WO2016039357A1 - 高復元性樹脂粒子及びその用途 - Google Patents
高復元性樹脂粒子及びその用途 Download PDFInfo
- Publication number
- WO2016039357A1 WO2016039357A1 PCT/JP2015/075532 JP2015075532W WO2016039357A1 WO 2016039357 A1 WO2016039357 A1 WO 2016039357A1 JP 2015075532 W JP2015075532 W JP 2015075532W WO 2016039357 A1 WO2016039357 A1 WO 2016039357A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- resin particles
- resin
- acid ester
- acrylate
- Prior art date
Links
Classifications
-
- 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
- C08F290/02—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 end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- 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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
-
- 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
- A61K8/18—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
- A61K8/87—Polyurethanes
-
- 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
- A61Q1/12—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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F299/06—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 polyurethanes
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3221—Polyhydroxy compounds hydroxylated esters of carboxylic acids other than higher fatty 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/6725—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing ester groups other than acrylate or alkylacrylate ester 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
- C08G18/8016—Masked aliphatic or cycloaliphatic polyisocyanates
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08J2375/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to highly recoverable resin particles and uses thereof. More specifically, the present invention relates to a self-restoring coating composition, a highly restorable resin particle useful for the purpose of forming a coating film such as a cosmetic, and a coating composition and cosmetic containing the particle.
- the car interior parts have a matte paint finish.
- a matte paint finish has been performed using a matting agent in which a gloss adjusting pigment represented by silica or talc is added to the coating composition.
- the coating film obtained by the matting agent has a problem that it has a hard feel and is easily scratched when an impact is applied from the outside. Therefore, a coating film having high scratch resistance, soft texture (soft feel), smooth texture and high elasticity is required. A coating film having such characteristics is also required in cosmetics.
- Patent Document 1 is obtained by polymerizing a mixture containing a specific crosslinkable monomer having a vinyl group at both ends of a molecule and a (meth) acrylic acid ester. Resin particles capable of forming a coating film having an excellent restoration rate and a soft touch feeling excellent in scratch resistance are described.
- the highly recoverable resin particles having an average particle diameter of 1 to 100 ⁇ m made of a crosslinked (meth) acrylic acid ester resin, the highly recoverable resin particles have a recovery rate of 22% or more; Highly resilient resin particles having a 30% compressive strength of 5 to 5.0 kgf / mm 2 are provided.
- the composition for coating containing the said highly resilient resin particle is provided.
- coating and drying the said coating composition is provided.
- the cosmetics containing the said highly resilient resin particle are provided.
- resin particles having high recoverability can be provided. If this resin particle is used for a coating film or a cosmetic, high scratch resistance, a soft tactile sensation or a feeling of use can be imparted to the coating film or the cosmetic.
- a plurality of radical polymerizable compounds obtained by reacting a crosslinked (meth) acrylic acid ester resin with (a) polyol, (b) polyisocyanate, and (c) (meth) acrylic acid ester having an OH group.
- a resin derived from a crosslinkable oligomer having a group and a (meth) acrylate monofunctional monomer When the crosslinkable oligomer is cured alone, it exhibits a Tg of 0 to 30 ° C. (measured from viscoelasticity).
- the highly recoverable resin particle is a (meth) acrylate monofunctional monomer 20 It is a polymer of a monomer mixture obtained by polymerizing a monomer mixture containing ⁇ 80% by mass and crosslinkable oligomer 80 ⁇ 20% by mass, and is a (meth) acrylic acid ester-based monofunctional monomer
- the body is a (meth) acrylic acid ester of an alcohol having 1 to 8 carbon atoms
- the crosslinked (meth) acrylic acid ester resin has a resin composition exhibiting a hysteresis loss of 30% or less If it is, the resin particle which has higher restoring property can be provided.
- the highly recoverable resin particles are resin particles having an average particle diameter of 1 to 100 ⁇ m made of a crosslinked (meth) acrylic ester resin. Resin particles having an average particle diameter in this range can further improve the restoring property and matting effect when used in a coating film.
- the average particle diameter is less than 1 ⁇ m, the unevenness formed in the coating film becomes small, so that a substantial matting effect may not be obtained.
- grains exceeds 100 micrometers, it will be in the state in which the coating film became rough and the external appearance may worsen.
- a preferable average particle diameter is 1 to 80 ⁇ m, and a more preferable average particle diameter is 1 to 50 ⁇ m.
- the average particle diameter can be 1 ⁇ m, 5 ⁇ m, 10 ⁇ m, 20 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m, 100 ⁇ m.
- Highly recoverable resin particles have a recovery rate of 22% or more.
- a restoration rate of 22% or more By having a restoration rate of 22% or more, a highly restoring coating film can be obtained.
- the restoration rate is less than 22%, it may be impossible to obtain a coating film having a high restoration property.
- a preferable restoration rate is 25% or more, and a more preferred restoration rate is 30% or more.
- the upper limit of the restoration rate is 100%.
- the restoration rate can be 22%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%.
- the highly recoverable resin particles have a 30% compressive strength of 1.5 to 5.0 kgf / mm 2 .
- a soft texture can be obtained.
- mixing at the time of manufacturing a coating composition can be suppressed.
- the 30% compressive strength is less than 1.5 kgf / mm 2 , the particles may be disintegrated by kneading when producing the coating composition.
- the 30% compressive strength exceeds 5.0 kgf / mm 2 , the coating feel may be felt hard.
- 30% compressive strength of 1.8 ⁇ 4.5kgf / mm 2 more preferably 30% compressive strength is 2.0 ⁇ 4.0kgf / mm 2.
- the constituents thereof are not particularly limited.
- a resin derived from a crosslinkable oligomer having a plurality of radical polymerizable groups and a (meth) acrylic acid ester monofunctional monomer can be used.
- the highly resilient resin particles are preferably composed of a resin composition exhibiting a hysteresis loss of 30% or less.
- a resin composition having a hysteresis loss of 30% or less it is possible to obtain a coating film with high followability to compression displacement due to a load or the like and higher scratch resistance.
- the hysteresis loss exceeds 30%, a highly recoverable coating film may not be obtained.
- a preferable hysteresis loss is 25% or less, and a more preferable hysteresis loss is 20% or less.
- the lower limit of hysteresis loss is 0%.
- the hysteresis loss can be 0%, 5%, 10%, 15%, 20%, 25%, and 30%.
- crosslinkable oligomer is, for example, urethane (meth) acrylate obtained by reacting (a) polyol, (b) polyisocyanate, and (c) (meth) acrylate having an OH group. Preferably there is. Highly restorable resin particles can be obtained when the crosslinked (meth) acrylic ester resin is a crosslinked resin derived from this urethane (meth) acrylate.
- the components (a) to (c) are preferably selected from those capable of giving a Tg (measured from viscoelasticity) of 0 to 30 ° C. to a resin cured with a crosslinkable oligomer alone.
- Tg measured from viscoelasticity
- the cross-linked resin may become sticky.
- the temperature exceeds 30 ° C., resin particles having high recoverability may not be obtained.
- a more preferable Tg is 0 to 28 ° C, and a more preferable Tg is 0 to 25 ° C.
- Tg can be 0 ° C, 5 ° C, 10 ° C, 15 ° C, 20 ° C, 25 ° C, 28 ° C, 30 ° C.
- the crosslinkable oligomer exhibits a (meth) acryl equivalent of 300 to 1000 g / mol.
- the (meth) acrylic equivalent is less than 300 g / mol, sufficient flexibility may not be obtained.
- it is larger than 1000 g / mol sufficient flexibility may not be obtained.
- a more preferred (meth) acryl equivalent is 350 to 800 g / mol, and a still more preferred (meth) acryl equivalent is 400 to 600 g / mol.
- the (meth) acryl equivalent can take 300 g / mol, 350 g / mol, 400 g / mol, 500 g / mol, 600 g / mol, 700 g / mol, 800 g / mol, 900 g / mol, 1000 g / mol.
- the (meth) acryl equivalent is a calculated value (g / mol) of the weight of the active energy ray-curable resin (crosslinkable oligomer) containing 1 mol of the (meth) acryloyl group.
- the (meth) acryl equivalent can be calculated as follows.
- (Meth) acrylic equivalent (mass of isocyanate adduct component consisting of components (a) and (b) (g) + mass of component (c) (g)) ⁇ number of moles of component (c)
- polyol examples include polyester polyols, polyether polyols, polycarbonate polyols, aliphatic hydrocarbon polyols, and alicyclic hydrocarbon polyols.
- the above polyols may be used alone or in combination of two or more.
- the polyol preferably has a number average molecular weight of 200 to 3000 and 2 to 4 OH groups.
- the number average molecular weight is less than 200 and more than 3000, the crosslinked resin may be too hard to obtain resin particles having high recoverability.
- the number of OH groups is less than 2, the crosslinkability may be lowered too much. If it exceeds 4, the crosslinkability is too high, and resin particles with high restoration properties may not be obtained.
- the number average molecular weight can be 200, 500, 1000, 1500, 2000, 2500, 3000.
- Polyester polyols include, for example, condensation polymers of polyhydric alcohols and polycarboxylic acids; ring-opening polymers of cyclic esters (lactones); polyhydric alcohols, polycarboxylic acids and cyclic esters. A reaction product of three kinds of components; and the like, in which each raw material is selected so as to contain three or more hydroxyl groups.
- polyhydric alcohol examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl.
- Methylene diol 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, methane Triol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, cyclohexanediol (1,4-cyclohexanediol, etc.), bisphenol (bisphenol A, etc.) , And sugar alcohols (xylitol and sorbitol) and the like.
- polyvalent carboxylic acid examples include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; -Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, and the like.
- cyclic ester (lactone) examples include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, and the like.
- polyether-based polyol examples include polyether-based polyols obtained by dehydrating and condensing polyhydric alcohols as raw materials so that three or more hydroxyl groups are contained in the molecular terminals (side chains). It is done.
- polystyrene resin examples include low molecular weight polyols such as methanetriol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, and polyoxyalkylene adducts of these polyols.
- low molecular weight polyols such as methanetriol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, and polyoxyalkylene adducts of these polyols.
- a trifunctional or higher functional polyol such as an alkylene polyol is exemplified.
- the polycarbonate polyol is, for example, a reaction product of a polyhydric alcohol and phosgene, wherein the polyhydric alcohol is selected so as to contain three or more hydroxyl groups; cyclic carbonate (alkylene carbonate, etc.) And those having 3 or more hydroxyl groups.
- polyhydric alcohol examples include low molecular weight (preferably molecular weight 64 to 250) polyhydric alcohols such as methanetriol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, and pentaerythritol. And trifunctional or higher polyhydric alcohols such as polyoxyalkylene polyhydric alcohols, which are adducts of alkylene oxides of these polyhydric alcohols.
- the polycarbonate-based polyol may be a compound having a carbonate bond in the molecule and having a terminal containing three or more hydroxyl groups, and may have an ester bond together with the carbonate bond.
- the polyolefin-based polyol may be any polyol having a total of three or more hydroxyl groups at the molecular ends (side chains) of the hydrocarbon skeleton having at least one branched structure.
- the above hydrogenated polybutadiene-based polyol is a structure in which all of the ethylenically unsaturated groups contained in the structure of the polybutadiene-based polyol are hydrogenated, and the total of hydroxyl groups at the molecular ends (side chains). What is necessary is just to have three or more.
- polyisocyanate examples include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.
- the polyisocyanate preferably has 2 to 4 NCO groups. When the number of NCO groups is less than 2, the crosslinkability may be lowered too much. If it exceeds 4, the crosslinkability is too high, and resin particles with high restoration properties may not be obtained.
- Aliphatic polyisocyanates include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1 , 5-diisocyanate, 3-methylpentane-1,5-diisocyanate and the like.
- alicyclic polyisocyanate examples include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like. Can be mentioned.
- Aromatic polyisocyanates include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-dibenzyl diisocyanate, 1,5 -Naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and the like.
- MDI 4,4′-diphenylmethane diisocyanate
- araliphatic polyisocyanate examples include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, ⁇ , ⁇ , ⁇ , ⁇ -tetramethylxylylene diisocyanate and the like. Moreover, modified bodies, such as a dimer, a trimer of these organic polyisocyanates, and a buret-ized isocyanate, are mentioned. The said polyisocyanate may be used independently or may use 2 or more types together.
- (C) (Meth) acrylic acid ester having OH group examples include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl.
- Acrylic acid ester polybutylene glycol mono (meth) acrylic acid ester, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, phenylglycidyl ether (meth) acrylate Rate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate.
- the (meth) acrylic acid ester having an OH group may be used alone or in combination of two or more.
- a (meth) acrylic acid ester having 1 to 8 carbon atoms having an OH group and pentaerythritol triacrylate are preferred.
- examples of the alcohol having 1 to 8 carbon atoms include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol and the like. These alcohols include structural isomers.
- the (meth) acrylic acid ester having an OH group is preferably a (meth) acrylic acid ester of an alcohol having 1 to 8 carbon atoms from the viewpoint of obtaining a coating film having higher resilience.
- 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate are preferably used.
- (D) Manufacturing method of crosslinkable oligomer The crosslinkable oligomer which has several radically polymerizable group can be manufactured by a well-known method. For example, the following method is mentioned. First, a predetermined amount of component (b) is added to a large excess amount of component (a) and reacted at 90 ° C. until a predetermined amount of free isocyanate is reached. Polyurethane is obtained from the resulting reaction mixture by thin film distillation at 130 ° C. and 0.04 kPa.
- the component (c) is added to the polyurethane (preferably in the presence of a polymerization inhibitor such as hydroquinone monomethyl ether), and free isocyanate is substantially detected at the same temperature.
- a crosslinkable oligomer can be produced by stirring until it is no longer produced.
- a tin-based catalyst such as dibutyltin dilaurate may be added.
- the ratio of the component (c) is preferably 1.0 to 2.0 molar ratio, more preferably 1.0 to 1.5 molar ratio with respect to the component (b) -component (a).
- the proportion of component (c) can be 1.0, 1.2, 1.4, 1.5, 1.7, 1.9, 2.0.
- the cross-linked (meth) acrylic ester resin may contain components derived from other monomers. This component can be contained by coexisting with the crosslinkable oligomer during polymerization.
- Other monomers include 2-ethylhexyl (meth) acrylate, styrene, methyl methacrylate, acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, benzyl (meth) acrylate, Polyethoxyphenyl (meth) acrylate, polyethoxyphenyl (meth) acrylate, phenylbenzyl (meth) acrylate, orthophenylphenol (meth) acrylate, orthophenylphenoxyethoxy (meth) acrylate, polyethoxyorthophenylphenoxyethoxy (meth) acrylate , Isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate , Dicyclopentenyl (me
- Highly resilient resin particles can be obtained by dissolving a crosslinkable oligomer in a monomer to form an oil phase and subjecting the resulting oil phase to suspension polymerization in an aqueous medium.
- the monomer used here is not particularly limited, but is preferably a (meth) acrylic acid ester monofunctional monomer of an alcohol having 1 to 8 carbon atoms. Specific examples include monomers having no OH group, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth) acrylate. These monomers may be used alone or in combination of two or more.
- the use ratio of the (meth) acrylic acid ester monofunctional monomer and the crosslinkable oligomer is preferably 20 to 80% by mass and 80 to 20% by mass. When the use ratio of the (meth) acrylic acid ester monofunctional monomer is less than 20% by mass, sufficient flexibility may not be obtained. When the amount is more than 80% by mass, resin particles having high recoverability may not be obtained.
- a preferred proportion of the (meth) acrylic acid ester monofunctional monomer is 40 to 80% by mass, and a more preferred proportion is 45 to 75% by mass.
- the use ratio of the (meth) acrylic acid ester monofunctional monomer is 20% by mass, 30% by mass, 40% by mass, 45% by mass, 50% by mass, 60% by mass, 70% by mass, 75% by mass, 80%. Can take mass%.
- radical polymerization initiators are oil-soluble such as benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, t-butyl hydroperoxide, etc.
- oil-soluble azo compounds such as peroxides, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) and the like.
- polymerization initiators can be used alone or in combination of two or more.
- the amount of the polymerization initiator used is about 0.1 to 1 part by mass with respect to 100 parts by mass of the total amount of the crosslinkable oligomer and the (meth) acrylic acid ester.
- a dispersing agent and / or surfactant, etc. for suspension polymerization.
- a commonly used suspension dispersant such as a poorly water-soluble inorganic salt such as calcium phosphate, magnesium pyrophosphate, colloidal silica, or a water-soluble polymer such as polyvinyl alcohol, methyl cellulose, or polyvinyl pyrrolidone is used. Can do.
- anionic surfactants such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkylnaphthalenesulfonate, alkylphosphate ester salt
- Nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, lauryl dimethylamine oxide And amphoteric surfactants.
- oil-soluble surfactant examples include caprolactone EO-modified phosphoric dimethacrylate, monoisodecyl phosphate, 2-ethylhexyl acid phosphate, and isodecyl acid phosphate.
- dispersants and surfactants can be used alone or in combination of two or more.
- a combination of a poorly water-soluble phosphate dispersant such as calcium phosphate and magnesium pyrophosphate and an anionic surfactant such as alkyl sulfate and alkyl benzene sulfonate.
- the use ratio of the dispersant is about 0.5 to 10 parts by mass with respect to 100 parts by mass of the total amount of monomers of the crosslinked (meth) acrylic ester resin, and the use ratio of the surfactant is 100 parts by mass of the aqueous medium.
- the content is about 0.01 to 0.2% by mass with respect to parts.
- an oil phase for example, a monomer, a polymerization initiator, a non-polymerizable organic solvent, etc.
- an aqueous phase for example, an aqueous medium, a dispersant, a surfactant, etc.
- the aqueous phase is preferably used in an amount of 100 to 1000 parts by mass with respect to 100 parts by mass of the oil phase.
- examples of the aqueous medium include water and a mixture of water and a water-soluble organic solvent (for example, a lower alcohol).
- the polymerization temperature is preferably about 40 to 90 ° C.
- the polymerization time while maintaining the reaction system at the polymerization temperature is usually about 1 to 10 hours.
- the average particle diameter of the resin particles can be appropriately controlled by adjusting the mixing ratio of the oil phase and the aqueous phase, the dispersant, the amount of surfactant used, the stirring conditions, and the dispersion conditions.
- a method to disperse the oil phase in the water phase with fine droplets a method using a stirring force such as a propeller blade, a homogenizer, an emulsifying disperser using a high shear applied to the gap between the rotating blade and the wall or between the rotating blades.
- a method used a method using an ultrasonic disperser, and a high-pressure jet disperser.
- a homogenizer when the number of rotations is large and the dispersion time is long, the obtained droplet diameter tends to be small.
- the desired resin particles can be obtained by decomposing and removing the dispersant with an acid or the like as desired, followed by filtration, water washing, dehydration, drying, pulverization, and classification.
- the coating composition contains a binder resin and a solvent as necessary.
- a binder resin an organic solvent, a water-soluble resin, or an emulsion-type aqueous resin that can be dispersed in water can be used.
- binder resin examples include acrylic resin, alkyd resin, polyester resin, polyurethane resin, chlorinated polyolefin resin, and amorphous polyolefin resin. These binder resins can be appropriately selected depending on the adhesion of the paint to the substrate to be coated, the environment in which it is used, and the like.
- the addition amount of the binder resin and the highly recoverable resin particles also varies depending on the film thickness of the coating film to be formed, the average particle diameter of the highly recoverable resin particles, and the coating method.
- the addition amount of the binder resin is preferably 5 to 50% by mass with respect to the total of the binder resin (solid content when an emulsion type aqueous resin is used) and the highly recoverable resin particles. If the content of the highly recoverable resin particles is less than 5% by mass, the matte effect may not be sufficiently obtained. Moreover, when content exceeds 50 mass%, since the viscosity of a coating composition becomes large too much, the dispersion
- the solvent is not particularly limited, but it is preferable to use a solvent that can dissolve or disperse the binder resin.
- a solvent that can dissolve or disperse the binder resin.
- hydrocarbon solvents such as toluene and xylene
- ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
- ester solvents such as ethyl acetate and butyl acetate
- dioxane ethylene glycol diethyl ether, ethylene glycol And ether solvents such as monobutyl ether.
- water, alcohols, etc. can be used.
- These solvents may be used alone or in combination of two or more.
- the solvent content in the coating composition is usually about 20 to 60% by mass relative to the total amount of the coating composition.
- the coating composition may include a known coating surface adjusting agent, fluidity adjusting agent, ultraviolet absorber, light stabilizer, curing catalyst, extender pigment, colored pigment, metal pigment, mica powder pigment, dye, etc., as necessary. It may be included.
- the method for forming a coating film using the coating composition is not particularly limited, and any known method can be used. For example, a spray coating method, a roll coating method, a brush coating method, or the like can be used.
- the coating composition may be diluted to adjust the viscosity as necessary.
- Diluents include hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as dioxane and ethylene glycol diethyl ether; water An alcohol solvent or the like. These diluents may be used alone or in combination of two or more.
- the cosmetics containing them have a very soft touch and a light feeling of use.
- the cosmetic preferably contains 1 to 40% by mass of highly recoverable resin particles. If the content is less than 1% by mass, the resin particles may be too small to clearly show the added effect. On the other hand, if the amount exceeds 40% by mass, even if the amount added is increased further, a remarkable increase in effect commensurate with the increase in amount added may not be observed.
- Cosmetics include soaps, body shampoos, facial cleansing creams, scrub facial cleansing cosmetics, lotions, creams, milky lotions, packs, funny products, foundations, lipsticks, lip balms, blushers, eyebrow cosmetics, nail polish cosmetics, Cosmetics for shampoo, hair dye, hair styling, aromatic cosmetics, toothpaste, bath preparation, antiperspirant, sunscreen products, suntan products, body powder, baby powder and other body cosmetics, shaving cream, pre-shave lotion, Examples include after-shave lotion and body lotion.
- ingredients generally used in cosmetics can be blended according to the purpose within a range not impairing the effects of the present invention.
- examples of such components include water, lower alcohols, fats and waxes, hydrocarbons, higher fatty acids, higher alcohols, sterols, fatty acid esters, metal soaps, moisturizers, surfactants, polymer compounds, coloring material raw materials, Perfumes, antiseptics / bactericides, antioxidants, UV absorbers, and special ingredients.
- Oils and waxes include avocado oil, almond oil, olive oil, cacao butter, beef tallow, sesame butter, wheat germ oil, safflower oil, shea butter, turtle oil, persimmon oil, persic oil, castor oil, grape oil, macadamia nut oil, Examples include mink oil, egg yolk oil, owl, palm oil, rosehip oil, hydrogenated oil, silicone oil, orange luffy oil, carnauba wax, candelilla wax, whale wax, jojoba oil, montan wax, beeswax, lanolin and the like.
- hydrocarbons examples include liquid paraffin, petrolatum, paraffin, ceresin, microcrystalline wax, squalane and the like.
- higher fatty acid examples include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid, oxystearic acid, linoleic acid, lanolin fatty acid, and synthetic fatty acid.
- Higher alcohols include lauryl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, lanolin alcohol, hydrogenated lanolin alcohol, hexyl decanol, octyl decanol, isostearyl alcohol, jojoba alcohol, decyltetradecane And the like.
- sterols include cholesterol, dihydrocholesterol, phytocholesterol and the like.
- Fatty acid esters include ethyl linoleate, isopropyl myristate, lanolin fatty acid isopropyl, hexyl laurate, myristyl myristate, cetyl myristate, octadodecyl myristate, decyl oleate, octadodecyl oleate, hexadecyl dimethyloctanoate, isooctanoic acid Cetyl, decyl palmitate, glyceryl trimyristate, glycerin tri (capryl / capric acid), propylene glycol dioleate, glyceryl triisostearate, glycerin triisooctanoate, cetyl lactate, myristyl lactate, diisostearyl malate and
- Examples of the metal soap include zinc laurate, zinc myristate, magnesium myristate, zinc palmitate, zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, and zinc undecylenate.
- Examples of the humectant include glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, sodium dl-pyrrolidonecarboxylate, sodium lactate, sorbitol, sodium hyaluronate, polyglycerin, xylit, maltitol and the like.
- surfactants include anionic surfactants such as higher fatty acid soaps, higher alcohol sulfates, N-acyl glutamates and phosphates, cationic surfactants such as amine salts and quaternary ammonium salts, betaines Type, amino acid type, imidazoline type, amphoteric surfactant such as lecithin, nonionic surfactant such as fatty acid monoglyceride, propylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, ethylene oxide condensate Can be mentioned.
- anionic surfactants such as higher fatty acid soaps, higher alcohol sulfates, N-acyl glutamates and phosphates
- cationic surfactants such as amine salts and quaternary ammonium salts
- betaines Type amino acid type, imidazoline type, amphoteric surfactant such as lecithin
- polymer compound examples include gum arabic, tragacanth gum, guar gum, locust bean gum, karaya gum, iris moss, quince seed, gelatin, shellac, rosin, casein, and other natural polymer compounds, sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, Semi-synthetic polymer compounds such as sodium alginate, ester gum, nitrocellulose, hydroxypropylcellulose, crystalline cellulose, polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, carboxyvinyl polymer, polyvinyl methyl ether, polyamide resin, silicone oil, nylon particles , Polymethyl methacrylate particles, crosslinked polystyrene particles, silicon particles, urethane particles, polyethylene Particles, synthetic polymer compounds such as resin particles of the silica particles and the like.
- Color material raw materials include iron oxide, ultramarine, conger, chromium oxide, chromium hydroxide, carbon black, manganese violet, titanium oxide, zinc oxide, talc, kaolin, mica, calcium carbonate, magnesium carbonate, mica, aluminum silicate, Inorganic pigments such as barium silicate, calcium silicate, magnesium silicate, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, hydroxyapatite, ceramic powder, azo, nitro, nitroso, xanthene And tar dyes such as quinoline, anthraquinoline, indigo, triphenylmethane, phthalocyanine, and pyrene.
- Inorganic pigments such as barium silicate, calcium silicate, magnesium silicate, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gyp
- the surface treatment may be performed in advance on the powder raw materials such as the polymer compound and the color material raw material.
- a conventionally known surface treatment technique can be used as the surface treatment method.
- oil treatment with hydrocarbon oil, ester oil, lanolin, etc. silicone treatment with dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, perfluoroalkyl group-containing ester, perfluoroalkylsilane, perfluoropolyether Fluorine compound treatment with a polymer having a perfluoroalkyl group, silane coupling agent treatment with 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, isopropyltriisostearoyl titanate, isopropyltris ( Dioctylpyrophosphate) Titanium coupling agent treatment with titanate, metal soap treatment, amino acid treatment with acylglutamic acid,
- fragrances include natural fragrances such as lavender oil, peppermint oil, and lime oil, and synthetic fragrances such as ethylphenyl acetate, geraniol, and p-tert-butylcyclohexyl acetate.
- synthetic fragrances such as ethylphenyl acetate, geraniol, and p-tert-butylcyclohexyl acetate.
- antiseptic / bactericidal agent include methyl paraben, ethyl paraben, propyl paraben, benzalkonium, benzethonium and the like.
- antioxidant examples include dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, tocopherol and the like.
- Ultraviolet absorbers include inorganic absorbents such as fine particle titanium oxide, fine particle zinc oxide, fine particle cerium oxide, fine particle iron oxide, fine particle zirconium oxide, benzoic acid-based, paraaminobenzoic acid-based, anthranilic acid-based, salicylic acid-based And organic absorbents such as cinnamic acid, benzophenone and dibenzoylmethane.
- Special ingredients include hormones such as estradiol, estrone, ethinylestradiol, cortisone, hydrocortisone, prednisone, vitamins such as vitamin A, vitamin B, vitamin C, vitamin E, citric acid, tartaric acid, lactic acid, aluminum chloride, sulfuric acid Skin astringents such as aluminum / potassium, allantochlorhydroxyaluminum, zinc paraphenolsulfonate, zinc sulfate, cantalis tincture, pepper tincture, ginger tincture, assembly extract, garlic extract, hinokitiol, carpronium chloride, pentadecanoic acid glyceride, vitamin E, estrogen, hair growth promoters such as photosensitizers, and whitening agents such as magnesium phosphate-L-ascorbate and kojic acid.
- hormones such as estradiol, estrone, ethinylestradiol, cortisone, hydrocortisone, prednis
- the diameter of the selected resin particles is measured with a particle size measurement cursor of MCTM-200.
- the resin particles to be selected are determined according to the particle diameter to be measured.
- the resin particles are gradually loaded up to a maximum load of 9.81 mN, and the diameter of the resin particles measured earlier is 10 Measure the load at the time of displacement of% or 30%.
- the individual compressive strength is obtained by the following equation. Measure the six resin particles, remove the maximum and minimum values from the six compressive strengths, and compress the compressive strength at the time when the average value of the remaining four compressive strengths is displaced by 10% or 30% (S10 or S30 strength) ).
- the restoration rate of the resin particles is measured by a load-unloading test using a micro compression tester (MCTM-200) manufactured by Shimadzu Corporation. That is, first, resin particles are placed on a lower pressure plate (SKS flat plate), and are separated into individual fine resin particles (within a diameter of at least 100 ⁇ m) by an MCTM-200 optical microscope (objective lens magnification: 50 times). A state in which no other resin particles exist is selected. The diameter of the selected resin particles is measured with a particle size measurement cursor of MCTM-200. The resin particles to be selected are determined according to the particle diameter to be measured.
- MCTM-200 micro compression tester manufactured by Shimadzu Corporation. That is, first, resin particles are placed on a lower pressure plate (SKS flat plate), and are separated into individual fine resin particles (within a diameter of at least 100 ⁇ m) by an MCTM-200 optical microscope (objective lens magnification: 50 times). A state in which no other resin particles exist is selected. The diameter of the selected resin particles is measured
- Restoration rate (%) restoration amount ( ⁇ m) / diameter ( ⁇ m) ⁇ 100 ⁇ Measurement conditions for restoration rate>
- Glass transition temperature of crosslinkable oligomer The glass transition temperature is viscoelasticity measuring device PHYSICA MCR301 (manufactured by Anton Paar), temperature control system CTD450 and liquid nitrogen supply device, analysis software Rheoplus, geometry is ⁇ 8mm upper and lower lattice processing parallel plate, ⁇ 10mm, thickness The distance between the plates is adjusted so that a normal force of 0.05 N is obtained by sandwiching a disk-shaped test piece of about 1 mm at 23 ° C., and the measurement is started after cooling to ⁇ 70 ° C. The frequency of vibration applied to the test piece is 1 Hz, the rate of temperature increase is 5 ° C./min, the measurement temperature range is ⁇ 70 ° C.
- the resin sheet having a thickness of 6 mm obtained in the example or the comparative example is cut into a square plate shape having a plane size of 12 mm ⁇ 12 mm, and the obtained square plate resin sheet is used as a test piece.
- a compression tester compress the test piece at a compression rate of 10 mm / min, compress the thickness of the test piece by 30%, and then increase the initial thickness at the same speed as the compression. Open and measure changes in load and strain from the start of compression to the point of opening to the initial thickness. For all of these values, three test pieces are measured, and the average value of the three is adopted as the final measurement value.
- the test piece was conditioned in a standard atmosphere of JIS K 7100: 1999 “23/50” (temperature 23 ° C., relative humidity 50%) over 2 hours in a second grade standard atmosphere, and then in the same standard atmosphere. Measure.
- the initial thickness of the test piece is measured as the thickness of the test piece when a load (initial load) of 0.5 N (stress of 3.5 kPa) is applied to the test piece.
- the displacement of the test piece is measured using the position of the pressure plate (movable plate) jig when the load (initial load) 0.5 N (stress 3.5 kPa) is applied to the test piece as the origin.
- Compression testing machine Tensilon universal testing machine “UCT-10T” (Orientec) Data processing software: Cycle test mode “UTPS-458C” (manufactured by Softbrain) Compression jig: Compression jig based on JIS K 6767: 1999 ⁇ Calculation method of hysteresis loss>
- the hysteresis energy and hysteresis loss in the first cycle are calculated from the pressurizing energy (J) and the depressurizing energy (J) in the first cycle by the following equations.
- Hysteresis energy (J) Pressurization energy (J)-Decompression energy (J)
- Hysteresis loss (%) 100 ⁇ (hysteresis energy (J) / pressure energy (J)
- volume average diameter of resin particles (arithmetic average diameter according to the volume-based particle size distribution) is measured by Coulter Multisizer II (Beckman Coulter, Inc.) by the following method. In this measurement, calibration is performed using a 50 ⁇ m aperture according to Reference MANUAL FOR THE COULTER MULTISIZER (1987) issued by Coulter Electronics Limited.
- 0.1 g of resin particles in 10 ml of 0.1 wt% nonionic surfactant was mixed with a touch mixer (“TOUCMIXER MT-31” manufactured by Yamato Kagaku Co., Ltd.) and an ultrasonic cleaner (manufactured by Vervo Courier “ ULTRASONIC CLEANER VS-150]) to obtain a dispersion, and then in a beaker filled with ISOTON (registered trademark) II (measurement electrolyte manufactured by Beckman Coulter, Inc.) installed in the Coulter Multisizer II body The dispersion is dripped with a dropper with gentle stirring, and the concentration meter reading on the Coulter Multisizer II main body is adjusted to about 10% .Next, the aperture size (diameter) is adjusted to the Coulter Multisizer II main body.
- a touch mixer (“TOUCMIXER MT-31” manufactured by Yamato Kagaku Co., Ltd.) and an ultrasonic cleaner (manufactured by Ver
- Example 7 100 ⁇ m, Current (aperture electrode) 1 00 ⁇ A, Gain (gain) of 2, Polarity (polarity of internal electrode) as +, manual (manual mode), Examples and comparative examples other than these examples are 50 ⁇ m, Current (aperture electrode) is 800 ⁇ A, Input Gain (gain) and Polarity (polarity of internal electrode) as +, and measure in manual (manual mode) . While measuring, stir gently in the beaker to the extent that bubbles do not enter. The measurement is terminated when the measurement of 10,000 resin particles is completed, and the arithmetic average diameter in the volume-based particle size distribution of 100,000 resin particles is defined as the volume average diameter.
- AVNV 2,2-azobis (2,4-dimethylvaleronitrile)
- Synthesis example 2 A hexamethylene diisocyanate adduct of trimethylolpropane ethylene oxide adduct (NCO content 9.4%, average trifunctional) 1340 g (1 mol), hydroquinone monomethyl ether 0.8 g, 2-hydroxyethyl acrylate (molecular weight 116 ) 365 g (3.15 mol) was charged and reacted at 70 to 80 ° C. until the amount of free isocyanate was 0.1% or less to obtain a crosslinkable oligomer B ((meth) acrylic equivalent 541 g / mol). Moreover, the glass transition temperature of the cured product B derived from the crosslinkable oligomer B was 8 ° C.
- Example 1 50 parts by mass of n-butyl acrylate as a (meth) acrylate monofunctional monomer, 50 parts by mass of the crosslinkable oligomer A obtained in Synthesis Example 1, and “KAYAMER (registered trademark) as an oil-soluble surfactant ) PM-21 ”(manufactured by Nippon Kayaku Co., Ltd.), 0.5 part by weight of AVNV (manufactured by Nippon Finechem) as a polymerization initiator and 0.1 part by weight of benzoyl peroxide were mixed. The oil phase was adjusted. Further, 200 parts by mass of deionized water as an aqueous medium and 6.1 parts by mass of magnesium pyrophosphate produced by the metathesis method as a dispersant were mixed to prepare an aqueous phase.
- KAYAMER registered trademark
- AVNV manufactured by Nippon Finechem
- the oil phase was dispersed in the water phase using a TK-homomixer (manufactured by Primix) at 8000 rpm for 5 minutes to obtain a dispersion liquid of about 8 ⁇ m. Thereafter, this dispersion was put into a polymerization vessel equipped with a stirrer and a thermometer, the internal temperature of the polymerization vessel was raised to 50 ° C., and the suspension was stirred for 3 hours. Dodecylbenzene as a surfactant After adding 0.05 part by mass of sodium sulfonate to the suspension, the internal temperature of the polymerization vessel is increased to 90 ° C. (secondary increase), and the suspension is stirred at 90 ° C. for 3 hours. To complete the suspension polymerization reaction.
- TK-homomixer manufactured by Primix
- the dispersant (magnesium pyrophosphate) contained in the suspension was decomposed with hydrochloric acid. Thereafter, the suspension was dehydrated by filtration to separate the solid content, and the solid content was washed with sufficient water. To the solid content after washing, 2.5 parts by mass of hydrophobic colloidal silica (manufactured by Nippon Aerosil Co., Ltd., trade name “AEROSIL (registered trademark) R974”) as an inorganic powder was added and dried under reduced pressure at 50 ° C. for 24 hours.
- hydrophobic colloidal silica manufactured by Nippon Aerosil Co., Ltd., trade name “AEROSIL (registered trademark) R974”
- the resin particles agglomerated at the time of drying were pulverized using a pulverizer “Labo Milser” (model number: LM-PLUS) manufactured by Osaka Chemical Co., Ltd. to obtain dried and crushed resin particles. Thereafter, the resin particles having a particle size of less than the upper limit (63 ⁇ m) were removed (cut) by passing through a mesh having a mesh size of 63 ⁇ m to obtain resin particles having a volume average particle size of 8.3 ⁇ m.
- the resin particles had a 30% compressive strength of 2.31 and a restoration rate of 33.1%.
- the resin constituting the resin particles had a hysteresis loss of 15%.
- Example 2 Resin particles having a volume average particle diameter of 7.5 ⁇ m were obtained in the same manner as in Example 1 except that the crosslinkable oligomer B obtained in Synthesis Example 2 was used in place of the crosslinkable oligomer A.
- the resin particles had a 30% compressive strength of 4.9 and a restoration rate of 25.4%.
- the resin constituting the resin particles had a hysteresis loss of 13%.
- Example 3 Resin particles having a volume average particle diameter of 7.8 ⁇ m were obtained in the same manner as in Example 1 except that 70 parts by mass of n-butyl acrylate and 30 parts by mass of crosslinkable oligomer A were used.
- the resin particles had a 30% compressive strength of 3.3 and a restoration rate of 22.5%.
- the resin constituting the resin particles had a hysteresis loss of 22%.
- Example 4 Resin particles having a volume average particle diameter of 9.2 ⁇ m were obtained in the same manner as in Example 1 except that 30 parts by mass of n-butyl acrylate and 70 parts by mass of crosslinkable oligomer A were used. The resin particles had a 30% compressive strength of 3.8 and a restoration rate of 27.5%. The resin constituting the resin particles had a hysteresis loss of 17%.
- Example 5 As in Example 1, except that 30 parts by mass of n-butyl acrylate, 10 parts by mass of 2-ethylhexyl acrylate, and 10 parts by mass of butyl methacrylate are used as the (meth) acrylate monofunctional monomer.
- Resin particles having a volume average particle diameter of 8.5 ⁇ m were obtained.
- the resin particles had a 30% compressive strength of 3.5 and a restoration rate of 30.3%.
- the resin constituting the resin particles had a hysteresis loss of 18%.
- Comparative Example 3 Volume average particles were obtained in the same manner as in Example 1 except that 80 parts by mass of n-butyl acrylate was used and 20 parts by mass of trimethylolpropane trimethacrylate (Tg> 250 ° C.) was used in place of the crosslinkable oligomer A. Resin particles having a diameter of 8.3 ⁇ m were obtained. The resin particles had a 30% compressive strength of 1.49 and a restoration rate of 19.1%. The resin constituting the resin particles had a hysteresis loss of 45%.
- Example 6 Example of small particle size
- Example 6 Example except that the oil phase and the aqueous phase were mixed and the dispersion liquid dispersed with a homomixer was passed once with a microfluidizer (HC-5000, manufactured by Mizuho Kogyo Co., Ltd.) at a pressure of 100 kg / cm 2.
- HC-5000 manufactured by Mizuho Kogyo Co., Ltd.
- resin particles having a volume particle diameter of 3.5 ⁇ m were obtained.
- the resin particles exhibited a 30% compressive strength of 4.5 and a restoration rate of 24.5%.
- the 10% compressive strength was 0.51, and the hysteresis loss of the resin was 15.
- Example 7 (Example of large particle size) Resin particles having a volume average particle diameter of 25.1 ⁇ m were obtained in the same manner as in Example 2 except that the rotation number of the TK homomixer was 1500 rpm. The resin particles exhibited a 30% compressive strength of 1.8 and a restoration rate of 37.5%. The 10% compressive strength was 0.13, and the hysteresis loss of the resin was 13. The raw materials used for the production of the resin particles and the physical properties of the resin particles are summarized in Table 1.
- Example 8 and Comparative Example 5 For each 0.8 g of the resin particles obtained in Examples 1 to 5 and Comparative Examples 1 to 4, 6 g of a binder resin (RST-201 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and a photopolymerization initiator (Darocur manufactured by BASF) 1173) A coating composition was obtained by blending 0.15 g and 4 g of toluene as a solvent. The coating compositions containing the resin particles obtained in Examples 1 to 5 and Comparative Examples 1 to 4 are collectively referred to as Example 8 and Comparative Example 5, respectively.
- a binder resin RST-201 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- a photopolymerization initiator Darocur manufactured by BASF
- Example 1 Production and blending amount of powder foundation Resin particles obtained in Example 1 10.0 parts by weight Red iron oxide 3.0 parts by weight Yellow iron oxide 2.5 parts by weight Black iron oxide 0.5 parts by weight Titanium oxide 10.0 Parts by weight mica 20.0 parts by weight talc 44.0 parts by weight liquid paraffin 5.0 parts by weight octyldodecyl myristate 2.5 parts by weight petrolatum 2.5 parts by weight preservative appropriate amount perfume appropriate amount / production method resin particles, red iron oxide , Yellow iron oxide, black iron oxide, titanium oxide, mica and talc are mixed with a Henschel mixer, and liquid paraffin, octyldodecyl myristate, petrolatum and preservative are mixed and added to this and mixed uniformly. After adding a fragrance
- polyethylene glycol and triethanolamine are added to purified water, dissolved by heating, and kept at 70 ° C. (aqueous phase).
- An oil phase is added to the aqueous phase, pre-emulsified, and then uniformly emulsified with a homomixer. After emulsification, the emulsion is cooled to 30 ° C. with stirring to obtain a cosmetic emulsion.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Cosmetics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
例えば、特許第5297845号公報(特許文献1)には、ビニル基を分子の両末端に有する特定の架橋性単量体と(メタ)アクリル酸エステルとを含む混合物を重合させることにより得られる、優れた復元率を有し、耐傷付き性に優れた柔らかな触感を有する塗膜を形成できる樹脂粒子が記載されている。
また、本発明によれば、上記高復元性樹脂粒子を含むコーティング用組成物が提供される。
更に、本発明によれば、上記コーティング組成物を塗布及び乾燥させて得られた塗膜が提供される。
また、本発明によれば、上記高復元性樹脂粒子を含む化粧料が提供される。
(1)架橋(メタ)アクリル酸エステル系樹脂が、(a)ポリオール、(b)ポリイソシアネート及び(c)OH基を有する(メタ)アクリル酸エステルを反応させて得られた複数のラジカル重合性基を有する架橋性オリゴマー及び(メタ)アクリル酸エステル系単官能単量体に由来する樹脂からなり、
架橋性オリゴマーを単独で硬化させた際に、0~30℃のTg(粘弾性から測定)を示す場合
(2)高復元性樹脂粒子が、(メタ)アクリル酸エステル系単官能単量体20~80質量%と、架橋性オリゴマー80~20質量%とを含む単量体混合物を重合させることによって得られた単量体混合物の重合物であり、(メタ)アクリル酸エステル系単官能単量体が、炭素数1~8のアルコールの(メタ)アクリル酸エステルである場合
(3)架橋(メタ)アクリル酸エステル系樹脂が、30%以下のヒステリシスロスを示す樹脂組成からなる場合
のいずれかであれば、より高い復元性を有する樹脂粒子を提供できる。
高復元性樹脂粒子は、架橋(メタ)アクリル酸エステル系樹脂からなる平均粒子径1~100μmの樹脂粒子である。この範囲内の平均粒子径を有する樹脂粒子は、塗膜に使用した場合、復元性及び艶消し効果をより向上できる。平均粒子径が1μm未満の場合、塗膜において形成される凹凸が小さくなるために、実質的な艶消し効果を得られない場合がある。また、粒子の平均粒子径が100μmを越える場合、塗膜がざらざらと荒れた状態となり、外観が悪くなる場合がある。好ましい平均粒子径は1~80μmであり、より好ましい平均粒子径は1~50μmである。平均粒子径は、1μm、5μm、10μm、20μm、30μm、40μm、50μm、60μm、70μm、80μm、90μm、100μmを取りえる。
架橋性オリゴマーは、例えば、(a)ポリオール、(b)ポリイソシアネート及び(c)OH基を有する(メタ)アクリル酸エステルを反応させて得られたウレタン(メタ)アクリレートであることが好ましい。架橋(メタ)アクリル酸エステル系樹脂が、このウレタン(メタ)アクリレートに由来する架橋樹脂であることで、高復元性樹脂粒子を得ることができる。
ポリオールとしては、例えば、ポリエステル系ポリオール、ポリエーテル系ポリオール、ポリカーボネートポリオール、脂肪族炭化水素系ポリオール、脂環族炭化水素系ポリオール等が挙げられる。
上記ポリオールは、単独で使用しても、2種以上を併用してもよい。
上記環状エステル(ラクトン)としては、例えば、γ-ブチロラクトン、δ-バレロラクトン、ε-カプロラクトン等が挙げられる。
なお、ポリカーボネート系ポリオールは、分子内にカーボネート結合を有し、末端がヒドロキシル基を3個以上含有する化合物であればよく、カーボネート結合とともにエステル結合を有していてもよい。
(a-5)上記水添化ポリブタジエン系ポリオールとは、ポリブタジエン系ポリオールの構造中に含まれるエチレン性不飽和基の全部が水素化された構造で、その分子末端(側鎖)に水酸基を合計3つ以上有するものであればよい。
ポリイソシアネートとしては、例えば、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香族ポリイソシアネート、芳香脂肪族ポリイソシアネートが挙げられる。
ポリイソシアネートは2~4個のNCO基を備えていることが好ましい。NCO基数が2未満の場合、架橋性が下がりすぎることがある。4を越える場合、架橋性が上がりすぎ、復元性の高い樹脂粒子を得られないことがある。
上記ポリイソシアネートは、単独で使用しても、2種以上を併用してもよい。
OH基を有する(メタ)アクリル酸エステルとしては、例えば、2-ヒドロキシエチルアクリレート、2-ヒドロキシエチルメタクリレート、2-ヒドロキシプロピルアクリレート、2-ヒドロキシプロピルメタクリレート、4-ヒドロキシブチルアクリレート、カプロラクトン変性-2-ヒドロキシエチルアクリレート等のOH基を有する炭素数1~8のアルコールの(メタ)アクリル酸エステル、ポリエチレングリコールモノ(メタ)アクリル酸エステル、ポリプロピレグリコールモノアクリル酸エステル、ポリブチレングリコールモノ(メタ)アクリル酸エステル、2-(メタ)アクリロイロキシエチル-2-ヒドロキシエチルフタレート、フェニルグリシジルエーテル(メタ)アクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート、カプロラクトン変性ジペンタエリスリトールペンタ(メタ)アクリレート等が挙げられる。
OH基を有する(メタ)アクリル酸エステル中、OH基を有する炭素数1~8のアルコールの(メタ)アクリル酸エステル及びペンタエリスリトールトリアクリレートが好ましい。ここで、炭素数1~8のアルコールとしては、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール等が挙げられる。これらアルコールには、構造異性体が含まれる。
OH基を有する(メタ)アクリル酸エステルは、より復元性の高い塗膜を得る観点から、炭素数1~8のアルコールの(メタ)アクリル酸エステルであることが好ましい。中でも2-ヒドロキシエチルアクリレート及び2-ヒドロキシプロピルアクリレートを使用することが好ましい。
複数のラジカル重合性基を有する架橋性オリゴマーは、公知の方法により製造できる。例えば、次の方法が挙げられる。まず、所定量の成分(b)を大過剰量の成分(a)に投入し、90℃で所定の遊離イソシアネート量になるまで反応させる。得られた反応混合物から130℃及び0.04kPaの条件での薄膜蒸留によりポリウレタンを得る。次いで、70~80℃の温度域で、ポリウレタンに成分(c)を投入し(ハイドロキノンモノメチルエーテル等の重合禁止剤の存在下であることが好ましい)、同じ温度で、遊離イソシアネートが実質的に検出されなくなるまで攪拌することで架橋性オリゴマーを製造できる。また、反応を促進させるために、ジブチルチンジラウレートのようなスズ系触媒を添加してもよい。
ここで、成分(c)の割合は、成分(b)-成分(a)に対し、1.0~2.0モル比が好ましく、1.0~1.5モル比がより好ましい。成分(c)の割合は、1.0、1.2、1.4、1.5、1.7、1.9、2.0を取りえる。
架橋(メタ)アクリル酸エステル系樹脂は、他のモノマー由来の成分を含んでいてもよい。この成分は、重合時に架橋性オリゴマーと併存させることにより含有させることができる。
高復元性樹脂粒子は、架橋性オリゴマーをモノマーに溶解して油相とし、得られた油相を水性媒体中で懸濁重合させることにより得ることができる。
ここで、使用されるモノマーとしては、特に限定されないが、炭素数1~8のアルコールの(メタ)アクリル酸エステル系単官能単量体であることが好ましい。具体的には、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、ペンチル(メタ)アクリレート等のOH基を備えないモノマーが挙げられる。これらモノマーは、単独で用いても、複数種を併用してもよい。
ラジカル重合開始剤としては、例えば過酸化ベンゾイル、過酸化ラウロイル、過酸化オクタノイル、オルソクロロ過酸化ベンゾイル、メチルエチルケトンパーオキサイド、ジイソプロピルパーオキシジカーボネート、クメンハイドロパーオキサイド、t-ブチルハイドロパーオキサイド等の油溶性過酸化物、2,2’-アゾビスイソブチロニトリル、2,2’-アゾビス(2,4-ジメチルバレロニトリル)等の油溶性アゾ化合物が挙げられる。
分散剤としては、例えば、リン酸カルシウム、ピロリン酸マグネシウム、コロイダルシリカ等の難水溶性無機塩、ポリビニルアルコール、メチルセルロース、ポリビニルピロリドン等の水溶性高分子等の通常用いることのできる懸濁分散剤を用いることができる。
分散剤の使用割合は、架橋(メタ)アクリル酸エステル系樹脂のモノマーの合計量100質量部に対して0.5~10質量部程度であり、界面活性剤の使用割合は、水性媒体100質量部に対して0.01~0.2質量%程度である。
重合温度は40~90℃程度が好ましい。反応系を重合温度に保持しながら重合させる時間は、通常、1~10時間程度である。樹脂粒子の平均粒子径は、油相と水相との混合割合や分散剤、界面活性剤の使用量及び攪拌条件、分散条件を調整することにより適宜制御できる。
重合反応終了後、所望により分散剤を酸等で分解除去し、濾過、水洗浄、脱水、乾燥、粉砕、分級を行うことによって目的とする樹脂粒子が得られる。
高復元性樹脂粒子は、特定の圧縮強度、復元率及びヒステリシスロスを有しているので、それを含むコーティング用組成物から得られた塗膜に軟質性及び/又は艶消し性を付与できる。
コーティング組成物は、必要に応じて、バインダー樹脂や溶剤が含まれる。バインダー樹脂としては、有機溶剤又は水に可溶な樹脂もしくは水中に分散できるエマルション型の水性樹脂を使用できる。
高復元性樹脂粒子は、特定の圧縮強度、復元率及びヒステリシスロスを有しているので、それを含む化粧料は非常に柔らかな触感および軽い使用感を有する。
化粧料は、高復元性樹脂粒子を1~40質量%の範囲で含んでいることが好ましい。含有量が1質量%未満であると、樹脂粒子が少なすぎて添加した効果が明確に認められないことがある。また、40質量%を超えると、それ以上に添加量を増加しても、添加量の増加に見合った顕著な効果の増進が認められないことがある。
〔圧縮強度の測定方法〕
樹脂粒子の10%及び30%圧縮変位時の圧縮強度S10及びS30の測定は、島津製作所社製の微小圧縮試験機(MCTM-200)を用いた圧縮試験によって行う。
すなわち、まず、樹脂粒子を下部加圧板(SKS平板)上に載置し、MCTM-200の光学顕微鏡(対物レンズ倍率50倍)で一個の独立した微細な樹脂粒子(少なくとも直径100μmの範囲内に他の樹脂粒子が存在しない状態)を選び出す。選び出した樹脂粒子の直径を、MCTM-200の粒子径測定カーソルで測定する。選び出す樹脂粒子は、測定対象とする粒子径に応じて決定する。次に、選び出した樹脂粒子の頂点に試験用圧子を下記の負荷速度で降下させることにより、最大荷重9.81mNまで、徐々に樹脂粒子に荷重をかけ、先に測定した樹脂粒子の直径が10%又は30%変位した時点の荷重を測定する。得られた測定値から、次式により、個別の圧縮強度を求める。6つの樹脂粒子に対して測定を行い、6つの圧縮強度から最大値及び最小値を除き、残る4つの圧縮強度の平均値を10%又は30%変位した時点での圧縮強度(S10又はS30強度)とする。
圧縮強度(Mpa)=2.8×荷重(N)/{π×(粒子径(mm))2}
<圧縮強度の測定条件>
試験温度:常温(20℃)相対湿度65%
上部加圧圧子:直径50μmの平面圧子(材質:ダイヤモンド)
下部加圧板:SKS平板
試験種類:圧縮試験
試験荷重:9.81mN
負荷速度:0.732mN/sec
樹脂粒子の復元率の測定は、島津製作所社製の微小圧縮試験機(MCTM-200)を用いた負荷-除荷試験によって行う。
すなわち、まず、樹脂粒子を下部加圧板(SKS平板)上に載置し、MCTM-200の光学顕微鏡(対物レンズ倍率50倍)で一個の独立した微細な樹脂粒子(少なくとも直径100μmの範囲内に他の樹脂粒子が存在しない状態)を選び出す。選び出した樹脂粒子の直径を、MCTM-200の粒子径測定カーソルで測定する。選び出す樹脂粒子は、測定対象とする粒子径に応じて決定する。次に、選び出した樹脂粒子の頂点に試験用圧子を下記の負荷速度で降下させることにより、最大試験力9.81mNまで樹脂粒子に荷重をかけたときの粒子径Aと、その後、最小試験力1.96mNまで除荷したときの粒子径Bを測定する。粒子径Aと粒子径Bとから得られる変位量(復元量)から、次式により、個別の復元率を求める。6つの樹脂粒子に対して測定を行い、6つの復元率から最大値及び最小値を除き、残る4データの平均値を復元率とする。
復元率(%)=復元量(μm)/直径(μm)×100
<復元率の測定条件>
試験温度:常温(20℃)相対湿度65%
上部加圧圧子:直径50μmの平面圧子(材質:ダイヤモンド)
下部加圧板:SKS平板
試験種類:負荷-除荷試験
最大試験力:9.81mN
最小試験力:1.96mN
負荷速度:0.732mN/sec
負荷保持時間:1sec
除荷保持時間:1sec
ガラス転移温度は、粘弾性測定装置PHYSICA MCR301(Anton Paar社製)、温度制御システムCTD450と液体窒素供給装置、解析ソフトRheoplus、ジオメトリーにはφ8mmの上下格子目加工パラレルプレートを用い、φ10mm、厚さ約1mmの円盤状試験片を23℃でプレートに挟んでノーマルフォース0.05Nになるようにプレート間距離を調整し、-70℃まで冷却してから測定を開始する。前記試験片に印加する振動の周波数を1Hzとし、昇温速度5℃/分、測定温度幅-70℃~200℃、-70℃→50℃の範囲では歪み0.01%→1%(対数昇降)でノーマルフォース3N、50℃→100℃の範囲では歪み1%→2%(対数昇降)でノーマルフォース3N→2N(線形昇降)、測定点間隔は0.2分、窒素雰囲気の条件にて測定した損失正接(tanδ)の極大値をガラス転移温度とする。
樹脂粒子の作製に用いた油相を配合液とし、シリコーンシートで作製した厚み6mmの枠内それぞれに配合液を注入し、PETフィルムで挟みこみ、更にガラス板で挟みこみ、クリップで固定した物を2つ用意する。一方の固定物を50℃で24時間、他方の固定物を90℃で8時間、それぞれ重合反応させて、厚み6mm、2mmの樹脂シート2種を樹脂粒子作製に用いた樹脂組成での物性測定用サンプルとして得る。
以下に示す測定条件及び環境下で、圧縮試験機を用いて、試験片を10mm/分の圧縮速度で圧縮し、試験片の厚みを30%圧縮させた後、圧縮と同じ速度で初期厚みまで開放し、圧縮開始時から初期厚みまで開放される時点までの荷重及び歪みの変化を測定する。なお、これらの値全てについてそれぞれ、試験片3個を測定し、3個の平均値を最終的な測定値として採用する。
圧縮試験機:テンシロン万能試験機「UCT-10T」(オリエンテック社製)
データ処理ソフト:サイクル試験モード「UTPS-458C」(ソフトブレーン社製)
圧縮治具:JIS K 6767:1999に準拠した圧縮治具
<ヒステリシスロスの算出方法>
1回目のサイクルにおけるヒステリシスエネルギー及びヒステリシスロスを、1回目のサイクルにおける加圧エネルギー(J)及び除圧エネルギー(J)から次式により算出する。
ヒステリシスエネルギー(J)=加圧エネルギー(J)-除圧エネルギー(J)
ヒステリシスロス(%)=100×(ヒステリシスエネルギー(J)/加圧エネルギー(J)
樹脂粒子の体積平均径(体積基準の粒度分布によける算術平均径)の測定は、コールターマルチサイザーII(ベックマンコールター社製測定装置)により、以下の方法で行う。なお、本測定に際しては、Coulter Electronics Limited発行のReference MANUAL FOR THE COULTER MULTISIZER(1987)に従って、50μmアパチャーを用いてキャリブレーションを行い、測定する。
合成例1
フラスコに1,6-ヘキサンジオールポリカーボネートジオールのヘキサメチレンジイソシアネートアロファネート付加体(NCO含有量13.5%、4官能)1400g(1モル)、ハイドロキノンモノメチルエーテル1.4g、2-ヒドロキシエチルアクリレートのカプロラクトン1モル付加物(分子量230)1265g(5.5モル)を仕込み、70~80℃にて遊離イソシアネート量が0.1%以下になるまで反応させ、架橋性オリゴマーAを得た((メタ)アクリル当量485g/mol)。なお、(メタ)アクリル当量は、(1400+1265)/5.5=485の計算式で算出した。
架橋性オリゴマーA100質量部に対して、2,2-アゾビス(2,4-ジメチルバレロニトリル)(以下「AVNV」と略記する)(日本ファインケム社製)1質量部を配合し、溶解した。これをポリエチレンテレフタレート基材(東レ社製PET、型番:#100 T60)上に膜厚が約1mmになるようにシリコーンパッキンで挟み込み、50℃のオーブンで24時間加熱し硬化させた。得られた硬化物Aのガラス転移温度は18℃であった。
フラスコにトリメチロールプロパンのエチレンオキサイド付加物のヘキサメチレンジイソシアネート付加体(NCO含有量9.4%、平均3官能)1340g(1モル)、ハイドロキノンモノメチルエーテル0.8g、2-ヒドロキシエチルアクリレート(分子量116)365g(3.15モル)を仕込み、70~80℃にて遊離イソシアネート量が0.1%以下になるまで反応させ、架橋性オリゴマーBを得た((メタ)アクリル当量541g/mol)。また、架橋性オリゴマーB由来の硬化物Bのガラス転移温度は8℃であった。
実施例1
(メタ)アクリル酸エステル系単官能単量体としてアクリル酸n-ブチル50質量部、合成例1にて得られた架橋性オリゴマーA50質量部、油溶性界面活性剤としてとしての「KAYAMER(登録商標)PM-21」(日本化薬社製)0.1質量部と、重合開始剤としてのAVNV(日本ファインケム社製)0.5質量部及び過酸化ベンゾイル0.1質量部とを混合して、油相を調整した。また、水性媒体としての脱イオン水200質量部と、分散剤としての、複分解法により生成させたピロリン酸マグネシウム6.1質量部とを混合して、水相を調整した。
架橋性オリゴマーAに代えて合成例2で得られた架橋性オリゴマーBを使用すること以外は、実施例1と同様にして体積平均粒子径7.5μmの樹脂粒子を得た。樹脂粒子は4.9の30%圧縮強度、25.4%の復元率を有していた。なお、樹脂粒子を構成する樹脂は13%のヒステリシスロスを有していた。
実施例3
アクリル酸n-ブチルを70質量部使用し、架橋性オリゴマーAを30質量部使用すること以外は、実施例1と同様にして体積平均粒子径7.8μmの樹脂粒子を得た。樹脂粒子は3.3の30%圧縮強度、22.5%の復元率を有していた。なお、樹脂粒子を構成する樹脂は22%のヒステリシスロスを有していた。
アクリル酸n-ブチルを30質量部使用し、架橋性オリゴマーAを70質量部使用すること以外は、実施例1と同様にして体積平均粒子径9.2μmの樹脂粒子を得た。樹脂粒子は3.8の30%圧縮強度、27.5%の復元率を有していた。なお、樹脂粒子を構成する樹脂は17%のヒステリシスロスを有していた。
実施例5
(メタ)アクリル酸エステル系単官能単量体としてアクリル酸n-ブチル30質量部、2-エチルヘキシルアクリレート10質量部及びメタクリル酸ブチル10質量部を使用すること以外は、実施例1と同様にして体積平均粒子径8.5μmの樹脂粒子を得た。樹脂粒子は3.5の30%圧縮強度、30.3%の復元率を有していた。なお、樹脂粒子を構成する樹脂は18%のヒステリシスロスを有していた。
架橋性オリゴマーAに代えて、市販のウレタン(メタ)アクリレートである日本合成化学社製 商品名:紫光 品番:UV-7000B(Tg=52℃、官能基数=2.5)を使用すること以外は、実施例1と同様にして体積平均粒子径8.9μmの樹脂粒子を得た。樹脂粒子は7.21の30%圧縮強度、17.8%の復元率を有していた。なお、樹脂粒子を構成する樹脂は15%のヒステリシスロスを有していた。
比較例2
架橋性オリゴマーAに代えて、市販のウレタン(メタ)アクリレートである日本合成社製UV-3200B(Tg=-8℃、官能基数=2)を使用すること以外は、実施例1と同様にして体積平均粒子径9.1μmの樹脂粒子を得た。樹脂粒子は8.31の30%圧縮強度、18.9%の復元率を有していた。得られた樹脂粒子は粘着性を有していた。なお、樹脂粒子を構成する樹脂は20%のヒステリシスロスを有していた。
アクリル酸n-ブチルを80質量部使用し、架橋性オリゴマーAに代えてトリメチロールプロパントリメタクリレート(Tg>250℃)を20質量部使用すること以外は、実施例1と同様にして体積平均粒子径8.3μmの樹脂粒子を得た。樹脂粒子は1.49の30%圧縮強度、19.1%の復元率を有していた。なお、樹脂粒子を構成する樹脂は45%のヒステリシスロスを有していた。
比較例4
アクリル酸n-ブチルを80質量部使用し、架橋性オリゴマーAに代えてポリエチレングリコールジメタクリレート(n(エチレングリコール繰り返し数)=14、Tg=-23℃、官能基数=2)を20質量部使用すること以外は、実施例1と同様にして体積平均粒子径8.8μmの樹脂粒子を得た。樹脂粒子は10.86の30%圧縮強度、14.1%の復元率を有していた。得られた樹脂粒子は粘着性を有していた。なお、樹脂粒子を構成する樹脂は50%のヒステリシスロスを有していた。
油相と水相を混合し、ホモミキサーにて分散した分散液をマイクロフルイダイザー(HC-5000、みずほ工業社製)で100kg/cm2の圧力下で1回通したこと以外は、実施例1と同様にして体積粒子径3.5μmの樹脂粒子を得た。樹脂粒子は4.5の30%圧縮強度、24.5%の復元率を示した。また、10%圧縮強度は0.51、樹脂のヒステリシスロスは15であった。
実施例7(大粒子径の実施例)
TKホモミキサーの回転数を1500rpmとしたこと以外は、実施例2と同様にして体積平均粒子径25.1μmの樹脂粒子を得た。樹脂粒子は1.8の30%圧縮強度、37.5%の復元率を示した。また、10%圧縮強度は0.13、樹脂のヒステリシスロスは13であった。
樹脂粒子の作製に使用した原料及び樹脂粒子の物性を表1にまとめて記載する。
実施例8及び比較例5
上記実施例1~5及び比較例1~4で得られた樹脂粒子各0.8gに対して、バインダー樹脂(第一工業製薬社製RST-201)6g、光重合開始剤(BASF社製ダロキュア1173)0.15g及び溶媒としてトルエンを4gを配合することでコーティング組成物を得た。実施例1~5及び比較例1~4で得られた樹脂粒子を含むコーティング組成物をそれぞれまとめて実施例8及び比較例5とする。これらを45μmのアプリケーターを使用し、ABS板上に塗布、乾燥後、紫外線を照射して硬化することによって塗膜を得た。得られた塗膜を用いて復元性を評価した。
復元性は、真鍮ブラシで10往復して、スジがほとんど残らないものを○、やや白くスジが残るものを△、白くスジが残るものを×とする。
実施例1~5の樹脂粒子を含む塗膜はいずれも復元性は○であったが、比較例1及び2の樹脂粒子を含む塗膜はいずれも復元性は△であり、比較例3及び4の樹脂粒子を含む塗膜はいずれも復元性は×であった。
(処方例1)
パウダーファンデーションの製造
・配合量
実施例1で得られた樹脂粒子 10.0質量部
赤色酸化鉄 3.0質量部
黄色酸化鉄 2.5質量部
黒色酸化鉄 0.5質量部
酸化チタン 10.0質量部
マイカ 20.0質量部
タルク 44.0質量部
流動パラフィン 5.0質量部
ミリスチン酸オクチルドデシル 2.5質量部
ワセリン 2.5質量部
防腐剤 適量
香料 適量
・製造法
樹脂粒子、赤色酸化鉄、黄色酸化鉄、黒色酸化鉄、酸化チタン、マイカ、タルクをヘンシェルミキサーで混合し、これに流動パラフィン、ミリスチン酸オクチルドデシル、ワセリン及び防腐剤を混合溶解したものを加えて均一に混合する。これに、香料を加えて混合した後、粉砕して篩いに通す。これを、金皿に圧縮成形してパウダーファンデーションを得る。
化粧乳液の製造
・配合量
実施例1で得られた樹脂粒子 10.0質量部
ステアリン酸 2.5質量部
セチルアルコール 1.5質量部
ワセリン 5.0質量部
流動パラフィン 10.0質量部
ポリエチレン(10モル)モノオレイン酸エステル 2.0質量部
ポリエチレングリコール1500 3.0質量部
トリエタノールアミン 1.0質量部
精製水 64.5質量部
香料 0.5質量部
防腐剤 適量
・製造法
まず、ステアリン酸、セチルアルコール、ワセリン、流動パラフィン、ポリエチレンモノオレイン酸エステルを加熱溶解して、ここへ樹脂粒子を添加・混合し、70℃に保温する(油相)。また、精製水にポリエチレングリコール、トリエタノールアミンを加え、加熱溶解し、70℃に保温する(水相)。水相に油相を加え、予備乳化を行い、その後ホモミキサーで均一に乳化し、乳化後かき混ぜながら30℃まで冷却させることで化粧乳液を得る。
Claims (11)
- 架橋(メタ)アクリル酸エステル系樹脂からなる平均粒子径1~100μmの高復元性樹脂粒子であり、前記高復元性樹脂粒子が、22%以上の復元率、1.5~5.0kgf/mm2の30%圧縮強度を有する高復元性樹脂粒子。
- 前記架橋(メタ)アクリル酸エステル系樹脂が、(a)ポリオール、(b)ポリイソシアネート及び(c)OH基を有する(メタ)アクリル酸エステルを反応させて得られた複数のラジカル重合性基を有する架橋性オリゴマー及び(メタ)アクリル酸エステル系単官能単量体に由来する樹脂からなり、
前記架橋性オリゴマーを単独で硬化させた際に、0~30℃のTg(粘弾性から測定)を示す請求項1に記載の高復元性樹脂粒子。 - 前記高復元性樹脂粒子が、(メタ)アクリル酸エステル系単官能単量体20~80質量%と、前記架橋性オリゴマー80~20質量%とを含む単量体混合物の重合体であり、前記(メタ)アクリル酸エステル系単官能単量体が、炭素数1~8のアルコールの(メタ)アクリル酸エステルである請求項2に記載の高復元性樹脂粒子。
- 前記架橋(メタ)アクリル酸エステル系樹脂が、30%以下のヒステリシスロスを示す樹脂組成からなる請求項1に記載の高復元性樹脂粒子。
- 前記架橋性オリゴマーが、300~1000g/molのアクリル当量を示す請求項2に記載の高復元性樹脂粒子。
- 前記ポリオールが、ポリエステル系ポリオール、ポリエーテル系ポリオール、ポリカーボネートポリオール、脂肪族炭化水素系ポリオール及び脂環族炭化水素系ポリオールから選択される請求項2に記載の高復元性樹脂粒子。
- 前記ポリイソシアネートが、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香族ポリイソシアネート及び芳香脂肪族ポリイソシアネートから選択される請求項2に記載の高復元性樹脂粒子。
- 前記OH基を有する(メタ)アクリル酸エステルが、2-ヒドロキシエチルアクリレート、2-ヒドロキシエチルメタクリレート、2-ヒドロキシプロピルアクリレート、2-ヒドロキシプロピルメタクリレート、4-ヒドロキシブチルアクリレート、カプロラクトン変性-2-ヒドロキシエチルアクリレート、ポリエチレングリコールモノ(メタ)アクリル酸エステル、ポリプロピレグリコールモノアクリル酸エステル、ポリブチレングリコールモノ(メタ)アクリル酸エステル、2-(メタ)アクリロイロキシエチル-2-ヒドロキシエチルフタレート、フェニルグリシジルエーテル(メタ)アクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート及びカプロラクトン変性ジペンタエリスリトールペンタ(メタ)アクリレートから選択される請求項2に記載の高復元性樹脂粒子。
- 請求項1に記載の高復元性樹脂粒子を含むコーティング用組成物。
- 請求項9に記載のコーティング組成物を塗布及び乾燥させて得られた塗膜。
- 請求項1に記載の高復元性樹脂粒子を含む化粧料。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201580045744.8A CN106795226B (zh) | 2014-09-11 | 2015-09-09 | 高复原性树脂粒子及其用途 |
JP2016547463A JP6568081B2 (ja) | 2014-09-11 | 2015-09-09 | 高復元性樹脂粒子及びその用途 |
US15/509,231 US10227456B2 (en) | 2014-09-11 | 2015-09-09 | High-recoverability resin particles of a crosslinked (meth)acrylic acid ester-based resin, and use thereof |
EP15839848.7A EP3192815B1 (en) | 2014-09-11 | 2015-09-09 | High-recoverability resin particles and use thereof |
KR1020177005578A KR101880431B1 (ko) | 2014-09-11 | 2015-09-09 | 고복원성 수지 입자 및 그 용도 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014185255 | 2014-09-11 | ||
JP2014-185255 | 2014-09-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016039357A1 true WO2016039357A1 (ja) | 2016-03-17 |
Family
ID=55459101
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/075532 WO2016039357A1 (ja) | 2014-09-11 | 2015-09-09 | 高復元性樹脂粒子及びその用途 |
Country Status (7)
Country | Link |
---|---|
US (1) | US10227456B2 (ja) |
EP (1) | EP3192815B1 (ja) |
JP (1) | JP6568081B2 (ja) |
KR (1) | KR101880431B1 (ja) |
CN (1) | CN106795226B (ja) |
TW (1) | TWI639643B (ja) |
WO (1) | WO2016039357A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018053206A (ja) * | 2016-09-30 | 2018-04-05 | 積水化成品工業株式会社 | 複合粒子及びその製造方法並びにその用途 |
JP2018123212A (ja) * | 2017-01-31 | 2018-08-09 | 松本油脂製薬株式会社 | 樹脂粒子及びそれを含むエラストマー組成物 |
KR20200018377A (ko) | 2017-06-12 | 2020-02-19 | 세키스이가가쿠 고교가부시키가이샤 | 수지 입자, 도전성 입자, 도전 재료, 접착제, 접속 구조체 및 액정 표시 소자 |
JP2021079687A (ja) * | 2019-11-22 | 2021-05-27 | 凸版印刷株式会社 | プリント鋼板 |
JP2021098781A (ja) * | 2019-12-20 | 2021-07-01 | 富士フイルムビジネスイノベーション株式会社 | 表面保護樹脂部材形成用キット、及び表面保護樹脂部材 |
WO2023171660A1 (ja) * | 2022-03-08 | 2023-09-14 | 株式会社日本触媒 | 化粧料用または医薬部外品用架橋重合体粒子 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11406585B2 (en) | 2016-12-19 | 2022-08-09 | Threebond Co., Ltd. | Photocurable resin composition for nail or artificial nail |
JP2020015852A (ja) * | 2018-07-26 | 2020-01-30 | 富士ゼロックス株式会社 | 表面保護樹脂部材添加用の樹脂粒子、及び表面保護樹脂部材 |
US20220041775A1 (en) * | 2018-09-14 | 2022-02-10 | Sekisui Kasei Co., Ltd. | Hollow polymer particles and method for manufacturing same |
CN111732829A (zh) * | 2020-06-05 | 2020-10-02 | 安徽省华瑞网业有限公司 | 一种反应注射成型互穿网络发汗耐磨筛网的制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012197436A (ja) * | 2011-03-08 | 2012-10-18 | Nippon Synthetic Chem Ind Co Ltd:The | 活性エネルギー線硬化性樹脂組成物及びコーティング剤 |
JP2013082924A (ja) * | 2011-09-30 | 2013-05-09 | Sanyo Chem Ind Ltd | 活性エネルギー線硬化性黒色樹脂組成物 |
JP2014105263A (ja) * | 2012-11-27 | 2014-06-09 | Toagosei Co Ltd | 活性エネルギー線硬化型コーティング剤組成物 |
JP2014122338A (ja) * | 2012-11-22 | 2014-07-03 | Nippon Synthetic Chem Ind Co Ltd:The | 活性エネルギー線硬化性樹脂組成物、コーティング剤組成物、及び積層体 |
JP2014133860A (ja) * | 2012-12-14 | 2014-07-24 | Asahi Glass Co Ltd | 硬化性樹脂組成物、およびそれを用いた透明積層体とその製造方法 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5297845A (en) | 1976-02-10 | 1977-08-17 | Matsushita Electric Works Ltd | Attachment for hair dryers |
JP3341848B2 (ja) * | 1992-02-04 | 2002-11-05 | 大日本インキ化学工業株式会社 | 重合性不飽和ポリウレタン及びこれを用いた紫外線硬化型樹脂組成物 |
JP2004231762A (ja) * | 2003-01-30 | 2004-08-19 | Nippon Shokubai Co Ltd | ウレタン(メタ)アクリレート及び樹脂組成物 |
TW200607526A (en) * | 2004-05-28 | 2006-03-01 | Kao Corp | Sheet cosmetic |
JP5208483B2 (ja) * | 2006-11-29 | 2013-06-12 | 三洋化成工業株式会社 | 弾性樹脂粒子 |
JP2010202707A (ja) | 2009-02-27 | 2010-09-16 | Sanyo Chem Ind Ltd | 樹脂粒子 |
JP5297845B2 (ja) | 2009-03-16 | 2013-09-25 | 積水化成品工業株式会社 | 樹脂粒子およびその用途 |
JP2011184544A (ja) * | 2010-03-08 | 2011-09-22 | Sekisui Plastics Co Ltd | 重合体粒子、その製造方法及びトナー用外添剤 |
JP5377374B2 (ja) * | 2010-03-12 | 2013-12-25 | 積水化成品工業株式会社 | 球状ウレタン系樹脂粒子及びその製造方法 |
JP2015038162A (ja) * | 2010-04-20 | 2015-02-26 | 日本ビー・ケミカル株式会社 | ポリエステル樹脂及びその用途 |
WO2013030977A1 (ja) * | 2011-08-31 | 2013-03-07 | 積水化成品工業株式会社 | 樹脂粒子集合体、その製造方法、およびその用途 |
KR101611210B1 (ko) * | 2011-09-28 | 2016-04-11 | 세키스이가세이힝코교가부시키가이샤 | 수지 입자, 수지 입자의 제조 방법 및 그 용도 |
JP6067235B2 (ja) | 2012-03-06 | 2017-01-25 | 第一工業製薬株式会社 | ウレタン(メタ)アクリレート及びそれを含有する硬化性樹脂組成物 |
WO2014081004A1 (ja) * | 2012-11-22 | 2014-05-30 | 日本合成化学工業株式会社 | 活性エネルギー線硬化性樹脂組成物、コーティング剤組成物、及び積層体 |
WO2014092002A1 (ja) | 2012-12-14 | 2014-06-19 | 旭硝子株式会社 | 硬化性樹脂組成物、およびそれを用いた積層体とその製造方法 |
JP6018007B2 (ja) * | 2013-03-29 | 2016-11-02 | 積水化成品工業株式会社 | アクリル系樹脂粒子、塗料組成物及び光学材料 |
JP6313974B2 (ja) * | 2013-03-29 | 2018-04-18 | 積水化成品工業株式会社 | 架橋アクリル系樹脂粒子及びその製造方法、樹脂組成物並びに包装物品 |
JP5988512B2 (ja) * | 2014-10-15 | 2016-09-07 | 京楽産業.株式会社 | 遊技機 |
-
2015
- 2015-09-09 US US15/509,231 patent/US10227456B2/en active Active
- 2015-09-09 JP JP2016547463A patent/JP6568081B2/ja active Active
- 2015-09-09 CN CN201580045744.8A patent/CN106795226B/zh active Active
- 2015-09-09 WO PCT/JP2015/075532 patent/WO2016039357A1/ja active Application Filing
- 2015-09-09 KR KR1020177005578A patent/KR101880431B1/ko active IP Right Grant
- 2015-09-09 EP EP15839848.7A patent/EP3192815B1/en active Active
- 2015-09-10 TW TW104129903A patent/TWI639643B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012197436A (ja) * | 2011-03-08 | 2012-10-18 | Nippon Synthetic Chem Ind Co Ltd:The | 活性エネルギー線硬化性樹脂組成物及びコーティング剤 |
JP2013082924A (ja) * | 2011-09-30 | 2013-05-09 | Sanyo Chem Ind Ltd | 活性エネルギー線硬化性黒色樹脂組成物 |
JP2014122338A (ja) * | 2012-11-22 | 2014-07-03 | Nippon Synthetic Chem Ind Co Ltd:The | 活性エネルギー線硬化性樹脂組成物、コーティング剤組成物、及び積層体 |
JP2014105263A (ja) * | 2012-11-27 | 2014-06-09 | Toagosei Co Ltd | 活性エネルギー線硬化型コーティング剤組成物 |
JP2014133860A (ja) * | 2012-12-14 | 2014-07-24 | Asahi Glass Co Ltd | 硬化性樹脂組成物、およびそれを用いた透明積層体とその製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3192815A4 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018053206A (ja) * | 2016-09-30 | 2018-04-05 | 積水化成品工業株式会社 | 複合粒子及びその製造方法並びにその用途 |
JP2018123212A (ja) * | 2017-01-31 | 2018-08-09 | 松本油脂製薬株式会社 | 樹脂粒子及びそれを含むエラストマー組成物 |
KR20200018377A (ko) | 2017-06-12 | 2020-02-19 | 세키스이가가쿠 고교가부시키가이샤 | 수지 입자, 도전성 입자, 도전 재료, 접착제, 접속 구조체 및 액정 표시 소자 |
JP2021079687A (ja) * | 2019-11-22 | 2021-05-27 | 凸版印刷株式会社 | プリント鋼板 |
JP7409039B2 (ja) | 2019-11-22 | 2024-01-09 | Toppanホールディングス株式会社 | プリント鋼板 |
JP2021098781A (ja) * | 2019-12-20 | 2021-07-01 | 富士フイルムビジネスイノベーション株式会社 | 表面保護樹脂部材形成用キット、及び表面保護樹脂部材 |
JP7447477B2 (ja) | 2019-12-20 | 2024-03-12 | 富士フイルムビジネスイノベーション株式会社 | 表面保護樹脂部材形成用キット、及び表面保護樹脂部材 |
WO2023171660A1 (ja) * | 2022-03-08 | 2023-09-14 | 株式会社日本触媒 | 化粧料用または医薬部外品用架橋重合体粒子 |
Also Published As
Publication number | Publication date |
---|---|
US20170260342A1 (en) | 2017-09-14 |
EP3192815A1 (en) | 2017-07-19 |
KR101880431B1 (ko) | 2018-07-20 |
JPWO2016039357A1 (ja) | 2017-08-03 |
EP3192815A4 (en) | 2018-04-25 |
KR20170036782A (ko) | 2017-04-03 |
TW201615733A (zh) | 2016-05-01 |
TWI639643B (zh) | 2018-11-01 |
US10227456B2 (en) | 2019-03-12 |
CN106795226B (zh) | 2019-08-23 |
EP3192815B1 (en) | 2021-03-31 |
CN106795226A (zh) | 2017-05-31 |
JP6568081B2 (ja) | 2019-08-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6568081B2 (ja) | 高復元性樹脂粒子及びその用途 | |
JP6284917B2 (ja) | 多孔質樹脂粒子、多孔質樹脂粒子の製造方法、およびその用途 | |
EP2810959B1 (en) | Porous resin particle, method for producing same, dispersion liquid, and application thereof | |
JP5919216B2 (ja) | 樹脂粒子、並びに、この樹脂粒子を含む塗料及び外用剤 | |
WO2014156994A9 (ja) | 多孔質樹脂粒子、その製造方法、分散液およびその用途 | |
WO2013046374A1 (ja) | 樹脂粒子、樹脂粒子の製造方法、及びその用途 | |
JP2024050739A (ja) | 中空粒子及びその製造方法 | |
JP4264366B2 (ja) | 複合粒子の製造方法、複合粒子及びそれを含む化粧料 | |
JP2017066306A (ja) | アクリルウレタン系樹脂粒子及びその製造方法、用途 | |
JP6645944B2 (ja) | 複合粒子及びその製造方法並びにその用途 | |
JP6294204B2 (ja) | 複合粒子、複合粒子の製造方法、及び、その用途 | |
JP6436578B2 (ja) | ポリエステル系樹脂粒子、その製造方法及びその用途 | |
JP6199222B2 (ja) | 複合粒子、複合粒子の製造方法、及び外用剤 | |
JP2000302624A (ja) | アクリル酸エステル系樹脂粒子及びそれを含む外用剤 | |
EP2783678B1 (en) | Porous resin particles, method of manufacturing the same, and use of the same | |
JP2021038339A (ja) | 顔料含有中空粒子及びその製造方法 | |
CN110325173A (zh) | 皮肤化妆料 | |
JP2020164666A (ja) | 多孔質微粒子及びその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15839848 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016547463 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20177005578 Country of ref document: KR Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2015839848 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015839848 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15509231 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |