Classifications

• • 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
  • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
• • 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
  • 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
  • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
  • C08G63/08—Lactones or lactides
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
  • C08G63/6952—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from hydroxycarboxylic acids
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/91—Polymers modified by chemical after-treatment
  • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
• • 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
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • 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
• • 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
• • 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

Definitions

• the present invention provides a radically polymerizable polycaprolactone-modified silicone compound that has a (meth)acrylic end group and can form novel silicone-polycaprolactone copolymer particles by radical polymerization with one component, and a method for producing the same. Furthermore, the present invention relates to novel silicone-polycaprolactone copolymer particles that have a silicon atom crosslinked structure derived from the radically polymerizable polycaprolactone-modified silicone compound and further a polycaprolactone structure, and can impart an excellent feel and usability to cosmetics.
• the novel silicone-polycaprolactone copolymer particles have a crosslinked structure that is active for biodegradation, the primary particles are expected to disintegrate in nature through decomposition reactions caused by microorganisms, etc., with the generation of non-crosslinked siloxane molecules, and the particles are expected to behave as biodegradable particles. Furthermore, the present invention relates to cosmetic raw materials, cosmetic compositions, organic resin additives, and other uses containing the silicone-polycaprolactone copolymer particles, and to a method for producing the silicone-polycaprolactone copolymer particles.
• Silicone elastomer particles are formed by curing an addition reaction curable silicone composition or a condensation reaction curable silicone composition, and although their particle size and oil absorption vary depending on the production method, they are widely used as cosmetic ingredients and stress relief agents for thermoplastic resins.
• the present applicant has proposed silicone particles with excellent dispersibility, high lipophilicity, and excellent storage stability, which are silicone particles containing alkylene groups having 4 to 20 carbon atoms and which are formed by curing a crosslinkable composition for forming silicone particles that contains an alkenyl group having 4 to 20 carbon atoms, such as a hexenyl group, and has a low content of silicon-bonded hydrogen atoms per unit mass, as described in Patent Document 1.
• conventional silicone elastomer particles are formed through a crosslinking reaction of organopolysiloxane raw materials by a hydrosilylation reaction or the like, but the crosslinked structure is chemically stable, and if these silicone elastomer particles were to be released into the natural environment, there is a possibility that, like so-called microplastics, they would continue to remain in the natural environment without decomposing, at least for a short period of time. Therefore, in order to reduce the risk to the global environment, there seems to be a latent demand in the market for silicone elastomer particles that have the performance to smoothly replace or substitute existing silicone elastomer particles and are expected to be highly biodegradable.
• silicone elastomer particles having a structure crosslinked by a divalent organic group having a partial structure formed by radical polymerization of vinyl acetate as described in Patent Document 2.
• the silicone elastomer particles are expected to be highly biodegradable, and compared to conventional silicone elastomer particles, they have reduced tendency to aggregate over time and give a smaller average secondary particle size, which has successfully achieved the properties of excellent dispersibility, ease of handling as a cosmetic raw material, storage stability, and compounding stability into systems.
• Patent Document 3 discloses an (AB)n-type block copolymer containing a polycaprolactone structure and a polysiloxane structure.
• Non-Patent Documents 1 to 3 disclose reacting a polycaprolactone compound having a polyol terminal structure with butyroyl chloride or the like, but do not disclose a radically polymerizable polycaprolactone-modified silicone compound of a specific structure that has multiple polycaprolactone structures with a relatively low degree of polymerization in the molecule, all of whose terminal structures are (meth)acrylic terminal groups, and that can form silicone elastomer particles through a crosslinking reaction between polysiloxane structures or a radical polymerization reaction with an organopolysiloxane containing a (meth)acrylic group.
• the present invention has been made to solve the above problems, and provides novel copolymer particles that, when incorporated into cosmetic compositions and the like, can achieve a feel and texture equal to or better than that of conventional silicone elastomer particles and have a structure that is active toward biodegradability, as well as a radical-polymerizable polycaprolactone-modified silicone compound with a specific structure that is useful as a raw material for the synthesis reaction of the particles, and a method for producing the same.
• the present invention aims to provide cosmetic raw materials, organic resin additives, and other applications that are excellent in terms of usability, etc., by using the copolymer particles.
• the present invention aims to provide cosmetic compositions that contain the copolymer particles and are excellent in terms of usability, etc.
• the present invention aims to provide copolymer particles, their synthetic raw materials, and uses thereof, which, in addition to having performance equal to or greater than that of conventional silicone elastomer particles, are expected to be biodegradable, thereby reducing potential risks to the global environment, enabling industrially sustainable and stable use, and which can be promoted as an eco-friendly material with biodegradability to users and general consumers who are concerned about the impact on the global environment.
• n is a number ranging from 1 to 5;
• R a has two or more modified polycaprolactone structures represented by a group selected from a hydrogen atom and a (meth)acrylic terminal group represented by -R 1 -CR 2 ⁇ CH 2 (R 1 is a carbonyl group or a divalent linking group containing one carbonyl group, and R 2 is a hydrogen atom or a methyl group);
• R 1 is a carbonyl group or a divalent linking group containing one carbonyl group, and R 2 is a hydrogen atom or a methyl group
• the present inventors have found that the above problems can be solved by using a radically polymerizable polycaprolactone-modified silicone compound and its use as a raw material for silicone-polycaprolactone copolymer particles, and have arrived at the present invention.
• silicone-polycaprolactone copolymer particles having a structure in which at least two silicon atoms in the particles are crosslinked by a radical polymerization reaction of the radically polymerizable polycaprolactone-modified silicone compound described in any one of claims 1 to 4, and by cosmetic raw materials, organic resin additives, cosmetics, or organic resins containing the same, and arrived at the present invention.
• the radically polymerizable polycaprolactone-modified silicone compound having the specific structure according to the present invention can be radically polymerized as one component to obtain silicone-polycaprolactone copolymer particles.
• silicone-polycaprolactone copolymer particles are blended into cosmetic compositions and the like, they can provide a feel and texture that is equal to or better than that of conventional silicone elastomer particles.
• silicone-polycaprolactone copolymer particles according to the present invention it is possible to provide cosmetic raw materials, organic resin additives, and other uses that contain the silicone-polycaprolactone copolymer particles.
• cosmetic compositions that contain the silicone-polycaprolactone copolymer particles according to the present invention it is possible to provide cosmetics that are excellent in feel when used, etc.
• the silicone-polycaprolactone copolymer particles according to the present invention have a structure in the elastomer particles that has both polyorganosiloxane chains and polycaprolactone chains, and the divalent organic group having the partial structure is active in biodegradable reactions, and is designed so that in a biodegradable environment, the crosslinked structure formed between silicon atoms in the copolymer particles at least partially cleaves, and the primary particles disintegrate with the generation of non-crosslinked polyorganosiloxanes.
• the elastomer particles according to the present invention are expected to be biodegradable, and can reduce risks to the global environment, and can be promoted as an eco-friendly material that can be used with a considerable sense of security to consumers and general consumers who place importance on the impact on the global environment.
• (meth)acrylic means “acrylic or methacrylic", and when it is expressed as “(meth)acrylic-modified”, it means that the modified group may be one or both of an acrylic-modified group and a methacrylic-modified group.
• (meth)acryloxy means “methacryloxy or acryloxy”
• (meth)acryloxy group-containing organic group means that it may be one or both of a methacryloxy group-containing organic group and an acryloxy group-containing organic group.
• the radically polymerizable polycaprolactone-modified silicone compound according to the present invention is designed as a reactive raw material for the novel silicone-polycaprolactone copolymer particles according to the present invention, and is a component that imparts crosslinked structures via divalent organic groups between polycaprolactone chains and to silicone chains within the elastomer particles through its radical polymerization reaction.
• the radical polymerizable polycaprolactone-modified silicone compound of the present invention has, in the molecule, a compound represented by the following structural formula (1): (1) wherein n is a number ranging from 1 to 5; R a has two or more modified polycaprolactone structures represented by a group selected from a hydrogen atom and a (meth)acrylic terminal group represented by -R 1 -CR 2 ⁇ CH 2 (R 1 is a carbonyl group or a divalent linking group containing one carbonyl group, and R 2 is a hydrogen atom or a methyl group);
• this radically polymerizable polycaprolactone-modified silicone compound has two or more (meth)acrylic end groups as part of the modified polycaprolactone structure in the molecule or as a functional group different from the modified polycaprolactone structure, and the component alone has radical polymerizability.
• the above Ra may be a hydrogen atom, in which case the molecule has a modified polycaprolactone structure having an OH terminal, but in order to impart radical polymerizability to the molecule as a whole, it is necessary for the molecule to have a specific functional group having a (meth)acrylic terminal group bonded to a silicon atom, which is different from the modified polycaprolactone structure.
• the modified polycaprolactone structure itself imparts radical polymerizability, so that this component alone can obtain radical polymerizability as the molecule as a whole, even if it does not have other radically polymerizable functional groups.
• the polysiloxane structure in the molecule is preferably chain-like, more preferably linear or branched, and particularly preferably has a linear polysiloxane structure.
• the modified polycaprolactone structure bonded to a silicon atom and represented by the structural formula (1) above, or a (meth)acrylic terminal group bonded to a silicon atom and represented by -R3 - CR4 CH2 ( R3 is a carbonyl group or a divalent linking group containing one carbonyl group, and R4 is a hydrogen atom or a methyl group) may be bonded to the end or side chain of the linear polysiloxane structure.
• radically polymerizable polycaprolactone-modified silicone compounds having the structure shown below are included in the scope of the present invention.
• x is a number ranging from 1 to 5
• n and m are each positive numbers of 2 or more.
• the functional group bonded to the bar (-) on the silicon atom is not particularly limited as long as it is a monovalent organic group that does not impair the technical effect of the present invention, and industrially it may be a methyl group, a phenyl group, a hydroxyl group, etc., or it may be a polyoxyalkylene group, or a monovalent organic group containing a macromonomer structure having a silicon atom or a carbosiloxane dendrimer structure.
• the top four are examples of molecular structures having a modified polycaprolactone structure bonded to a silicon atom at the end of a chain polysiloxane structure
• the bottom three are examples of molecular structures having a modified polycaprolactone structure bonded to a silicon atom at the side chain of a chain polysiloxane structure.
• the radical polymerizable polycaprolactone-modified silicone compound has two or more (meth)acrylic terminal groups in its molecule.
• the radical polymerizable polycaprolactone-modified silicone compound of the present invention has a linear or branched polysiloxane structure and is bonded to a silicon atom at a molecular chain terminal or a molecular chain side chain directly or via a divalent linking group, and has the following structural formula (1): (1) wherein n is a number ranging from 1 to 5; Ra has two or more modified polycaprolactone structures represented by a group selected from a hydrogen atom and a (meth)acrylic end group represented by -R 1 -CR 2 ⁇ CH 2 (R 1 is a carbonyl group or a divalent linking group containing one carbonyl group, and R 2 is a hydrogen atom or a methyl group), and when the modified polycaprolactone structure in the molecule contains less than two (meth)acrylic end groups, the molecule has two or more (meth)acrylic end groups bonded to silicon atoms and represented by -R 3 -CR 4 ⁇ CH 2 (R
• the radical polymerizable polycaprolactone-modified silicone compound of the present invention has a linear polysiloxane structure having modified polycaprolactone structures at both ends of the molecular chain, that is, a compound represented by the following structural formula (2): (2) (Q is a group represented by the following structural formula (1): (1) wherein n is a number ranging from 1 to 5; R a is a modified polycaprolactone structure represented by a group selected from a hydrogen atom or a (meth)acrylic terminal group represented by -R 1 -CR 2 ⁇ CH 2 (R 1 is a carbonyl group or a divalent linking group containing one carbonyl group, and R 2 is a hydrogen atom or a methyl group); R q is a (meth)acrylic terminal group bonded to a silicon atom and represented by -R 3 -CR 4 ⁇ CH 2 (R 3 is a carbonyl group or a divalent linking group containing one carbonyl group, and R 4
• Ra is a hydrogen atom in one or both of the terminal groups Q
• s is a positive number and is a number having at least two (meth)acrylic terminal groups in the molecule.
• a radical polymerizable polycaprolactone-modified silicone compound represented by the following formula is preferred.
• the radical polymerizable polycaprolactone-modified silicone compound represented by the above structural formula (2) is a radical polymerizable polycaprolactone-modified silicone compound that satisfies either the following condition (I) or (II) depending on the presence or absence of a (meth)acrylic terminal group in the modified polycaprolactone structure.
• Ra is a hydrogen atom, s is a number in the range of 2 to 50, and t is a number in the range of 1 to 500;
• Ra is a (meth)acrylic terminal group represented by -R 1 -CR 2 ⁇ CH 2 (R 1 is a carbonyl group or a divalent linking group containing one carbonyl group, and R 2 is a hydrogen atom or a methyl group), and s is a number in the range of 0 to 50 and t is a number in the range of 1 to 500.
• the modified polycaprolactone structure (Q) represented by structural formula (1) is bonded to a silicon atom directly or via a divalent linking group.
• the divalent linking group is preferably a linear or branched alkylene group having 2 to 20 carbon atoms.
• the radically polymerizable polycaprolactone-modified silicone compound according to the present invention is designed as a crosslinking agent between silicon atoms in the particles, and since the number of caprolactone units in each structure is relatively small and the number of repeating caprolactone units in the molecule as a whole is also relatively small, it has the advantage of not significantly impairing the feel and sensation of use derived from the organopolysiloxane main chain of the copolymer particles.
• the sum of the number of repeating caprolactone units in the molecule is preferably in the range of 2 to 20, and may be in the range of 2.5 to 15, or in the range of 3.0 to 10. If the number of repeating caprolactone units in the radically polymerizable polycaprolactone-modified silicone compound molecule exceeds the upper limit, the properties derived from the polycaprolactone structure will be strongly reflected in the resulting silicone elastomer particles, which may adversely affect the feel and usability of cosmetics, etc.
• Ra is a hydrogen atom
• it means a structure derived from a polycaprolactone compound having a polyol (alcohol) hydroxyl group terminal
• the modified polycaprolactone structure itself does not have radical polymerizability.
• Ra is a (meth)acrylic terminal group of the above structure
• the modified polycaprolactone structure itself has radical polymerizability.
• R 2 is a hydrogen atom or a methyl group, which respectively give an acrylic modified group or a methacrylic modified group.
• the radically polymerizable polycaprolactone-modified silicone compound of the present invention although it is a single component, forms a crosslinked structure within the copolymer particles by a radical polymerization reaction, and when the resulting silicone-polycaprolactone copolymer particles are used as a cosmetic ingredient, the feeling of use or feel is not impaired, and the crosslinked structure formed between the two silicon atoms is expected to be biodegradable.
• the radically polymerizable polycaprolactone-modified silicone compound of the present invention has two or more reactive (meth)acrylic-modified groups, and therefore can form a crosslinked structure between silicon atoms in the molecules as a result of a radical polymerization reaction.
• the (meth)acrylic-modified group may be present in the modified polycaprolactone structure, or may be a (meth)acrylic-modified group bonded to a side chain.
• the manufacturing method (synthesis method) of the radically polymerizable polycaprolactone-modified silicone compound of the present invention is not particularly limited, but it is preferable to introduce a modified polycaprolactone structure into the organohydrogenpolysiloxane by a hydrosilylation reaction, and, if necessary, introduce a (meth)acrylic modifying group into the polyol-based (alcohol-based) hydroxyl group terminal in the modified polycaprolactone structure.
• (1') wherein x is a number ranging from 1 to 5; Ra is a group selected from a hydrogen
• a polycaprolactone compound having a vinyl group terminal structure represented by the formula: (c) The compound can be synthesized by a method for producing a radical polymerizable polycaprolactone-modified silicone compound, which method includes a step of carrying out a hydrosilylation reaction in the presence of a hydrosilylation reaction catalyst.
• Rb forms a divalent linking group that links the modified polycaprolactone structure of structural formula (1) described above or its precursor structure to the polysiloxane structure by hydrosilylation reaction between the silicon-bonded hydrogen atoms of the organohydrogenpolysiloxane, component (a), and the terminal vinyl group of Rb.
• R' may be an alkylene group having 1 to 20 carbon atoms, and is particularly preferably an alkylene group having 1 to 10 carbon atoms.
• a (meth)acrylic terminal group represented by -R 1 -CR 2 ⁇ CH 2 (R 1 is a carbonyl group or a divalent linking group containing one carbonyl group, and R 2 is a hydrogen atom or a methyl group) can be introduced into the modified polycaprolactone structure by further carrying out a step (d) of reacting the modified polycaprolactone structure having a hydroxyl group terminal with a (meth)acryloyl chloride compound represented by Cl-C( ⁇ O)-R 1 -CR 2 ⁇ CH 2 (R 1 is a chemical bond between CH and C( ⁇ O) or a divalent organic group having 1 to 20 carbon atoms, and R 2 is a hydrogen atom or a methyl group) in the presence of a basic catalyst.
• a (meth)acrylic terminal group represented by -R 1 -CR 2 ⁇ CH 2 (R 1 is a carbonyl group or a divalent linking group containing one carbonyl group, and R 2 is a
• the basic catalyst that can be used in the reaction is not particularly limited, but may be an alkali metal salt such as an inorganic base such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, or sodium hydrogen carbonate; an amine compound such as triethylamine, pyridine, or dimethylaminopyridine, or a nitrogen-containing heterocyclic compound.
• an alkali metal salt such as an inorganic base such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, or sodium hydrogen carbonate
• an amine compound such as triethylamine, pyridine, or dimethylaminopyridine, or a nitrogen-containing heterocyclic compound.
• the organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in the molecule, which is the component (a), is a component that determines the polysiloxane structure of the radically polymerizable polycaprolactone-modified silicone compound of the present invention.
• the polysiloxane structure in the molecule is preferably chain-like, more preferably linear or branched, and is particularly preferably an organohydrogenpolysiloxane having a linear polysiloxane structure.
• the organohydrogenpolysiloxane is a linear organohydrogenpolysiloxane having silicon-bonded hydrogen atoms at both ends of the molecular chain.
• the organohydrogenpolysiloxane of component (a) may have (meth)acrylic terminal groups introduced into its side chains in advance by an equilibrium reaction between a (meth)acrylic-modified silane (e.g., (meth)acryloxypropylmethyldialkoxysilane) and the organohydrogenpolysiloxane in the presence of an acid catalyst.
• a (meth)acrylic-modified silane e.g., (meth)acryloxypropylmethyldialkoxysilane
• a radical polymerizable polycaprolactone-modified silicone compound or its precursor having a (meth)acrylic end group at the side chain site can be obtained independently of the modified polycaprolactone structure.
• the acid catalyst that can be used in this reaction is not particularly limited, but may be trifluoromethanesulfonic acid, sulfuric acid, hydrochloric acid, etc.
• the hydrosilylation catalyst used in the above manufacturing method is not particularly limited, but is preferably a hydrosilylation catalyst containing a platinum-based metal.
• Specific examples include chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, complexes of chloroplatinic acid and ketones, complexes of chloroplatinic acid and vinylsiloxane, platinum tetrachloride, platinum fine powder, solid platinum supported on an alumina or silica carrier, platinum black, olefin complexes of platinum, alkenylsiloxane complexes of platinum, carbonyl complexes of platinum, and platinum catalysts in thermoplastic organic resin powders such as methyl methacrylate resin, polycarbonate resin, polystyrene resin, and silicone resin that contain these platinum-based catalysts.
• platinum alkenylsiloxane complexes such as a complex of chloroplatinic acid and divinyltetramethyldisiloxane, a complex of chloroplatinic acid and tetramethyltetravinylcyclotetrasiloxane, a platinum divinyltetramethyldisiloxane complex, and a platinum tetramethyltetravinylcyclotetrasiloxane complex can be preferably used.
• a catalyst for promoting the hydrosilylation reaction a non-platinum metal catalyst such as iron, ruthenium, or iron/cobalt may be used.
• the amount used may be a catalytic amount, and usually, the amount in which the amount of platinum metal contained in component (c) is in the range of 1 to 1,000 ppm, and more preferably in the range of 5 to 500 ppm, relative to the total mass of the radical polymerizable polycaprolactone-modified silicone compound.
• a chain transfer agent can be added as desired.
• this chain transfer agent include mercapto compounds such as 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, and polydimethylsiloxane having a mercaptopropyl group; and halides such as methylene chloride, chloroform, carbon tetrachloride, butyl bromide, and 3-chloropropyltrimethoxysilane.
• the polycaprolactone compound having a vinyl group terminal structure represented by structural formula (1'), which is component (b), can be obtained by ring-opening addition polymerization of a vinyl group-containing alcohol and ⁇ -caprolactone, and a polycaprolactone compound having a terminal hydroxyl group (i.e., one in which Ra is a hydrogen atom) can be obtained.
• a polycaprolactone compound having a terminal hydroxyl group i.e., one in which Ra is a hydrogen atom
• a polycaprolactone compound having a vinyl group terminal structure with a (meth)acrylic terminal group as Ra can be obtained.
• a radical polymerizable polycaprolactone-modified silicone compound having a modified polycaprolactone structure having a (meth)acrylic terminal group can be obtained in a one-step reaction by the hydrosilylation reaction of the above-mentioned components (a) and (b).
• the basic catalysts that can be used in this reaction are the same as those described above.
• the reaction of introducing (meth)acrylic end groups into the polycaprolactone compound may be carried out in an organic solvent.
• organic solvents that can be used include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; amides such as formamide, acetamide, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide, and dimethylacetamide; halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, benzotrifluoride, and hexafluoro-2-propanol; sulfoxides such as dimethyl sulfoxide (DMSO), diethyl sulfoxide, and benzyl phenyl sulfoxide; ethers such as diethyl ether, diisopropy
• one or more types of polymerization inhibitors may be included in the system to suppress further radical polymerization reaction of the synthesized (meth)acrylic-modified polycaprolactone compound.
• one or more types selected from hindered phenol-based polymerization inhibitors, hydroquinone-based polymerization inhibitors (typically hydroquinone monomethyl ether, MEHQ, etc.), and catechol-based polymerization inhibitors may be included.
• the reaction conditions should be appropriately selected depending on the synthesis amount and the reaction apparatus, but it is preferable to drop the (meth)acryloyl chloride compound while stirring the mixed solution containing the polycaprolactone compound, the basic catalyst, and an optional polymerization inhibitor under a flow of inert gas such as nitrogen. After the reaction is completed, it is particularly preferable to separate the desired (meth)acrylic-modified polycaprolactone compound and purify it by distilling off the unnecessary organic solvent under reduced pressure.
• the radically polymerizable polycaprolactone-modified silicone compound according to the present invention has been developed as a raw material for novel silicone-polycaprolactone copolymer particles (hereinafter, sometimes simply referred to as "copolymer particles") that have a feel and performance equal to or greater than those of conventional silicone elastomer particles and are also biodegradable through the radical polymerization reaction.
• copolymer particles in particular their uses including as a cosmetic raw material, their production method, and cosmetic compositions and organic resins (including paints and coating agents) that contain them will be described in detail below.
• the silicone-polycaprolactone copolymer particles of the present invention are characterized by having a structure in which at least two silicon atoms within the particle are crosslinked by a radical polymerization reaction of the above-mentioned radically polymerizable polycaprolactone-modified silicone compound.
• the copolymer particles of the present invention further include -(R 1 2 SiO) n - (In the formula, R 1 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, and n is a number ranging from 1 to 1000.) It is preferable that the copolymer further has a polyorganosiloxane structure represented by the following formula: This is a linear polysiloxane structure derived from the radical polymerizable polycaprolactone-modified silicone compound already described, and imparts appropriate hardness and flexibility to the resulting copolymer particles.
• the copolymer particles of the present invention are preferably obtained by curing cross-linking reactive emulsion particles through a cross-linking reaction.
• the copolymer particles of the present invention are defined by their manufacturing process and may be silicone-polycaprolactone copolymer particles obtained by radically polymerizing (A) 100 parts by mass of the radical polymerizable polycaprolactone-modified silicone compound in the presence of (B) 0.1 to 10 parts by mass of a radical polymerization initiator.
• the copolymer particles of the present invention may be silicone-polycaprolactone copolymer particles that contain at least (A) 100 parts by mass of the radically polymerizable polycaprolactone-modified silicone compound and (B) 0.1 to 10 parts by mass of a radical polymerization initiator, and are formed by crosslinking in water crosslinkable emulsion particles obtained by emulsifying in water a crosslinkable silicone composition that can be crosslinked by a radical polymerization reaction.
• Component (A) is as described above.
• Component (B) is a radical polymerization initiator, which promotes the radical polymerization reaction of the radically polymerizable polycaprolactone-modified silicone compound, and a conventionally known compound is used.
• component (B) is exemplified by 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 may be used
• the amount of radical polymerization initiator used is in the range of 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total of the above component (A).
• component (B) is a water-soluble persulfate such as potassium persulfate
• the addition and reaction of component (B) is extremely easy when the above radically polymerizable polycaprolactone-modified silicone compound is emulsified in water to cause a radical polymerization reaction in water.
• the copolymer particles obtained through such a manufacturing process may be able to further improve the appearance, spreadability, and feel of the cosmetic, particularly when used as a cosmetic ingredient, and the particles obtained by this manufacturing method tend to be able to more suitably solve the problems of the present invention.
• one of the preferred forms for achieving the technical effects of the present invention can and appropriately be determined by the manufacturing process.
• the average primary particle diameter of the copolymer particles according to the present invention is not particularly limited, but from the standpoint of imparting a smooth feel and comfortable use to the cosmetic, not causing poor appearance, and having storage stability and blending stability as a cosmetic ingredient, the average primary particle diameter measured by a laser diffraction scattering method is preferably in the range of 0.5 to 20 ⁇ m, and more preferably in the range of 0.5 to 15 ⁇ m.
• the particle diameter of the silicone-polycaprolactone copolymer particles can be controlled according to the emulsified particles of the radically polymerizable polycaprolactone-modified silicone compound and the crushing/classification process of the obtained copolymer particles.
• the shape of the copolymer particles according to the present invention can be, for example, spherical, true spherical, elliptical, or irregular, with spherical and true spherical shapes being particularly preferred.
• Spherical elastomer particles can be easily obtained by preparing the particles in the form of an aqueous suspension as described below and drying them using a vacuum dryer, a hot air circulation oven, or a spray dryer.
• the radical polymerizable polycaprolactone-modified silicone compound used to form the silicone-polycaprolactone copolymer particles has a JIS-A hardness in the range of 10 to 80 when cured into a sheet by a JIS-A hardness tester as specified in JIS K6301. If the JIS-A hardness of the rubber sheet measured by curing the crosslinking reactive silicone composition into a sheet is within the above range, the resulting elastomer particles are sufficiently suppressed in agglomeration and tend to have rich fluidity, dispersibility, silky feel, smoothness, and softness.
• copolymer particles according to the present invention are used as a cosmetic raw material or a stress relaxation agent for organic resins, it is particularly preferable to use copolymer particles having a JIS-A hardness in the range of 30 to 80, particularly 50 to 80.
• the copolymer particles of the present invention may have a structure in which a part or all of the surface thereof is coated with one or more selected from organopolysiloxane resins, silica, and other silicone elastomer particles. This coating may be expected to further reduce cohesiveness, control oil absorption, improve feel, etc.
• the copolymer particles of the present invention may have a mesoporous structure having micropores.
• the copolymer particles of the present invention may contain an oil that is liquid at 40°C.
• the oil can be easily contained in the copolymer particles by emulsifying it together with the crosslinking reactive composition described below, and the inclusion of the oil may be expected to further reduce cohesiveness, control oil absorption, improve feel, and the like.
• a biodegradable oil such as olive oil may be contained.
• the copolymer particles of the present invention are substantially free of structures containing silalkylene groups.
• the silicone-polycaprolactone copolymer particles of the present invention are copolymers obtained by radically polymerizing the radically polymerizable polycaprolactone-modified silicone compound itself as a radically polymerizable monomer component that forms a copolymer structure by radical polymerization.
• the touch and feel of the particles are not significantly impaired, and the particles are active in biodegradable reactions.
• the crosslinked structure formed between silicon atoms in the copolymer particles is at least partially cleaved, and the primary particles are disintegrated with the generation of non-crosslinked polyorganosiloxane.
• the copolymer particles are easily disintegrated into linear polyorganosiloxane molecules by biodegradable reactions, and are decomposed into fine liquid components rather than into solid powders with fine particle sizes like microplastics. This is expected to prevent problems of bioaccumulation through the food chain and accumulation/deposition in the environment, and to have a small impact or burden on the global environment.
• the copolymer particles according to the present invention can be produced by a method including a step of curing crosslinked reactive emulsion particles obtained by emulsifying in water a crosslinked reactive composition containing the above-mentioned radical polymerizable polycaprolactone-modified silicone compound in the presence of a radical polymerization initiator to obtain spherical copolymer particles.
• the copolymer particles according to the present invention can be prepared, and are preferable, by a production method including the following steps (I) and (II).
• the crosslinkable composition containing the radically polymerizable polycaprolactone-modified silicone compound used to form the copolymer particles can be mixed uniformly using mechanical force such as a mixer.
• the crosslinkable composition may contain an oil that is liquid at 40°C.
• the oil can be emulsified together with the crosslinkable composition to ultimately be contained in the copolymer particles.
• a biodegradable oil such as olive oil.
• the above-mentioned crosslinkable composition is emulsified in an aqueous surfactant solution and cured to obtain silicone elastomer particles.
• the particle size can be easily adjusted by adjusting the emulsion particle size.
• this surfactant include nonionic, anionic, cationic, betaine, and water-soluble polymers such as polyvinyl alcohol.
• the particle size of the resulting copolymer particles varies depending on the type and content of the surfactant. To prepare copolymer particles with a small particle size, the amount of this surfactant added is preferably within the range of 0.5 to 50 parts by mass per 100 parts by mass of the crosslinkable composition.
• an emulsifier to uniformly disperse the above-mentioned crosslinkable composition in water in the form of crosslinkable reactive emulsified particles.
• emulsifiers include a homomixer, a paddle mixer, a Henschel mixer, a homodisper, a colloid mill, a propeller agitator, a homogenizer, an in-line continuous emulsifier, an ultrasonic emulsifier, and a vacuum kneader.
• the aqueous dispersion of crosslinked reactive emulsion particles prepared by the above method can be heated or left at room temperature to harden the crosslinked reactive emulsion particles in the aqueous dispersion, thereby preparing an aqueous dispersion of copolymer particles.
• the heating temperature is preferably 100°C or lower, particularly preferably 10 to 95°C, from the viewpoint of hydrosilylation reactivity or radical polymerization reactivity.
• Methods for heating the aqueous dispersion containing crosslinked reactive emulsion particles include, for example, a method of directly heating the aqueous dispersion and a method of adding the aqueous dispersion to hot water.
• the liquid crosslinked reactive emulsion particles are hardened in water by the crosslinking reaction, forming an aqueous dispersion of copolymer particles.
• the silicone-polycaprolactone copolymer particles of the present invention obtained can be used as is as an aqueous dispersion (aqueous suspension).
• aqueous suspension aqueous dispersion
• they may be used as a cosmetic raw material in the form of this aqueous suspension, and this is preferable.
• blending the particles as an aqueous dispersion containing the copolymer particles of the present invention may facilitate uniform dispersion of the copolymer particles, thereby achieving the desired performance and usability.
• the silicone-polycaprolactone copolymer particles according to the present invention can be isolated by removing water from the aqueous dispersion of the copolymer particles.
• methods for removing water from the aqueous dispersion include drying using a vacuum dryer, a hot air circulation oven, and a spray dryer.
• the heating and drying temperature of the spray dryer must be appropriately set based on the heat resistance and crosslinking temperature of the silicone elastomer particles.
• the copolymer particles thus obtained can be recovered using a cyclone, a bag filter, or the like.
• the dispersion may be concentrated by a method such as heating and dehydration, filtration separation, centrifugation, or decantation, or the dispersion may be washed with water if necessary.
• the silicone-polycaprolactone copolymer particles of the present invention may be surface-treated as necessary, which may further improve the aggregation-inhibiting effect of the copolymer particles of the present invention.
• the surface may be treated with other known hydrophilic or hydrophobic treatment agents.
• the obtained copolymer particles may be further coated on a part or all of their surfaces with inorganic fine particles such as silica, silicone resin, etc., as described above.
• the obtained copolymer particles may be crushed or disintegrated using mechanical force as necessary, and may be classified using known methods.
• the silicone-polycaprolactone copolymer particles of the present invention are useful as a cosmetic raw material. When blended into cosmetic compositions and the like, they are soft and have an outstanding effect of improving the feel and usability of the cosmetics, etc., and are remarkably easy to handle as a cosmetic raw material, and have excellent storage stability and blending stability into systems.
• the silicone-polycaprolactone copolymer particles of the present invention have the advantages of being superior in usability and feel compared to known silicone particles, having a high degree of freedom in formulation design, and when incorporated into cosmetics, not absorbing oily ingredients over time to cause thickening or changes in feel, and when applied to the skin or hair, suppressing the oiliness and stickiness of the cosmetics, imparting smooth spread, a soft feel, and a moist feel, and improving compatibility with the skin, resulting in superior usability.
• the silicone-polycaprolactone copolymer particles of the present invention may be able to improve the UV protection effect of cosmetics without impairing their feel and usability compared to other powders or existing silicone elastomer particles.
• the silicone-polycaprolactone copolymer particles of the present invention have performance equal to or greater than that of conventionally known silicone elastomer particles, but are active in biodegradable reactions, and in a biodegradable environment, the crosslinked structures formed between silicon atoms in the particles at least partially cleave, and the primary particles disintegrate while generating non-crosslinked polyorganosiloxanes, making them a material that poses little risk and burden to the global environment. Furthermore, they can be used in place of conventionally known silicone elastomer particles, making them extremely versatile.
• the cosmetic composition containing the silicone-polycaprolactone copolymer particles of the present invention is not particularly limited in type, but examples thereof include cleansing cosmetics such as soap, body shampoo, and face wash cream; basic cosmetics such as lotion, cream/lotion, and pack; base makeup cosmetics such as face powder and foundation; eyebrow cosmetics such as lipstick, blusher, eye shadow, eyeliner, and mascara; makeup cosmetics such as nail polish; hair cosmetics such as shampoo, hair rinse, hair styling products, hair growth agents, hair tonics, and hair dyes; aromatic cosmetics such as perfume and eau de cologne; toothpaste; bath products; special cosmetics such as depilatories, shaving lotions, antiperspirants/deodorants, and sunscreens.
• Examples of the formulation of these cosmetic compositions include aqueous liquids, oily liquids, emulsions, creams, foams, semi-solids, solids, and powders. These cosmetic compositions can also be used by spraying.
• the content of the silicone-polycaprolactone copolymer particles is preferably within the range of 0.5 to 99.0% by mass in the cosmetic composition, and more preferably within the range of 1.0 to 95% by mass. This is because if the content of the copolymer particles exceeds the upper limit of the above range, the cosmetic effect is lost, and if it is below the lower limit of the above range, it becomes difficult to improve the feel of use of the cosmetic composition.
• the silicone-polycaprolactone copolymer particles of the present invention can be used to replace part or all of the silicone-based particles in cosmetic compositions (particularly the formulation examples) containing silicone particles (such as silicone rubber powder) or silicone composite particles proposed in JP 07-316014 A, International Patent Publication WO2017/191798, International Patent Application PCT/JP2021/46142, JP 02-243612 A, JP 2002-146026 A (Patent No. 3512399), JP 2011-105663 A, JP 2011-168634 A, JP 2011-102354 A, and JP 2014-122316 A, and may further improve the usability and production efficiency of the cosmetic compositions proposed in these patent documents.
• examples of cosmetic compositions containing silicone particles (such as silicone rubber powder) or silicone composite particles that can be blended with the silicone elastomer particles of the present invention are not limited to those mentioned above, and a formulation in which part or all of the silicone particle components in commercially available cosmetics are replaced with the silicone-polycaprolactone copolymer particles of the present invention using general techniques employed by those skilled in the art may be designed.
• silicone-polycaprolactone copolymer particles of the present invention can be applied to the uses and formulations of cosmetic compositions disclosed in the above-mentioned patent documents, etc., by replacing part or all of these silicone-based particles, and such uses are included within the scope of the present invention.
• the silicone-polycaprolactone copolymer particles of the present invention may be used in combination with any optional ingredient such as a cosmetic medium (aqueous medium or oily medium), an oily medium (including oils and volatile oils), water, colorants, pigments, UV protection ingredients, alcohols, water-soluble polymers, film-forming agents, oils, oil-soluble gelling agents, organically modified clay minerals, surfactants, resins, salts, moisturizers, preservatives, antibacterial agents, antioxidants, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, skin-beautifying ingredients (skin whitening agents, cell activators, skin roughness improving agents, blood circulation promoters, skin astringents, and antiseborrheic agents), vitamins, amino acids, nucleic acids, hormones, clathrate compounds, etc., physiologically active substances, active pharmaceutical ingredients, and fragrances, by selecting the same method and quantitative range as those disclosed in International Patent Publication WO2017/191798, and it is preferable to use them
• the silicone-polycaprolactone copolymer particles of the present invention are superior in usability, feel, handling, storage stability, dispersibility, and high oil absorption properties to those of conventionally known silicone particles, silicone composite particles coated with silsesquioxane, and oil-containing silicone particles, and are therefore particularly (1) Cosmetic compositions and formulations containing an oily medium (oil-based cosmetic raw material) such as an oil agent, (2) Cosmetic compositions and formulations containing a lipophilic UV protection component (e.g., octyl paramethoxycinnamate, etc.), and (3) Cosmetic compositions and formulations containing inorganic powders such as colorants or pigments can achieve particularly favorable appearances, usability, etc. Specific formulations will be described in more detail in the following examples.
• silicone-polycaprolactone copolymer particles of the present invention allow for easy design of aqueous dispersions, and therefore provide excellent freedom in formulation design and blend stability, even in aqueous cosmetic compositions and formulations, and can achieve a favorable feel when used. Specific formulations are described in more detail in the following examples.
• the cosmetic preparation of the present invention can be easily produced by simply homogenously mixing the cosmetic raw materials of the present invention as described above with other cosmetic raw materials.
• a mixing means various mixing and kneading devices that are usually used in the production of cosmetics can be used. Examples of such devices include a homomixer, a paddle mixer, a Henschel mixer, a homodisper, a colloid mixer, a propeller agitator, a homogenizer, an in-line continuous emulsifier, an ultrasonic emulsifier, and a vacuum kneader.
• the silicone-polycaprolactone copolymer particles of the present invention have the above-mentioned properties, and therefore are extremely useful as an organic resin additive. Specifically, the silicone elastomer particles of the present invention are excellent in uniform dispersibility in organic resins and, if desired, stress relaxation properties, and are also unlikely to aggregate even after long-term storage, so that they are extremely excellent in handling, workability, and storage stability.
• members, coating films, or coating films obtained by curing an organic resin containing the silicone-polycaprolactone copolymer particles have improved flexibility (including the softness of the coating layer), durability, and adhesion and conformability to the substrate, and are particularly excellent in flexibility and thermal shock resistance, making them extremely useful as high-performance organic resins, paints, or coating agents used in electronic materials.
• organic resins containing the silicone-polycaprolactone copolymer particles of the present invention include curable organic resin compositions and thermoplastic resins. Of these, curable resins are suitable for electronic materials such as semiconductor substrates.
• examples of the curable organic resin composition 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, and copolymer resins of these resins, and two or more of these curable resins can be combined.
• the curable resin is preferably at least one selected from the group consisting of epoxy resins, phenolic resins, imide resins, and silicone resins.
• the epoxy resin may be any compound containing a glycidyl group or an alicyclic epoxy group, and examples thereof include o-cresol novolac type epoxy resins, phenol novolac type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, naphthol aralkyl type epoxy resins, polyvinylphenol type epoxy resins, diphenylmethane type epoxy resins, diphenylsulfone type epoxy resins, triphenol alkane type epoxy resins, cresol-naphthol co-condensed type epoxy resins, bisphenylethylene type epoxy resins, fluorene type epoxy resins, stilbene type epoxy resins, spirocoumarone type epoxy resins, norbornene type epoxy resins, terpene type epoxy resins, phenolcyclohexane
• phenolic resin examples include polyvinylphenol type, phenol novolac type, naphthol type, terpene type, phenol dicyclopentadiene type, phenol aralkyl type, naphthol aralkyl type, triphenol alkane type, dicyclopentadiene type, cresol naphthol co-condensation type, and xylene naphthol co-condensation type.
• silicone resin include epoxy-modified silicone resins obtained by reacting an epoxy resin with a silanol group or a silicon-bonded alkoxy group in a silicone resin.
• Examples of the curing mechanism of such a curable resin include a heat curing type, a high-energy ray curing type such as ultraviolet light or radiation, a moisture curing type, a condensation reaction curing type, and an addition reaction curing type.
• the properties of such a curable resin at 25° C. are not limited, and it may be either a liquid or a solid that is softened by heating.
• the organic resin containing the silicone-polycaprolactone copolymer particles of the present invention can contain other optional components such as a curing agent, a curing accelerator, a filler, a photosensitizer, a higher fatty acid metal salt, an ester wax, and a plasticizer.
• a curing agent examples include organic acids such as carboxylic acids and sulfonic acids and their anhydrides; organic hydroxy compounds; organosilicon compounds having a silanol group, an alkoxy group, or a halogeno group; and primary or secondary amino compounds, and two or more of these can be combined.
• curing accelerator examples include tertiary amine compounds, organometallic compounds such as aluminum and zirconium; organophosphorus compounds such as phosphines; and other heterocyclic amine compounds, boron complex compounds, organic ammonium salts, organic sulfonium salts, organic peroxides, and hydrosilylation catalysts.
• the filler examples include fibrous fillers such as glass fiber, asbestos, alumina fiber, ceramic fiber containing alumina and silica, boron fiber, zirconia fiber, silicon carbide fiber, metal fiber, polyester fiber, aramid fiber, nylon fiber, phenol fiber, and natural animal and vegetable fibers; and 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, and zirconia, which may be used in combination of two or more.
• fibrous fillers such as glass fiber, asbestos, alumina fiber, ceramic fiber containing alumina and silica, boron fiber, zirconia fiber, silicon carbide fiber, metal fiber, polyester fiber, aramid fiber, nylon
• the silicone-polycaprolactone copolymer particles of the present invention may be blended as an additive with thermoplastic resins other than those mentioned above, and may be used as a modifier of physical properties such as a surface lubricant or a stress relaxation agent, or as a modifier of optical properties such as a light scattering agent.
• thermoplastic resin is not particularly limited, and may be at least one polymer selected from the group consisting of polycaprolactone-based resins, polyester-based resins, polyether-based resins, polylactic acid-based resins, polyolefin-based resins such as polyethylene, polypropylene, and ethylene-propylene-based copolymers, polystyrene-based resins, styrene-based copolymers, fluorine-based polymers such as tetrafluoroethylene, polyvinyl ethers, and cellulose-based polymers, or a composite resin consisting of a combination thereof.
• the silicone resin-coated silicone elastomer particles of the present invention can be uniformly dispersed in these thermoplastic resins (including masterbatches) using a mixing device such as a twin-screw or single-screw extruder or a kneader mixer, and may be molded into a desired shape such as a film for use.
• a mixing device such as a twin-screw or single-screw extruder or a kneader mixer
• the amount of silicone-polycaprolactone copolymer particles of the present invention added can be appropriately selected depending on the physical properties required for the organic resin, but is generally in the range of 0.1 to 30 parts by mass, and may be in the range of 0.5 to 10 parts by mass, per 100 parts by mass of organic resin. If the amount of the particles added is less than the lower limit, the performance such as stress relaxation properties for the resin may be insufficient, and the flexibility and thermal shock resistance of the obtained organic resin cured product may decrease, and in particular, the thermal shock resistance after moisture absorption tends to decrease. On the other hand, if the amount exceeds the upper limit, the organic resin or paint/coating agent after blending may thicken, reducing handling and workability, and the mechanical properties of the obtained organic resin cured product tend to decrease.
• the silicone-polycaprolactone copolymer particles of the present invention have excellent stress relaxation properties when blended with organic resins, they may be blended with epoxy resins for printed wiring boards to form prepregs, or they may be used for copper clad laminates (CCLs) by forming copper foil with a filler particle-containing resin layer for printed wiring boards, which has a resin layer containing the silicone-polycaprolactone copolymer particles of the present invention on one side of the copper foil.
• CTLs copper clad laminates
• paints and coating agents containing the silicone-polycaprolactone copolymer particles of the present invention include room temperature curing types, room temperature drying types and heat curing types, and depending on the properties, examples include water-based, oil-based and powder-based paints. Furthermore, depending on the vehicle resin, examples include polyurethane resin paints, butyral resin paints, long oil phthalic acid resin paints, alkyd resin paints, amino alkyd resin paints consisting of amino resins and alkyd resins, epoxy resin paints, acrylic resin paints, phenolic resin paints, silicone modified epoxy resin paints, silicone modified polyester resin paints and silicone resin paints.
• the amount of silicone-polycaprolactone copolymer particles of the present invention added can be appropriately selected depending on the physical properties required for the paint/coating agent, but in order to impart a uniform and soft matte finish to the resulting coating film, it is preferably within the range of 0.1 to 150 parts by mass, more preferably 0.1 to 100 parts by mass, and particularly preferably 0.1 to 50 parts by mass, or 0.1 to 20 parts by mass, per 100 parts by mass of the solid content of the paint. If the amount of the particles added is less than the lower limit, the performance of the coating film, such as matte finish, adhesion, and stress relaxation properties, may be insufficient, and if it exceeds the upper limit, the organic resin or paint/coating agent after blending may thicken, reducing handling and workability.
• the paint/coating agent containing the silicone-polycaprolactone copolymer particles of the present invention may contain 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; organic solvents such as aromatic hydrocarbons such as toluene and xylene; known inorganic fillers such as reinforcing silica, organic fillers, curing accelerators, silane coupling agents, pigments such as carbon black, dyes, antioxidants, thickeners made of polymer compounds, flame retardants, and weather resistance agents.
• alcohols such as methanol and ethanol
• ketones such as methyl ethyl ketone and methyl isobuty
• the silicone-polycaprolactone copolymer particles of the present invention are different from conventional non-biodegradable thermoplastic resin particles and silicone particle materials in that in a biodegradable environment, the crosslinked structure formed between silicon atoms in the silicone-polycaprolactone copolymer particles is at least partially cleaved, and the primary particles are expected to have biodegradable properties, with the generation of non-crosslinked polyorganosiloxane.
• the silicone-polycaprolactone copolymer particles can be used as an "eco-friendly” cosmetic ingredient or industrial ingredient with low environmental load and environmental risk in response to regulations on microplastics, etc., and can be promoted as an "eco-friendly” material with biodegradability to consumers and general consumers who place importance on the impact on the global environment.
• silicone particles are a general term for particles (cured silicone particles) made of a silicone cured product (including the silicone-polycaprolactone copolymer particles of the present invention), and do not include emulsions.
• Average primary particle size of emulsion particles The emulsion before the addition of the radical polymerization initiator was measured using a laser diffraction particle size distribution analyzer (LS-230 manufactured by Beckman Coulter), and the median diameter (particle size equivalent to 50% of the cumulative distribution, 50% particle size) was taken as the average particle size.
• the particle size of the cured silicone particles was measured with a laser diffraction particle size distribution analyzer (Malvern Panalytical's Mastersizer 3000) to obtain the median diameter (particle size equivalent to 50% of the cumulative distribution, D90, ⁇ m) and arithmetic dispersity (indicating the degree of dispersion of the particle size distribution, SD, ⁇ m2) of the cured elastomer particles in ethanol.
• the measurement sample was prepared by dispersing cured silicone particles (1 g) and ethanol (100 mL) in a 300 mL cup using a stirring blade and ultrasonic vibrator.
• the liquid temperature was heated to 70°C.
• the pressure was further reduced to 100 mmHg, and the by-product methanol was removed for about 1 hour.
• the mixture was reacted at 70°C for 3 hours.
• ammonia gas was bubbled to neutralize the 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 the volatile components.
• Si-NMR analysis revealed that a both-terminal SiH/side-chain methacryl-modified silicone polymer had a dimethylsiloxane unit content of 45.3, a methacryl group-introduced siloxane unit content of 2.0, and a viscosity of 55.4 cSt.
• Example 1 Siloxane compound modified with (meth)acrylic-polycaprolactone at both ends
• a four-necked separable flask was charged with 35.50 parts by weight of a SiH siloxane having a degree of polymerization of 43 at both ends, 31.90 parts by weight of the vinyl-terminated polycaprolactone, 32.60 parts by weight of toluene, and 0.01 parts by weight of a 2% sodium acetate methanol solution.
• the mixture was heated to 60° C. while aerating with nitrogen.
• An isopropyl alcohol solution of chloroplatinic acid an amount such that the platinum metal in the composition was 10 ppm by mass was added and reacted for 5 hours.
• the toluene was removed under reduced pressure to obtain a white wax-like polymer.
• the obtained polymer (37.00 parts by weight), chloroform (53.40 parts by weight), potassium carbonate (6.20 parts by weight), and hydroquinone monomethyl ether (63 ppm) were charged.
• the mixture was stirred while passing nitrogen through, and acryloyl chloride (3.40 parts by weight) was added dropwise.
• the reaction was carried out for 5 hours while adjusting the heat generation so as not to exceed 30°C.
• the chloroform-dissolved portion was collected, and the chloroform was removed under reduced pressure.
• the obtained polymer had the following structure by H-NMR analysis. (In the formula, a methyl group is bonded to the rod (-) on the silicon atom, and (m+n) and x are the numbers 43.0 and 2, respectively.)
• Example 2 Side-chain methacryl-modified siloxane/both-end polycaprolactone-modified compound
• Synthesis Example 1 A four-necked separable flask was charged with 40.60 parts by weight of Synthesis Example 1, 25.70 parts by weight of the vinyl-terminated polycaprolactone, 33.70 parts by weight of toluene, and 0.01 parts by weight of a 2% sodium acetate methanol solution.
• the flask was heated to 60°C while aerating with nitrogen.
• An isopropyl alcohol solution of chloroplatinic acid (in an amount such that the platinum metal in the composition was 10 ppm by mass) was added and reacted for 5 hours.
• the toluene was removed under reduced pressure to obtain a white wax-like polymer.
• the obtained polymer had the following structure by H-NMR analysis. (In the formula, a methyl group is bonded to the rod (-) on the silicon atom, and m, n, and x are 2.0, 45.3, and 2, respectively.)
• the radically polymerizable polycaprolactone-modified silicone compound according to the present invention was obtained from the above-mentioned Examples 1 and 2.
• Examples 3 and 4 are used to show examples of the production of silicone-polycaprolactone copolymer particles obtained from the above-mentioned side chain (meth)acrylic-modified siloxane/both terminal polycaprolactone-modified compound and both terminal (meth)acrylic/polycaprolactone-modified siloxane compound as raw materials.
• Comparative Example 1 is a non-silicone polymer particle obtained from only the (meth)acrylic-modified polycaprolactone compound as raw material.
• Example 3 Silicone-polycaprolactone copolymer particles No. 1
• the siloxane compound modified with (meth)acrylic polycaprolactone at both ends of Example 1 was dispersed in a 25°C aqueous solution consisting of 0.23 parts by mass of Gohsenol EG-05C (manufactured by Mitsubishi Chemical: polyvinyl alcohol), 0.47 parts by mass of Gohsenol EG-18P (manufactured by Mitsubishi Chemical: polyvinyl alcohol) and 46 parts by mass of pure water, and then uniformly emulsified using a colloid mill, followed by dilution with 526 parts by mass of pure water to prepare an emulsion.
• Gohsenol EG-05C manufactured by Mitsubishi Chemical: polyvinyl alcohol
• Gohsenol EG-18P manufactured by Mitsubishi Chemical: polyvinyl alcohol
• the mixture was heated in a 1L flask, and after reaching 70°C, an aqueous solution in which 0.5 g of potassium persulfate (manufactured by Sigma-Aldrich) was dissolved in 9.5 g of water was added dropwise over 1 minute.
• the emulsion was radically polymerized at 70°C for 3 hours, further heated to 80°C and continued to react for 2 hours, and 0.8 g of aminomethylpropanediol was added to complete the reaction, preparing a uniform aqueous suspension of copolymer particles.
• this 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-polycaprolactone copolymer particles No. 1.
• the average primary particle size and average secondary particle size of the obtained particles were 4.84 ⁇ m and 273 ⁇ m.
• Example 4 Silicone-polycaprolactone copolymer particles No. 2
• the same procedure as in Example 3 was carried out, except that the material to be emulsified was changed to the side-chain methacryl-modified siloxane/both-terminally polycaprolactone-modified compound of Example 2, to obtain silicone/polycaprolactone copolymer particles No. 2.
• the average primary particle size and average secondary particle size of the obtained particles were 3.48 ⁇ m and 141 ⁇ m.
• Non-silicone polymer particles were obtained in the same manner as in Example 3, except that no polyorganosiloxane component was used and only 100 parts by mass of (meth)acrylic-modified polycaprolactone compound No. 1 was used.
• the average primary particle size and average secondary particle size were 2.91 ⁇ m and 70.0 ⁇ m.
• Examples 5 and 6 Comparative Examples 3 and 4
• the feel of water-in-oil sunscreens was compared and evaluated by a panel of people using the compositions shown in the table below.
• the SPF and PA values were measured using an SPF analyzer. (Tactile evaluation) The samples were applied to the inside of the forearms of 18 panelists, and the spreadability and white residue were evaluated.
• the water-in-oil sunscreens containing silicone-polycaprolactone copolymer particles No. 1 (Example 3) and silicone-polycaprolactone copolymer particles No. 2 (Example 4) of the present invention were evaluated as having a good feel and SPF improving effect, unlike water-in-oil sunscreens that did not contain the particles (Comparative Example 3) or that used other particles (Comparative Example 4).
• Examples 7 and 8, Comparative Examples 5 and 6 The feel upon use of an oil-in-water type skin cream using silicone elastomer particles with the composition shown in Table 5 was compared and evaluated by a panel. (Tactile evaluation) Eighteen panelists applied the samples to the inside of their forearms and evaluated the spreadability, smoothness, and moist feeling according to the criteria in Table 4 below.
• the water-in-oil sunscreens using silicone-polycaprolactone copolymer particles No. 1 (Example 3) and silicone-polycaprolactone copolymer particles No. 2 (Example 4) of the present invention were evaluated as having good spreadability and a moist feel after drying, unlike skin creams that did not contain elastomer particles (Comparative Example 6) and those that used other particles (Comparative Example 5).

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• 2023
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