Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/0241—Containing particulates characterized by their shape and/or structure
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
  • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/12—Face or body powders for grooming, adorning or absorbing
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F18/02—Esters of monocarboxylic acids
  • C08F18/04—Vinyl esters
  • C08F18/08—Vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
  • C08F290/148—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/04—Aromatic polycarbonates
  • C08G64/045—Aromatic polycarbonates containing aliphatic unsaturation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/06—Preparatory processes
  • C08G77/08—Preparatory processes characterised by the catalysts used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/12—Powdering or granulating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/10—General cosmetic use
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/41—Particular ingredients further characterized by their size
  • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2230/00—Compositions for preparing biodegradable polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences

Definitions

• the present invention has a plurality of vinyl modifying groups (functional groups having a vinyloxycarbonyl structure via a spacer of a certain chain length) bonded to specific silicon atoms in the molecule, and is useful as a raw material for radical polymerization reaction.
• the present invention relates to a modified organopolysiloxane and a process for its preparation characterized by transvinylation of carboxylic acid modifying groups with vinyl acetate.
• the present invention also relates to a radically polymerizable polymer or a radically polymerizable copolymer (particularly containing silicone elastomer particles) made from the vinyl-modified organopolysiloxane, and its application, production method and use.
• Organosilicon compounds containing one vinyloxycarbonyl group in the molecule are known, and since the vinyloxycarbonyl group is radically polymerizable, it is known to be used as a raw material for polymers by a homopolymerization or copolymerization reaction (for example, Patent Document 1 and Non-Patent Document 1).
• Patent Document 1 and Non-Patent Document 1 disclose so-called raw materials for monomers, compounds having a plurality of vinyloxycarbonyl groups via a spacer of a specific chain length in the molecule and containing an organopolysiloxane structure is not specifically disclosed.
• organopolysiloxane having at least three (meth)acryloxy group-containing organic groups is proposed as a main component and has a structure crosslinked by divalent organic groups having a partial structure formed by radical polymerization of vinyl acetate.
• the silicone elastomer particles can be expected to have a high degree of biodegradability, and compared to conventional silicone elastomer particles, their aggregation over time is suppressed, giving a smaller average secondary particle size.
• organopolysiloxanes containing (meth)acryloxy group-containing organic groups still have room for improvement in terms of their industrial productivity and structural optimization as radically polymerizable raw materials in biodegradable polymers or copolymers.
• the present invention has been made to solve the above problems, and provides a vinyl-modified organopolysiloxane useful as a raw material for radical polymerization reactions, particularly for use in biodegradable polymers or copolymers, and a method for producing the same. Furthermore, the present invention provides a radically polymerizable polymer or radically polymerizable copolymer containing at least a portion of the vinyl-modified organopolysiloxane as a starting material, and uses and production methods thereof.
• R 1 is a divalent organic group having 4 to 20 carbon atoms
• R 2 is a hydrogen atom or a methyl group
• R 3 is an unsubstituted or halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 22 carbon atoms or a hydroxyl group
• n is 1 to numbers in the range of 1000
• the inventors have found that the above problems can be solved by a vinyl-modified organopolysiloxane having a polyorganosiloxane structure represented by the present invention.
• the present inventors have found the above-described vinyl-modified organopolysiloxane production method comprising the step of transvinylating a specific carboxylic acid-modified organopolysiloxane with a vinyl carboxylate compound in the presence of a palladium metal catalyst. We have found that the problem can be solved and arrived at the present invention.
• the present inventors have found that the above problems can be solved by a radically polymerizable polymer or a radically polymerizable copolymer, particularly silicone elastomer particles, containing the vinyl-modified organopolysiloxane as at least a part of the starting materials. arrived at the invention. Furthermore, the present inventors have found that the above problems can be solved by a cosmetic raw material, organic resin additive, cosmetic or organic resin containing these radically polymerizable polymers or radically polymerizable copolymers. reached.
• the present invention provides a vinyl-modified organopolysiloxane that is useful as a raw material for radical polymerization reactions, particularly for biodegradable polymers or copolymers, and a method for producing the same. Furthermore, the present invention provides a radically polymerizable polymer or radically polymerizable copolymer containing at least a portion of the vinyl-modified organopolysiloxane as a starting material, and uses and production methods thereof.
• the vinyl modified group (R Ac ) in the formula is a functional group in which a methacryloxycarbonyl group or a vinyloxycarbonyl group is bonded via a silicon atom and a spacer R 1 having a certain chain length, and is used in the present invention.
• Such vinyl-modified organopolysiloxane has 2 or more, preferably 2 to 20, more preferably 2 to 15 vinyl-modified groups (R Ac ) in the molecule.
• the binding site of the vinyl modifying group (R Ac ) may be a side chain or a terminal of the organopolysiloxane. In some cases, it is easy to synthesize an organopolysiloxane having a vinyl-modified group (R Ac ) at the side chain site.
• R 1 is a divalent organic group having 4 to 20 carbon atoms and is a functional group serving as a spacer between a methacryloxycarbonyl group or a vinyloxycarbonyl group and an Si atom. If this length is too short, the biodegradability may decrease, especially when it is used as a raw material for a biodegradable polymer. In copolymers, the tactile sensation and feeling of use peculiar to silicone may be lost, and soft properties may not be obtained.
• Such R 1 is preferably an alkylene group having 4 to 20 carbon atoms, particularly preferably an alkylene group having 6 to 15 carbon atoms.
• R2 is a hydrogen atom or a methyl group and is a functional group that gives a vinyloxycarbonyl group or a methacryloxycarbonyl group.
• n is the number of repeating diorganosiloxane units, n is a number in the range of 1 to 1000, and from the viewpoint of the flexibility of the resulting radically polymerizable polymer or copolymer, n is in the range of 50 to 750. It can be a range of numbers.
• R 3 is an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with a halogen atom and having 1 to 20 carbon atoms, an aryl group having 6 to 22 carbon atoms or a hydroxyl group. Or it may be a phenyl group.
• Such a vinyl-modified organopolysiloxane is preferably a dimethylpolysiloxane having vinyl-modified groups (R Ac ) in side chains and has the following structural formula: Vinyl-modified organopolysiloxane represented by can be preferably exemplified.
• n is a number in the range of 1-1000, preferably in the range of 50-750.
• m is a number in the range of 3-100, more preferably in the range of 3-20, more preferably in the range of 3-15.
• R Ac is the aforementioned silicon-bonded vinyl modifying group.
• a carboxylic acid-modified organopolysiloxane having a polyorganosiloxane structure represented by is transvinylized with vinyl acetate in the presence of a palladium metal catalyst.
• the carboxylic acid-modified organopolysiloxane is a precursor raw material, and the linking group (spacer) between the Si atom and the carboxylic acid-modified group may be a divalent organic group represented by R1 above.
• R1 divalent organic group represented by R1 above.
• a vinyl carboxylate compound is a raw material for transvinylation of a carboxylic acid modifying group, and provides a vinyl modifying group (R Ac ) in the presence of palladium metal catalyst such as palladium acetate, palladium chloride, palladium black.
• the vinyl carboxylate compound is not particularly limited as long as it can be transvinylized. It is preferable to use vinyl acetate because of its excellent reactivity.
• a palladium metal catalyst may be used in combination with a heavy metal ligand such as 1,10-phenanthroline.
• the reaction may be carried out in an organic solvent or in a liquid vinyl carboxylate compound such as vinyl acetate.
• the reaction conditions are not limited, it is preferable to convert the carboxylic acid terminal group to a vinyl ester structure by heating in the range of room temperature to 100° C. with stirring and N2 gas flow.
• the reaction time depends on the reaction scale and reaction temperature, it is generally in the range of several hours to several tens of hours.
• the vinyl-modified organopolysiloxane according to the present invention is radically polymerizable, and the resulting radically polymerizable polymer or radically polymerizable copolymer is expected to be biodegradable.
• a radically polymerizable polymer or radically polymerizable copolymer is composed of the vinyl-modified organopolysiloxane of the present invention alone, or together with the vinyl-modified organopolysiloxane of the present invention, in the presence of a radical initiator. It can be obtained by a radical polymerization reaction using two or more kinds of radically polymerizable monomers in combination.
• radical initiator conventionally known compounds generally used in radical polymerization methods are used. Specifically, 2,2′-azobis(isobutyrate)dimethyl, 2,2′-azobis(isobutyronitrile ), 2,2′-azobis (2-methylbutyronitrile), and 2,2′-azobis (2,4-dimethylvaleronitrile) azo compounds; benzoyl peroxide, lauroyl peroxide, tert-butyl Organic peroxides such as peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, and tert-hexyl peroxy-2-ethylhexanoate; peroxides such as potassium persulfate, sodium persulfate and ammonium persulfate; Sulfate is exemplified. These radical initiators may be used singly or in combination of two or more.
• the amount of the radical initiator to be used is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the radically polymerizable components including the vinyl-modified organopolysiloxane.
• a radically polymerizable polymer or a radically polymerizable copolymer can be obtained without the need for a solvent.
• the radical initiator is a water-soluble persulfate such as potassium persulfate
• the crosslinkable silicone emulsified particles obtained by emulsifying the crosslinkable silicone composition by the radical polymerization reaction described below in water are crosslinked in water.
• reacting it has the advantage of being extremely easy to add and react.
• a chain transfer agent can optionally be added in the polymerization reaction using the above radical initiator.
• the chain transfer agent include mercapto compounds such as 2-mercaptoethanol, butylmercaptan, n-dodecylmercaptan, 3-mercaptopropyltrimethoxysilane, and polydimethylsiloxane having a mercaptopropyl group; Halides such as carbon chloride, butyl bromide, and 3-chloropropyltrimethoxysilane are included.
• radically polymerizable monomers are generally exemplified by acrylic acid ester-based monomers or methacrylic acid ester-based monomers having 4 to 13 carbon atoms, and acrylic acid esters having 4 to 10 carbon atoms. Or it may be a methacrylic acid ester.
• acrylic acid ester-based monomers or methacrylic acid ester-based monomers having 4 to 13 carbon atoms, and acrylic acid esters having 4 to 10 carbon atoms. Or it may be a methacrylic acid ester.
• Representative examples include methyl (meth)acrylate, ethyl (meth)acrylate, and n-propyl (meth)acrylate.
• polyfunctional vinyl monomers can also be used, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate.
• the other radically polymerizable monomers are vinyl acetate and (meth)acrylic modified polycaprolactone compounds. Including these components as raw materials may improve the biodegradability of the resulting radically polymerizable copolymer.
• the radically polymerizable copolymer of the present invention may contain vinyl acetate as its starting material.
• the structure derived from such a monomer component may improve the biodegradability of the resulting radically polymerizable copolymer, as well as improve oil absorption and blending stability.
• the radically polymerizable polymer of the present invention includes, as a starting material, a (meth)acrylic-modified polycaprolactone compound having the following structural formula (1) in the molecule: (1) may include a (meth)acrylic-modified polycaprolactone compound having two or more modified polycaprolactone structures having The structure derived from such a monomer component may improve the biodegradability of the resulting radically polymerizable copolymer, and may also improve the texture and feeling of use.
• R2 is a hydrogen atom or a methyl group, which gives an acrylic modified group or a methacrylic modified group, respectively.
• the (meth)acrylic-modified polycaprolactone compound of the present invention is a compound represented by one or more structural formulas selected from the following structural formulas (1-1) to (1-3), good. Each compound has two, three and four modified polycaprolactone structures represented by the following structural formula (1).
• Structural formula (1-1) (1-1) Structural formula (1-2): (1-2) Structural formula (1-3): (1-3)
• Ra is the same group as described above.
• m and n are each independently a number ranging from 1 to 5, m+n is a number ranging from 2 to 20, and m+n is a number ranging from 2.5 to 10. and may be a number in the range of 3-7.
• w, x, y, and z are each independently a number ranging from 1 to 5
• x+y+z is a number ranging from 3 to 20
• w+x+y+z may be a number in the range of 4-20.
• x+y+z may be a number in the range of 3-7 and w+x+y+z may be a number in the range of 4-10.
• Such a (meth)acrylic-modified polycaprolactone compound can be obtained by reacting a precursor polycaprolactone compound having a polyol terminal structure with a (meth)acryloyl chloride compound in the presence of a basic catalyst. can.
• the radically polymerizable polymer or radically polymerizable copolymer containing the vinyl-modified organopolysiloxane of the present invention as at least a part of the starting material may be gel or particulate.
• they may be silicone elastomer particles as described below.
• the vinyl-modified organopolysiloxane according to the present invention is useful as a starting material for silicone elastomer particles, and comprises (A) the vinyl-modified organopolysiloxane and (B) one or more radically polymerizable monomers. is obtained by radical polymerization in the presence of (C) a radical initiator.
• the silicone elastomer particles according to the present invention are preferably obtained by curing cross-linkable silicone emulsified particles through a cross-linking reaction.
• the silicone elastomer particles of the present invention are defined by their manufacturing process, comprising (A) the vinyl-modified organopolysiloxane described above, (B) one or more radically polymerizable monomers and (C ) Silicone elastomer particles obtained by cross-linking in water cross-linkable silicone emulsified particles obtained by emulsifying a cross-linkable silicone composition that contains at least a radical polymerization initiator and can be cross-linked by a radical polymerization reaction in water.
• the silicone elastomer particles of the present invention contain the above vinyl-modified organopolysiloxane as a part or all of component (B). , vinyl acetate and (meth)acrylic-modified polycaprolactone compounds are preferably used.
• silicone elastomer particles obtained through such a production process may further improve the appearance, spreadability, and feel of cosmetics, especially when used as raw materials for cosmetics.
• problems of the present invention can be solved more favorably.
• one of the preferred modes for realizing the technical effects of the present invention can and is suitable to be defined by the manufacturing process.
• the crosslinkable silicone composition described above may contain one or more polymerization inhibitors from the standpoint of preventing unintended side reactions.
• one or more selected from hindered phenol-based polymerization inhibitors, hydroquinone-based polymerization inhibitors, and catechol-based polymerization inhibitors may be included.
• the amount used can be appropriately selected, but the total concentration of the polymerization inhibitor is preferably 50 ppm by mass or less, and 30 ppm by mass or less, relative to the sum of the components (A) to (C). is more preferable.
• the crosslinkable silicone composition may contain components other than the above components within the range that does not impair the technical effects of the present invention.
• aliphatic hydrocarbons such as n-hexane, cyclohexane and n-heptane
• aromatic hydrocarbons such as toluene, xylene and mesitylene
• ethers such as tetrahydrofuran and dipropyl ether
• ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone.
• Organic solvents such as phenolic, quinone, amine, phosphorus, phosphite, sulfur, or thioether antioxidants; triazole or benzophenone light stabilizers; phosphate esters, Flame retardants such as halogen-based, phosphorus-based, or antimony-based; one or more antistatic agents consisting of cationic surfactants, anionic surfactants, or nonionic surfactants; dyes; pigments, etc. be able to.
• Organic solvents such as phenolic, quinone, amine, phosphorus, phosphite, sulfur, or thioether antioxidants; triazole or benzophenone light stabilizers; phosphate esters, Flame retardants such as halogen-based, phosphorus-based, or antimony-based; one or more antistatic agents consisting of cationic surfactants, anionic surfactants, or nonionic surfactants; dyes; pigments, etc. be able to.
• the silicone elastomer particles of the present invention optionally have a structure in which (a) part or all of the surface is coated with one or more selected from organopolysiloxane resin, silica, and other silicone elastomer particles; (c) a structure containing an oil agent that is liquid at 40°C; and (d) a structure crosslinked by silalkylene groups having 2 to 20 carbon atoms, and any structure that provides these structures. Combinations of ingredients may also be used.
• the radically polymerizable polymer or radically polymerizable copolymer (including the silicone elastomer particles described above) according to the present invention is useful as a raw material for cosmetics. It is much more excellent in improving the feeling of use and handling, and is remarkably excellent in handling workability as a cosmetic raw material, storage stability, and blending stability in a system.
• the radically polymerizable polymers or copolymers (including the silicone elastomer particles described above) of the present invention are also very useful as organic resin additives.
• the radically polymerizable polymer or radically polymerizable copolymer of the present invention is excellent in uniform dispersibility in organic resins and, if desired, in stress relaxation properties and the like. remarkably excellent in durability and storage stability.
• members, coatings, or coatings made by curing organic resins containing the silicone elastomer particles have improved flexibility (including the softness of the coating layer), durability, and adhesion and conformability to substrates. Because of its excellent flexibility and thermal shock resistance, it is extremely useful as a highly functional organic resin, paint or coating agent for use in electronic materials.
• the crosslinked structure formed between silicon atoms is at least partially It is expected to have a biodegradable property in which it is cleaved into two and disintegrated with the generation of non-crosslinked polyorganosiloxane. For this reason, it can be used as an "eco-friendly" cosmetic raw material and industrial raw material with low environmental impact and low environmental risk in response to regulations such as microplastics. It can be expected that it will be able to appeal that it is an "eco-friendly" material with biodegradability.
• Example 1 Synthesis of vinyl-modified organopolysiloxane No. 1
• a carboxylic acid-modified silicone oil represented by (molecular weight: 31649.36)
• 24.6 parts by weight of vinyl acetate manufactured by Fuji Film Wako, molecular weight: 86.09 were charged.
• Example 2 Synthesis of gel composed of radically polymerizable polymer
• N2 was bubbled into the flask while stirring at 200 rpm.
• 4 parts by weight of an oil-soluble azo polymerization initiator "trade name V-601" (dimethyl 2,2'-azobis(isobutyrate), manufactured by Fuji Film Wako, molecular weight: 230.26) was added.
• the raw materials were heated to 70° C. with stirring, and after 3 hours, a gel-like material, which was a single radical polymer of vinyl-modified organopolysiloxane No. 1, was formed in the flask.
• Example 3 shows an example of the production of silicone elastomer particles obtained using the vinyl-modified organopolysiloxane No. 1 and the (meth)acrylic-modified polycaprolactone compound as starting materials.
• Comparative Example 1 is a non-silicone polymer particle obtained using only a (meth)acrylic-modified polycaprolactone compound as a raw material.
• the (meth)acrylic-modified polycaprolactone compound represented by is mixed uniformly at room temperature at a mass ratio of 30:70, and then added and mixed with vegetable oil (manufactured by AAK) in an amount that will be 20% of the total composition. bottom.
• this composition was dispersed in an aqueous solution containing 0.24 parts by mass of GOHSENOL EG-05C and 0.47 parts by mass of GOHSENOL EG-18P in an aqueous solution of 46 parts by mass of pure water at 25°C.
• Silicone elastomer particles were obtained in the same manner as in Example 3 except that 100 parts by mass of the (meth)acrylic-modified polycaprolactone compound used as a raw material in Example 3 was used without using polyorganosiloxane.
• the average secondary particle size of the obtained silicone elastomer particles was 70.0 ⁇ m.
• Example 3 The average primary particle size and average secondary particle size of each particle obtained in Example 3 and Comparative Example 1 are summarized in Table 1 below.
• Example 4 A panelist comparatively evaluated the feeling of use of loose powders using the silicone elastomer particles with the composition shown in Table 3. (tactile evaluation) The smoothness of the samples applied to the inside of the forearms of 18 panelists was evaluated according to the criteria shown in Table 2 below.
• Example 3 the loose powder using the silicone elastomer particles of the present invention (Example 3) was evaluated as having relatively good slip properties, unlike the loose powder using other particles (Comparative Example 1). was done.

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