned crosslinkable composition, it is preferably an amount in the range where the amount of platinum group metal contained in the (c2) component is 1 to 1,000 ppm, and more preferably an amount in the range of 5 to 500 ppm. It should be noted that the amount of platinum metal in the silicone elastomer particles can also be reduced according to the method proposed by the present inventors in Japanese Patent Application Laid-Open No. 2014-122316.

[0136] The timing of adding the component (c2) to the crosslinkable composition can be selected according to the method for forming the silicone elastomer particles. It can be added to the composition in advance, or it can be in a form where the component (a2) or the component (B) is supplied from different spray pipelines, added to any one of them, and mixed in the spray. The silicone elastomer particles containing an oil agent in the present invention are preferably formed via an aqueous suspension formed by emulsification in water. The component (c2) can also be added to the crosslinkable silicone composition in advance, or an emulsion containing the component (c2) can be added to water separately.

[0137] The above-mentioned crosslinkable silicone composition may also contain a curing retarder represented by a hydrosilylation reaction inhibitor. Examples of the curing retarder include: acetylene compounds, enyne compounds, organic nitrogen compounds, organic phosphorus compounds, and oxime compounds. Specific examples of the compounds include: alkynols such as 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 1-ethynyl-1-cyclohexanol (ETCH); enyne compounds such as 3-methyl-3-trimethylsilyloxy-1-butyne, 3-methyl-3-trimethylsilyloxy-1-pentyne, 3,5-dimethyl-3-trimethylsilyloxy-1-hexyne, 3-methyl-3-penten-1-yne, and 3,5-dimethyl-3-hexen-1-yne; vinyl siloxanes such as 1-ethynyl-1-trimethylsilyloxycyclohexane, bis(2,2-dimethyl-3-butynyloxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane. The addition amount is in the range of 0.001 to 5 parts by mass per 100 parts by mass of the component (a), but can be appropriately designed according to the type of the curing retarder used, the characteristics and the amount of the hydrosilylation reaction catalyst used, etc.

[0138] From the viewpoint of preventing unexpected side reactions, etc., the above-mentioned crosslinkable silicone composition may contain one or more polymerization inhibitors. For example, it may contain one or more selected from hindered phenol polymerization inhibitors, hydroquinone polymerization inhibitors, and catechol polymerization inhibitors. The dosage can be appropriately selected, but the total concentration of the polymerization inhibitor is preferably 50 mass ppm or less, more preferably 30 mass ppm or less, relative to the sum of the above components (A) to (C).

[0139] Within the scope that does not impair the technical effects of the present invention, the crosslinkable organosilicon composition may contain components other than the above components. For example, it may contain: 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, etc. organic solvents; antioxidants such as phenols, quinones, amines, phosphorus compounds, phosphites, sulfur compounds, or thioethers; light stabilizers such as triazoles or benzophenones; flame retardants such as phosphates, halogens, phosphorus compounds, or antimony compounds; one or more antistatic agents composed of cationic surfactants, anionic surfactants, or nonionic surfactants; dyes; pigments, etc.

[0140] The organosilicon elastomer particles of the present invention may optionally have a structure in which (i) part or all of its surface is covered with one or more selected from organopolysiloxane resins, silica, and other organosilicon elastomer particles; (ii) a mesoporous structure; (iii) a structure containing an oil agent that is liquid at 40°C; and (iv) a structure crosslinked by a silicon alkylene group having 2 to 20 carbon atoms, and any components that impart these structures may also be used in combination.

[0141] [Hardness of organosilicon elastomer]

[0142] Although the hardness of the organosilicon elastomer particles cannot be directly measured, it can be indirectly measured by curing the crosslinkable organosilicon composition used as its raw material to form the organosilicon elastomer particles. Specifically, the crosslinkable organosilicon composition can be cured into a sheet in a state where it is not emulsified in water, and for this organosilicon elastomer sheet, the hardness is measured by a JIS A hardness tester specified in JIS K6301. The hardness of the organosilicon elastomer related to the present invention varies depending on the type of the crosslinkable organosilicon composition, the amount of the component (a) / (b), and the crosslink density, but is preferably in the range of 10 to 80. In addition, the preferred hardness is as described above.

[0143] [Formation of organosilicon elastomer particles and its manufacturing method]

[0144] The method for the organosilicon elastomer particles related to the present invention may include the following steps: in the presence of a (C) curing agent, crosslinkable organosilicon emulsion particles formed by emulsifying the crosslinkable organosilicon composition used to form the above organosilicon elastomer particles in water are cured to obtain spherical organosilicon elastomer particles.

[0145] More specifically, the organosilicon elastomer particles related to the present invention can be prepared using a manufacturing method including the following steps (I) and (II), and is preferred.

[0146] Step (I):

[0147] (A) At least one reactive organopolysiloxane selected from the above components (a1) and component (a2),

[0148] (B) A polycarbonate compound containing reactive groups (specifically, at least one modified polycarbonate compound selected from the (meth)acryloyl-modified polycarbonate compound and the alkenyl-modified polycarbonate compound)

[0149] (C) One or more curing agents selected from radical polymerization initiators and hydrosilylation reaction catalysts

[0150] Emulsify in water to form crosslinking reactive silicone emulsion particles;

[0151] Step (II):

[0152] Cure the crosslinking reactive silicone emulsion particles obtained in step (I) in the presence of the (C) curing agent to obtain silicone elastomer particles.

[0153] The crosslinkable silicone composition for forming silicone elastomer particles can be uniformly mixed by mechanical force such as a mixer.

[0154] In this method, silicone elastomer particles can be obtained by emulsifying and curing the above crosslinkable silicone composition in an aqueous surfactant solution. In addition, the particle size can be easily adjusted by adjusting the emulsion particle size. Examples of such surfactants include: nonionic, anionic, cationic, betaine, and water-soluble polymers such as polyvinyl alcohol. Depending on the type and content of the surfactant, the particle size of the obtained silicone elastomer particles is different. In order to prepare silicone elastomer particles with a small particle size, the addition amount of the surfactant is preferably in the range of 0.5 to 50 parts by mass relative to 100 parts by mass of the crosslinkable silicone composition.

[0155] In order to uniformly disperse the above crosslinkable silicone composition in the form of crosslinking reactive silicone emulsion particles in water, it is preferable to use an emulsifier. Examples of such emulsifiers include: a homogenizing mixer, a paddle mixer, a Henschel mixer, a homo-disper, a colloid mill, a propeller stirrer, a homogenizer, a pipeline continuous emulsifier, an ultrasonic emulsifier, a vacuum kneader.

[0156] Next, by heating or leaving at room temperature the aqueous dispersion of crosslinking-reactive silicone emulsion particles prepared by the above method, the crosslinking-reactive silicone emulsion particles in the aqueous dispersion are cured, and an aqueous dispersion of silicone elastomer particles can be prepared. When heating the aqueous dispersion involved, from the viewpoint of hydrosilylation reactivity or radical polymerization reactivity, the heating temperature is preferably 100 °C or lower, particularly preferably 10 to 95 °C. In addition, as a method for heating the aqueous dispersion containing crosslinking-reactive silicone emulsion particles, for example, there can be mentioned: a method of directly heating the aqueous dispersion, a method of adding the aqueous dispersion to hot water. The liquid crosslinking-reactive silicone particles through this crosslinking reaction are cured in water, and an aqueous dispersion of silicone elastomer particles is formed.

[0157] The obtained silicone elastomer particles of the present invention can be directly used as an aqueous dispersion (aqueous suspension). In particular, it can be preferably used in the form of this aqueous suspension in cosmetic raw materials and the like. When an aqueous solution is formulated as a dispersion medium in a cosmetic (for example, a hair cosmetic, etc.), sometimes by formulating in the form of an aqueous dispersion containing the silicone elastomer particles of the present invention, the silicone elastomer particles can be easily and uniformly dispersed, and desired performance and usability can be achieved.

[0158] Preferably, the silicone elastomer particles of the present invention can be separated by removing water from the aqueous dispersion of silicone elastomer particles. As a method for removing water from the aqueous dispersion, for example, there can be mentioned methods of drying using a vacuum dryer, a hot air circulation oven, a spray dryer. It should be noted that the heating / drying temperature of the spray dryer needs to be appropriately set based on the heat resistance of the silicone elastomer particles, the crosslinking temperature, etc. It should be noted that in order to prevent secondary aggregation of the obtained fine particles, it is preferable to control the temperature of the silicone elastomer particles below their glass transition temperature. The silicone elastomer particles thus obtained can be recovered using a cyclone separator, a bag filter, etc. It should be noted that as a pretreatment for this operation, the dispersion can be concentrated by methods such as heat dehydration, filtration separation, centrifugal separation, decantation, and if necessary, the dispersion can also be washed with water.

[0159] As needed, the silicone elastomer particles of the present invention can be surface-treated, and sometimes the aggregation inhibition effect of the silicone elastomer particles of the present invention can be further improved. Further, surface treatment can also be performed with other known hydrophilic treatment agents or hydrophobic treatment agents, etc. Optionally, as described above, the obtained silicone elastomer particles can be further coated on a part or all of their surfaces with inorganic fine particles such as silica, silicone resins, etc. In addition, as needed, the obtained silicone elastomer particles can be mechanically broken or pulverized, or they can be classified using known techniques.

[0160] [Cosmetic raw materials and cosmetic compositions]

[0161] The silicone elastomer particles of the present invention can be used as a cosmetic raw material. When formulated in a cosmetic composition, the particles are soft and have an excellent effect of improving the touch and feel of the cosmetics. The particles are also excellent in workability as a cosmetic raw material, storage stability, and stability after formulation in a system.

[0162] In particular, compared with known silicone particles, the silicone elastomer particles of the present invention have excellent use and touch, high degree of freedom in formula design, and when formulated into cosmetics, they absorb oily raw materials over time without thickening or changes in touch, and when applied to the skin or hair, they suppress the greasy and sticky feeling of the cosmetics, impart smooth ductility and soft touch or moisturizing feeling, and improve the sense of integration with the skin, etc., and have the advantages of excellent use feeling. In addition, compared with other powders or existing silicone elastomer particles, when the silicone elastomer particles of the present invention are used in combination with ultraviolet protection ingredients, the ultraviolet protection effect of the cosmetics can be improved without damaging the touch and use feeling of the cosmetics.

[0163] Furthermore, the silicone elastomer particles of the present invention have performances equal to or better than those of conventionally known silicone elastomer particles, and are active in biodegradation reactions. In a biodegradable environment, the cross-linked structure formed between silicon atoms in the silicone elastomer particles is at least partially broken, and the primary particles of the silicone elastomer particles have the property of being broken with the generation of polyorganosiloxanes with non-cross-linked structures, and are therefore materials with low risks and environmental loads to the global environment. Furthermore, the silicone elastomer particles can be used in place of conventionally known silicone elastomer particles, and are extremely versatile.

[0164] The types of cosmetic compositions containing the silicone elastomer particles of the present invention are not particularly limited, but examples thereof include: cleansing cosmetics such as soaps, shower gels, and facial cleansers; basic cosmetics such as lotions, creams / emulsions, and facial masks; base makeup cosmetics such as powders and foundations; eye makeup cosmetics such as lipsticks, blushers, eye shadows, eyeliners, and mascara; color cosmetics such as nail polishes; hair cosmetics such as shampoos, conditioners, hair lotions, hair tonics, hair nourishers, and hair dyes; aromatic cosmetics such as perfumes and colognes; toothpastes; bath preparations; special cosmetics such as depilatories, shaving lotions, antiperspirants / deodorants, and sunscreens. In addition, examples of the dosage forms of these cosmetic compositions include: aqueous liquids, oily liquids, emulsions, creams, foams, semisolids, solids, and powders. In addition, these cosmetic compositions can also be used by spraying.

[0165] In these cosmetic compositions, the content of the above-mentioned silicone elastomer particles is preferably in the range of 0.5 to 99.0% by mass in the cosmetic composition, and particularly preferably in the range of 1.0 to 95% by mass. This is because, when the content of the above-mentioned silicone elastomer particles exceeds the upper limit of the above range, the effects as a cosmetic are lost. In addition, if it is less than the lower limit of the above range, it is difficult to improve the usability, etc. of the cosmetic composition.

[0166] Regarding the cosmetic compositions (especially each formulation example) containing silicone particles (such as silicone rubber powder) or silicone composite particles proposed in Patent Document 1 (Japanese Patent Laid-Open No. 07-316014), Patent Document 2 (International Patent Publication WO2017 / 191798), Patent Document 3 (Japanese Patent Laid-Open No. 02-243612), Japanese Patent Laid-Open No. 2011-105663, Japanese Patent Laid-Open No. 2011-168634, Japanese Patent Laid-Open No. 2011-102354, and Japanese Patent Laid-Open No. 2014-122316), the silicone elastomer particles of the present invention can be used to replace a part or all of these silicone-based particles, and sometimes can further improve the usability and production efficiency of the cosmetic compositions proposed in these patent documents. It should be noted that the silicone elastomer particles of the present invention are not limited to the above examples as examples of cosmetic compositions containing deployable silicone particles (such as silicone rubber powder) or silicone composite particles. A formulation can be designed by the general technical means of those skilled in the art to replace a part or all of the silicone particles in commercially available cosmetics with the silicone elastomer particles of the present invention.

[0167] Furthermore, the silicone elastomer particles of the present invention can replace and be applied to a part or all of these silicone-based particles regarding the uses and formulations of the cosmetic compositions disclosed in the above-mentioned patent documents, etc., and these uses are included in the scope of the invention of this application. As an example, the silicone elastomer particles of the present invention can be selected in the same method and the same range of amounts as the articles disclosed in Patent Document 2 (International Patent Publication WO2017 / 191798), and any components such as a cosmetic medium (aqueous medium or oily medium), oily medium (including oil agents, volatile oil agents), water, colorants, pigments, ultraviolet ray-resistant components, alcohols, water-soluble polymers, film-forming agents, oil agents, oil-soluble gelling agents, organically modified clay minerals, surfactants, resins, salts, moisturizers, preservatives, antibacterial agents, antioxidants, pH regulators, chelating agents, cooling agents, anti-inflammatory agents, skin beautifying components (such as whitening agents, cell activators, skin roughness improvers, blood circulation promoters, skin astringents, and anti-seborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, clathrates, etc., physiologically active substances, pharmaceutical active ingredients, and fragrances can be combined and used, and are preferred.

[0168] In particular, compared with conventionally known silicone particles, silicone composite particles coated with silsesquioxane, and silicone particles containing an oil agent, the silicone elastomer particles of the present invention have a usability, touch feeling, handling workability, storage stability, dispersibility, and high oil absorption property equal to or better than those of the above. In particular, in

[0169] (1) Cosmetic compositions and formulations containing oily media such as oil agents (oily cosmetic raw materials);

[0170] (2) Cosmetic compositions and formulations containing lipophilic ultraviolet ray-absorbing components (such as octyl methoxycinnamate, etc.);

[0171] (3) In cosmetic compositions and formulations containing inorganic powders such as colorants or pigments,

[0172] particularly suitable appearance, usability, etc. can be achieved. These specific formulations are described in more detail in the following examples.

[0173] In addition, since the silicone elastomer particles of the present invention can easily design an aqueous dispersion, even in aqueous cosmetic compositions and formulations, the degree of freedom in formulation design and blending stability are excellent, and a comfortable usability can be achieved. These specific formulations are described in more detail in the following examples.

[0174] Regarding the production of the cosmetics of the present invention, they can be easily produced by simply and uniformly mixing the cosmetic raw materials of the present invention as described above and other cosmetic raw materials. As the mixing method, various mixing devices and kneading devices used in the production of ordinary cosmetics can be used. As the devices involved, for example, a homogenizing mixer, paddle mixer, Henschel mixer, homogeneous disperser, colloid mixer, propeller stirrer, homogenizer, in-line continuous emulsifier, ultrasonic emulsifier, vacuum kneader can be exemplified.

[0175] [Organic resin additives, organic resins, coatings, coating agents]

[0176] Since the silicone elastomer particles of the present invention have the above characteristics, they are also very useful as organic resin additives. Specifically, the silicone elastomer particles of the present invention are excellent in the uniform dispersibility in organic resins and the desired stress relaxation characteristics, etc., and are not likely to agglomerate even after long-term storage, so the handling workability and storage stability are significantly excellent. Further, the flexibility (including the flexibility of the coating), durability, and adhesion / followability to the substrate of the member, coating film, or coating film formed by curing the organic resin blended with the silicone elastomer particles are improved. In particular, the flexibility and heat shock resistance are excellent, so it is extremely useful as a highly functional organic resin, coating, or coating agent for electronic materials.

[0177] [Organic resin]

[0178] As the organic resin containing the silicone elastomer particles of the present invention, curable organic resin compositions or thermoplastic resins can be preferably exemplified. Among them, curable resins are suitable for electronic materials such as semiconductor substrates. More specifically, as the curable organic resin composition, examples include: phenolic 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, and two or more of these curable resins can also be combined. In particular, as the curable resin, at least one selected from the group consisting of epoxy resins, phenolic resins, imide resins, and silicone resins is preferred. As this epoxy resin, as long as it is a compound containing a glycidyl group or an alicyclic epoxy group, examples include: o-cresol novolac type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthol aralkyl type epoxy resin, polyvinylphenol type epoxy resin, diphenylmethane type epoxy resin, diphenylsulfone type epoxy resin, triphenolalkane type epoxy resin, cresol-naphthol co-condensed type epoxy resin, biphenyl vinyl type epoxy resin, fluorene type epoxy resin, stilbene type epoxy resin, spirocoumarone type epoxy resin, norbornene type epoxy resin, terpene type epoxy resin, phenol cyclohexane type epoxy resin, halogenated epoxy resin, epoxy resin containing an imide group, epoxy resin containing a maleimide group, allyl-modified epoxy resin, silicone-modified epoxy resin. In addition, as this phenolic resin, examples include: polyvinylphenol type, phenol novolac type, naphthol type, terpene type, phenol dicyclopentadiene type, phenol aralkyl type, naphthol aralkyl type, triphenolalkane type, dicyclopentadiene type, cresol / naphthol co-condensed type, xylene / naphthol co-condensed type. In addition, as the silicone resin, examples include: epoxy-modified silicone resin obtained by reacting a silanol group or a silicon atom-bonded alkoxy group in an epoxy resin and a silicone resin. As the curing mechanism of such a curable resin, examples include: heat-curable type, high-energy ray-curable type such as ultraviolet rays or radiation, moisture-curable type, condensation reaction-curable type, addition reaction-curable type. In addition, the properties of such a curable resin at 25°C are not limited and can be either liquid or a solid state softened by heating.

[0179] In the organic resin containing the silicone elastomer particles of the present invention, as other optional components, a curing agent, a curing accelerator, a filler, a photosensitizer, a metal salt of a higher fatty acid, an ester wax, a plasticizer, etc. can be formulated. Examples of the curing agent include: organic acids such as carboxylic acid and sulfonic acid and their anhydrides; organic hydrocarbon compounds; silicone compounds having a silanol group, an alkoxy group or a halogen group; primary or secondary amino compounds, and two or more of these can also be combined. In addition, examples of the curing accelerator include: tertiary amine compounds, organometallic compounds such as aluminum or zirconium; organic phosphorus compounds such as phosphine; other isocyclic amine compounds, boron compounds, organic ammonium salts, organic sulfonium salts, organic peroxides, and catalysts for hydrosilylation. In addition, examples of the filler include: fibrous fillers such as glass fiber, asbestos, alumina fiber, ceramic fiber composed of alumina and silica, boron fiber, zirconia fiber, silicon carbide fiber, metal fiber, polyester fiber, aramid fiber, nylon fiber, phenol fiber, natural animal and plant fibers; powdery fillers such as fused silica, precipitated silica, fumed silica, calcined silica, zinc oxide, calcined clay, carbon black, glass beads, alumina, talc, calcium carbonate, clay, aluminum hydroxide, barium sulfate, titanium dioxide, aluminum nitride, silicon carbide, magnesium oxide, beryllium oxide, kaolin, mica, zirconia, and two or more of these can also be combined. In the case of an epoxy resin, an amine-based curing agent is particularly preferably included.

[0180] The silicone elastomer particles of the present invention can be formulated as an additive in thermoplastic resins other than the above, and can also be used as a modifier for physical properties such as a surface lubricant or a stress reliever, or a modifier for optical properties such as a light scattering agent. The type of the thermoplastic resin is not particularly limited, and it can be at least one polymer selected from the group consisting of polycarbonate resins, polyester resins, polyether resins, polylactic acid resins, polyolefin resins such as polyethylene, polypropylene, ethylene-propylene copolymers, polystyrene resins, styrene copolymers, fluoropolymers such as tetrafluoroethylene, polyvinyl ethers, and cellulose polymers, or a composite resin formed by combining these. For the silicone resin-coated silicone elastomer particles of the present invention, a mixing device such as a twin-screw / single-screw extruder or a kneader can be used to uniformly disperse them in these thermoplastic resins (including masterbatches), and they can be formed into a desired shape such as a film and used.

[0181] The addition amount of the silicone elastomer particles of the present invention can be reasonably selected according to the physical properties required by the organic resin. Generally, however, it is in the range of 0.1 to 30 parts by mass, or can also be in the range of 0.5 to 10 parts by mass, relative to 100 parts by mass of the organic resin. This is because when the addition amount of the particles is less than the above lower limit, sometimes the stress relaxation characteristics and other properties of the resin and the like become insufficient, and there is a tendency that the flexibility and heat shock resistance of the obtained cured organic resin decrease. In particular, the heat shock resistance after moisture absorption decreases. On the other hand, when the addition amount of the above particles exceeds the above upper limit, sometimes the organic resin, coating / coating agent after formulation thickens and the operation workability decreases. In addition, there is a tendency that the mechanical properties of the obtained cured organic resin decrease.

[0182] Furthermore, when the silicone elastomer particles of the present invention are formulated in an organic resin, their stress relaxation effect is excellent. Therefore, they can be formulated in an epoxy resin for printed circuit boards to form a prepreg. Further, a copper foil for printed circuit boards with a resin layer containing the silicone elastomer particles of the present invention on one side of the copper foil can be formed, thereby realizing the use for a copper-clad laminate (CCL).

[0183] [Coating, coating agent]

[0184] Examples of the coating / coating agent containing the silicone elastomer particles of the present invention include: room temperature curing type, room temperature drying type, heat curing type. In addition, according to its properties, examples include: water-based, oil-based, powder type. Further, according to the carrier resin, examples include: polyurethane resin coating, butyral resin coating, long oil phthalic resin coating, alkyd resin coating, amino alkyd resin coating composed of amino resin and alkyd resin, epoxy resin coating, acrylic resin coating, phenolic resin coating, silicone-modified epoxy resin coating, silicone-modified polyester resin coating, silicone resin coating.

[0185] The addition amount of the silicone elastomer particles of the present invention is reasonably selected according to the physical properties required by the coating / coating agent. However, in order to uniformly impart a soft matte finish to the obtained coating film, 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 preferably in the range of 0.1 to 50 parts by mass, 0.1 to 20 parts by mass, relative to 100 parts by mass of the solid content of the coating. When the addition amount of the particles is less than the above lower limit, sometimes the properties such as the matte finish, adhesion, and stress relaxation characteristics of the coating film are insufficient. If the addition amount of the above particles exceeds the above upper limit, sometimes the organic resin, coating / coating agent after formulation thickens and the operation workability decreases.

[0186] In the coating / coating agent containing the silicone elastomer particles of the present invention, the following may also be contained: 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; amides such as N,N-dimethylformamide; olefins such as hexane, heptane, and octane; aromatic hydrocarbons such as toluene and xylene and other organic solvents; known inorganic fillers such as reinforcing silica, organic fillers, curing accelerators, silane coupling agents, pigments such as carbon black, dyes, antioxidants, thickeners composed of high molecular compounds, flame retardants, and weather resistance imparting agents.

[0187] [As an environmentally friendly material]

[0188] As described above, the silicone elastomer particles of the present invention are different from conventional non-biodegradable thermoplastic resin particles and silicone particle materials. In a biodegradable environment, it can be expected that at least a part of the crosslinked structure formed between silicon atoms in the silicone elastomer particles breaks, and the primary particles of the silicone elastomer particles are broken along with the generation of non-crosslinked polyorganosiloxane, showing biodegradable properties. Therefore, in addition to being used as "environmentally friendly" cosmetic raw materials and industrial raw materials with low environmental burden and environmental risks to cope with restrictions such as plastic micro-particles, it is also expected to be promoted as a "environmentally friendly" raw material with biodegradability to those who attach importance to the impact on the global environment and ordinary consumers.

[0189] Examples

[0190] The polycarbonate compound containing reactive groups (specifically, (meth)acryloyl-modified polycarbonate compound and alkenyl-modified polycarbonate compound) related to the present invention, the silicone elastomer particles using this compound as a raw material, and their manufacturing methods will be described in detail through examples and comparative examples. However, the present invention is not limited to these examples. The viscosity in the examples is the value at 25°C. In addition, the characteristics of each silicone particle are measured as follows. It should be noted that unless otherwise specified in the examples and the like, silicone particles refer to the general term of particles composed of silicone cured products (cured silicone particles) and do not include emulsions.

[0191] [Average primary particle size of emulsion particles]

[0192] The emulsion before adding the radical polymerization initiator and before adding the hydrosilylation catalyst is measured by a laser diffraction particle size distribution analyzer (LS-230 of Beckman Coulter), and its median diameter (the particle size corresponding to 50% of the cumulative distribution, 50% particle size) is set as the average particle size.

[0193] [Average secondary particle size of silicone particles (powder)]

[0194] Using ethanol as the dispersion medium, the particle size of the cured silicone particles was measured using a laser diffraction particle size distribution analyzer (Mastersizer 3000 from Malvern Panalytical), and the median diameter (particle size corresponding to 50% of the cumulative distribution, D90, μm), arithmetic dispersion (indicating the degree of dispersion of the particle size distribution, SD, μm2) of the cured silicone particles in ethanol were obtained. The test sample was used to disperse the cured silicone particles (1 g) and ethanol (100 mL) in a 300 mL cup using a stirring blade and an ultrasonic vibrator.

[0195] The components (A) used in the examples and comparative examples are as described below. It should be noted that "Me" represents methyl.

[0196] (a1) The methacryloyl-modified silicone polymer represented by the structural formula:

[0197] [Chemical formula 6]

[0198]

[0199] (wherein, m = 4, n = 267)

[0200] shown (viscosity at 25°C is 1524 mPas). (Reference [Synthesis Example])

[0201] (a2) The dimethylsiloxane / methylhydrogensiloxane copolymer capped with trimethylsilyloxy at both ends represented by the following structural formula:

[0202] Me3SiO-(Me2SiO) 47 -(Me(H)SiO) 15 -SiMe3

[0203] shown

[0204] [Synthesis Example]

[0205] In a four-neck separable flask, 92.07 parts by weight of dodecamethylcyclosiloxane, 0.01 part by weight of MEHQ ( = p-methoxyphenol, inhibitor), and 5.88 parts by weight of 3-methacryloxypropylmethyldimethoxysilane were charged. While introducing nitrogen, heating and stirring were carried out. When the temperature reached 50 °C, 0.05 part by weight of trifluoromethanesulfonic acid and 1.09 parts by weight of water were added. After reacting at 65 °C for 1 hour, the liquid temperature was heated to 70 °C. Further reduced pressure to 100 mmHg for about 1 hour to remove the by-product methanol. Then, 0.90 part by weight of hexamethyldisiloxane was added and reacted for 3 hours. After the reaction, ammonia gas was introduced to neutralize trifluoromethanesulfonic acid, and the generated salt was removed by filtration. The filtrate was subjected to reduced pressure treatment at 150 °C for 3 hours to remove volatile components. By C, Si-NMR analysis, a (a1) methacryloyl-modified silicone polymer with 267 dimethylsiloxane units, 4 methacryloyl-introduced siloxane units, and a viscosity of 1524 mPas was obtained.

[0206] [Example 1: Undecanol-modified polycarbonate compound b1]

[0207] In a four-neck separable flask equipped with a reflux condenser, 37.55 parts by weight of DMC (dimethyl carbonate), 52.6 parts by weight each of 1,4-butanediol and 1,6-hexanediol, and 9.85 parts by weight were charged. Further, 2536 ppm of DMAP (4-dimethylaminopyridine) was added. While introducing nitrogen, heating / stirring was carried out, and reflux was carried out for 1 hour when the internal liquid temperature of the flask reached 90 °C. Then, the outlet of the reflux condenser was opened to distillate, and after the distillation was completed, the pressure was reduced to 2 mmHg and reacted for 5 hours. After the reaction, the pressure was returned to normal pressure and cooled to room temperature. After cooling, 6.25 parts by weight of KYOWARD 700PL (manufactured by Kyowa Chemical Industry Co., Ltd.: synthetic aluminosilicate) was added and stirred for 1 hour. KYOWARD 700PL was removed by filtration to obtain a transparent liquid polymer. By H-NMR analysis, the following diol polycarbonate (PC2) was obtained.

[0208] [Chemical formula 7]

[0209]

[0210] (wherein, m + n ≥ 1)

[0211] 11.86 parts by weight of the obtained (PC2), 48.06 parts by weight of chloroform, and 16.6 parts by weight of potassium carbonate were charged into a four-neck separable flask. While introducing nitrogen and stirring, 23.48 parts by weight of undecenoyl chloride was added dropwise. It was carried out while cooling so that the heat release did not exceed 30 °C. After the dropwise addition, the reaction was carried out for about 5 hours and left overnight. The reaction solution was filtered, and the liquid part was recovered and chloroform was removed under reduced pressure. The obtained transparent liquid polymer was analyzed by H-NMR to be a polycarbonate (b1) modified at the terminal with an undecanol group and having the following structure.

[0212] (b1) is represented by the following structural formula:

[0213] [Chemical Formula 8]

[0214]

[0215] (wherein, x = 1 or 3, y = 1 or 3, n≥1)

[0216] [Example 2: Acrylic acid-modified polycarbonate compound b2]

[0217] Except that (PC2) in Example 1 was changed to 20.9 parts by weight, chloroform was changed to 46.35 parts by weight, potassium carbonate was changed to 22.12 parts by weight, MEHQ (hydroquinone monomethyl ether, polymerization inhibitor) was changed to 63 ppm, and acryloyl chloride was changed to 10.63 parts by weight, the same operations as in Example 1 were carried out to obtain a polycarbonate with an acryloyl-terminated modification (a (meth)acryloyl-modified polycarbonate compound) (b2) having the following structure.

[0218] (b2) is represented by the following structural formula:

[0219] [Chemical Formula 9]

[0220]

[0221] (wherein, x = 1 or 3, y = 1 or 3, n≥1)

[0222] [Examples 3 - 4, Comparative Example 1: Manufacture of polycarbonate elastomer particles]

[0223] Hereinafter, in Examples 3 - 4, production examples of organosilicon elastomer particles obtained using the above-mentioned undecanol-modified polycarbonate compound and (meth)acryloyl-modified polycarbonate compound as raw materials are shown. It should be noted that Comparative Example 1 is non-organosilicon polymer particles obtained only using the (meth)acryloyl-modified polycarbonate compound as a raw material.

[0224] [Example 3: Organosilicon elastomer particles No.1 (hydrosilylation reaction type)]

[0225] The organohydrogenpolysiloxane as the (a2) component and the undecanol-modified polycarbonate compound as the (b1) component were uniformly mixed at room temperature at a mass ratio of 53:47. Subsequently, the composition was dispersed in an aqueous solution at 25 °C composed of 0.5 part by mass of polyoxyethylene alkyl (C12-14) ether and 30 parts by mass of pure water, and further uniformly emulsified using a colloid mill and then diluted with 526 parts by mass of pure water to prepare an emulsion. Subsequently, an isopropanol solution of chloroplatinic acid (in this composition, an amount such that the platinum metal is 10 ppm by mass unit) and polyoxyethylene alkyl (C12-14) ether were used as an aqueous dispersion in pure water, added to the emulsion, stirred, and then the emulsion was allowed to stand at 60 °C for 6 hours to prepare a uniform aqueous suspension of elastomer particles. Subsequently, the aqueous suspension was filtered, and the residue was dried in an oven at 70 °C for 5 hours to obtain silicone elastomer particles No.1. The average primary particle diameter and average secondary particle diameter of the obtained silicone elastomer particles were 4.05 μm and 18.6 μm.

[0226] [Example 4: Silicone Elastomer Particles No.2 (Free Radical Polymerization Type)]

[0227] The methacryloyl-modified silicone polymer as the (a1) component and the (meth)acryloyl-modified polycarbonate compound as the (b2) component were uniformly mixed at room temperature at a mass ratio of 50:50. Subsequently, the composition was dispersed in an aqueous solution at 25 °C composed of 0.23 part by mass of Gohsenol EG-05C (manufactured by Mitsubishi Chemical: polyvinyl alcohol), 0.47 part by mass of Gohsenol EG-18P (manufactured by Mitsubishi Chemical: polyvinyl alcohol), and 46 parts by mass of pure water, and further uniformly emulsified using a colloid mill and then diluted with 526 parts by mass of pure water to prepare an emulsion. It was heated in a 1 L flask, and after reaching 70 °C, an aqueous solution obtained by dissolving 0.5 g of potassium persulfate (manufactured by Sigma-Aldrich) in 9.5 g of water was added dropwise for 1 minute. The emulsion was subjected to free radical polymerization at 70 °C for 3 hours, further heated, and the reaction was continued at 80 °C for 2 hours. 0.8 g of aminomethylpropanediol was added to terminate the reaction, and a uniform aqueous suspension of silicone elastomer particles was prepared. Subsequently, the aqueous suspension was filtered and washed with 200 ml of ethanol and 100 ml of acetone. The residue was dried in an oven at 70 °C for 5 hours to obtain silicone elastomer particles No.2. The average primary particle diameter and average secondary particle diameter of the obtained silicone elastomer particles were 5.04 μm and 53.0 μm.

[0228] [Comparative Example 1 (Free Radical Polymerization Type)]

[0229] Except for not using a polyorganosiloxane component and using only 100 parts by mass of the (b2) (meth) acryloyl-modified polycarbonate compound No. 1, non-silicone polymer particles were obtained in the same manner as in Example 5. The average primary particle diameter and average secondary particle diameter of the obtained particles were 2.80 μm and 259 μm, respectively.

[0230] The average primary particle diameter and average secondary particle diameter of each particle obtained through Examples 3 to 4 and Comparative Example 1 above are summarized in Table 1 below.

[0231] [Table 1]

[0232] Average primary particle size (μm) Average secondary particle size (μm) Silicone elastomer particle No.1 4.05 18.6 Silicone elastomer particle No.2 5.04 53.0 Particles of Comparative Example 1 2.80 259

[0233] [Cosmetic formulation example]

[0234] The following will show a formulation example of the cosmetic of the present invention capable of formulating silicone elastomer particles as one of the embodiments of the present invention. However, the present invention is not limited to these examples.

[0235] [Examples 5 and 6, Comparative Examples 2 and 3]

[0236] The following compositions described in Table 3 were used by experts to comparatively evaluate the usability of loose powders using silicone elastomer particles.

[0237] (Touch evaluation)

[0238] Based on the criteria in Table 2 below, the smoothness was evaluated when the samples were applied to the inner forearm of 18 panelists.

[0239] [Table 2]

[0240] Evaluation result Evaluation index ○ 12 or more out of 18 people answered that the smoothness was good Δ 7 - 11 out of 18 people answered that the smoothness was good × 6 or fewer out of 18 people answered that the smoothness was good

[0241] [Table 3]

[0242]

[0243] (Preparation method)

[0244] 1. Mix Phase A.

[0245] 2. Mix Phase B.

[0246] 3. Stir Phase A and Phase B until homogeneous.

[0247] As shown in Table 3, different from the loose powders using those without addition (Comparative Example 2) and other particles (Comparative Example 3), the loose powders using the silicone elastomer particles of the present invention (Examples 3 and 4) were evaluated to have good smoothness.

[0248] [Examples 7 and 8, Comparative Examples 4, 5 and 6]

[0249] Using the compositions described in Table 5, experts made a comparative evaluation of the feel of a water-in-oil sunscreen containing silicone elastomer particles.

[0250] (Evaluation of feel)

[0251] For the good extensibility, smoothness, moist feeling, and lack of roughness when applying the sample to the inner forearm of 18 panel members, evaluation was carried out according to the criteria in Table 4 below.

[0252] [Table 4]

[0253] Evaluation result Evaluation index ○ 12 or more out of 18 people answered good Δ 7 - 11 out of 18 people answered good × 6 or fewer out of 18 people answered good

[0254] [Table 5]

[0255]

[0256]

[0257] (Preparation method)

[0258] 1. Mix Phase A.

[0259] 2. Mix Phase B.

[0260] 3. Slowly add Phase B to Phase A while stirring.

[0261] 4. Add Phase C to the above step 3 and stir until homogeneous.

[0262] As shown in Table 5, the water-in-oil sunscreen using the silicone elastomer particles of the present invention (Examples 7 and 8) is different from the case of using no elastomer particles (Comparative Example 4) and the sunscreen using other particles (Comparative Example 6), and was evaluated to have good extensibility, be smooth and moist, and not prone to becoming astringent. In Comparative Example 5, DOWSILTM EP-9610 Cosmetic Powder absorbed the oil agent (polydimethylsiloxane) and the emulsifier (DOWSIL TM ES-5612 Formulation Aid), and could not be emulsified.

[0263] [Examples 9 and 10, Comparative Examples 7 and 8]

[0264] Using the compositions described in Table 7, experts made a comparative evaluation of the feel of a water-in-oil skin cream containing silicone elastomer particles.

[0265] (Evaluation of feel)

[0266] For the good extensibility, smoothness, moist feeling, and astringency when applying the sample to the inner forearm of 18 panel members, evaluation was carried out according to the criteria in Table 6 below.

[0267] [Table 6]

[0268] Evaluation result Evaluation index ○ 12 or more out of 18 people answered good Δ 7 - 11 out of 18 people answered good × 6 or fewer out of 18 people answered good

[0269] [Table 7]

[0270]

[0271] As shown in Table 7, the water-in-oil type skin care cream using the silicone elastomer particles of the present invention (Examples 9 and 10) is different from the skin care cream using no elastomer particles (Comparative Example 7) and the skin care cream using other particles (Comparative Example 8), and is evaluated to have good ductility, be smooth and have a moist feeling, and be not easily astringent.

[0272] [Example 11: Acrylate-modified polycarbonate compound b3]

[0273] Except that the polycarbonate (UH-50, ETERNACOLL(R) UH series, manufactured by UBE Industries, Ltd.) represented by the following structural formula:

[0274] [Chemical formula 10]

[0275]

[0276] (Mw = 500; n≥0 in the formula)

[0277] was changed to 26.7 parts by weight, chloroform was changed to 26.7 parts by weight, potassium carbonate was changed to 36.9 parts by weight, MEHQ (monomethyl ether of hydroquinone, polymerization inhibitor) was changed to 63 ppm, and acryloyl chloride was changed to 9.7 parts by weight, the same operations as in Example 1 were carried out to obtain a polycarbonate having the following structural formula:

[0278] [Chemical formula 11]

[0279]

[0280] The polycarbonate with the terminal modified to acryloyl group ((meth)acryloyl group-modified polycarbonate compound) (b3). This acryloyl group-modified polycarbonate (b3) can be used as a raw material for manufacturing silicone elastomer particles in the same way as the (b1) component or (b2) component in Example 3 (hydrosilylation reaction type) or Example 4 (free radical polymerization reaction type).

Claims

1. A polycaprolactone compound containing reactive groups, wherein, Having two or more within the molecule represented by the following structural formula (1): [Chemical formula 1] {In the formula, x and y are numbers in the range of 0 to 18, n is a number in the range of 0 to 30, and Ra is -C(=O)-R 1 -CR 2 =CH2 (R 1 is a chemical bond between CH and C(=O) or a divalent organic group having 0 to 20 carbon atoms, and R 2 is a hydrogen atom or a methyl group), and the modified polycarbonate structure is represented by a reactive group selected from (meth)acryloyl end groups and alkenyl end groups having 2 to 20 carbon atoms} 2. The polycarbonate compound containing reactive groups according to claim 1, wherein, In the modified polycarbonate structure represented by the above structural formula (1), x is a number in the range of 1 to 18.

3. The polycarbonate compound containing reactive groups according to claim 1, wherein, In the functional group Ra in the following structural formula (1), R 1 is a chemical bond between an oxygen atom (O) and C(=O) or an alkylene group having 1 to 20 carbon atoms.

4. The polycarbonate compound containing a reactive group according to any one of claims 1 to 3, which is represented by the following structural formula (1-1): [Chemical formula 2] (In the formula, Ra is the same group as described above, and x, y, and n are the same numbers as described above) as shown.

5. The polycarbonate compound containing a reactive group according to any one of claims 1 to 4, which is a raw material for synthesizing organosilicon elastomer particles.

6. The method for producing a polycarbonate compound containing a reactive group according to any one of claims 1 to 4, characterized in that a polycarbonate compound represented by the following structural formula (1'): [Chemical formula 3] (In the formula, x, y, and n are the same numbers as described above) as shown and From Cl-C(=O)-R 1 -CR 2 =CH2 (R 1 and R 2 being the same groups as described above) The (meth)acryloyl chloride compound or enoyl chloride compound shown is reacted in the presence of a basic catalyst.

7. An organosilicon elastomer particle having the following structure: at least two silicon atoms in the organosilicon elastomer particle are crosslinked by one or more reactions selected from the radical polymerization reaction of the polycarbonate compound containing a reactive group according to any one of claims 1 to 4 and the hydrosilylation reaction of a hydrogen atom bonded to a silicon atom.

8. The silicone elastomer particles according to claim 7, wherein, The organosilicon elastomer particle further has a structure represented by -(R2SiO) m - (In the formula, R is an unsubstituted or halogen atom-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 22 carbon atoms, or a hydroxyl group, and m is a number in the range of 1 to 1000) of a polyorganosiloxane structure.

9. The organosilicon elastomer particle according to claim 7 or 8, comprising at least: (A) at least one reactive organopolysiloxane selected from the following component (a1) and component (a2): (a1) an organopolysiloxane having at least three (meth)acryloyloxy-containing organic groups selected from at least one of an organic group containing a methacryloyloxy group and an organic group containing an acryloyloxy group in the molecule; and (a2) an organopolysiloxane having at least three hydrogen atoms bonded to silicon atoms in the molecule; (B) the polycarbonate compound containing a reactive group according to any one of claims 1 to 4; and (C) a curing agent selected from one or more of a radical polymerization initiator and a hydrosilylation reaction catalyst The organosilicon elastomer particle is formed by subjecting crosslinkable reactive organosilicon emulsion particles to a crosslinking reaction in water, and the crosslinkable reactive organosilicon emulsion particles are obtained by emulsifying a crosslinkable reactive organosilicon composition capable of being crosslinked by one or more reactions selected from a radical polymerization reaction and a hydrosilylation reaction of a hydrogen atom bonded to a silicon atom in water.

10. The silicone elastomer particles according to any one of claims 7 to 9, wherein, The average primary particle size measured by the laser diffraction scattering method is 0.5 to 20 μm.

11. The silicone elastomer particles according to any one of claims 7 to 10, wherein, The JIS-A hardness measured by curing the crosslinkable reactive organosilicon composition used to form the organosilicon elastomer particle into a sheet is in the range of 10 to 80.

12. The silicone elastomer particles according to any one of claims 7 to 10, wherein, It has a structure in which a part or all of its surface is coated with one or more selected from an organopolysiloxane resin, silica, and other organosilicon elastomer particles.

13. The silicone elastomer particles according to any one of claims 7 to 10, wherein, The silicone elastomer particles have a mesoporous structure.

14. The silicone elastomer particles according to any one of claims 7 to 10, wherein, The silicone elastomer particles contain an oil agent that is liquid at 40°C.

15. The silicone elastomer particles according to any one of claims 7 to 14, characterized in that, It has biodegradability.

16. The silicone elastomer particles according to any one of claims 7 to 14, wherein, The divalent organic groups having a partial structure formed by radical polymerization or hydrosilylation reaction of a polycarbonate compound containing a reactive group in the silicone elastomer particles are active in the biodegradation reaction. And in a biodegradable environment, the crosslinked structure formed between silicon atoms in the silicone elastomer particles is at least partially broken, and the primary particles of the silicone elastomer particles have the property of being broken along with the generation of a polyorganosiloxane with a non-crosslinked structure.

17. A cosmetic raw material containing the silicone elastomer particles according to any one of claims 7 to 16.

18. A cosmetic composition containing the silicone elastomer particles according to any one of claims 7 to 16.

19. An organic resin additive containing the silicone elastomer particles according to any one of claims 7 to 16.

20. An organic resin containing the silicone elastomer particles according to any one of claims 7 to 16.

21. A method for manufacturing the silicone elastomer particles according to any one of claims 7 to 16, which comprises the following steps (I) to (II): Step (I): Emulsifying at least one reactive organopolysiloxane selected from the following components (a1) and (a2) in water to form crosslinking-reactive silicone emulsion particles: (a1) An organopolysiloxane having at least three organic groups selected from organic groups containing methacryloxy groups and organic groups containing acryloxy groups in the molecule, and (a2) An organopolysiloxane having at least three silicon atoms bonded to hydrogen atoms in the molecule; (B) The polycarbonate compound containing a reactive group according to any one of claims 1 to 4; and (C) A curing agent selected from one or more of a radical polymerization initiator and a hydrosilylation reaction catalyst in water to form crosslinking-reactive silicone emulsion particles; Step (II): Curing the crosslinking-reactive silicone emulsion particles obtained in step (I) in the presence of the curing agent (C) to obtain silicone elastomer particles.

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