WO2018016080A1 - 熱可塑性樹脂からなる略球状樹脂粒子、その製造方法及びその用途 - Google Patents
熱可塑性樹脂からなる略球状樹脂粒子、その製造方法及びその用途 Download PDFInfo
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- WO2018016080A1 WO2018016080A1 PCT/JP2016/071636 JP2016071636W WO2018016080A1 WO 2018016080 A1 WO2018016080 A1 WO 2018016080A1 JP 2016071636 W JP2016071636 W JP 2016071636W WO 2018016080 A1 WO2018016080 A1 WO 2018016080A1
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- thermoplastic resin
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- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- UPHWVVKYDQHTCF-UHFFFAOYSA-N octadecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCCCCCN UPHWVVKYDQHTCF-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000008379 phenol ethers Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001020 poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Polymers 0.000 description 1
- 229920000739 poly(3-hydroxycarboxylic acid) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229940077935 zinc phosphate Drugs 0.000 description 1
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/031—Powdery paints characterised by particle size or shape
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- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
Definitions
- the present invention relates to substantially spherical resin particles made of a thermoplastic resin having high sphericity, excellent optical characteristics, and excellent handling characteristics at the time of blending, a method for producing the same, and a use thereof.
- Thermoplastic resin particles are used to modify and improve various materials by utilizing a large specific surface area and particle structure.
- Major applications include cosmetics such as foundations, antiperspirants, scrubs, matting agents for paints, rheology modifiers, anti-blocking agents, slipperiness agents, light diffusing agents, and medical diagnostic tests.
- Applications such as additives to molded products such as automobile materials and building materials.
- materials derived from non-petroleum raw materials in all fields where resins are used in order to reduce the environmental burden. For example, such a demand is also made in fields where resin particles such as cosmetics and paints are used.
- Patent Laid-Open No. 2001-288273 Japanese Patent Laid-Open No. 2001-288273: Patent Document 1
- Patent Document 2 Japanese Patent Laid-Open No. 2005-2302: Patent Document 3
- Patent Laid-Open No. 2009-242728 Japanese Patent Laid-Open No. 2009-242728
- Patent Document 5 In a mixer such as a twin screw extruder, a thermoplastic resin and an incompatible resin are mixed, and the thermoplastic resin is used as a dispersed phase. A melt-kneading method for obtaining thermoplastic resin particles by forming a resin composition having a thermoplastic resin and an incompatible resin in a continuous phase and then removing the incompatible resin (Japanese Patent Application Laid-Open No. 2004-269865). issue Distribution: Patent Document 6, JP 2005-200663 JP: Patent Document 7) are known.
- Patent Document 1 a chip or block made of polylactic acid resin is cooled to a low temperature of ⁇ 50 ° C. to ⁇ 180 ° C. without using an organic solvent.
- Patent Documents 2 to 4 after the polylactic acid-based resin is dissolved in an organic solvent, the solution is dropped into a poor solvent such as water, or neutralized and chlorinated to be precipitated in fine particles. Proposed.
- Patent Document 8 International Publication WO2012-105140
- polylactic acid and a different kind of resin are dissolved in an ether solvent, and then an emulsion is formed by applying a shearing force, followed by contact with a poor solvent.
- a method for obtaining porous polylactic acid resin particles having a large oil absorption with a particle diameter has been proposed.
- JP 2001-288273 A Japanese Unexamined Patent Publication No. 2000-7789 Japanese Patent Laying-Open No. 2005-2302 JP 2009-242728 A JP 11-35693 A JP 2004-269865 A Japanese Patent Laying-Open No. 2005-200633 International Publication WO2012-105140
- the conventional thermoplastic resin particles made by the production methods of Patent Documents 1 to 7 are not spherical, the particle diameter is not fine, the particle size distribution is wide, and in some cases, the particles include fibrous particles.
- Convention thermoplastic resin particles have not been fully effective in adding fine particles as they are.
- a biodegradable resin having thermoplasticity is too soft or too sticky.
- Patent Document 1 Although it is possible to produce a powder by using this technique, it is still difficult to produce a fine powder. In addition, complicated facilities for handling refrigerants such as liquid nitrogen are required, and the time required for production is significantly increased due to the addition of processes, resulting in extremely low productivity. End up. Further, Patent Documents 2 to 4 require not only productivity but also a large amount of waste solvent containing impurities because a multi-step process such as dissolution, precipitation, and drying is required. When this waste solvent is discharged, there is a high possibility that it will adversely affect the environment, and a great deal of labor is required to remove impurities for reuse. In addition, there is a high possibility that a substance that may adversely affect the environment is generated during this treatment. In addition, a trace amount of solvent always remains in the obtained powder, and this residual solvent may adversely affect the quality of the final product.
- Patent Document 4 a polylactic acid resin is dissolved in benzene, and then m-xylene is mixed at less than 60 ° C. to precipitate a polylactic acid resin powder, which requires a large amount of organic solvent.
- organic solvent remains in the resin.
- Patent Document 8 although fine particles having smooth surfaces can be obtained, those having sufficiently excellent sphericity and light scattering index cannot be obtained.
- this resin particle is a solvent for emulsifying and dispersing thermoplastic resin particles, but the solubility of the resin at normal temperature is low, but the solubility of the resin at high temperature is high, and the safety of a specific structure is high. It has been found that it can be produced by using an alcohol solvent, and has led to the present invention.
- the sphericity is 0.90 to 1.00
- the light scattering index is 0.5 to 1.0
- the linseed oil absorption is 30 to 150 mL / 100 g.
- Substantially spherical resin particles are provided.
- the substantially spherical resin particles made of the above thermoplastic resin may contain 3-alkoxy-3-methyl-1-butanol and / or 3-alkoxy-3-methyl-1-butyl acetate (carbon of alkoxy group).
- a method for producing particles is provided. Furthermore, a cosmetic containing substantially spherical resin particles made of the thermoplastic resin is provided. Moreover, the coating material which mix
- substantially spherical thermoplastic resin particles having high light scattering properties can be provided.
- the manufacturing method which can produce this resin particle simply can be provided.
- substantially spherical thermoplastic resin particles having higher light scattering properties can be provided.
- the thermoplastic resin is at least one resin selected from the group consisting of polyolefin resins, polyester resins, polyether resins, and polyamide resins.
- the thermoplastic resin is polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid ester copolymer, polylactic acid, polybutylene succinate.
- thermoplastic resin is at least one resin selected from the group consisting of a biodegradable polyester resin and a polyether resin.
- thermoplastic resin is added to 3-alkoxy-3-methyl-1-butanol and / or 3-alkoxy-3-methyl-1-butyl acetate (the alkoxy group has 1 to 5 carbon atoms) at 100 ° C. This is a resin that is dissolved or plasticized and does not dissolve at room temperature.
- substantially spherical particles made of thermoplastic resin: hereinafter also referred to as substantially spherical particles
- the substantially spherical particles have a sphericity of 0.90 to 1.00, a light scattering index of 0.5 to 1.0, and a linseed oil absorption of 30 to 150 mL / 100 g.
- the methods for measuring the sphericity, light scattering index and linseed oil absorption are described in the Examples section. When the sphericity is less than 0.90, when blended with cosmetics or the like, fluidity may be reduced, and touch and slipperiness may be deteriorated.
- the sphericity can be 0.90, 0.92, 0.93, 0.95, 0.97, 1.00.
- a preferable sphericity is 0.92 to 1.00, and a more preferable sphericity is 0.93 to 1.00.
- the light scattering index is 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0. obtain.
- a preferred light scattering index is 0.55 to 1.0, and a more preferred light scattering index is 0.6 to 1.0.
- the handling characteristics at the time of blending the substantially spherical particles can be improved.
- the handling characteristics at the time of blending the substantially spherical particles can be improved.
- the linseed oil absorption is larger than 150 mL / 100 g, other components are absorbed and the fluidity is lowered, so that the handling property may be deteriorated.
- the linseed oil absorption can be 30 mL / 100 g, 50 mL / 100 g, 80 mL / 100 g, 100 mL / 100 g, 120 mL / 100 g, 145 mL / 100 g, 150 mL / 100 g.
- a more preferred linseed oil absorption is 30 to 145 mL / 100 g.
- the substantially spherical particles preferably have a volume average particle diameter of 1 to 500 ⁇ m.
- the volume average particle diameter can be 1 ⁇ m, 3 ⁇ m, 10 ⁇ m, 20 ⁇ m, 50 ⁇ m, 100 ⁇ m, 200 ⁇ m, 300 ⁇ m, 400 ⁇ m, and 500 ⁇ m.
- the substantially spherical particles can be used in various particle sizes depending on the application. For example, 3 to 20 ⁇ m for a foundation application, 200 to 500 ⁇ m for a scrub agent, 3 to 100 ⁇ m for a paint application, and the like can be appropriately selected according to the application. The method for measuring the average particle size is described in the column of Examples.
- thermoplastic resin is not particularly limited.
- at least one resin selected from the group consisting of polyolefin resins, polyester resins, polyether resins, and polyamide resins can be used.
- the polyolefin resin include polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid ester copolymer, and the like.
- ester component of (meth) acrylic acid ester include methyl, ethyl, propyl, and butyl.
- Polyester resins include polylactic acid, polybutylene succinate, polyhydroxyalkanoate, polycaprolactam and the like.
- polyhydroxyalkanoates preferred is the general formula (1) [—CH (R) —CH 2 CO—O—] (wherein R is an alkyl group represented by —C n H 2n + 1 , n is an integer of 1 to 15), and is a poly (3-hydroxyalkanoate) polymer or copolymer.
- the (3-hydroxyalkanoate) polymer or copolymer include a homopolymer of the 3-hydroxyalkanoate, a copolymer composed of two or more different 3-hydroxyalkanoates of n, and the homopolymer.
- examples thereof include a mixture obtained by blending two or more selected from the group of polymers and copolymers.
- a copolymer comprising at least one repeating unit selected from the group consisting of -hydroxyhexanoate and 3-hydroxyoctanoate.
- poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) which is a copolymer of 3-hydroxybutyrate repeating units and 3-hydroxyhexanoate units. More specifically, the product name Aonilex series manufactured by Kaneka Corporation can be mentioned.
- the polyether resin include polyethersulfone.
- the polyamide-based resin include nylon 12, nylon 6, and the like. These exemplary resins may be used alone or in combination.
- the molecular weight of the thermoplastic resin is not particularly limited. It can be appropriately selected according to the final application / purpose.
- the production method of the present invention can be applied to at least one resin selected from the group consisting of a polyester resin and a polyether resin, which has biodegradability that is generally difficult to form into particles.
- a resin include polyester resins such as polylactic acid, polybutylene succinate, polyhydroxyalkanoate, and polycaprolactone.
- the thermoplastic resin is preferably a resin that dissolves or plasticizes at a high temperature in a specific solvent described in the column of the production method below, but does not dissolve at room temperature (about 25 ° C.).
- the resin having this property has an effect that it can easily provide substantially spherical particles having a specific sphericity and a light scattering index.
- the substantially spherical particles are, as necessary, known fluidity adjusting agents, ultraviolet absorbers, light stabilizers, pigments (for example, extender pigments, colored pigments, metal pigments, mica powder pigments), dyes Etc. may be included.
- Spherical particles are used in cosmetics such as foundations, antiperspirants, scrubs, matting agents for paints, rheology modifiers, antiblocking agents, slipperiness agents, light diffusing agents, fines. It can be used in various applications such as ceramic sintering molding aids, adhesive fillers, medical diagnostic inspection agents, additives for molding products such as automobile materials and building materials.
- thermoplastic resin is made of 3-alkoxy-3-methyl-1-butanol and / or 3-alkoxy-3-methyl-1-butyl acetate (the alkoxy group has 1 to 5 carbon atoms, specifically, , Methyl, ethyl, propyl, butyl, pentyl) (specific solvent), water, emulsifying and dispersing the thermoplastic resin at a temperature of 100 ° C. or higher in the presence of a dispersion stabilizer (emulsifying / dispersing step) , (2) Step of cooling to obtain thermoplastic resin as particles (cooling step) It can be obtained by going through.
- a dispersion stabilizer emulsifying / dispersing step
- a skin irritating organic solvent for example, xylene, toluene, n-methylpyrrolidone, chloroform, methylene chloride, dioxolane, THF, etc.
- a highly safe alcohol solvent it is possible to produce thermoplastic resin particles having a spherical shape, a small particle size, a narrow particle size distribution, and excellent optical properties.
- 3-alkoxy-3-methyl-1-butanol and / or 3-alkoxy-3-methyl-1-butyl acetate has biodegradability and low skin irritation, The bad influence by the residue at the time of using for a use can be suppressed.
- the production method of the present invention is a method of wet-spheronizing a biodegradable thermoplastic resin having crystallinity such as polylactic acid (PLA), polybutylene succinate (PBS), polyhydroxyalkanoate (PHA), etc.
- a biodegradable thermoplastic resin having crystallinity such as polylactic acid (PLA), polybutylene succinate (PBS), polyhydroxyalkanoate (PHA), etc.
- PBS polybutylene succinate
- PHA polyhydroxyalkanoate
- 3-alkoxy-3-methyl-1-butanol and / or 3-alkoxy-3-methyl-1-butyl acetate dissolves or plasticizes a thermoplastic resin at a high temperature, but does not melt the thermoplastic resin at a normal temperature. Since it does not dissolve, these alcohol solvents can be easily reused, which is industrially advantageous.
- the substantially spherical particles obtained by this production method have the effect of being superior in optical properties (soft focus effect) and oil absorption properties as
- Emulsification / dispersion step (i) Solvent
- the solvent contains 3-alkoxy-3-methyl-1-butanol and / or 3-alkoxy-3-methyl-1-butyl acetate (hereinafter also referred to as a specific solvent).
- the proportion of the specific solvent in the solvent is preferably 50% by weight or more. 70% by weight or more is more preferable, and 100% by weight is even more preferable.
- Usable solvents other than the specific solvent include lower alcohols such as methanol and ethanol, and acetate solvents such as ethyl acetate and butyl acetate.
- As the specific solvent a solvent commercially available from Kuraray under the trade name of Solfit can also be used.
- 3-alkoxy-3-methyl-1-butanol can be produced, for example, by the method described in International Publication No. WO2013 / 146370.
- the alkoxy group in the specific solvent has 1 to 5 carbon atoms.
- the solubility may be deteriorated.
- Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group.
- the propoxy group, butoxy group and pentyloxy group include not only a straight chain but also possible structural isomers.
- Preferred alkoxy groups are a methoxy group, an ethoxy group, and a propoxy group.
- the amount of the solvent used is preferably 100 to 1200 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
- the amount used is less than 100 parts by weight, the concentration of the thermoplastic resin may be too high to be sufficiently stirred and mixed.
- the amount is more than 1200 parts by weight, the production amount may be smaller than the size of the apparatus.
- the amount used can be 100 parts by weight, 200 parts by weight, 400 parts by weight, 500 parts by weight, 700 parts by weight, 800 parts by weight, 1000 parts by weight, or 1200 parts by weight.
- a more preferred use amount is 100 to 800 parts by weight, and a still more preferred use amount is 100 to 400 parts by weight.
- hydrophobic treated inorganic fine particles can be suitably used.
- hydrophobic fumed silica manufactured by Nippon Aerosil Co., Ltd .; trade name AEROSIL (R: R) R972, AEROSIL (R) R974 , AEROSIL (R) R976S, AEROSIL (R) R104, AEROSIL (R) R106 , AEROSIL (R) R202, AEROSIL (R) R805, AEROSIL (R) R812, AEROSIL (R) R812S, AEROSIL (R) R816, AEROSIL (R) R7200, AEROSIL (R) R8200, AEROSIL (R) R9200, AEROSIL (R) R711, AEROSIL (R ) RY50, AEROSIL (R) NY50, AEROSIL (R) RY200, AEROSIL (R) RY200, AEROSIL (R) RY200, AEROSIL (
- tricalcium phosphate (manufactured by Taihei Chemical Industrial Co., Ltd .; trade name: TCP-10U, etc.), phosphates such as magnesium phosphate, aluminum phosphate, zinc phosphate, calcium pyrophosphate, magnesium pyrophosphate, pyrroline Pyrophosphates such as aluminum oxide and zinc pyrophosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, colloidal silica (manufactured by Nissan Chemical Co., Ltd .: trade name) (Snowtex series Snowtex 40, Snowtex S, Snowtex XS, etc.) and the like may be used.
- phosphates such as magnesium phosphate, aluminum phosphate, zinc phosphate, calcium pyrophosphate, magnesium pyrophosphate, pyrroline Pyrophosphates such as aluminum oxide and zinc pyrophosphate, calcium carbonate, magnesium
- the addition amount of the dispersion stabilizer to the thermoplastic resin is preferably 0.5 to 15% by weight.
- the amount added is 0.5 wt%, 0.7 wt%, 1.0 wt%, 1.2 wt%, 1.5 wt%, 3 wt%, 5 wt%, 8 wt%, 10 wt%, It can take 15% by weight.
- a surfactant such as an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, and a nonionic surfactant may be used in combination.
- anionic surfactants include fatty acid oils such as sodium oleate and castor oil potassium, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylnaphthalene sulfonates.
- Nonionic surfactants include 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, oxyethylene- Examples include oxypropylene block polymers.
- Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.
- Examples of the zwitterionic surfactant include lauryl dimethylamine oxide.
- the addition amount of the surfactant is preferably 0.01 to 0.5% by weight with respect to water.
- the water usage is preferably 100 to 2200 parts by weight with respect to 100 parts by weight of the thermoplastic resin. If the amount used is less than 100 parts by weight, the concentration of the thermoplastic resin may be too high and it may be difficult to sufficiently stir and mix. When the amount is more than 2200 parts by weight, the production amount may be smaller than the size of the apparatus.
- the amount of water used may be 100 parts by weight, 150 parts by weight, 200 parts by weight, 300 parts by weight, 600 parts by weight, 800 parts by weight, 1000 parts by weight, 1500 parts by weight, 2000 parts by weight, or 2200 parts by weight. A more preferable usage amount is 150 to 1000 parts by weight, and a further preferable usage amount is 200 to 800 parts by weight.
- Heating and stirring are performed at a heating temperature of 100 ° C. or higher.
- the heating temperature is less than 100 ° C.
- the thermoplastic resin may not be softened and may not be finely divided.
- Heating and stirring can be performed at a temperature of 180 ° C. or lower.
- the heating temperature can be 100 ° C, 120 ° C, 140 ° C, 160 ° C, 180 ° C.
- the substantially spherical particles obtained by this production method become particles having a small particle size distribution, because a very uniform emulsion can be obtained at the stage of emulsion formation.
- stirring by a known method, and usually a liquid phase stirring method using a stirring blade, a mixing method using a homogenizer, an ultrasonic irradiation method, etc. It can mix by a well-known method.
- the stirring speed and time are not particularly limited as long as the thermoplastic resin can be dissolved in the solvent or evenly dispersed in the solvent, and is preferably selected as appropriate. Heating and stirring is usually performed under atmospheric pressure, but may be performed under reduced pressure or under pressure as necessary.
- Cooling step In order to precipitate the thermoplastic resin as particles, the solvent containing the thermoplastic resin is cooled after heating and stirring.
- the cooling temperature is usually room temperature (about 25 ° C.).
- the time to reach the cooling temperature from the temperature during heating and stirring is preferably as fast as possible.
- the stirring speed can be in the same range as the stirring speed of heating and stirring.
- the substantially spherical particles in the solvent after cooling may be taken out from the solvent through filtration, dehydration, and drying as necessary. Filtration, dehydration, and drying are not particularly limited, and can be performed by a known method.
- a surfactant solution as a dispersant preferably 0.05 g of alkylbenzene sulfonate, is added to 20 mL of ion-exchanged water to obtain a surfactant aqueous solution.
- the resin particle group to be measured is added to the surfactant aqueous solution, and ultrasonic waves are applied using a BRANSON ultrasonic disperser “BRANSON SONIFIER 450” (output 400 W, frequency 20 kHz) as a disperser. Irradiation for 5 minutes is performed to disperse the resin particle group in the surfactant aqueous solution to obtain a dispersion for measurement.
- the above-mentioned flow type particle image analyzer equipped with a standard objective lens (10 ⁇ ) is used.
- a particle sheath (trade name “PSE-900A”, Sysmex).
- the measurement dispersion prepared according to the above procedure is introduced into the flow particle image analyzer and measured under the following measurement conditions.
- Measurement mode HPF measurement mode Particle diameter measurement range: 2.954 ⁇ m to 30.45 ⁇ m Measurement range of sphericity of particles: 0.5 to 1.0 Measurement number of particles: 1000 Before measurement, a suspension of standard polymer particles (for example, “5200A” manufactured by Thermo Fisher Scientific (diluted standard polystyrene particles with ion-exchanged water)) Is used to perform automatic focus adjustment of the flow type particle image analyzer. Note that the sphericity is a value obtained by dividing the perimeter calculated from the diameter of a perfect circle having the same projected area as the image captured of the resin particles by the perimeter of the image captured of the resin particles.
- volume average particle diameter of the resin particles is measured by Coulter Multisizer TM 3 (measuring device manufactured by Beckman Coulter, Inc.). The measurement shall be performed using an aperture calibrated according to the Multisizer TM 3 User's Manual published by Beckman Coulter.
- the aperture used for the measurement is appropriately selected depending on the size of the resin particle to be measured.
- the assumed volume average particle diameter of the resin particles to be measured is 1 ⁇ m or more and 10 ⁇ m or less, an aperture having a size of 50 ⁇ m is selected, and when the assumed volume average particle diameter of the resin particles to be measured is greater than 10 ⁇ m and 30 ⁇ m or less, 100 ⁇ m.
- an aperture having a size of 280 ⁇ m is selected, and the assumed volume average particle diameter of the resin particles is larger than 90 ⁇ m and 150 ⁇ m.
- an aperture having a size of 400 ⁇ m is selected as appropriate.
- the aperture is changed to an aperture having an appropriate size, and measurement is performed again.
- Current (aperture current) and Gain (gain) are appropriately set according to the size of the selected aperture. For example, when an aperture having a size of 50 ⁇ m is selected, the current (aperture current) is set to ⁇ 800, the gain (gain) is set to 4, and when an aperture having a size of 100 ⁇ m is selected, the current (aperture current) is set to ⁇ 1600. , Gain (gain) is set to 2, and when an aperture having a size of 280 ⁇ m and 400 ⁇ m is selected, Current (aperture current) is set to ⁇ 3200 and Gain (gain) is set to 1.
- the amount of linseed oil absorbed by the resin particles was determined by referring to the measurement method of JIS K 5101-13-2-2004, using refined linseed oil instead of boiled linseed oil, and changing the criteria for determining the end point ("Measurement plate Is measured by the method of paste (changed to the point that the kneaded mixture of resin particles and produced linseed oil starts to flow) when the is vertically set.
- the details of the linseed oil absorption measurement are as follows.
- (C) Measurement method (1) Take 1 g of resin particles at the center of the measurement plate, and gradually add 4 or 5 drops of refined linseed oil at a time from the burette to the center of the resin particles. The particles and the whole refined linseed oil are kneaded together with a palette knife. (2) The above dripping and kneading are repeated, and when the resin particles and the refined linseed oil become a hard putty-like mass, knead each drop and paste (resin particles) by the last drop of refined linseed oil. And the refined linseed oil kneaded product) is suddenly softened and the end point is the point at which flow begins.
- the diffusibility of the light reflected on the surface of the resin particles is evaluated by the following method.
- the reflected luminous intensity distribution of the resin particles is measured using a three-dimensional photometer (Goniophotometer GP-200 manufactured by Murakami Color Research Laboratory) in an environment of room temperature 20 ° C. and relative humidity 65%.
- a double-sided tape (ORT-1 manufactured by Nitto Denko) 3 cut into a 2 cm square is pasted at the center of a black ABS resin plate (made by Takiron Co.) 4 having a thickness of 2 mm.
- the resin particle 2 is apparently used with a funnel and funnel stand (JIS K5101-12-1-2004) of a density measuring device. After dropping, excess resin particles 2 on the adhesive surface are blown off with compressed air of 0.05 to 0.1 MPa.
- the luminous intensity distribution of the reflected light 6 incident and reflected at a reflection angle of ⁇ 90 ° to + 90 ° is measured with a three-dimensional photometer.
- the position of the test piece 1 is adjusted so that all incident light enters the black portion of the test piece 1.
- the reflected light is detected by a photomultiplier having a spectral sensitivity of 185 to 850 nm and a maximum sensitivity wavelength of 530 nm.
- Example 1 20 g of polybutylene succinate (GS-Pla (R) product number: FZ71PD manufactured by Mitsubishi Chemical Corporation) as a thermoplastic resin in a 300 mL autoclave and 3-methoxy-3-methyl-1-butanol (Solfit Fine Grade manufactured by Kuraray Co., Ltd.) as a solvent ) 60 g, 100 g of ion-exchanged water, 20 g of 10% aqueous tribasic calcium phosphate (TCP-10U manufactured by Taihei Chemical Industrial Co., Ltd.) as a dispersant, and 0.24 g of sodium lauryl sulfate as a surfactant are added to the reaction temperature (heating and stirring temperature) The mixture was stirred for 90 minutes at 120 ° C.
- TCP-10U aqueous tribasic calcium phosphate
- Example 2 20 g of polybutylene succinate (GS-Pla (R) product number: FZ71PD manufactured by Mitsubishi Chemical Corporation) as a thermoplastic resin in a 300 mL autoclave and 3-methoxy-3-methyl-1-butanol (Solfit Fine Grade manufactured by Kuraray Co., Ltd.) as a solvent ) 60 g, ion exchanged water 120 g, a hydrophobic fumed silica (Nippon Aerosil AEROSIL (R) R972) mixed solution prepared by dispersing 1.5g was charged as a dispersing agent. After the addition, the mixture was stirred for 90 minutes at a reaction temperature of 120 ° C. and a stirring speed of 400 rpm. Then, after rapidly cooling (30 minutes to 25 ° C.) while maintaining the stirring speed, the contents were taken out. The spherical contents were obtained by subjecting the contents to dehydration, filtration and drying.
- GS-Pla (R) product number: FZ71PD manufactured by Mitsubishi Chemical Corporation 3-
- Example 3 40 mL of polybutylene succinate (GS-Pla (R) product number: FZ71PD manufactured by Mitsubishi Chemical Corporation) as a thermoplastic resin in a 300 mL autoclave and 3-methoxy-3-methyl-1-butanol (Solfit Fine Grade manufactured by Kuraray Co., Ltd.) as a solvent ) 60 g, ion exchanged water 100 g, a hydrophobic fumed silica (Nippon Aerosil AEROSIL (R) R972) mixed solution was dispersed 3g was charged as a dispersing agent. After the addition, the mixture was stirred for 90 minutes at a reaction temperature of 120 ° C. and a stirring speed of 400 rpm. Then, after rapidly cooling (30 minutes to 25 ° C.) while maintaining the stirring speed, the contents were taken out. The spherical contents were obtained by subjecting the contents to dehydration, filtration and drying.
- Example 4 20 g of polybutylene succinate (GS-Pla (R) product number: FZ71PD manufactured by Mitsubishi Chemical Corporation) as a thermoplastic resin in a 300 mL autoclave and 3-methoxy-3-methyl-1-butanol (Solfit Fine Grade manufactured by Kuraray Co., Ltd.) as a solvent ) 60 g, 120 g of ion-exchanged water, 0.12 g of polyoxyethylene styrenated phenol ether (product name; Neugen EA-167, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a surfactant, and hydrophobic fumed silica (Japan) A mixed solution in which 1.5 g of Aerosil (R) R972) manufactured by Aerosil Co.
- GS-Pla (R) product number: FZ71PD manufactured by Mitsubishi Chemical Corporation 3-methoxy-3-methyl-1-butanol (Solfit Fine Grade manufactured by Kuraray Co., Ltd.) as a solvent
- Example 5 120 g of polybutylene succinate (GS-Pla (R) product number: FZ71PD manufactured by Mitsubishi Chemical Corporation) as a thermoplastic resin in a 1500 mL autoclave and 3-methoxy-3-methyl-1-butanol (Solfit Fine Grade manufactured by Kuraray Co., Ltd.) as a solvent ) 360 g, ion exchanged water 720 g, hydrophobic fumed silica (Nippon Aerosil AEROSIL (R) R972) was charged a mixed solution prepared by 6g dispersed as a dispersant. After the addition, the mixture was stirred for 90 minutes at a reaction temperature of 120 ° C. and a stirring speed of 400 rpm. Then, after rapidly cooling (30 minutes to 25 ° C.) while maintaining the stirring speed, the contents were taken out. The spherical contents were obtained by subjecting the contents to dehydration, filtration and drying.
- GS-Pla (R) product number: FZ71PD manufactured by Mitsubishi Chemical Corporation 3-
- Example 6 In a 1500 mL autoclave, 240 g of polybutylene succinate (GS-Pla (R) product number: FZ71PD manufactured by Mitsubishi Chemical Corporation) is used as a thermoplastic resin, and 3-methoxy-3-methyl-1-butanol (Solfit Fine Grade manufactured by Kuraray Co., Ltd.) is used as a solvent. ) 420 g, ion exchanged water 540 g, hydrophobic silica (Nippon Aerosil AEROSIL (R) R972) was charged a mixed solution prepared by 18g dispersed as a dispersant. After the addition, the mixture was stirred for 90 minutes at a reaction temperature of 120 ° C. and a stirring speed of 600 rpm. Then, after rapidly cooling (30 minutes to 25 ° C.) while maintaining the stirring speed, the contents were taken out. The spherical contents were obtained by subjecting the contents to dehydration, filtration and drying.
- Example 7 In a 1500 mL autoclave, 240 g of polybutylene succinate (GS-Pla (R) product number: FZ91PD manufactured by Mitsubishi Chemical Corporation) is used as a thermoplastic resin, and 3-methoxy-3-methyl-1-butanol (Solfit Fine Grade manufactured by Kuraray Co., Ltd.) is used as a solvent. ) 480 g, ion exchanged water 480 g, hydrophobic fumed silica (Nippon Aerosil AEROSIL (R) R972) was charged a mixed solution prepared by 18g dispersed as a dispersant. After the addition, the mixture was stirred for 90 minutes at a reaction temperature of 120 ° C. and a stirring speed of 600 rpm. Then, after rapidly cooling (30 minutes to 25 ° C.) while maintaining the stirring speed, the contents were taken out. The spherical contents were obtained by subjecting the contents to dehydration, filtration and drying.
- Example 8 In a 1500 mL autoclave, 240 g of polybutylene succinate (GS-Pla (R) product number: FZ71PD manufactured by Mitsubishi Chemical Corporation) is used as a thermoplastic resin, and 3-methoxy-3-methyl-1-butanol (Solfit Fine Grade manufactured by Kuraray Co., Ltd.) is used as a solvent. ) 480 g, ion exchanged water 480 g, hydrophobic fumed silica (Nippon Aerosil AEROSIL (R) R976S) was charged a mixed solution prepared by 12g dispersed as a dispersant. After the addition, the mixture was stirred for 90 minutes at a reaction temperature of 120 ° C. and a stirring speed of 600 rpm. Then, after rapidly cooling (30 minutes to 25 ° C.) while maintaining the stirring speed, the contents were taken out. The spherical contents were obtained by subjecting the contents to dehydration, filtration and drying.
- Example 9 In a 1500 mL autoclave, 240 g of polybutylene succinate (GS-Pla (R) product number: FZ71PD manufactured by Mitsubishi Chemical Corporation) is used as a thermoplastic resin, and 3-methoxy-3-methyl-1-butanol (Solfit Fine Grade manufactured by Kuraray Co., Ltd.) is used as a solvent.
- polybutylene succinate GS-Pla (R) product number: FZ71PD manufactured by Mitsubishi Chemical Corporation
- 3-methoxy-3-methyl-1-butanol Solfit Fine Grade manufactured by Kuraray Co., Ltd.
- Example 10 In a 1500 mL autoclave, 240 g of polylactic acid (Terramac® product number: TE-2500 manufactured by Unitika ) as a thermoplastic resin, 480 g of 3-methoxy-3-methyl-1-butanol (Solfit Fine Grade manufactured by Kuraray Co., Ltd.) as a solvent, ion-exchanged water 480 g, hydrophobic fumed silica (Nippon Aerosil AEROSIL (R) R972) was charged a mixed solution prepared by 18g dispersed as a dispersant. After the addition, the mixture was stirred for 90 minutes at a reaction temperature of 140 ° C. and a stirring speed of 600 rpm. Then, after rapidly cooling (30 minutes to 25 ° C.) while maintaining the stirring speed, the contents were taken out. The spherical contents were obtained by subjecting the contents to dehydration, filtration, and drying.
- polylactic acid Teerramac® product number: TE-2500 manufactured by Unitika
- thermoplastic resin 3-hydroxybutyrate / 3-hydroxy hexanoate copolymer benzoate manufactured by Kaneka Corporation Kaneka biopolymer A demon Rex (R) part number: X131A
- 3- methoxy -3 240 g as a solvent -480 g of methyl-1-butanol (Kuraray Solfit Fine Grade), 480 g of ion-exchanged water, and a mixed solution in which 24 g of hydrophobic fumed silica (AEROSIL (R) 974, Nippon Aerosil Co., Ltd.) was dispersed as a dispersing agent did.
- AEROSIL (R) 974 hydrophobic fumed silica
- the mixture was stirred for 90 minutes at a reaction temperature of 130 ° C. and a stirring speed of 600 rpm. Thereafter, the contents were taken out after an abrupt case (30 minutes up to 25 ° C.) with the stirring speed maintained.
- the spherical contents were obtained by subjecting the contents to dehydration, filtration, and drying.
- the substantially spherical particles obtained in the examples are spherical because the specific solvent is used and the heating and stirring temperature is obtained by heating and stirring the thermoplastic resin at a temperature of 100 ° C. or higher and then cooling. It can be seen that the particle size is small, the particle size distribution is narrow, and the light scattering property is high.
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Abstract
Description
一方、近年の環境問題への関心が高まる中、環境負荷を低減するため、樹脂を使用するあらゆる分野で、非石油原料由来の材料を使用することが求められている。例えば、化粧品、塗料等の樹脂粒子が使用される分野でもそのように求められている。
特許文献8(国際公開WO2012-105140号)では、ポリ乳酸及び異なる種類の樹脂をエーテル系溶剤に溶解させ、次いで、せん断力を加えてエマルションを形成した後、貧溶媒に接触させることで、小粒子径で吸油量の大きな多孔質状のポリ乳酸系樹脂粒子を得る方法が提案されている。
特に、熱可塑性を有した生分解性の樹脂は、柔らかすぎたり、粘りが強すぎたりする。そのために一般的な機械粉砕にて粉体を製造しようとした場合、
(1)微細な粉体にすることが困難である
(2)脆すぎるために得られる粉体は大粒径のものから微小な粒径のものまでが混在してしまう
(3)使用中に更に微粉化してしまうために研磨効果が持続しない
ことがあった。
また、特許文献2~4では、溶解や析出、乾燥といった多段階の工程を要するために生産性が悪いだけではなく、不純物を含んだ廃溶媒が多量に発生する。この廃溶媒は、排出すると環境に悪影響を与えてしまう可能性が高く、また、再利用するための不純物を取り除く処理には多大な労力が必要になる。加えて、この処理の際にも環境に悪影響を与える恐れのある物質が生成してしまう可能性が高い。また、得られる粉体中には必ず微量の溶媒が残ってしまい、この残留溶媒が最終製品の品質に悪影響を及ぼす恐れもある。
特許文献8では、表面平滑な微粒子が得られるものの、真球度と光散乱指数が十分に優れたものは得られなかった。
また、本発明によれば、上記熱可塑性樹脂からなる略球状樹脂粒子が、3-アルコキシ-3-メチル-1-ブタノール及び/又は3-アルコキシ-3メチル-1-ブチルアセテート(アルコキシ基の炭素数は1~5個)を含む溶媒、水及び分散安定剤の存在下、熱可塑性樹脂を100℃以上の温度で乳化・分散し、その後冷却することで得られる熱可塑性樹脂からなる略球状樹脂粒子の製造方法が提供される。
更に、上記熱可塑性樹脂からなる略球状樹脂粒子を配合した化粧料が提供される。
また、上記熱可塑性樹脂からなる略球状樹脂粒子を配合したコーティング材料が提供される。
以下のいずれかの場合、より高い光散乱性を有する略球状の熱可塑性樹脂粒子を提供できる。
(1)熱可塑性樹脂が、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリエーテル系樹脂及びポリアミド系樹脂からなる群より選ばれた少なくとも1種の樹脂である。
(2)熱可塑性樹脂が、ポリエチレン、ポリプロピレン、エチレン/酢酸ビニル共重合体、エチレン/(メタ)アクリル酸共重合体、エチレン/(メタ)アクリル酸エステル共重合体、ポリ乳酸、ポリブチレンサクシネート、ポリヒドロキシアルカノエート、ナイロン12、ナイロン6及びポリカプロラクタムからなる群より選ばれた少なくとも1種の樹脂である。
(3)熱可塑性樹脂が、生分解性を有し、かつポリエステル系樹脂及びポリエーテル系樹脂、からなる群より選ばれた少なくとも1種の樹脂である。
(4)記熱可塑性樹脂が、3-アルコキシ-3-メチル-1-ブタノール及び/又は3-アルコキシ-3メチル-1-ブチルアセテート(アルコキシ基の炭素数は1~5個)に、100℃以上で溶解又は可塑化し、常温で溶解しない樹脂である。
(1)諸物性
略球状粒子は、0.90~1.00の真球度、0.5~1.0の光散乱指数、30~150mL/100gのアマニ油吸油量を有する。真球度及び光散乱指数及びアマニ油吸油量の測定法は、実施例の欄に記載する。
真球度が0.90未満の場合、化粧料等に配合した際に、流動性が低下し、触感や滑り性が悪くなることがある。真球度は、0.90、0.92、0.93、0.95、0.97、1.00を取り得る。好ましい真球度は0.92~1.00であり、より好ましい真球度は0.93~1.00である。
光散乱指数が0.5より小さい場合、十分な光散乱性を示さず、化粧料等に配合した場合にはソフトフォーカス特性に劣ることがある。光散乱指数は、0.5、0.55、0.6、0.65、0.7、0.75、0.8、0.85、0.9、0.95、1.0を取り得る。好ましい光散乱指数は0.55~1.0であり、より好ましい光散乱指数は0.6~1.0である。
熱可塑性樹脂は、特に限定されない。例えば、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリエーテル系樹脂及びポリアミド系樹脂からなる群より選ばれた少なくとも1種の樹脂が挙げられる。ポリオレフィン系樹脂としては、ポリエチレン、ポリプロピレン、エチレン/酢酸ビニル共重合体、エチレン/(メタ)アクリル酸共重合体、エチレン/(メタ)アクリル酸エステル共重合体等が挙げられる。(メタ)アクリル酸エステルのエステル成分は、例えば、メチル、エチル、プロピル、ブチル等が挙げられる。ポリエステル系樹脂としては、ポリ乳酸、ポリブチレンサクシネート、ポリヒドロキシアルカノエート、ポリカプロラクタム等が挙げられる。ポリヒドロキシアルカノエートの中でも好ましいのは、一般式(1)[-CH(R)-CH2CO-O-](ただし、式中Rは-CnH2n+1で表されるアルキル基であり、nは1~15の整数)で示される繰り返し単位からなるポリ(3-ヒドロキシアルカノエート)重合体又は共重合体である。より具体的には、3-ヒドロキシブチレートと、3-ヒドロキシプロピオネート、3-ヒドロキシバレレート、3-ヒドロキシヘキサノエート、3-ヒドロキシヘプタノエート、3-ヒドロキシオクタノエート、3-ヒドロキシナノエート、3-ヒドロキシデカノエート、3-ヒドロキシテトラデカノエート、3-ヒドロキシヘキサデカノエート、3-ヒドロキシオクタデカノエート、4-ヒドロキシブチレート、4-ヒドロキシバレレート、5-ヒドロキシバレレート、6-ヒドロキシヘキサノエートからなる群から選ばれる、少なくとも1種のモノマーとのコポリマーを使用できる。具体的な(3-ヒドロキシアルカノエート)重合体または共重合体としては、前記3-ヒドロキシアルカノエートのホモポリマー、又はnの異なる2種以上の3-ヒドロキシアルカノエートからなる共重合体、前記ホモポリマー及び前記共重合体の群より選ばれる2種以上をブレンドした混合体が挙げられる。なかでも、n=1の3-ヒドロキシブチレート繰り返し単位、n=2の3-ヒドロキシバレレート繰り返し単位、n=3の3-ヒドロキシヘキサノエート繰り返し単位、n=5の3-ヒドロキシオクタノエート繰り返し単位、n=15の3-ヒドロキシオクタデカノエート繰り返し単位からなる群より構成されるホモポリマー、共重合体及び混合物が好ましく、3-ヒドロキシブチレート繰り返し単位と、3-ヒドロキシバレレート、3-ヒドロキシヘキサノエート、及び3-ヒドロキシオクタノエートからなる群より選ばれる少なくとも1つの繰り返し単位とからなる共重合体がより好ましい。最も好ましくは、3-ヒドロキシブチレート繰り返し単位と3-ヒドロキシヘキサノエート単位の共重合体であるポリ(3-ヒドロキシブチレート-コ-3-ヒドロキシヘキサノエート)である。より具体的には、カネカ社製 製品名アオニレックスシリーズが挙げられる。ポリエーテル系樹脂としては、ポリエーテルスルホン等が挙げられる。ポリアミド系樹脂としては、ナイロン12、ナイロン6等が挙げられる。
これら例示樹脂は、1種のみで使用してもよく、複数種混合して使用してもよい。なお、熱可塑性樹脂の分子量は特に限定されない。最終的な用途・目的に応じて適宜選択することができる。
略球状粒子は、必要に応じて、公知の流動性調整剤、紫外線吸収剤、光安定剤、顔料(例えば、体質顔料、着色顔料、金属顔料、マイカ粉顔料等)、染料等を含んでいてもよい。
略球状粒子は、ファンデーション、制汗剤、スクラブ剤等の化粧品用の配合剤、塗料用艶消し剤、レオロジー改質剤、ブロッキング防止剤、滑り性付与剤、光拡散剤、ファインセラミックス焼結成形用助剤、接着剤用充填剤、医療用診断検査剤等の各種剤、自動車材料、建築材料等の成形品への添加剤等の用途で使用できる。
略球状粒子は、
(1)熱可塑性樹脂を、3-アルコキシ-3-メチル-1-ブタノール及び/又は3-アルコキシ-3-メチル-1-ブチルアセテート(アルコキシ基の炭素数は1~5個、具体的には、メチル、エチル、プロピル、ブチル、ペンチル)(特定溶媒)を含む溶媒、水、分散安定剤の存在下、前記熱可塑性樹脂を100℃以上の温度で乳化・分散する工程(乳化・分散工程)、
(2)その後冷却することで熱可塑性樹脂を粒子として得る工程(冷却工程)
を経ることで得ることができる。
この製造方法により得られた略球状粒子は、他の製造方法により得られた粒子に比べ、光学特性(ソフトフォーカス効果)及び吸油特性に優れるという効果を奏する。
(i)溶媒
溶媒は、3-アルコキシ-3-メチル-1-ブタノール及び/又は3-アルコキシ-3-メチル-1-ブチルアセテート(以下、特定溶媒とも称する)を含む。特定溶媒が溶媒中に占める割合は、50重量%以上が好ましく。70重量%以上がより好ましく、100重量%であることが更に好ましい。特定溶媒以外の使用可能溶媒としては、メタノール、エタノール等の低級アルコール、酢酸エチル、酢酸ブチル等の酢酸エステル系溶剤が挙げられる。特定溶媒としては、クラレ社製からソルフィットの商品名で市販されている溶媒も使用できる。また、3-アルコキシ-3-メチル-1-ブタノールは、例えば、国際公開WO2013/146370号に記載の方法により製造できる。
溶媒の使用量は、熱可塑性樹脂100重量部に対して、100~1200重量部であることが好ましい。使用量が100重量部未満の場合、熱可塑性樹脂の濃度が高すぎて充分に撹拌混合することが難しいことがある。1200重量部より多い場合、装置の大きさに比して生産量が少なくなることがある。使用量は、100重量部、200重量部、400重量部、500重量部、700重量部、800重量部、1000重量部、1200重量部を取り得る。より好ましい使用量は100~800重量部であり、更に好ましい使用量は100~400重量部である。
分散安定剤としては、疎水化処理した無機微粒子が好適に使用できる。具体例としては、疎水性フュームドシリカ(日本アエロジル社製;商品名 AEROSIL(R:登録商標) R972、AEROSIL(R) R974、AEROSIL(R) R976S、AEROSIL(R) R104、AEROSIL(R) R106、AEROSIL(R) R202、AEROSIL(R) R805、AEROSIL(R) R812、AEROSIL(R) R812S、AEROSIL(R) R816、AEROSIL(R) R7200、AEROSIL(R) R8200、AEROSIL(R) R9200、AEROSIL(R) R711、AEROSIL(R) RY50、AEROSIL(R) NY50、AEROSIL(R) RY200、AEROSIL(R) RY200S、AEROSIL(R) RX50、AEROSIL(R) NAX50、AEROSIL(R) RX200、AEROSIL(R) RX300、AEROSIL(R) R504)、疎水性アルミナ(日本アエロジル社製;商品名 AEROXIDO(R) Alu C)、疎水性酸化チタン(日本アエロジル社製;商品名AEROXIDE(R) TiO2 T805:チタン工業社製;商品名 超微粒子酸化チタンSTシリーズ、ST-455、STV-455、ST-557SA、ST-457EC、ST-457EC、ST-605EC:堺化学工業社製;商品名 超微粒子酸化チタンSTRシリーズ、STR-100C-LP、STR-60c-LP、STR-100W-LP、STR-100C-LF)等が挙げられる。
また、分散安定剤として、第三リン酸カルシウム(太平化学産業社製;商品名 TCP-10U等)、リン酸マグネシウム、リン酸アルミニウム、リン酸亜鉛等のリン酸塩、ピロリン酸カルシウム、ピロリン酸マグネシウム、ピロリン酸アルミニウム、ピロリン酸亜鉛等のピロリン酸塩、炭酸カルシウム、炭酸マグネシウム、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、メタケイ酸カルシウム、硫酸カルシウム、硫酸バリウム、コロイダルシリカ(日産化学社製:商品名 スノーテックスシリーズ スノーテックス40、スノーテックスS、スノーテックスXS等)等の親水性の難水溶性無機化合物等を用いることもできる。
上記の中でも、目的とする樹脂粒子を安定して得ることができるという点において、第三リン酸カルシウム、コロイダルシリカが特に好ましい。
分散安定剤の熱可塑性樹脂に対する添加量は、0.5~15重量%が好ましい。添加量は、0.5重量%、0.7重量%、1.0重量%、1.2重量%、1.5重量%、3重量%、5重量%、8重量%、10重量%、15重量%を取り得る。
アニオン性界面活性剤としては、オレイン酸ナトリウム、ヒマシ油カリ等の脂肪酸油、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム等のアルキル硫酸エステル塩、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、アルカンスルホン酸塩、ジアルキルスルホコハク酸塩、アルキルリン酸エステル塩、ナフタレンスルホン酸ホルマリン縮合物、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩、ポリオキシエチレンアルキル硫酸エステル塩等がある。ノニオン性界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシソルビタン脂肪酸エステル、ポリオキシエチレンアルキルアミン、グリセリン脂肪酸エステル、オキシエチレン-オキシプロピレンブロックポリマー等がある。カチオン性界面活性剤としては、ラウリルアミンアセテート、ステアリルアミンアセテート等のアルキルアミン塩、ラウリルトリメチルアンモニウムクロライド等の第四級アンモニウム塩等がある。両性イオン界面活性剤としては、ラウリルジメチルアミンオキサイド等がある。
界面活性剤の添加量は、水に対して0.01~0.5重量%が好ましい。
これら分散安定剤や界面活性剤は、得られる樹脂粒子の粒子径及び分散安定性を考慮して、それらの選択や組合せ、使用量等を適宜調整して使用される。
水の使用量は、熱可塑性樹脂100重量部に対して、100~2200重量部であることが好ましい。使用量が100重量部未満の場合、熱可塑性樹脂の濃度が濃すぎて十分に撹拌混合することが難しいことがある。2200重量部より多い場合は、装置の大きさに比して生産量が少なくなることがある。水の使用量は、100重量部、150重量部、200重量部、300重量部、600重量部、800重量部、1000重量部、1500重量部、2000重量部、2200重量部を取り得る。より好ましい使用量は150~1000重量部であり、更に好ましい使用量は200~800重量部である。
加熱撹拌は、100℃以上の加熱温度下で行われる。加熱温度が、100℃未満の場合、熱可塑性樹脂が軟化せず、微粒子化できないことがある。加熱撹拌は、180℃以下の温度で行うことができる。加熱温度は、100℃、120℃、140℃、160℃、180℃を取り得る。
本製造方法で得られる略球状粒子は、粒子径分布の小さな粒子になるが、これは、エマルション形成の段階において、非常に均一なエマルションが得られるからである。このため、エマルションを形成させるに十分な剪断力を得るためには、公知の方法による撹拌を用いれば十分であり、撹拌羽根による液相撹拌法、ホモジナイザーによる混合法、超音波照射法等の通常公知の方法で混合することができる。
撹拌の速度及び時間は、熱可塑性樹脂が溶媒に溶解又は溶媒中に均一に分散できさえすれば特に限定されず、適宜選択するのが好ましい。
加熱撹拌は、通常、大気圧下で行われるが、必要に応じて、減圧下又は加圧下で行ってもよい。
熱可塑性樹脂を粒子として析出させるために、熱可塑性樹脂を含む溶媒は、加熱撹拌後、冷却される。冷却温度は、通常、常温(約25℃)である。加熱撹拌時の温度から冷却温度に達する時間はできるだけ早いことが好ましい。また、冷却は、撹拌しつつ行うことが好ましい。撹拌速度は、加熱撹拌の撹拌速度と同様の範囲とすることができる。
冷却後の溶媒中の略球状粒子は、必要に応じて、ろ過、脱水、乾燥を経て、溶媒から取り出されてもよい。ろ過、脱水、乾燥は、特に限定されず、公知の方法により行うことができる。
フロー式粒子像分析装置(商品名「FPIA(登録商標)-3000S」、シスメックス社製)を用いて測定する。
具体的な測定方法としては、イオン交換水20mLに、分散剤として界面活性剤、好ましくはアルキルベンゼンスルホン酸塩0.05gを加えて界面活性剤水溶液を得る。その後、上記界面活性剤水溶液に、測定対象の樹脂粒子群0.2gを加え、分散機としてBRANSON社製の超音波分散機「BRANSON SONIFIER 450」(出力400W、周波数20kHz)を用いて超音波を5分間照射して、樹脂粒子群を界面活性剤水溶液中に分散させる分散処理を行い、測定用の分散液を得る。
測定には、標準対物レンズ(10倍)を搭載した上記フロー式粒子像分析装置を用い、上記フロー式粒子像分析装置に使用するシース液としては、パーティクルシース(商品名「PSE-900A」、シスメックス社製)を使用する。上記手順に従い調整した測定用の分散液を上記フロー式粒子像分析装置に導入し、下記測定条件にて測定する。
粒子径の測定範囲:2.954μm~30.45μm
粒子の真球度の測定範囲:0.5~1.0
粒子の測定個数:1000個
測定にあたっては、測定開始前に標準ポリマー粒子群の懸濁液(例えば、Thermo Fisher Scientific社製の「5200A」(標準ポリスチレン粒子群をイオン交換水で希釈したもの))を用いて上記フロー式粒子像分析装置の自動焦点調整を行う。なお、真球度は、樹脂粒子を撮像した画像と同じ投影面積を有する真円の直径から算出した周囲長を、樹脂粒子を撮像した画像の周囲長で除した値である。
・コールターカウンター法
樹脂粒子の体積平均粒子径は、コールターMultisizerTM3(ベックマン・コールター社製測定装置)により測定する。測定は、ベックマン・コールター社発行のMultisizerTM3ユーザーズマニュアルに従って校正されたアパチャーを用いて実施するものとする。
Current(アパチャー電流)及びGain(ゲイン)は、選択したアパチャーのサイズによって、適宜設定する。例えば、50μmサイズを有するアパチャーを選択した場合、Current(アパチャー電流)は-800、Gain(ゲイン)は4と設定し、100μmのサイズを有するアパチャーを選択した場合、Current(アパチャー電流)は-1600、Gain(ゲイン)は2と設定し、280μm及び400μmのサイズを有するアパチャーを選択した場合、Current(アパチャー電流)は-3200、Gain(ゲイン)は1と設定する。
樹脂粒子の粒子径の変動係数(CV値)を、以下の数式によって算出する。
樹脂粒子の粒子径の変動係数=(樹脂粒子の体積基準の粒度分布の標準偏差÷樹脂粒子の体積平均粒子径)×100
樹脂粒子のアマニ油吸油量は、JIS K 5101-13-2-2004の測定方法を参考にして、煮アマニ油に代えて精製アマニ油を使用し、終点の判断基準を変更した(「測定板を垂直に立てた時にペースト(樹脂粒子及び生成アマニ油の混錬物)が流動を始める」点に変更した)方法によって、測定する。アマニ油吸油量の測定の詳細は、以下の通りである。
(A)装置及び器具
測定板:300×400×5mmより大きい平滑なガラス板
パレットナイフ(ヘラ):鋼製又はステンレス製の刃を持った柄つきのもの
化学はかり(計量器):10mgオーダーまで計れるもの
ビュレット:JIS R 3505:1994に規定する容量10mLのもの
(B)試薬
精製アマニ油:ISO 150:1980に規定するもの(今回は一級アマニ油(和光純薬工業社製)を用いる)
(1)樹脂粒子1gを測定板上の中央部に取り、精製アマニ油をビュレットから一回に4、5滴ずつ、徐々に樹脂粒子の中央に滴下し、その都度、樹脂粒子及び精製アマニ油の全体をパレットナイフで充分練り合わせる。
(2)上記の滴下及び練り合わせを繰り返し、樹脂粒子及び精製アマニ油の全体が固いパテ状の塊になったら1滴ごとに練り合わせて、精製アマニ油の最後の1滴の滴下によりペースト(樹脂粒子及び精製アマニ油の混練物)が急激に軟らかくなり、流動を始める点を終点とする。
(3)流動の判定
精製アマニ油の最後の1滴の滴下により、ペーストが急激に軟らかくなり、測定板を垂直に立てた時にペーストが動いた場合に、ペーストが流動していると判定する。測定板を垂直に立てた時もペーストが動かない場合には、更に精製アマニ油を1滴加える。
(4)終点に達したときの精製アマニ油の消費量をビュレット内の液量の減少分として読み取る。
(5)1回の測定時間は7~15分以内に終了するように実施し、測定時間が15分を超えた場合は再測定し、規定の時間内で測定を終了した時の数値を採用する。
下記式により試料100g当たりのアマニ油吸油量を計算する。
O=(V/m)×100
ここで、O:アマニ油吸油量(mL/100g)、m:樹脂粒子の重量(g)、V:消費した精製アマニ油の容量(mL)
(i)反射光度分布の測定
以下に示す方法により、樹脂粒子の表面で反射した光の拡散性を評価する。
樹脂粒子の反射光度分布を、三次元光度計(村上色彩研究所社製のゴニオフォトメーターGP-200)を用い、室温20℃、相対湿度65%の環境下で測定する。
(1)図1に示すように、厚み2mmの黒色ABS樹脂板(タキロン社製)4の中心に、2cm角の正方形にカットした両面テープ(日東電工製 ORT-1)3を貼る。
(2)次いで、前記黒色ABS樹脂板4の黒色部分上の両面テープ3の粘着面に、樹脂粒子2を見かけ密度測定器の漏斗及び漏斗台(JIS K5101-12-1-2004)を用いて落としてから、その粘着面上の余分な樹脂粒子2を0.05~0.1MPaの圧縮空気で吹き飛ばす。
(3)前記黒色ABS樹脂板4を平坦なガラス板の上に載せ、別の平坦な5cm角の正方形の250gのガラス板を樹脂粒子2の点着面に載せ、樹脂粒子2に荷重を加えて1分間静置する。その後、再び、前記粘着面上の余分な樹脂粒子を圧縮空気で吹き飛ばす。
(4)(2)及び(3)の操作を3回繰り返した試験片を反射光度分布測定用の試験片1とする。そして、得られた試験片1の反射光を次のようにして測定する。図1に示すように、試験片1(樹脂粒子2)の法線(0°)に対して-45°の角度で、ハロゲンランプを光源とした光5を試験片1(樹脂粒子2)に入射させ、反射した反射光6の反射角-90°~+90°における光度分布を三次元光度計により測定する。測定に際しては全ての入射光が試験片1の黒色部分に入射するように試験片1の位置を調整する。なお、反射光検出は分光感度185~850nm、最高感度波長530nmの光電子増倍管により検出する。
前記反射光度分布の測定により得られた反射角0°、+45°における反射光強度データ(ピーク光度データ)から、反射角+45°の反射光強度(ピーク光度)を100としたときの、反射角0°における反射光強度(ピーク光度)を求める。反射角+45°(正反射方向)の反射光強度を100としたとき、反射角0°の反射光強度が100に近づくほど、化粧料に配合したときのソフトフォーカス効果が大きくなる。光散乱指数は下記式により算出する。
光散乱指数=(0°の散乱光強度)/(45°の散乱光強度)
より1に近い値を示すほど、角度依存性のない高い光散乱特性を示すといえる。
300mLオートクレーブに熱可塑性樹脂としてポリブチレンサクシネート(三菱化学社製GS-Pla(R) 品番:FZ71PD)を20g、溶剤として3-メトキシ-3-メチル-1-ブタノール(クラレ社製 ソルフィットファイングレード)60g、イオン交換水100g、分散剤として10%第三リン酸カルシウム水溶液(太平化学産業社製TCP-10U)20g、界面活性剤としてラウリル硫酸ナトリウム0.24gを投入し、反応温度(加熱撹拌温度)120℃、撹拌回転数400rpmにて90分撹拌した。
その後、撹拌回転数を維持したまま急冷(25℃まで30分間)した後、内容物を取り出した。内容物を脱水・ろ過・乾燥に付すことで略球状粒子を得た。
300mLオートクレーブに熱可塑性樹脂としてポリブチレンサクシネート(三菱化学社製GS-Pla(R) 品番:FZ71PD)を20g、溶剤として3-メトキシ-3-メチル-1-ブタノール(クラレ社製 ソルフィットファイングレード)60g、イオン交換水120g、分散剤として疎水性フュームドシリカ(日本アエロジル社製AEROSIL(R)R972)1.5gを分散させた混合溶液を投入した。投入後、反応温度120℃、撹拌回転数400rpmで90分撹拌した。
その後、撹拌回転数を維持したまま急冷(25℃まで30分間)した後、内容物を取り出した。内容物を脱水・ろ過・乾燥に付すことで略球状粒子を得た。
300mLオートクレーブに熱可塑性樹脂としてポリブチレンサクシネート(三菱化学社製GS-Pla(R) 品番:FZ71PD)を40g、溶剤として3-メトキシ-3-メチル-1-ブタノール(クラレ社製 ソルフィットファイングレード)60g、イオン交換水100g、分散剤として疎水性フュームドシリカ(日本アエロジル社製AEROSIL(R)R972)3gを分散させた混合溶液を投入した。投入後、反応温度120℃、撹拌回転数400rpmで90分撹拌した。
その後、撹拌回転数を維持したまま急冷(25℃まで30分間)した後、内容物を取り出した。内容物を脱水・ろ過・乾燥に付すことで略球状粒子を得た。
300mLオートクレーブに熱可塑性樹脂としてポリブチレンサクシネート(三菱化学社製GS-Pla(R) 品番:FZ71PD)を20g、溶剤として3-メトキシ-3-メチル-1-ブタノール(クラレ社製 ソルフィットファイングレード)60g、イオン交換水120g、界面活性剤としてポリオキシエチレンスチレン化フェノルエーテル(第一工業製薬社製 製品名;ノイゲンEA-167)を0.12g、分散剤として、疎水性フュームドシリカ(日本アエロジル社製AEROSIL(R)R972)1.5gを分散させた混合溶液を投入した。投入後、反応温度120℃、撹拌回転数400rpmで90分撹拌した。
その後、撹拌回転数を維持したまま急冷(25℃まで30分間)した後、内容物を取り出した。内容物を脱水・ろ過・乾燥に付すことで略球状粒子を得た。
1500mLオートクレーブに熱可塑性樹脂としてポリブチレンサクシネート(三菱化学社製GS-Pla(R) 品番:FZ71PD)を120g、溶剤として3-メトキシ-3-メチル-1-ブタノール(クラレ社製 ソルフィットファイングレード)360g、イオン交換水720g、分散剤として疎水性フュームドシリカ(日本アエロジル社製AEROSIL(R)R972)を6g分散させた混合溶液を投入した。投入後、反応温度120℃、撹拌回転数400rpmで90分撹拌した。
その後、撹拌回転数を維持したまま急冷(25℃まで30分間)した後、内容物を取り出した。内容物を脱水・ろ過・乾燥に付すことで略球状粒子を得た。
1500mLオートクレーブに熱可塑性樹脂としてポリブチレンサクシネート(三菱化学社製GS-Pla(R) 品番:FZ71PD)を240g、溶剤として3-メトキシ-3-メチル-1-ブタノール(クラレ社製 ソルフィットファイングレード)420g、イオン交換水540g、分散剤として疎水性シリカ(日本アエロジル社製AEROSIL(R)R972)を18g分散させた混合溶液を投入した。投入後、反応温度120℃、撹拌回転数600rpmで90分撹拌した。
その後、撹拌回転数を維持したまま急冷(25℃まで30分間)した後、内容物を取り出した。内容物を脱水・ろ過・乾燥に付すことで略球状粒子を得た。
1500mLオートクレーブに熱可塑性樹脂としてポリブチレンサクシネート(三菱化学社製GS-Pla(R) 品番:FZ91PD)を240g、溶剤として3-メトキシ-3-メチル-1-ブタノール(クラレ社製 ソルフィットファイングレード)480g、イオン交換水480g、分散剤として疎水性フュームドシリカ(日本アエロジル社製AEROSIL(R)R972)を18g分散させた混合溶液を投入した。投入後、反応温度120℃、撹拌回転数600rpmで90分撹拌した。
その後、撹拌回転数を維持したまま急冷(25℃まで30分間)した後、内容物を取り出した。内容物を脱水・ろ過・乾燥に付すことで略球状粒子を得た。
1500mLオートクレーブに熱可塑性樹脂としてポリブチレンサクシネート(三菱化学社製GS-Pla(R) 品番:FZ71PD)を240g、溶剤として3-メトキシ-3-メチル-1-ブタノール(クラレ社製 ソルフィットファイングレード)480g、イオン交換水480g、分散剤として疎水性フュームドシリカ(日本アエロジル社製AEROSIL(R)R976S)を12g分散させた混合溶液を投入した。投入後、反応温度120℃、撹拌回転数600rpmで90分撹拌した。
その後、撹拌回転数を維持したまま急冷(25℃まで30分間)した後、内容物を取り出した。内容物を脱水・ろ過・乾燥に付すことで略球状粒子を得た。
1500mLオートクレーブに熱可塑性樹脂としてポリブチレンサクシネート(三菱化学社製GS-Pla(R) 品番:FZ71PD)を240g、溶剤として3-メトキシ-3-メチル-1-ブタノール(クラレ社製 ソルフィットファイングレード)480g、イオン交換水240g、分散剤として10%第三リン酸カルシウム水溶液(太平化学産業社製 TCP-10U)240g、界面活性剤としてラウリル硫酸ナトリウム0.48gを投入し、反応温度(加熱撹拌温度)120℃、撹拌回転数600rpmにて90分撹拌した。
その後、撹拌回転数を維持したまま急冷(25℃まで 30分間)した後、内容物を取り出した。内容物を脱水・ろ過・乾燥に付すことで略球状粒子を得た。
1500mLオートクレーブに熱可塑性樹脂としてポリ乳酸(ユニチカ社製 テラマック(R) 品番:TE-2500)を240g、溶剤として3-メトキシ-3-メチル-1-ブタノール(クラレ社製 ソルフィット ファイングレード)480g、イオン交換水480g、分散剤として疎水性フュームドシリカ(日本アエロジル社製AEROSIL(R)R972)を18g分散させた混合溶液を投入した。投入後、反応温度140℃、撹拌回転数600rpmで90分撹拌した。
その後、撹拌回転数を維持したまま急冷(25℃まで30分間)した後、内容物を取り出した。内容物を脱水・ろ過・乾燥に付することで略球状粒子を得た。
1500mLオートクレーブに熱可塑性樹脂として3-ヒドロキシブチレート/3-ヒドロキシヘキサノエートの共重合体(カネカ社製 カネカバイオポリマーアオニレックス(R) 品番:X131A)を240g、溶剤として3-メトキシ-3-メチル-1-ブタノール(クラレ社製 ソルフィットファイングレード)480g、イオン交換水480g、分散剤として疎水性フュームドシリカ(日本アエロジル社製AEROSIL(R)974)を24g分散させた混合溶液を投入した。投入後、反応温度130℃、撹拌回転数600rpmで90分撹拌した。
その後、撹拌回転数を維持したまま急例(25℃まで30分間)した後、内容物を取り出した。内容物を脱水・ろ過・乾燥に付することで略球状粒子を得た。
アイカ工業社製ガンツパール GMX-0810を用いて各種測定を行った。
300mLオートクレーブに熱可塑性樹脂としてポリブチレンサクシネート(三菱化学社製GS-Pla(R) 品番:FZ71PD)を20g、溶剤として3-メトキシ-3-メチル-1-ブタノール(クラレ社製 ソルフィットファイングレード)60g、イオン交換水120g、分散剤として疎水性フュームドシリカ(日本アエロジル社製AEROSIL(R)R972)1.5gを分散させた混合溶液を投入した。投入後、反応温度90℃、撹拌回転数400rpmで90分撹拌した。
その後、撹拌回転数を維持したまま急冷(25℃まで30分間)した後、内容物を取り出したところ、ペレット形状のまま残っており、微粒子化することができなかった。
実施例で得られた略球状粒子の各種物性を下記表に示す。
Claims (8)
- 真球度が0.90~1.00、かつ光散乱指数が0.5~1.0、かつアマニ油吸油量が30~150mL/100gである熱可塑性樹脂からなる略球状樹脂粒子。
- 前記熱可塑性樹脂が、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリエーテル系樹脂及びポリアミド系樹脂からなる群より選ばれた少なくとも1種の樹脂である請求項1に記載の熱可塑性樹脂からなる略球状樹脂粒子。
- 前記熱可塑性樹脂が、ポリエチレン、ポリプロピレン、エチレン/酢酸ビニル共重合体、エチレン/(メタ)アクリル酸共重合体、エチレン/(メタ)アクリル酸エステル共重合体、ポリ乳酸、ポリブチレンサクシネート、ポリヒドロキシアルカノエート、ポリカプロラクタム、ナイロン12及びナイロン6からなる群より選ばれた少なくとも1種の樹脂である請求項1に記載の熱可塑性樹脂からなる略球状樹脂粒子。
- 前記熱可塑性樹脂が、生分解性を有し、かつポリエステル系樹脂及びポリエーテル系樹脂からなる群より選ばれた少なくとも1種の樹脂である請求項1に記載の熱可塑性樹脂からなる略球状樹脂粒子。
- 前記熱可塑性樹脂が、3-アルコキシ-3-メチル-1-ブタノール及び/又は3-アルコキシ-3メチル-1-ブチルアセテート(アルコキシ基の炭素数は1~5個)に、100℃以上で溶解又は可塑化し、常温で溶解しない樹脂である請求項1に記載の熱可塑性樹脂からなる略球状樹脂粒子。
- 請求項1に記載の熱可塑性樹脂からなる略球状樹脂粒子が、3-アルコキシ-3-メチル-1-ブタノール及び/又は3-アルコキシ-3メチル-1-ブチルアセテート(アルコキシ基の炭素数は1~5個)を含む溶媒、水及び分散安定剤の存在下、熱可塑性樹脂を100℃以上の温度で乳化・分散し、その後冷却することで得られる熱可塑性樹脂からなる略球状樹脂粒子の製造方法。
- 請求項1に記載の熱可塑性樹脂からなる略球状樹脂粒子を配合した化粧料。
- 請求項1に記載の熱可塑性樹脂からなる略球状樹脂粒子を配合したコーティング材料。
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WO2023149511A1 (ja) * | 2022-02-07 | 2023-08-10 | 株式会社カネカ | ポリヒドロキシアルカン酸粉体およびその利用 |
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KR20180103667A (ko) | 2017-03-09 | 2018-09-19 | (주)엘지하우시스 | 열가소성 고분자 입자 |
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KR20190034150A (ko) | 2019-04-01 |
KR102560234B1 (ko) | 2023-07-26 |
US20210309811A1 (en) | 2021-10-07 |
US20190276611A1 (en) | 2019-09-12 |
EP3489281B1 (en) | 2023-04-19 |
US12065548B2 (en) | 2024-08-20 |
EP3489281A4 (en) | 2020-04-01 |
EP3489281A1 (en) | 2019-05-29 |
EP4234611A1 (en) | 2023-08-30 |
CN109312079B (zh) | 2023-01-13 |
CN115850738A (zh) | 2023-03-28 |
US11078338B2 (en) | 2021-08-03 |
CN109312079A (zh) | 2019-02-05 |
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