PROCESS TO PRODUCE RESIN MICROPARTICLES, RESIN MICROPARTICLES AND COSMETICS

专利摘要:
process for producing resin microparticles, resin microparticles and cosmetics. refers to a method for producing microparticles of a polylactic acid-based resin, porous microparticles of a polylactic acid-based resin, said microparticles have a small particle diameter, which shows a high oil absorbing capacity and useful for cosmetics; smooth surface microparticles of a polylactic acid-based resin, said microparticles have a spherical shape, which shows a narrow particle diameter distribution and useful for toners; and a cosmetic that uses the aforementioned microparticles of a polylactic acid-based resin. the method for producing microparticles of a polylactic acid-based resin comprising: dissolving a polylactic acid-based resin (a) and a polymer (b), which is different from polylactic acid-based resins, in an organic solvent to ether base (c); apply a shear force to form an emulsion; and then contacting the emulsion with a weak solvent of the polylactic acid-based resin (a). according to this production method, it provides microparticles that have a polylactic acid-based resin melt enthalpy (a) of 5 µg/g or more, have a small particle diameter and show a high oil absorption capacity, and provide smooth surface microparticles of polylactic acid-based resin, said microparticles have a melting enthalpy of less than 5 µ/g, have a spherical shape and show a narrow particle diameter distribution.
公开号:BR112013018678B1
申请号:R112013018678-0
申请日:2011-12-22
公开日:2021-04-13
发明作者:Hiroshi Takezaki；Hiroshi Kobayashi；Itaru Asano；Makiko Saito
申请人:Toray Industries, Inc；
IPC主号:

专利说明:

FIELD OF THE TECHNIQUE OF THE INVENTION
[001] The present invention relates to a process for producing resin microparticles based on polylactic acid, resin microparticles based on polylactic acid and a cosmetic that uses them. BACKGROUND OF THE TECHNIQUE OF THE INVENTION
[002] Unlike polymer-molded products, such as films, fibers, injection-molded products and extrusion-molded products, polymeric microparticles are used for modifying and enhancing various materials by using the large specific surface area and the structure of microparticles. Its main uses include modifiers for cosmetics, additives for toners, rheology modifiers for paints and the like, agents for medical examinations and diagnostics and additives for molded products such as automotive materials and construction materials.
[003] On the other hand, with growing interest in recent environmental problems, there are growing demands for the use of materials not derived from oil in order to reduce environmental loads, even in the fields where polymeric microparticles are used such as cosmetics and paints. Polylactic acid is one of the representative examples of such polymers not derived from oil.
[004] As a conventional method for producing microparticles or polylactic acid-based resin powders, there are several known methods: for example, crushing methods (Patent Document 1 and 2) typified by freeze crushing methods; dissolution-deposition methods (Patent Document 3 and 4) in which deposition is performed by cooling after being dissolved in a solvent at a high temperature or where deposition is performed by adding a weak solvent after being dissolved in a solvent and molten mixing methods (Patent Document 5 and 6) in which a resin compound containing both a dispersed phase polylactic acid resin and a continuous phase incompatible resin is formed by mixing the polylactic acid resin together with the incompatible resin in a mixing machine such as a two-axis extruder and in which the incompatible resin is subsequently removed for the purpose of producing the resin microparticles based on polylactic acid.
[005] However, the microparticles of polylactic acid-based resin produced by the methods described above have several problems since the particles produced are not spherical in shape, the particle diameter does not become smaller, than the particle diameter distribution is wide and that, in some cases, it is impossible to keep the particles in a round shape, because of the fiber ones, etc. Particularly, in fields such as cosmetics where touch and printing is considered very important, or in fields such as inks where it is important to control rheology, the effects produced by the addition of such microparticles have not been sufficient to date.
[006] On the other hand, as a method for the production of polymeric microparticles, the method described in Patent Document 7 is known as a method that uses emulsion. However, in Patent Document 7, a concrete example of a polylactic acid-based resin is not disclosed and it is not clear how to produce polylactic acid-based resin microparticles. BACKGROUND DOCUMENTS
[007] Patent Document
[008] Patent Document 1: JP-UM-2000-007789
[009] Patent Document 2: JP-UM-2001-288273
[010] Patent Document 3: JP-UM-2005-002302
[011] Patent Document 4: JP-UM-2009-242728
[012] Patent Document 5: JP-UM-2004-269865
[013] Patent Document 6: JP-UM-2005-200663
[014] Patent Document 7: WO 2009-142231 BRIEF DESCRIPTION OF THE INVENTION
[015] Problems to be solved by the Invention
[016] An objective of the present invention is to provide a process for producing polylactic acid-based resin microparticles, wherein the porous polylactic acid-based resin microparticles have small medium particle diameter and high oil absorption capacity and are appropriately useful for cosmetics, etc., and the polylactic acid-based resin smooth-surface microparticles have a spherical shape and narrow particle diameter distribution and are suitably useful for toners, etc.
[017] Way to solve the Problems
[018] To achieve the objective described above, the inventors of the present invention have achieved the following inventions as the result of serious research. Namely, the present inventions (i.e., a process for producing polylactic acid-based resin microparticles, polylactic acid-based resin microparticles and cosmetics comprising said microparticles) are as follows.
[019] (1) A process for producing polylactic acid-based resin microparticles comprising:
[020] a dissolution process to form a system, which can cause the phase separation into two phases of a solution phase mainly composed of resin based on polylactic acid (A) and a solution phase mainly composed of polymer (B ) different from resin based on polylactic acid, by dissolving said resin based on polylactic acid (A) and said polymer (B) different from resin based on polylactic acid in an organic solvent based on ether (C);
[021] an emulsion formation process to form an emulsion by applying a shear force to said system; and
[022] a microparticle formation process for precipitating the microparticles of resin based on polylactic acid put said emulsion in contact with a weak solvent that has lower solubility of said resin based on polylactic acid (A) compared to said organic solvent based on ether (C).
[023] (2) The process for producing polylactic acid-based resin microparticles according to (1), wherein said ether-based organic solvent (C) has a boiling point of 100 ° C or higher.
[024] (3) The process for producing resin microparticles based on polylactic acid according to (2), wherein said organic solvent based on ether (C) is diethylene glycol dimethyl ether.
[025] (4) The process for producing microparticles of polylactic acid-based resin according to any one of (1) to (3), wherein said polymer other than a polylactic acid-based resin (B) is a polyvinyl alcohol, a hydroxypropylcellulose, a polyethylene oxide or a polyethylene glycol.
[026] (5) The process for producing resin microparticles based on polylactic acid as defined in any of claims (1) to (4), wherein said weak solvent is water.
[027] (6) The process for producing polylactic acid-based resin microparticles according to any of (1) to (5), wherein said polylactic acid-based resin (A) has a melting enthalpy of 5 J / g or greater.
[028] (7) The process for producing resin microparticles based on polylactic acid according to (6), wherein the contact temperature of said weak solvent is equal to or greater than the crystallization temperature of said resin based of polylactic acid (A).
[029] (8) The process for producing polylactic acid-based resin microparticles according to any of (1) to (5), wherein said polylactic acid-based resin (A) has a melting enthalpy of less than 5 J / g.
[030] (9) Polylactic acid-based resin microparticles characterized by the fact that said microparticles have an average particle diameter number from 1 to 90 μm and a flaxseed oil absorption of 90 ml / 100g or greater.
[031] (10) The polylactic acid-based resin microparticles according to (9), wherein said microparticles comprise a polylactic acid-based resin that has a melting enthalpy of at least 5 J / g.
[032] (11) The polylactic acid-based resin microparticles according to (9) or (10), wherein said microparticles have a particle diameter distribution index of 1 to 2.
[033] (12) Resin microparticles based on polylactic acid characterized by the fact that said microparticles have a sphericity of at least 90 and a particle diameter distribution index of 1 to 2.
[034] (13) The polylactic acid-based resin microparticles according to (12), wherein said microparticles comprise a polylactic acid-based resin that has a melting enthalpy of less than 5 J / g.
[035] (14) The polylactic acid-based resin microparticles according to (12) or (13), wherein said microparticles have an average particle diameter number from 1 to 100 μm and an oil absorption of flaxseed less than 70 ml / 100g.
[036] (15) Cosmetics comprising said polylactic acid-based resin microparticles as defined in any one of claims 9 to 14. EFFECT ACCORDING TO THE INVENTION
[037] According to the process of the present invention to produce polylactic acid-based resin microparticles, it becomes possible to produce polylactic acid-based microparticles easily and, in addition, it becomes possible to produce desired polylactic acid-based resin microparticles as required, for example, porous polylactic acid resin microparticles which have excellent oil absorption capacity and which have excellent hygroscopic properties or spherical polylactic acid resin microparticles which have a smooth surface and which have a high sliding capacity . The polylactic acid-based resin microparticles produced by the present invention are suitable for various uses such as cosmetic bases, lipsticks, cosmetic material such as washing agent for male cosmetics, rapid molding material, rapid prototype creation / rapid manufacturing material , Plastic Sol bulk resin, powder block forming agent, powder flow capacity enhancing agent, adhesive, lubricant, rubber composition ingredient, polishing agent, viscosity enhancer, filler / auxiliary compound filler, gelatin former, coagulation agent, paint additive, oil absorbent material, mold release agent, slip enhancing agent for plastic films / foils, block antiforming agent, gloss adjustment agent, matte finish, light diffusing agent, surface hardness enhancing agent, various other modifying agents such as the resistance enhancing material, spacer for liquid crystal display equipment, charge / carrier for chromatography, base material / additive for cosmetic base, auxiliary for microcapsules, medical materials for drug delivery system / diagnostic reagents, support agent for perfume / pesticide, catalyst / carrier for chemical reactions, gas adsorption agent, sintered material for ceramic processing, standard particle material for measurement / analysis, particle material for the food manufacturing industry, powder coating and toner material for electrophotographic development. BRIEF DESCRIPTION OF THE DRAWINGS
[038] Figure 1 is an electron scanning microscope observation diagram showing polylactic acid-based resin microparticles produced in Practical Example 2.
[039] Figure 2 is an electron scanning microscope observation diagram showing polylactic acid-based resin microparticles produced in Practical Example 4.
[040] Figure 3 is an electron scanning microscope observation diagram showing polylactic acid-based resin microparticles produced in Practical Example 5.
[041] Figure 4 is an electron scanning microscope observation diagram showing polylactic acid-based resin microparticles produced in Practical Example 7.
[042] Figure 5 is an electron scanning microscope observation diagram showing polylactic acid-based resin microparticles produced in Practical Example 9.
[043] Figure 6 is an electron scanning microscope observation diagram showing polylactic acid-based resin microparticles produced in Comparative Example 3.
[044] Figure 7 is an electron scanning microscope observation diagram showing polylactic acid-based resin microparticles produced in Comparative Example 4.
[045] Figure 8 is an electron scanning microscope observation diagram showing polylactic acid-based resin microparticles produced in Comparative Example 5. ACHIEVEMENTS TO CARRY OUT THE INVENTION
[046] Hereinafter, the present invention will be explained in detail.
[047] The process for producing resin microparticles based on polylactic acid according to the present invention is characterized by having: a dissolution process to form a system, which can cause the phase separation in two phases of a solution phase mainly composed of resin based on polylactic acid (A) and a solution phase mainly composed of polymer (B) different from resin based on polylactic acid, by dissolving said resin based on polylactic acid (A) and said polymer ( B) different from resin based on polylactic acid in organic solvent based on ether (C); an emulsion forming process to form an emulsion by applying a shear force to said system; and a microparticle forming process to precipitate microparticles of resin based on polylactic acid by putting said emulsion in contact with a weak solvent that has lower solubility of said resin based on polylactic acid (A) compared to said organic solvent based of ether (C).
[048] The process for producing resin microparticles based on polylactic acid is characterized by the fact that the organic solvent used is an organic solvent based on ether (C). By using an ether-based organic solvent (C), it is possible to prevent microparticles of polylactic acid-based resin from melting when a weak polylactic acid-based resin solvent (A) is brought into contact. In the case of using an organic solvent other than an ether-based organic solvent (C), for example, an ester-based solvent, such as ethyl acetate and methyl acetate, an alkyl halide-based solvent such as such as chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene and 2,6-dichlorotoluene, a ketone-based solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl butyl ketone, an acetate-based solvent such as dimethyl acetal, diethyl acetal, dipropyl acetal and dioxolane, aprotic solvent, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethyl formamide, N, N -dimethyl acetamide, propylene carbonate, trimethyl phosphate, 1,3-dimethyl-2-imidazolidinone and sulfolane or a solvent based on carboxylic acid, such as formic acid, acetic acid, propionic acid, butyric acid and lactic acid, in With respect to good solubility of polylactic acid-based resin, the precipitation performance Polylactic acid-based resin is not sufficient and it is difficult to form particles. And in addition, when a weak polylactic acid-based resin solvent is brought into contact, the solvent remains inside precipitated polylactic acid-based resin microparticles, polylactic acid-based resin microparticles are prone to melt, and increases the possibility of a negative effect on particle shape and particle diameter distribution.
[049] Practically, the representative organic solvents based on ether (C) described above include linear aliphatic ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, dioctyl ether, diisopropyl ether, tert-butyl methyl ether, tert-butyl methyl ether, methyl butyl ether, ethyl butyl ether, 1-methoxy ethane (monoglyme), 1-ethoxy, diethylene glycol dimethyl ether (diglyme), ethylene glycol diethyl ether , 2-methoxy ethyl ether, di (ethylene glycol) diethyl ether, di (ethylene glycol) dibutyl ether and triethylene glycol dimethyl ether, cyclic aliphatic ethers such as tetrahydrofuran, 2-methyl tetrahydrofuran, tetrahydrofuran 2,5-dimethylyl hydrofuran, 2,2,5,5-tetramethylhydrofuran, 2,3-dihydro-furan, 2,5-dihydro-furan, tetrahydropyran, 3-methyl tetrahydropyran and 1,4-dioxane and aromatic ethers, such as anisole, phenetola (ethylphenol), diphenyl ether, 3-phenoxytoluene, p-tolyl ether o, 1,3-diphenoxybenzene and 1,2-diphenoxyethane. Particularly, from the point of view of industrial availability, dipropyl ether, diisopropyl ether, dibutyl ether, 1-ethoxyethane, diethylene glycol dimethyl ether (diglyme), ethylene glycol diethyl ether, 2-methoxyethyl ether, di diethyl ether (ethylene) glycol), tetrahydrofuran, 2-methylyl tetrahydrofuran, tetrahydropyran, 1,4-dioxane and anisole are preferred.
[050] Additionally, from the point of view of simplifying the process in which the ether-based organic solvent (C) is recycled by removing the weak polylactic acid-based resin solvent from the ether-based organic solvent (C) and polymer (B) other than polylactic acid-based resin separated in a solid-liquid separation process when producing the polylactic acid-based resin microparticles described above, it is preferred that the ether-based organic solvent described above has a boiling point of 100 degrees Celsius or higher. For such an ether-based organic solvent, for example, diethylene glycol, dimethyl ether (diglyme) and 1,4-dioxane can be used. Such an ether-based organic solvent can be used alone or in a mixture, however, from the point of view of simplifying the process to recycle the ether-based organic solvent, it is preferable to be alone.
[051] In addition, other organic solvents can be added to the ether-based organic solvent (C) as long as the effect according to the present invention is not impaired. If the amount of ether-based organic solvent is 100 parts by mass, the amount of other organic solvents added is generally less than 100 parts by mass, preferably 75 parts by mass or less, more preferably 50 parts by mass or less , even more preferably 30 parts by mass or less, particularly preferably 20 parts by mass or less and most preferably 10 parts by mass or less. Typical examples of other organic solvents include ester-based solvents such as ethyl acetate and methyl acetate, alkyl halide-based solvents such as chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1,1, 1-trichloroethane, chlorobenzene and 2,6-dichlorotoluene, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl butyl ketone, acetate-based solvent such as dimethyl acetal, diethyl acetal, dipropyl acetal and dioxolane , aprotic solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethyl formamide, N, N-dimethyl acetamide, propylene carbonate, trimethyl phosphate, 1,3-dimethyl-2-imidazolidinone and sulfolane and carboxylic acid-based solvents such as formic acid, acetic acid, propionic acid, butyric acid and lactic acid. These other organic solvents can be used alone or in a mixture.
[052] The polylactic acid (A) resin described above is a polymer in which the main components are L-lactic acid and D-lactic acid. "A polymer in which the main components are L-lactic acid and D-lactic acid" means that, in the monomer units that make up the copolymers in the resin based on polylactic acid (A), the total of the monomer units of acid L-lactic and D-lactic acid are 50 mol% or greater in molar ratio. The molar ratio of total L-lactic acid and D-lactic acid monomer units is preferably 50 mol% or more, more preferably 70 mol% or more, additionally more preferably 80 mol% or more, particularly preferably 90 mol% or more. The upper limit is generally 100 mol%.
[053] When "L" and "D" refer to the types of optical isomers; lactic acid that has a native type configuration is described as "L-lactic acid" or "L-lactic type", and lactic acid that has a non-native type configuration is described as "D-lactic acid" or “D-lactic acid type”.
[054] In the polylactic acid (A) resin described above, the arrangement of lactic acid monomer units is not particularly limited and can be any one of a block copolymer, an alternating copolymer, a random copolymer and a copolymer graft. From the point of view of decreasing a melting temperature, random copolymer is preferred.
[055] Another feature of the present invention is that a wide variety of polylactic acid (A) resin from crystalline to amorphous can be used to produce microparticles of resin based on polylactic acid and that it is possible to control the shape of microparticles of resin based on polylactic acid by the selection of resin based on crystalline or amorphous polylactic (A) acid.
[056] When polylactic acid-based resin (A) has high crystallization characteristics, it becomes possible to produce porous microparticles of polylactic acid-based resin. The crystallization characteristics of the resin based on polylactic acid (A) can be expressed in melting enthalpy. The upper melting enthalpy indicates the superior crystal characteristics and the lower melting enthalpy indicates that the polylactic acid-based resin is more amorphous.
[057] When the melting enthalpy of the polylactic acid-based resin (A) is 5 J / g or greater, the crystallization characteristics of the polylactic acid-based resin (A) become high and the resin microparticles based on of polylactic acid that have a porous surface can be obtained. When the crystallization characteristics of the polylactic acid-based resin (A) become superior, the polylactic acid-based resin microparticles in a more porous format can be obtained and the advantageous structure properties, such as oil absorption properties and hygroscopic property of resin microparticles based on polylactic acid, improve. Therefore, when producing polylactic acid-based resin microparticles that have a porous surface, the lower melting enthalpy limit is preferably 10 J / g or greater, more preferably 20 J / g or greater, and with maximum preferably 30 J / g or greater. In addition, the upper limit is preferably 100 J / g or less, although it is not particularly limited.
[058] On the other hand, in the chaos where the polylactic acid-based resin (A) is amorphous, it is possible to produce microparticles of polylactic acid-based resin that have a smooth surface. Although the tangible reason is not clear, in the case that the resin based on polylactic acid (A) precipitates in an amorphous state, presumably due to the inhibition of partial crystallization, the particles precipitate in a homogeneous state and the surface of these makes it smooth.
[059] When producing polylactic acid-based resin microparticles that have a smooth surface, the lower the melting enthalpy the resin based on polylactic acid (A), the more likely that precipitation will occur in a homogeneous state. Therefore, the upper limit of melting enthalpy is preferably less than 5 J / g, more preferably less than 3 J / g, additionally more preferably less than 2 J / g, and most preferably less than 1 J / g . In addition, the lower limit is 0 J / g, which means that the resin based on polylactic acid (A) is completely in an amorphous state.
[060] When melting enthalpy refers to a value calculated from a peak area, which shows melting thermocapacity at approximately 160 degrees Celsius, in a differential scanning calorimetry (DSC) where a temperature is raised to 200 degrees Celsius with the temperature rise of 20 degrees Celsius per minute.
[061] As with a fusion enthalpy regulation method, it is possible to use known methods, such as a method to control the copolymerization ratio (L / D) between the L-lactic acid and the D-lactic acid that make up the polylactic acid-based resin (A), a method for adding an additive agent to promote crystallization for polylactic acid-based resin (A) and a method for forming a stereo block structure. Above all, due to its ease of controlling the melting enthalpy of the resin based on polylactic acid (A), the method of controlling the L / D copolymerization ratio is preferred. When the L / D ratio is 95/5 or greater, the melting enthalpy becomes 5 J / g or greater and the resin based on polylactic acid becomes crystalline. It is preferred that the copolymerization ratio of L-lactic acid is high due to the fact that the higher ratio facilitates crystallization. L / D is most preferably 97/3 or greater, and most preferably 98/2 or greater. The upper limit of L / D is less than 100/0. Additionally, when the L / D is less than 95/5, the melting enthalpy becomes less than 5 J / g and the resin based on polylactic acid becomes amorphous. It is preferred that the copolymerization ratio of L-lactic acid is low due to the fact that the lower ratio facilitates it to be amorphous. The ratio is more preferably less than 92/8 and most preferably less than 89/11. In addition, the lower limit of L / D is 50/50 or greater. Because both optical isomers such as L and D are materials in which the molecular structures are mirror images of each other and the physical properties are no different, the fusion enthalpy remains unchanged when the L / D described above is replaced by D / l and therefore the present invention also includes the extension where L / D is replaced by D / L.
[062] Additionally, the resin based on polylactic acid (A) can contain copolymerization ingredients in addition to lactic acid as long as the effect according to the present invention is not impaired. The other copolymerization ingredient units can be, for example, a multivalent carboxylic acid, a polyhydric alcohol, a hydroxycarboxylic acid or a lactone and, specifically, can be multivalent carboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebázic acid, dodecanedioic acid, fumaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, 5-sulfoisophthalic acid and phosphonium 5-tetrabutyl sulfoisophthalic acid; polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentylglycol, glycerin, pentaerythritol, bisphenol, a polyhydric alcohol produced by an aromatic polyhydric reaction adding ethylene oxide to a bisphenol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol; hydroxycarboxylic acids such as glycolic acid, 3-hydroxy butyric acid, 4-hydroxy butyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid and hydroxybenzoic acid; or lactones such as glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β-butyrolactone, Y — butyrolactone, pivalolactone and δ-valerolactone. The volume content of the other copolymerization units is preferably 30 mol% or less, more preferably 20 mol% or less, additionally more preferably 10 mol% or less, most preferably 5 mol% or less, in relation to the total units of resin monomer based on polylactic acid (A) as 100 mol%.
[063] Although the molecular weight and molecular weight distribution of the polylactic acid (A) resin are not particularly limited as long as they can be dissolved in the ether-based organic solvent (C) substantially, from the point of view of ease of maintenance of the particle structure and improvement of resistance to hydrolysis, the lower limit of the weighted average molecular weight of the resin based on polylactic acid (A) is preferably 10,000 or greater, more preferably 50,000 or greater, additionally with more preferably 100,000 or greater, with maximum preference 200,000 or greater. In addition, although not limited in particular, the weighted average upper molecular weight limit is preferably 1,000,000 or less. The weighted average molecular weight mentioned in this document is the weighted average molecular weight in terms of polymethyl methacrylate (PMMA), measured in gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.
[064] For the production of polylactic acid (A) -based resin, this is not particularly limited and known methods can be used, such as direct polymerization of polylactic acid and polymerization with ring opening via a lactide.
[065] The polymer described above (B) other than resin based on polylactic acid may include a thermoplastic resin and a thermo-adjustable resin, however, in view of better solubility in the organic solvent based on ether (C), thermoplastic resin is preferred .
[066] More specifically, the polymer (B) other than a polylactic acid-based resin can include one or more of the following: a synthetic resin such as poly (vinyl alcohol) (can be a type of complete saponification or a type of saponification partial poly (vinyl alcohol)), poly (vinyl alcohol-ethylene) copolymer (can be a type of complete saponification or a partial saponification type of poly (vinyl alcohol-ethylene) copolymer), polyvinylpyrrolidone, poly (ethylene glycol) , poly (ethylene oxide), sucrose fatty acid ester, poly (oxyethylene fatty acid ester), poly (oxyethylene lauric acid ester), poly (oxyethylene glycol mono fatty acid ester), poly (oxyethylene alkyl) phenyl ether), poly (oxyalkyl ether), polyacrylic acid, sodium polyacrylate, poly (methacrylic acid), sodium polymethacrylate, polystyrene sulfonic acid, sodium polystyrene sulfonate, poly (vinyl pyrrolidinium chloride), poly (styrene maleic acid) copolymer ), aminopoly (acrylic to poly), poly-p-vinylphenol, polyarylamine, polyvinyl ether, polyvinyl formal, poly (acrylic amide), poly (methacrylamide), poly (oxyethyleneamine), poly (vinyl pyrrolidone), poly (vinyl pyridine), polyaminesulfone and polyethyleneimine, disaccharides such as maltose, cellobiose, lactose and sucrose; cellulose derivatives such as cellulose, chitosan, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylethylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose and cellulose ester; polysaccharides and their derivatives such as amylose and its derivatives, starch and its derivatives, dextrin, cyclodextrin, sodium alginate and its derivatives; gelatin, casein, collagen, albumin, fibrin, keratin, fibrin, carrageenan, chondroitin sulfate, gum arabic, agar and protein; and from the point of view of narrowing the particle diameter distribution, it preferably includes one or more of the following: poly (vinyl alcohol) (may be a type of complete saponification or a type of partial saponification of poly (vinyl alcohol)), poly (alcohol-ethylene vinyl) (can be a type of complete saponification or a type of partial saponification of poly (alcohol-ethylene vinyl)), poly (ethylene glycol), poly (ethylene oxide), sucrose fatty acid ester, poly (oxyethylene alkyl phenyl ether), poly (oxyethylene alkyl phenyl ether), polyacrylic acid, poly (methacrylic acid), carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methyl cellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose. such as cellulose ester and polyvinylpyrrolidone; most preferably includes one or more of the following: poly (vinyl alcohol) (may be a type of complete saponification or a type of partial saponification of poly (vinyl alcohol)), poly (alcohol-ethylene vinyl) (may be a type of complete saponification or a type of partial saponification of poly (vinyl alcohol-ethylene), poly (ethylene glycol), poly (ethylene oxide), carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methyl cellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose, carboxymethylcellulose carboxymethylcellulose, cellulose derivatives such as cellulose ester and polyvinylpyrrolidone; particularly preferably it includes one or more of the following: poly (vinyl alcohol) (may be a type of complete saponification or a type of partial saponification of poly (vinyl alcohol)), poly (ethylene glycol), poly (ethylene oxide) and hydroxypropylcellulose.
[067] The molecular weight of the polymer (B) other than resin based on polylactic acid is preferably in the range of 1,000 to 100,000,000, more preferably in the range of 1,000 to 10,000,000, additionally more preferably in a range of 5,000 to 1,000,000, particularly preferably in the range of 10,000 to 500,000, most preferably in the range of 10,000 to 100,000, in terms of weighted average molecular mass.
[068] The weighted average molecular weight mentioned in this document denotes a weighted average molecular weight measured in terms of polyethylene glycol by gel permeation chromatography (GPC) using water as a solvent. In the event that water cannot be used for measurement, dimethylformamide is used as a solvent and if the measurement cannot be performed, tetrahydrofuran will be used. And in the event that measurement is still impossible, hexafluoroisopropanol will be used.
[069] The “a system that can cause phase separation in two phases of a solution phase mainly composed of resin based on polylactic acid (A) and a solution phase mainly composed of polymer (B) other than resin based polylactic acid, by dissolving said resin based on polylactic acid (A) and said polymer (B) other than resin based on polylactic acid in an organic solvent based on ether (C) ”described above denotes a system comprising a solution in which the resin based on polylactic acid (A) and the polymer (B) other than resin based on polylactic acid are dissolved in the organic solvent based on ether (C) and are capable of phase separation in two phases a solution phase mainly composed of the resin based on polylactic acid (A) and a solution phase mainly composed of the polymer (B) other than resin based on polylactic acid.
[070] By using such a system with phase separation capability, it is possible to emulsify the system by mixing it under the condition of phase separation and consequently to form an emulsion.
[071] In the above description, whether the polymers can be dissolved or not determined by dissolving the polylactic acid-based resin (A) and the polymer (B) other than polylactic acid-based resin in the ether-based organic solvent (C) and checking whether the polymers can be dissolved in the ether-based organic solvent (C) by 1% by weight or greater, at a temperature at which the phase separation is caused.
[072] In this emulsion, the resin solution phase based on polylactic acid (A) becomes a dispersed phase and the polymer solution phase B becomes a continuous phase. Additionally, by placing a weak resin solvent based on polylactic acid (A) in contact with the emulsion, the microparticles of resin based on polylactic acid are precipitated from the phase of resin solution based on polylactic acid (A) in the emulsion and consequently, polymeric microparticles consisting of resin based on polylactic acid (A) can be obtained.
[073] The weak resin solvent based on polylactic acid (A) refers to a solvent that has a lower solubility of resin based on polylactic acid (A) compared to the organic solvent based on ether described above (C) and that it is difficult to dissolve the resin based on polylactic acid (A), and more specifically, it refers to a solvent in which the solubility of resin based on polylactic acid (A) is 1% by weight or less. The upper limit of the solubility of polylactic acid-based resin (A) in the weak solvent is more preferably 0.5% by weight or less, additionally more preferably 0.1% by weight or less.
[074] In the production process described above, the weak polylactic acid-based resin solvent (A) used is preferably a weak polylactic acid-based resin solvent (A) that can dissolve the polymer (B) other than polylactic acid based resin. By using this, it becomes possible to effectively precipitate polylactic acid-based resin microparticles consisting of polylactic acid (A) resin. In addition, the weak polylactic acid-based resin solvent (A) is preferably a solvent that can be mixed homogeneously with a solvent capable of dissolving both the polylactic acid-based resin (A) and the polymer (B) other than polylactic acid based resin.
[075] In relation to the weak solvent described above, an ideally suitable one can be selected as appropriate according to the type of resin based on polylactic acid (A), preferably with the type of resin based on polylactic acid (A) and the type of polymer (B) other than resin based on polylactic acid. More specifically, this may include one or more solvents selected from the group consisting of the following: an aliphatic hydrocarbon based solvent, such as pentane, hexane, heptane, octane, nonane, n-decane, n-dodecane, n-tridecane, cyclohexane and cyclopentane; an aromatic hydrocarbon-based solvent, such as benzene, toluene and xylene; an alcohol-based solvent, such as methanol, ethanol, 1-propanol and 2-propanol; and water. From the point of view of efficient precipitation of resin based on polylactic acid (A), the weak solvent of resin based on polylactic acid is preferably a solvent based on aliphatic hydrocarbon, a solvent based on aromatic hydrocarbon, a solvent at alcohol or water based, more preferably an alcohol or water based solvent, most preferably water.
[076] By selecting the polylactic acid-based resin (A) described above, the polymer (B) other than polylactic acid-based resin, the ether-based organic solvent (C) capable of dissolving and using these in combination , it becomes possible to precipitate the resin based on polylactic acid effectively and consequently obtain the polymeric microparticles.
[077] It is necessary that a liquid in which the resin based on polylactic acid (A), the polymer (B) other than resin based on polylactic acid and organic solvent based on ether (C) capable of dissolving these are dissolved and mixed can cause the phase separation in two phases of a solution phase mainly composed of the resin based on polylactic acid (A) and a solution phase mainly composed of the polymer (B) other than resin based on polylactic acid. The two organic solvents based on ether (C), one solvent is in the solution phase mainly composed of resin based on polylactic acid (A) and the other solvent is in the solution phase mainly composed of polymer (B) other than resin based on polylactic acid, they can be identical or they can be different from each other. However, it is preferred that these solvents are substantially identical.
[078] The condition for causing the two-phase separation varies according to the types of polylactic acid-based resin (A) and polymer (B) other than polylactic acid-based resin, the molecular masses of polylactic acid-based resin polylactic acid (A) and polymer (B) other than resin based on polylactic acid, the type of organic solvent based on ether (C), the concentrations of resin based on polylactic acid (A) and different polymer (B) of resin based on polylactic acid and the temperature and pressure to carry out the invention.
[079] In order to satisfy the conditions under which phase separation is prone to occur, it is preferable that there is a significant difference in solubility parameter (hereinafter also referred to as the SP value) between the resin at polylactic acid based (A) and polymer (B) other than polylactic acid based resin.
[080] Preferably, the lower limit of the difference between the SPs value is 1 (J / cm3) 1/2 or greater, more preferably 2 (J / cm3) 1/2 or greater, even more preferably 3 (J / cm3) 1/2 or greater, particularly preferably 5 (J / cm3) 1/2 or greater, and most preferably 8 (J / cm3) 1/2 or greater. When SP values are in this range, phase separation tends to occur easily and the tendency to phase separation makes it possible to produce polylactic acid-based resin microparticles that contain more polylactic acid-based resin ingredients. The upper limit of the difference in SP values is preferably 20 (J / cm3) 1/2 or less, more preferably 15 (J / cm3) 1/2 or less, additionally more preferably 10 (J / cm3) 1 / 2 or less, however, is not particularly limited to this since both polylactic acid-based resin (A) and polymer (B) other than polylactic acid-based resin can be dissolved in an ether-based organic solvent ( Ç). Where, the SP value mentioned in this document is calculated according to the Fedor estimation method (hereinafter, in this document, it can also be called Computational Method) which is a calculation method based on coagulation energy density and molar molecular mass (Hideki YAMAMOTO, “THE BASIS, APPLICATION AND CALCULATION METHOD OF SP VALUE”, Johokiko co., Ltd., Published March 31, 1999). In addition, in the event that the calculation method described above cannot be used, the solubility parameter that is determined by experiment based on whether it can be dissolved in a known solvent or not (hereinafter, may also be called Experimental method) is used as a substitute for the SP value (J. Brand, “POLYMER HANDBOOK FOURTH EDITION”, Wiley, published in 1998).
[081] In order to determine the appropriate conditions under which the phase separation occurs, it is possible to use a three-component phase diagram that can be prepared by a simple preliminary test of changes in the state of observation by varying the ratio between the three components, namely, the resin based on polylactic acid (A), the polymer (B) other than resin based on polylactic acid and the organic solvent based on ether (C) in which they are dissolved.
[082] The phase diagram is prepared by assessing whether an interface is formed between the phases or not when the polylactic acid-based resin (A), the polymer (B) other than polylactic acid-based resin and the organic solvent ether-based (C) are mixed at an arbitrary rate, dissolved and left for a certain period of time. To prepare the diagram, assessments are carried out under at least three different conditions, preferably at least five different conditions, more preferably at least ten different conditions. By distinguishing between a two-phase separation region and a single-phase region according to the phase diagram that can be prepared as described above, it becomes possible to determine the conditions under which the phase separation occurs.
[083] In order to determine whether phase separation occurs or not, after volumes of resin based on polylactic acid (A), polymer (B) other than resin based on polylactic acid and organic solvent based on ether (C) are changed to an arbitrary ratio, the polylactic acid-based resin (A) and the polymer (B) other than polylactic acid-based resin are dissolved in an ether-based organic solvent (C) completely and are sufficiently stirred under certain conditions of temperature and pressure where the dissolution process will be carried out. Then, after maintaining them for three days, it is macroscopically examined whether phase separation occurs or not. However, in the event that the emulsion becomes considerably stable, phase separation does not occur even after maintaining them for three days. In such cases, the presence or absence of the phase separation is determined based on whether the phase separation can be observed microscopically or not using an optical microscope, a phase contrast microscope, etc.
[084] Phase separation occurs as a result of phase separation of polylactic acid solution mainly composed of resin based on polylactic acid (A) and polymer solution phase B mainly composed of polymer (B) other than resin based on polylactic acid in an organic solvent based on ether (C). Where, the polylactic acid-based resin solution phase (A) is a phase in which polylactic acid-based resin (A) is mainly distributed and the polymer solution phase B is a phase in which the polymer (B ) other than polylactic acid-based resin is mainly distributed. In this case, it is assumed that the polylactic acid-based resin solution phase (A) and polymer B-solution phase have a volume ratio that varies with the types and amounts of polylactic acid-based resin ( A) and polymer (B) other than resin based on polylactic acid.
[085] As an industrially plausible concentration where phase separation occurs, both concentrations of polylactic acid-based resin (A) and polymer concentrations (B) other than polylactic acid-based resin in organic solvent-based ether are not particularly limited as long as the concentrations are within a range that is dissolved in an ether-based organic solvent. From the point of view of provoking phase separation and industrially plausible concentration, the lower limit of each concentration is preferably greater than 1% by mass, more preferably 2% by mass, additionally more preferably 3% by mass , additionally more preferably 5% by weight, in relation to the total amount of mass. In addition, the upper limit of each concentration is preferably 50% by weight, more preferably 30% by weight, additionally more preferably 20% by weight.
[086] It is assumed that, in relation to the two phases described above of the resin solution phase based on polylactic acid (A) and the polymer solution phase B, the interface tension between the two phases becomes small due to the fact that both phases are organic solvents and, as a result, the emulsion generated is stabilized and the particle diameter distribution becomes narrow.
[087] The interfacial tension between the two phases described above is too small to measure directly with the commonly used drop drop method in which a solution is added to another type of solution to perform measurements. The interfacial tension, however, can be estimated from the surface tension of each phase exposed to the air. Thus, considering that r1 and r2 represent the surface tension of each phase exposed to air, the interfacial tension r12 is estimated to be the absolute value of the difference between them as follows: r12 = | r1-r2 | (the absolute value of r1-r2).
[088] With respect to the preferred range of r12, the upper limit is preferably 10 mN / m, more preferably 5 mN / m, in addition more preferably 3 mN / m, and particularly preferably 2 mN / m. In addition, the lower limit is greater than 0 mN / m.
[089] The viscosity ratio between the two phases influences the average particle diameter and the particle diameter distribution, and the particle diameter distribution tends to decrease with a decreasing viscosity ratio.
[090] Regarding the preferred range of the viscosity ratio between the two phases described above, the lower limit is preferably 0.1 or greater, more preferably 0.2 or greater, additionally more preferably 0.3 or greater, particularly preferably 0.5 or greater, notably preferably 0.8 or greater. In addition, the upper limit is preferably 10 or less, more preferably 5 or less, additionally more preferably 3 or less, particularly preferably 1.5 or less, notably preferably 1.2 or less. Where, the viscosity ratio between the two phases mentioned in this document is defined as “a viscosity of the solution phase of resin based on polylactic acid (A) / a viscosity of the solution phase of polymer (B) other than resin at polylactic acid base ”at a temperature at which the dissolution process will be carried out.
[091] By using the system that can cause phase separation, polymeric microparticles are produced, then a separate liquid phase is mixed to be emulsified.
[092] In order to form the microparticles, the emulsion formation process and the microparticle formation process can be performed in a common reaction vessel. Regarding a temperature to carry out the emulsion formation process and the microparticle formation process, from the point of view of industrial practicability, the lower limit is generally 0 degrees Celsius or higher, preferably 10 degrees Celsius or higher, with more preferably 20 degrees Celsius or higher. In addition, the upper limit is preferably 300 degrees Celsius or less, more preferably 200 degrees Celsius or less, additionally more preferably 160 degrees Celsius or less, particularly preferably 140 degrees Celsius or less, notably preferably 100 degrees Celsius or less , although it is not particularly limited as long as the temperature is in a range where polylactic acid-based resin (A) and polymer (B) other than polylactic acid-based resin can be dissolved to cause phase separation so that the desired microparticles can be produced.
[093] From the point of view of industrial feasibility, through the execution of the emulsion formation process, the pressure is in a range of the standard pressure at 10 atm.
[094] The lower pressure limit is preferably 1 atm. The upper pressure limit is preferably 5 atm, more preferably 3 atm, more preferably 2 atm.
[095] Additionally, it is preferable to use an inert gas in the reaction vessel. The inert gas includes, more specifically, nitrogen, helium, argon and carbon dioxide and preferably includes nitrogen and argon.
[096] The emulsion is formed by mixing the phase separation system described above under such conditions. In other words, the emulsion is formed by applying a shear force to a solution which is the phase separation system obtained from the dissolution process described above.
[097] In a process to form an emulsion, an emulsion is formed in such a way that the resin solution phase based on polylactic acid (A) forms droplets similar to the particle. Generally, in a phase separation, such an emulsion tends to be formed when the volume of the polymer solution phase (B) other than the polylactic acid-based resin is greater than the volume of the polylactic acid-based resin solution phase (THE). In particular, the volume ratio of the polylactic acid-based resin solution phase (A) is preferably less than 0.5, more preferably in the range of 0.4 to 0.1, relative to the total volume two-phase like 1.
[098] It is possible to define an appropriate range of the volume ratio by measuring the volume ratio and the concentration of each component simultaneously when preparing the phase diagram described above.
[099] The microparticles produced by the present production process have a narrow particle diameter distribution due to the fact that a remarkably homogeneous emulsion is produced at an emulsion formation stage. This trend becomes obvious when using a single solvent that can dissolve both polylactic acid-based resin (A) and polymer (B) other than polylactic acid-based resin. Thus, in order to obtain a sufficient shear force to form the emulsion in the present production process, it is possible to use generally known methods, such as liquid phase stirring method using blades and agitation, stirring method with a continuous mixer biaxial, mixing method with a homogenizer and ultrasonic irradiation method.
[0100] Particularly, in the case where agitation blades are used, the agitation speed is preferably 50 rpm at 1,200 rpm, more preferably 100 rpm at 1,000 rpm, additionally more preferably 200 rpm at 800 rpm, particularly preferably 300 rpm to 600 rpm, although the speed is also affected by the shape of the stirring blades.
[0101] The stirring blades can have such shapes as a propeller, paddle, flat paddle, turbine, double cone, single cone, single ribbon, double ribbon, thread and helical ribbon, although they are not particularly limited to this as long as a force enough shear can be applied to the system. In addition, in order to perform the stirring effectively, flow regulators and the like can be provided in the reaction vessel.
[0102] Additionally, in order to produce the emulsion, it is possible to use not only a stirrer, but also a generally known device such as an emulsifier and a disperser. Specific examples include batch-type emulsifiers such as Homogenizer (supplied by IKA), Politron (supplied by Kinematica, Inc.), TK Autohomomixer (supplied by Tokushu Kika Kogyo Co., Ltd.), and others such as Ebara Milder (supplied Ebara Corporation), TK Filmeics, TK Pipeline Homomixer (supplied by Tokushu Kika Kogyo Co., Ltd.), Colloid Mill (supplied by Shinko-Pantec Co., Ltd.), and Slusher, Trigonal Wet Grinder (Mitsui Miike Kakoki Co ., Ltd.), as well as ultrasonic homogenizers and static mixers.
[0103] The emulsion thus obtained is subsequently supplied to the microparticle formation process to precipitate the microparticles.
[0104] In order to obtain the polylactic acid-based resin microparticles (A), a weak polylactic acid-based resin solvent (A) is brought into contact with the emulsion produced by the process described above and the microparticles which have a diameter corresponding to the diameter of the emulsion are produced as a result.
[0105] Although the method for bringing the weak solvent into contact with the emulsion may be a method for putting the emulsion in the weak solvent or a method for putting the weak solvent in emulsion, the method for putting the weak solvent in the emulsion is preferred. For the method of bringing the weak solvent into contact, although both the method of putting the emulsion in the weak solvent and the method of putting the weak solvent in the emulsion are available, the method of putting the weak solvent in the emulsion is preferred.
[0106] For the method for placing the weak solvent, this is not particularly limited as long as the desired polymeric microparticles can be produced, and any methods such as continuous drip, split drip and batch addition can be used. However, in order to prevent the emulsion from coagulating, melting and coalescing, which can cause the expansion of particle diameter distribution or the generation of bulky grains greater than 1,000 μm while adding the weak solvent, continuous dripping and dripping divided are preferred. In addition, from the point of view of industrially efficient operation, continuous drip is most preferably used.
[0107] For the temperature of putting the weak solvent in contact, this is not particularly limited as long as microparticle waves based on polylactic acid can be precipitated. Their lower limit is 0 degrees Celsius or higher, and the upper limit is 300 degrees Celsius or lower. The lower temperature limit is preferably 10 degrees Celsius or higher, more preferably 20 degrees Celsius or higher, due to the fact that the weak solvent solidifies and therefore cannot be used if the temperature is too low. In addition, the upper temperature limit is preferably 200 degrees Celsius or less, more preferably 100 degrees Celsius or less, additionally more preferably 90 degrees Celsius or less, due to the fact that the resin based on polylactic acid (A) and polymer (B) other than polylactic acid-based resin are prone to become spoiled by heat if the temperature is too high.
[0108] When a crystalline polylactic acid (A) resin that has a melting enthalpy of 5 J / g or greater is used in the production process described above, polylactic acid-based resin microparticles that have porous shapes are produced under normal conditions. However, it is also possible to produce microparticles of resin based on polylactic acid that have a smooth surface by controlling the contact temperature of the weak solvent to a temperature higher than the crystallization temperature of the resin based on polylactic acid (A). Although the tangible reason is not clear, it can be considered that the temperature control of the resin based on crystalline polylactic acid (A) to a higher temperature of the crystallization temperature changes the resin to a molten amorphous state and consequently smooths the surface of the resin.
[0109] When the crystallization temperature of a polylactic acid-based resin (A) refers to a recrystallization temperature in a process for cooling a molten polylactic acid-based resin. As for the method of measuring crystallization temperature, an upper peak temperature showing endothermic thermocapacity is measured as decreasing the temperature at a rate of 1 degree Celsius per minute after raising the temperature to 200 degrees Celsius at a rate of 20 degrees Celsius per minute in a differential scanning calorimetry (DSC). Additionally, in the event that the peak does not appear while lowering the temperature, it is possible to measure this as an upper peak temperature that shows endothermic thermocapacity as the temperature rise of up to 200 degrees Celsius at a rate of 0.5 degrees Celsius per minute.
[0110] When using a crystalline polylactic acid (A) resin that has a melting enthalpy of 5 J / g or greater, the weak solvent contact temperature to produce polylactic acid-based resin microparticles that have surfaces smooth is preferably higher than the crystallization temperature defined above. Due to the fact that polylactic acid-based resin microparticles tend to turn into an amorphous state and tend to have smooth surfaces when the temperature is higher than the crystallization temperature, the lower temperature limit is preferably 10 degrees higher than the crystallization temperature, more preferably 20 degrees higher than the crystallization temperature, additionally more preferably 30 degrees higher than the crystallization temperature. In addition, the upper temperature limit is preferably 100 degrees higher than the crystallization temperature, although it is not particularly limited to that.
[0111] Additionally, a time to add the weak solvent is preferably within a range of 10 minutes to 50 hours, more preferably within a range of 15 minutes to 10 hours, additionally more preferably within a range of 30 minutes to 5 hours hours. If the time for addition is shorter than these ranges, there is a fear that an increase in particle diameter distribution or formation of bulky grains may occur due to coagulation, melting and coalescence of the emulsion. Additionally, from the point of view of industrial feasibility, it is impracticable to spend time longer than these ranges. By performing the addition within such a range, it becomes possible to prevent the particles from coagulating while transforming the emulsion into polymer particles, and it becomes possible to produce polymer particles that have narrow particle diameter distribution as a result.
[0112] The amount of the weak solvent for addition depends on an emulsion state and is preferably 0.1 to 10 part by mass, more preferably 0.1 to 5 part by mass, more preferably 0.2 to 3 part by mass, particularly preferably 0.2 to 2 part by mass, most preferably 0.2 to 1.0 part by mass, in relation to the total mass of the emulsion as 1 part by mass.
[0113] The contact time between the weak solvent and the emulsion is not limited as long as it is sufficient to precipitate the microparticles. Although, in order to cause sufficient precipitation and achieve high productivity, the contact time is preferably from 5 minutes to 50 hours, more preferably from 5 minutes to 10 hours, additionally more preferably from 10 minutes to 5 hours, particularly preferably from 20 minutes to 4 hours, most preferably from 30 minutes to 3 hours, after the addition of the weak solvent.
[0114] By separating the dispersed liquid in polymeric microparticle thus produced into solids and liquids by a known method such as filtration, vacuum filtration, pressure filtration, centrifugation, centrifugal filtration and spray drying, microparticle powders can be obtained . The polymeric microparticles, obtained by separating them into solids and liquids, are purified by removing impurities adhered to or contained by washing with a solvent, etc., as needed.
[0115] In the production process described above, the ether-based organic solvent (C) and the polymer (B) other than polylactic acid-based resin, which are separated by the solid-liquid separation process in the production of powders microparticle, can be recycled and used again.
[0116] A solvent obtained by solid-liquid separation is a mixture of polymer (B) other than resin based on polylactic acid, the organic solvent based on ether (C) and the weak solvent. That solvent can be used as a solvent to form an emulsion again by removing the weak solvent therefrom. As a method for removing the weak solvent, known methods can be used, such as simple distillation, reduced pressure distillation, precision distillation, thin film distillation, membrane extraction and separation and simple distillation, reduced pressure distillation or Precision distillation is preferably used.
[0117] When distillation such as simple distillation and low pressure distillation is carried out, as in the case of polymeric microparticles production, there is a possibility that the system will be heated and that the thermal decomposition of polymer (B) other than resin based on polylactic acid and the organic solvent based on ether (C) is promoted as a result. Therefore, the operation is preferably carried out in an oxygen-free atmosphere as much as possible, most preferably in an inert atmosphere. Specifically, this is preferably performed in an atmosphere of nitrogen, helium, argon or carbon dioxide. In addition, antioxidants such as phenol-based compounds etc. can be added to that.
[0118] When performing the recycling described above, it is preferable that the weak solvent is removed as much as possible. Specifically, the remaining amount of the weak solvent is generally 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less, particularly preferably 1% by weight or less, relative to the total amount of recycled, namely, the ether-based organic solvent (C) and the polymer (B) other than polylactic acid-based resin. If the remaining amount of the weak solvent exceeds such a range, there is a fear that the particle diameter distribution of the microparticles will expand and the particles will coagulate.
[0119] The volume of the weak solvent in a solvent used in recycling can be measured by known methods, such as gas chromatography and the Karl Fischer method.
[0120] In the operation of removing the weak solvent, due to the fact that there may be a loss of the organic solvent based on ether (C) or polymer (B) other than resin based on polylactic acid, it is preferable that the composition ratio is adjusted to the initial ratio as appropriate.
[0121] In the following, the polylactic acid-based resin microparticles of the present invention will be explained in detail.
[0122] The characteristics of the porous microparticles of resin based on polylactic acid in the present invention are that the average number of particle diameter is small, the surface is in a porous format, it is possible to improve the lipophilic functionality and the hydrophilic functionality due to the the fact that a considerable amount of oil or water can be formed in the pores and due to the fact that the particle diameter is small, it is possible to check the smoothness that cannot be achieved by traditional porous microparticles. Such porous microparticles of resin based on polylactic acid are suitably used in fields such as cosmetics, high performance is required both in oil absorption and smoothness.
[0123] With reference to the average particle diameter number of the porous microparticles of resin based on polylactic acid, it is possible to determine an appropriate range of the average number of particle diameter. For example, in uses such as cosmetics, due to the fact that the average number of smaller particle diameter improves smoothness, the upper limit of the average number of particle diameter is generally 30 μm or less. Additionally, in uses such as cosmetics, due to the fact that particle coagulation tends to occur when the average number of particle diameter is very small, the lower limit of the average number of particle diameter is generally 1 μm or greater, from preferably greater than 1 μm, more preferably 2 μm or greater, most preferably 3 μm or greater.
[0124] In reference to the particle diameter distribution index that shows the particle diameter distribution of the polylactic acid-based resin microparticles that have porous shapes, this is preferably 2 or less due to the fact that it becomes possible in uses such as cosmetics to improve particle flow and give a softer touch. The upper limit of the particle diameter distribution index is preferably 1.5 or less, more preferably 1.3 or less, most preferably 1.2 or less. Additionally, the lower limit is 1 in theory.
[0125] The average number of particle diameter described above of polylactic acid-based resin microparticles that have porous shapes can be calculated by measuring the diameters of 100 random particles in a scanning electron microscope image and averaging computation. arithmetic. If a particle shape in the SEM image is not a perfect circle, for example, an ellipse, the maximum particle diameter is used as its diameter. In order to measure the particle diameter precisely, the measurement is carried out with a magnification of at least 1,000 times or greater, preferably with an enlargement of 5,000 times or greater.
[0126] Additionally, the particle diameter distribution index is calculated based on the conversion equations described below, using measurements of the particle diameters obtained by the measurement described above.

[0127] Where, Ri: single particle diameter, n: the number of measurements (= 100), Dn: average particle diameter, Dv: average particle volume diameter, PDI: particle diameter distribution index .
[0128] Although the actual amount of pores in a porous polylactic acid-based resin microparticle in the present invention is difficult to measure directly, it is possible to use the flaxseed oil absorption capacity as an indirect index, which is defined in methods pigment test methods such as Japan Industrial Standards (Refined Linseed Oil Method, JIS K 5101).
[0129] In particular, in uses such as cosmetics and paints, the upper flaxseed oil capacity is preferred and the lower flaxseed oil capacity limit is preferably 90 ml / 100g or greater, more preferably 100 ml / 100g or greater, additionally more preferably 120 ml / 100g or greater, particularly preferably 150 ml / 100g or greater, notably preferably 200 ml / 100g or greater, most preferably 300 ml / 100g or greater. The upper limit of flaxseed oil absorption capacity is preferably 1,000 ml / 100g or less.
[0130] Additionally, it is preferred that the porous microparticles of polylactic acid-based resin described above have melting enthalpy of 5 J / g or greater. Superior melting enthalpy tends to superior crystallization, and as a result, heat resistance and durability tend to become high. The lower limit of melting enthalpy is preferably 10 J / g or greater, more preferably 20 J / g or greater, additionally more preferably 30 J / g or greater. In addition, the upper limit is preferably 100 J / g or less. Where, the melting enthalpy can be calculated from a peak area that shows the thermal melting capacity at approximately 160 degrees Celsius in Differential Scanning Calorimetry (DSC) where a temperature is raised to 200 degrees Celsius with an elevation of temperature of 20 degrees Celsius per minute.
[0131] The sphericity of the porous polylactic acid-based resin microparticles described above is preferably 80 or greater, more preferably 85 or greater, additionally more preferably 90 or greater, particularly preferably 92 or greater, most preferably 95 or greater. In addition, in theory, the upper limit is 100. When the sphericity is within the range described above, it is possible to achieve an improvement in quality such as sliding capacity. Where, sphericity is calculated by observing the particles through a scanning electron microscope, measuring both the longest and the shortest diameters of 30 random particles and subsequently replacing the measurements in the equation described below.

[0132] Where, S: sphericity, n: the number of measurements (= 30), DS: the shortest single particle diameter, DL: the longest single particle diameter.
[0133] On the other hand, the characteristics of polylactic acid-based resin microparticles that have smooth surfaces are that the surfaces are smooth, the particles are highly spherical in shape and the particle diameter distribution is narrow. By using such microparticles of resin based on polylactic acid as powders, it becomes possible to improve fluidity, achieve improvements in quality such as smoothness and increase the ease of viscosity control in case they are added to paints etc. In addition, due to the fact that such polylactic acid-based resin microparticles that have smooth surfaces can move on a surface of a base member smoothly and can be fused in place on the base member homogeneously due to the narrow particle diameter distribution , these particles are particularly suitable for use in fields such as toners where excellent fluidity and low temperature fusing characteristics are required.
[0134] Preferably, the sphericity of polylactic acid-based resin microparticles that have smooth surfaces is 90 or greater. From the point of view of improving mobility in use as toners, the lower limit of sphericity is preferably 92 or greater, with maximum preference 95 or greater. Additionally, the upper limit is 100 in theory. Where, sphericity is calculated by observing the particles with a scanning electron microscope, by measuring both the longest and the shortest diameters of 30 random particles and by subsequently replacing the measurements in the equation described below.

[0135] Where, S stands for Sphericity, n stands for the number of measurements (= 30), DS stands for the shortest single particle diameter and DL stands for the longest single particle diameter.
[0136] With reference to the average particle diameter of polylactic acid-based resin microparticles that have smooth surfaces, a range of average particle diameter can be determined appropriately according to the uses. The upper limit of mean particle diameter is generally 100 μm or less, preferably 50 μm or less, more preferably 30 μm or less. Additionally, in uses such as toner, due to the fact that particle coagulation tends to occur when the average particle diameter is very small, the lower limit of average particle diameter is generally 1 μm or greater, preferably greater than 1 μm, more preferably 2 μm or greater, most preferably 3 μm or greater.
[0137] The particle diameter distribution index showing the particle diameter distribution of polylactic acid-based resin microparticles having smooth surfaces is preferably 2 or less. Due to the fact that the smaller particle diameter distribution index makes it possible for toners to be melted onto a substrate more homogeneously, the upper limit of particle diameter distribution index is preferably 1.8 or less, more preferably 1 , 5 or less, additionally more preferably 1.3 or less, most preferably 1.2 or less. In addition, the lower limit is 1 in theory.
[0138] The above described average particle diameter number of polylactic acid-based resin microparticles that have smooth surfaces can be calculated by measuring the diameters of 100 random particles in a scanning electron microscope image and averaging computation. arithmetic. If a particle shape in the SEM image is not a perfect circle, for example, an ellipse, the maximum particle diameter is used as its diameter. In order to measure the particle diameter precisely, the measurement is carried out with a magnification of at least 1,000 times or greater, preferably with an enlargement of 5,000 times or greater.
[0139] Additionally, the particle diameter distribution index is calculated on the basis of the conversion equations described below, using measurements of the particle diameters obtained by the measurement described above.

[0140] Where, Ri: single particle diameter, n: the number of measurements (= 100), Dn: average particle diameter number, Dv: average particle volume diameter, PDI: diameter distribution index of particle.
[0141] Although the melting enthalpy of polylactic acid-based resin microparticles that have smooth surfaces is not particularly limited, it is preferred that the melting enthalpy is less than 5 J / g due to the fact that the melting point decreases and consequently it becomes possible to use such microparticles properly in uses such as toners where low temperature fusing characteristics are required. The upper limit of melting enthalpy is preferably less than 3 J / g, more preferably less than 2 J / g, most preferably less than 1 J / g. In addition, the lower theoretical limit is 0, which indicates that the resin based on polylactic acid is completely amorphous. Where, the melting enthalpy can be calculated from the area of a peak that shows thermal melting capacity at approximately 160 degrees Celsius in Differential Scanning Calorimetry (DSC) where a temperature is raised to 200 degrees Celsius with a temperature rise 20 degrees Celsius per minute.
[0142] Additionally, for the amount of pores in a porous microparticle of resin based on polylactic acid, the absorption capacity of linseed oil, which is defined in the pigment test methods such as Japan Industrial Standards (Refined Linseed Oil Method , JIS K 5101), is used as an indicator.
[0143] In particular, when the polylactic acid-based resin microparticles described above that have smooth surfaces are used as toners etc., the absorption capacity of lower linseed oil is preferred due to the fact that the melting on a substrate it occurs more homogeneously. The upper limit of flaxseed oil absorption capacity is preferably less than 70 ml / 100g, more preferably less than 65 ml / 100g, more preferably less than 60 ml / 100g. In addition, the lower limit is preferably 30 ml / 100g.
[0144] Thus, the porous microparticles of resin based on polylactic acid, which have small particle diameters and high capacity for absorbing linseed oil according to the present invention, and the smooth surface microparticles of resin based on polylactic acid, which have spherical shapes and narrow particle diameter distribution in accordance with the present invention, are quite useful and practical for various uses in the industry. Specifically, these can be used as, for example, skin care agents such as facial wash, sunscreens, cleansing agents, cosmetic water, lotions, cosmetic liquid, creams, cold creams, aftershaves, soaps for shaving hair, oil-absorbent and moisturizing sheets, cosmetics and modifying agents such as bases, powder base, liquid face powder, mask, face powder, Dohran, eyebrow pencil, mask, eye liner, eye shadow , eyeshadow base, nose shadow, lipsticks, shine, cheek brushes, tooth wax, manicure and finish, additives for hair care products such as shampoo, dry shampoo, conditioner, rinse, shampoo that contains rinse, treatment ingredients, hair tonic, hair conditioner, hair oil, ointment and hair coloring agent, additives for convenience products such as perfume, cologne, deodorant, baby powder, tooth powder, wash mouthwash, soap and lip balm, rheology enhancing agents such as a toner and ink additive, diagnostic test agents for medical purposes, machine feature enhancing agents for molded products such as car materials and construction materials , materials for improving machine characteristics such as film and fiber, raw materials for molding resin such as rapid prototyping and rapid fabrication, fast molding material, bulk resin for Plastic Sol, dust blocking agent, various modifying agents such as powder flow capacity enhancing agent, lubricant, rubber compound ingredient, polishing agent, viscosity enhancer, filler / filler compound, gelatin former, coagulation agent, additive for paints, oil absorbent material, mold release agent, film / slide glide enhancing agent plastics, block anti-forming agent, gloss adjustment agent, matte finishing agent, light diffusing agent, surface hardness enhancing agent and malleability enhancing material, spacer for liquid crystal display equipment, charge / chromatography carrier, base material / additive for cosmetic base, auxiliary for microcapsules, medical materials for drug delivery system / diagnostic reagents, support agent for perfume / pesticide, catalyst / carrier for chemical reactions, gas adsorption agent, material sintered for ceramic processing, standard particle material for measurement / analysis, particle material for the food manufacturing industry, powder coating material, and toner for electrophotographic development.
[0145] Additionally, resin microparticles based on polylactic acid have the potential to replace the polymeric microparticles traditionally used due to the fact that they are non-petroleum materials and have characteristics as low as environmentally charged materials. Electricity, electronic parts that are represented, for example, for concrete uses such as the resin molding body mentioned above, a film, the fiber for the electrical appliance housing, the OA appliance housing, various covers, various gears, several housings, a sensor, an LED lamp, a connector, a socket, a resistor, a relay housing, a switch, several terminal boards, a plug, a printed cabling card, a tuner, a speaker, a microphone, headphones, a small motor, a magnetic head base, a power module, a housing, a semiconductor, liquid crystal, FDD cart, FDD chassis, an engine brush retainer, a satellite dish, a piece of computer connection. The aforementioned applications such as resin moldings, films and fibers include, for example, electrical or electronic parts, typified by an electrical appliance housing, an OA appliance housing, various covers, various gears, various housings, a sensor, a LED lamp, a connector, a socket, a resistor, a relay housing, a switch, several terminal cards, a plug, a printed cabling card, a tuner, a speaker, a microphone, headphones, a small motor, a magnetic head base, a power module, a housing, a semiconductor, liquid crystal, FDD cart, FDD chassis, an engine brush retainer, a satellite dish and a computer connection part, parts TV sets, irons, hair dryers, rice cooking parts, microwave oven parts, audio equipment parts such as a sound piece, an audio, a laser disc (a trademark) and a compact disc , parts related to equ video devices such as a camera, a VCR, an image capture lens (for projection TV, etc.), a viewfinder, a filter, a prism and a Fresnel lens, home and office appliances such as a part lighting, a cooler part, an air conditioner part, a typewriter part and a word processor part, information device related parts such as an office computer related part, a telephone related part , a facsimile-related part, a copier-related part, films for protecting multiple disc plates, a Laser Disk player selection lens, optical fiber, a light switch and an optical connector, liquid crystal display, flat panel display, light guide panel for plasma display, Fresnel lens, polarization plate, protection film for polarization plate, phase difference film, light diffusion film, field expansion film angle, reflective film, fi reflection prevention film, anti-glare film, gloss enhancement film, prism blade and light guide film for touch panel, machine related parts, typified by a washing jig, an engine part, a writer and a typewriter, optical equipment typified by a microscope, binoculars and a watch, parts related to a precision instrument, various pipes for fuel, exhaust and intake, a breathing tube with air intake nozzle, an intake pipe, a pump fuel, a fuse connector, horn terminal, an insulating plate for a piece of electrical equipment, a lamp socket, a lamp reflector, a lamp housing, an engine oil filter and an ignition housing, and are notably useful for such various uses. EXAMPLES
[0146] Hereinafter, the present invention will be explained in detail on the basis of the examples, but the present invention is not limited to those examples. (1) MEASUREMENT METHODS FOR FUSION ENTHALPY AND CRYSTALLIZATION TEMPERATURE:
[0147] The melting enthalpy was calculated from the area size of a peak, which appears at approximately 160 degrees Celsius and shows thermal melting capacity, when performing a measurement up to 200 degrees Celsius with a temperature rise of 20 degrees Celsius per minute by using a differential scanning calorimeter (robot DSC RDC220, supplied by SEIKO Instruments Inc.) under a nitrogen atmosphere.
[0148] Additionally, the crystallization temperature was determined as a vortex temperature of a peak crystallization temperature, which appears in a range of approximately 80 to 130 degrees Celsius during cooling, when performing a measurement with a temperature drop of 1 degree Celsius per minute after raising the temperature to 200 degrees Celsius using the instrument described above under the same conditions. (2) WEIGHTED AVERAGE MOLECULAR MASS: (1) DETERMINATION OF MOLECULAR WEIGHT OF POLYLATIC ACID-BASED RESIN (A):
[0149] The weighted average molecular mass was calculated using gel permeation chromatography with reference to the polymethyl methacrylate (PMMA) calibration curve.
[0150] Device: LC system supplied by Waters Corporation
[0151] Speakers: two HFIP-806Ms supplied by Showa Denko K.K.
[0152] Mobile phase: sodium trifluoroacetate 10 mmol / l hexafluoroisopropanol solution
[0153] Flow rate: 1.0ml / min
[0154] Detector: refractive index detector
[0155] Column temperature: 30 degrees Celsius
[0156] (ii) Determination of the molecular weight of the polymer (B) other than resin based on polylactic acid:
[0157] The weighted average molecular mass was calculated using gel permeation chromatography with reference to the polymethyl methacrylate (PMMA) calibration curve.
[0158] Device: LC-10A series supplied by Shimazu Corporation
[0159] Speakers: two GF-7MHQs supplied by Showa Denko K.K.
[0160] Mobile phase: water solution and lithium bromide 10 mmol / l
[0161] Flow rate: 1.0ml / min
[0162] Detector: refractive index detector
[0163] Column temperature: 40 degrees Celsius (3) INTERFACIAL TENSION DETERMINATION
[0164] With reference to a polylactic acid-based resin solution phase (A) and a polymer solution phase (B) other than polylactic acid-based resin, the liquid-air surface stresses, r1 and r2 respectively, from both phases were measured on a hot plate using an automatic DM-501 contact angle meter supplied by Kyowa Interface Science Co., Ltd., and the interfacial tension was calculated from the absolute value of the differential ( r1 - r2). (4) MEASUREMENT METHODS FOR AVERAGE PARTICLE DIAMETER AND DISTRIBUTION OF PARTICLE DIAMETER:
[0165] Each microparticle particle diameter was measured by a scanning electron microscope (JSM-6301NF, a scanning electron microscope supplied by JEOL Ltd.) with a magnification of 1,000 times. When a particle was not spherical, the longest diameter was measured as the particle diameter of the same.
[0166] The average particle diameter was calculated by measuring the particle diameter of 100 random particles in a scanning electron microscope image and computing their arithmetic mean.
[0167] The particle diameter distribution index showing the particle diameter distribution was calculated based on the following conversion equations, using the particle diameter measurement values obtained by the measurement described above.

[0168] In the above equations, Ri stands for single particle diameter, n stands for the number of measurements (= 100), Dn stands for the mean number of the particle diameter, Dv stands for the average particle volume diameter, and PDI stands for the index of particle diameter distribution. (5) SPHERICITY DETERMINATION:
[0169] Sphericity was calculated by observing the particles with a scanning electron microscope, measuring both the longest and the shortest diameter of each of 30 random particles and assigning the measurement values to the following equation.

[0170] In the above equations, S stands for sphericity, n stands for the number of measurements (= 30), DS stands for the shortest diameter of a single particle and DL stands for the longest diameter for a single particle. (6) DETERMINATION OF LINSEED OIL ABSORPTION CAPACITY:
[0171] For an evaluation of the oil absorption capacity, which is a porosity index of polylactic acid-based resin microparticles, Japan Industrial Standards (JIS) K 5101 “Pigment Test Method: Refined Linseed Oil Method” was used. Approximately 100 mg of polylactic acid-based resin microparticles were weighed in an observation glass with high accuracy. Then, refined flaxseed oil (supplied by Kanto Chemical Co., Inc.) was added drop by drop with a burette and massaged with a reed knife. The mixing process by addition was repeated until the sample became a block and the end point was determined as a point where the sample paste exhibited light hardness. The oil absorption capacity (ml / 100g) was calculated from the amount of refined flaxseed oil used in the process. PRODUCTION EXAMPLE 1: PROCESS 1 TO PRODUCE POLYLATIC ACID
[0172] The amount of 70.2 g of L-lactide (supplied by Sigma-Aldrich Co. LLC .: greater than 98% ee in optical purity), 30.1 g of D-lactide (supplied by Sigma-Aldrich Co. LLC .: greater than 98% ee in optical purity) and 1.1 g of octanol were placed in a reaction tank that has a mixing machine and were dissolved homogeneously at a temperature of 150 degrees Celsius under a nitrogen atmosphere. Then, 0.90 g of tin octylate (supplied by Sigma-Aldrich Co. LLC.) Was added to this as a toluene solution in which the concentration ratio was adjusted to 10% dry toluene mass and the polymerization reaction was performed for six hours. After the polymerization reaction was over, the reagent was dissolved in chloroform and re-precipitated in methanol with stirring and a solid matter was obtained by removing monomers and catalysts from it. By performing the filtration of the solid matter obtained and performing the vacuum heat drying at 80 degrees Celsius, the resin based on polylactic acid which has a 70/30 L / D copolymerization ratio, a melting enthalpy of 0 J / g and a molecular weight of 11,200 (in terms of PMMA) was obtained. The SP value of this polymer was 23.14 (J / cm3) 1/2 according to the computational method described above. PRODUCTION EXAMPLE 2: PROCESS 2 TO PRODUCE POLYLATIC ACID
[0173] A polylactic acid-based resin was produced in a similar manner to Production Example 1 except that 49.9 g of L-lactide (supplied by Sigma-Aldrich Co. LLC .: greater than 98% ee in optical purity), 49.8 g of D-lactide (supplied by Sigma-Aldrich Co. LLC .: greater than 98% ee in optical purity) and 0.95 g of tin octylate (supplied by Sigma-Aldrich Co. LLC.) was used. The polylactic acid resin obtained had a L / D copolymerization ratio of 50/50, a melting enthalpy of 0 J / g and a molecular weight (in terms of PMMA) of 9,800. The SP value of this polymer was 23.14 (J / cm3) 1/2 according to the computational method described above. PRODUCTION EXAMPLE 3: PROCESS 3 TO PRODUCE POLYLATIC ACID
[0174] A polylactic acid-based resin was produced in a similar manner to Production Example 1 except that 70.1g of L-lactide (supplied by Sigma-Aldrich Co. LLC .: greater than 98% ee in optical purity), 29.8 g of D-lactide (supplied by Sigma-Aldrich Co. LLC .: greater than 98% ee in optical purity) and 0.90 g of tin octylate (supplied by Sigma-Aldrich Co. LLC.) was used. The polylactic acid-based resin obtained had an L / D copolymerization ratio of 70/30, a melting enthalpy of 0 J / g and a molecular weight (in terms of PMMA) of 98,000. The SP value of this polymer was 23.14 (J / cm3) 1/2 according to the computational method described above. EXAMPLE 1
[0175] The amount of 0.5 g of polylactic acid (L / D = 98.8 / 1.2, molecular weight (in terms of PMMA) = 160,000, melting enthalpy = 31.1 J / g, SP value = 23.14 (J / cm3) 1/2), 0.5g of hydroxypropylcellulose (supplied by Tokyo Chemical Industry Co., Ltd., weighted average molecular weight = 118,000, SP value = 29.0 (J / cm3) 1 / 2) as a polymer other than polylactic acid and 9.0 g of tetrahydrofuran as an ether-based organic solvent were placed in a 100 ml four-necked flask, heated to 50 degrees Celsius and stirred until the polymers had completely dissolved. After bringing the temperature back to room temperature, 5g of ion-exchanged water as a weak solvent was added by dropping it with a pipette by stirring with a stirrer. Stirring was continued for another 30 minutes after the entire amount of water was added and the resulting suspension was filtered and washed with 50g of water with exchanged ion. Then, by drying the filtered material in a vacuum at 80 degrees Celsius for 10 hours, 0.4 g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the powder obtained was microparticles of polylactic acids that have a porous microparticle shape, which has an average particle diameter of 33.0 μm and a particle diameter distribution index. of 1.55. EXAMPLE 2
[0176] The amount of 1.5 g of polylactic acid (L / D = 98.8 / 1.2, molecular weight (in terms of PMMA) = 160,000, melting enthalpy = 31.1 J / g, SP value = 23.14 (J / cm3) 1/2), 2.5g of hydroxypropylcellulose (supplied by Tokyo Chemical Industry Co., Ltd., weighted average molecular weight = 118,000, SP value = 29.0 (J / cm3) 1 / 2) as a polymer other than polylactic acid and 46.0g of tetrahydrofuran as an ether-based organic solvent were placed in a 100 ml four-necked flask, heated to 50 degrees Celsius and stirred until the polymers had completely dissolved. After bringing the temperature back to room temperature, 50g of ion-exchanged water as a weak solvent was added by dropping it with a pump at a rate of 0.41g per minute by stirring with a stirrer. Stirring was continued for another 30 minutes after the entire amount of water was added and the resulting suspension was filtered and washed with 50g of water with exchanged ion. Then, by drying the filtered material in a vacuum at 80 degrees Celsius for 10 hours, 0.4 g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the powder obtained was microparticles of polylactic acids that have a porous microparticle shape, which has an average particle diameter of 25.1 μm, which has a diameter distribution index 1.35 particle, which has a sphericity of 89 and a flaxseed oil absorption of 432 ml / 100g. Additionally, the melting enthalpy of these polylactic acid microparticles was 57.8 J / g. A diagram of observation of these microparticles by a scanning electron microscope is shown in Figure 1. EXAMPLE 3
[0177] The amount of 2.5 g of polylactic acid (L / D = 98.8 / 1.2, molecular weight (in terms of PMMA) = 160,000, melting enthalpy = 31.1 J / g, SP value = 23.14 (J / cm3) 1/2), 2.5g of hydroxypropylcellulose (supplied by Tokyo Chemical Industry Co., Ltd., weighted average molecular weight = 118,000, SP value = 29.0 (J / cm3) 1 / 2) as a polymer other than polylactic acid and 45.0g of tetrahydrofuran as an ether-based organic solvent were placed in a 100 ml four-necked flask, heated to 50 degrees Celsius and stirred until the polymers were completely dissolved. After bringing the temperature back to room temperature, 50g of ion-exchanged water as a weak solvent was added by dropping it with a pump at a rate of 0.41g per minute by stirring with a stirrer. Stirring was continued for another 30 minutes after the entire amount of water was added and the resulting suspension was filtered and washed with 50g of water with exchanged ion. Then, by drying the filtered material in a vacuum at 80 degrees Celsius for 10 hours, 2.2 g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the powder obtained was microparticles of polylactic acids that have a porous microparticle shape, which has an average particle diameter of 59.5 μm, which has a diameter distribution index particle size of 11.5 and an absorption of linseed oil of 661 ml / 100g. EXAMPLE 4
[0178] The amount of 2.5g of polylactic acid (L / D = 98.8 / 1.2, molecular weight (in terms of PMMA) = 160,000, melting enthalpy = 31.1 J / g, SP value = 23.14 (J / cm3) 1/2), 2.5g of hydroxypropylcellulose (supplied by Tokyo Chemical Industry Co., Ltd., weighted average molecular weight = 118,000, SP value = 29.0 (J / cm3) 1 / 2) as a polymer other than polylactic acid, 33.75g of diethylene glycol dimethyl ether (diglyme) as an ether-based organic solvent and 11.25g of N-methyl-2-pyrrolidone as another organic solvent were placed in a flask of four 100 ml necks, heated to 80 degrees Celsius and stirred until the polymers had completely dissolved. With the temperature maintained, 50g of ion-exchanged water as a weak solvent was added by dropping it with a pump at a rate of 0.82g per minute by stirring with a stirrer. Stirring was continued for another 30 minutes after the entire amount of water was added and the resulting suspension was filtered and washed with 50g of water with exchanged ion. Then, by drying the filtered material in a vacuum at 80 degrees Celsius for 10 hours, 2.4 g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the powder obtained was microparticles of polylactic acids that have a porous microparticle shape, which has an average particle diameter of 13.7 μm, which has a diameter distribution index particle of 1.24, which has a sphericity of 82 and an absorption of linseed oil of 524 ml / 100g. In addition, the melting enthalpy of these polylactic acid microparticles was 58.2 J / g. An observation diagram of these microparticles through a scanning electron microscope is shown in Figure 2. EXAMPLE 5
[0179] The amount of 1.5 g of polylactic acid (L / D = 96/4, molecular weight (in terms of PMMA) = 150,000, melting enthalpy = 28.6 J / g, SP value = 23.14 ( J / cm3) 1/2), 2.5g of hydroxypropylcellulose (supplied by Tokyo Chemical Industry Co., Ltd., weighted average molecular weight = 118,000, SP value = 29.0 (J / cm3) 1/2) as a polymer other than polylactic acid and 46.0 g of tetrahydrofuran as an ether-based organic solvent were placed in a 100 ml four-necked flask, heated to 60 degrees Celsius and stirred until the polymers had completely dissolved. After bringing the temperature back to room temperature, 50g of ion-exchanged water as a weak solvent was added by dropping it with a pump at a rate of 0.41g per minute by stirring with a stirrer. Stirring was continued for another 30 minutes after the entire amount of water was added and the resulting suspension was filtered and washed with 50g of water with exchanged ion. Then, by drying the filtered material in a vacuum at 80 degrees Celsius for 10 hours, 1.3 g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the powder obtained was microparticles of polylactic acids that have a porous microparticle shape, which has an average particle diameter of 10.0 μm, which has a diameter distribution index particle size of 1.10, which has a sphericity of 85 and a flaxseed oil absorption of 96 ml / 100g. Additionally, the melting enthalpy of these polylactic acid microparticles was 34.3 J / g. An observation diagram of these microparticles by a scanning electron microscope is shown in Figure 3. EXAMPLE 6
[0180] The amount of 2.5g of polylactic acid (L / D = 96/4, molecular weight (in terms of PMMA) = 150,000, melting enthalpy = 28.6 J / g, SP value = 23.14 ( J / cm3) 1/2), 2.5g of hydroxypropylcellulose (supplied by Tokyo Chemical Industry Co., Ltd., weighted average molecular weight = 118,000, SP value = 29.0 (J / cm3) 1/2) as a polymer other than polylactic acid and 45.0 g of diethylene glycol dimethyl ether as an ether-based organic solvent were placed in a 100 ml four-necked flask, heated to 80 degrees Celsius and stirred until the polymers had completely dissolved . With the temperature maintained, 50g of ion-exchanged water as a weak solvent was added by dropping it with a pump at a rate of 0.82g per minute by stirring with a stirrer. Stirring was continued for another 30 minutes after the entire amount of water had been dripped and the resulting suspension was filtered and washed with 50g of water with exchanged ion. Then, by drying the filtered material in a vacuum at 80 degrees Celsius for 10 hours, 2.3 g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the powder obtained was a microparticle polylactic acid that has a porous microparticle shape, which has an average particle diameter of 14.0 μm, which has a diameter distribution index 1.25 particle, which has a sphericity of 93 and a flaxseed oil absorption of 149 ml / 100g. In addition, the melting enthalpy of these polylactic acid microparticles was 32.6 J / g. EXAMPLE 7
[0181] The amount of 1.5 g of polylactic acid (L / D = 98.8 / 1.2, molecular weight (in terms of PMMA) = 160,000, melting enthalpy = 31.1 J / g, SP value = 23.14 (J / cm3) 1/2, crystallization temperature during cooling = 108 degrees Celsius), 2.5g of hydroxypropylcellulose (supplied by Tokyo Chemical Industry Co., Ltd., weighted average molecular weight = 118,000, SP value = 29.0 (J / cm3) 1/2) as a polymer other than polylactic acid and 46.0g of diethylene glycol dimethyl ether as an ether-based organic solvent were placed in a 100 ml autoclave, heated to 140 degrees Celsius and stirred until the polymers had completely dissolved. With the temperature maintained, 50g of ion-exchanged water as a weak solvent was added by dropping it with a pump at a rate of 0.41g per minute by stirring with a stirrer. Stirring was continued for another 30 minutes after the entire amount of water had been added and a suspension obtained was filtered and washed with 50g of water with exchanged ion. Then, by drying the filtered material in a vacuum at 80 degrees Celsius for 10 hours, 1.3 g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the powder obtained was microparticles of polylactic acids that have a smooth surface microparticle format, which has an average particle diameter of 1.6 μm, which has a diameter distribution index particle size of 1.40, which has a sphericity of 95 and a flaxseed oil absorption of 51 ml / 100g. Additionally, the melting enthalpy of these polylactic acid microparticles was 40.8 J / g. A diagram of observing these microparticles through a scanning electron microscope is shown in Figure 4. EXAMPLE 8
[0182] The amount of 1.5 g of polylactic acid (L / D = 96/4, molecular weight (in terms of PMMA) = 150,000, melting enthalpy = 28.6 J / g, SP value = 23.14 ( J / cm3) 1/2, crystallization temperature during cooling = 108 degrees Celsius), 2.5g of hydroxypropylcellulose (supplied by Tokyo Chemical Industry Co., Ltd., weighted average molecular weight = 118,000, SP value = 29.0 (J / cm3) 1/2) as a polymer other than polylactic acid and 46.0g of diethylene glycol dimethyl ether as an ether-based organic solvent were placed in a 100 ml autoclave, heated to 140 degrees Celsius and stirred to that the polymers had been completely dissolved. While the system temperature was maintained, 50g of ion-exchanged water as a weak solvent was added by dropping it with a pump at a rate of 0.41g per minute by stirring with a stirrer. Stirring was continued for another 30 minutes after the entire amount of water was added and the resulting suspension was filtered and washed with 50g of water with exchanged ion. Then, by drying the filtered material in a vacuum at 80 degrees Celsius for 10 hours, 1.3 g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the obtained powder was microparticles of polylactic acids that have a smooth surface microparticle format, which has an average particle diameter of 1.8 μm, which has a diameter distribution index 1.82 particle, which has a sphericity of 97 and an absorption of linseed oil of 58 ml / 100g. In addition, a melting enthalpy of these polylactic acid microparticles was 30.4 J / g. EXAMPLE 9
[0183] The amount of 1.5 g of polylactic acid (L / D = 88/12, molecular weight (in terms of PMMA) = 150,000, melting enthalpy = 0 J / g, SP value = 23,14 (J / cm3) 1/2), 2.5g of hydroxypropylcellulose (supplied by Tokyo Chemical Industry Co., Ltd., weighted average molecular weight = 118,000, SP value = 29.0 (J / cm3) 1/2) as a polymer other than polylactic acid and 46.0 g of tetrahydrofuran as an ether-based organic solvent were placed in a 100 ml four-necked flask, heated to 60 degrees Celsius and stirred until the polymers had completely dissolved. After bringing the temperature back to room temperature, 50g of ion-exchanged water as a weak solvent was added by dropping it with a pump at a rate of 0.41g per minute by stirring with a stirrer. Stirring was continued for another 30 minutes after the entire amount of water was added and the resulting suspension was filtered and washed with 50g of water with exchanged ion. Then, by drying the filtered material in a vacuum at 80 degrees Celsius for 10 hours, 1.3 g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the powder obtained was microparticles of polylactic acids that have a smooth surface shaped microparticle, which has an average particle diameter of 4.5 μm, which has a diameter distribution index particle size of 1.1, which has a sphericity of 95 and a flaxseed oil absorption of 58 ml / 100g. In addition, a melting enthalpy of these polylactic acid microparticles was 0 J / g. An observation diagram of these microparticles through a scanning electron microscope is shown in Figure 5. EXAMPLE 10
[0184] By performing a procedure in Practical Example 9 except for the use of polylactic acid in Production Example 1, 1.3 g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the powder obtained was microparticles of polylactic acids that have a smooth surface microparticle format, which has an average particle diameter of 7.8 μm, which has a diameter distribution index particle of 1.31 and a sphericity of 91. EXAMPLE 11
[0185] By carrying out a procedure as in Practical Example 9 except for the use of polylactic acid from Production Example 2, 1.3 g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the powder obtained was microparticles of polylactic acids that have a smooth microparticle-shaped surface, which has an average particle diameter of 10.2 μm, which has a diameter distribution index particle of 1.20 and a sphericity of 94. EXAMPLE 12
[0186] By carrying out a procedure as in Practical Example 9 except for the use of polylactic acid from Production Example 3, 1.3 g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the powder obtained was microparticles of polylactic acids that have a smooth microparticle-shaped surface, which has an average particle diameter of 12.1 μm, which has a diameter distribution index particle size of 1.33 and a sphericity of 90. EXAMPLE 13
[0187] The amount of 2.5 g of polylactic acid (L / D = 88/12, molecular weight (in terms of PMMA) = 150,000, melting enthalpy = 0 J / g, SP value = 23,14 (J / cm3) 1/2), 2.5g of hydroxypropylcellulose (supplied by Tokyo Chemical Industry Co., Ltd., weighted average molecular weight = 118,000, SP value = 29.0 (J / cm3) 1/2) as a polymer other than polylactic acid and 45.0 g of diethylene glycol dimethyl ether as an ether-based organic solvent were placed in a 100 ml four-necked flask, heated to 80 degrees Celsius and stirred until the polymers had completely dissolved. With the temperature maintained, 50g of ion-exchanged water as a weak solvent was added by dropping it with a pump for one hour by stirring with a stirrer. Stirring was continued for another 30 minutes after the entire amount of water was added and the resulting suspension was filtered and washed with 50g of water with exchanged ion. Then, by drying the filtered material in a vacuum at 80 degrees Celsius for 10 hours, 1.3 g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the obtained powder was microparticles of polylactic acids that have a smooth surface microparticle format, which has an average particle diameter of 10.2 μm, which has a diameter distribution index 1.32 particle, which has a sphericity of 94 and a flaxseed oil absorption of 67 ml / 100g. Additionally, a melting enthalpy of these polylactic acid microparticles was 0 J / g. COMPARATIVE EXAMPLE 1
[0188] The amount of 1.5 g of polylactic acid (L / D = 98.8 / 1.2, molecular weight (in terms of PMMA) = 160,000, melting enthalpy = 31.1 J / g, the SP value = 23.14 (J / cm3) 1/2), 2.5g of hydroxypropylcellulose (supplied by Tokyo Chemical Industry Co., Ltd., weighted average molecular weight = 118,000, the SP value = 29.0 (J / cm3 ) 1/2) as a polymer other than polylactic acid and 46.0g of N-methyl-2-pyrrolidone as an alternative to an ether-based organic solvent were placed in a 100 ml autoclave, heated to 50 degrees Celsius and stirred until the polymers had completely dissolved. After bringing the temperature back to room temperature, 50g of ion-exchanged water as a weak solvent was added by dropping it with a pump at a rate of 0.41g per minute by stirring with a stirrer. Stirring was continued for another 30 minutes after the entire amount of water had been added. By filtering the resulting aqueous slurry liquid, handling was not easy and it was difficult to extract it in powder form. According to the measurements of average particle volume diameter and average particle diameter in aqueous paste state using a laser diffraction particle size analyzer (supplied by Shimadzu Corporation, SALD-2100), the microparticles obtained had an average particle diameter (average particle volume diameter) of 24.3 μm and a particle diameter distribution index of 9.1. COMPARATIVE EXAMPLE 2
[0189] The amount of 5g of polylactic acid (D-isomer = 1.2%, molecular weight (in terms of PMMA) = 160,000, melting point = 168 degrees Celsius) and 50.0g of diethylene glycol dimethyl ether (diglyme ) as an ether-based organic solvent were placed in a 100 ml four-necked flask and dissolved in an oil bath under heat reflux conditions. After the temperature was slowly cooled to room temperature by the interruption, a suspension of microparticles based on polylactic acid was obtained. The suspension was filtered and washed with 50g of water with exchanged ion, and by drying the filtered matter in a vacuum at 80 degrees Celsius for 10 hours, 4.88g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the powder obtained was microparticles of polylactic acids that have a porous microparticle shape, which has an average particle diameter of 64.0 μm, which has a diameter distribution index particle size of 3 or greater and a sphericity of 50 or less. COMPARATIVE EXAMPLE 3
[0190] Polylactic acid-based resin microparticles were prepared according to a procedure disclosed in Patent Document 4 (JP-UM-2009-242728). 1.0g of polylactic acid (L / D = 98.8 / 1.2, molecular weight (in terms of PMMA) = 160,000, melting enthalpy = 31.1 J / g, SP value = 23.14 (J / cm3) 1/2) and 9.0 g of ortho-dichlorobenzene were placed in a 100 ml autoclave, heated to 160 degrees Celsius and completely dissolved. The autoclave was immersed in an oil bath of 30 degrees Celsius for 15 minutes and the resulting powder was filtered and washed with 50g of water with exchanged ion. By drying the filtered material in a vacuum at 80 degrees Celsius for 10 hours, 0.9 g of white solid was obtained as a powder. According to an observation with a scanning electron microscope, the powder obtained was microparticles of polylactic acids that have a porous microparticle shape, which has an average particle diameter of 234.3 μm, which has a diameter distribution index particle of 1.10, which has a sphericity of 86 and an absorption of linseed oil of 86 ml / 100g. Additionally, the melting enthalpy of these polylactic acid microparticles was 21.2 J / g. An observation diagram of these microparticles through the scanning electron microscope is shown in Figure 6. COMPARATIVE EXAMPLE 4
[0191] Polylactic acid-based resin microparticles were prepared according to a procedure disclosed in Patent Document 2 (JP-UM-2004-269865). 24.0g of polylactic acid (L / D = 98.8 / 1.2, molecular weight (in terms of PMMA) = 160,000, melting enthalpy = 31.1 J / g, SP value = 23.14 (J / cm3) 1/2), 40.0g of oligosaccharide (hydrogenated starch hydrolyzate PO-10 supplied by Mitsubishi Shoji Foodtech Co., Ltd.) and 16.0g of pentaerythritol were placed in a Labo-Plast Mill at a temperature of 200 degrees Celsius and were massaged for 5 minutes at a speed of 50 revolutions per minute. After cooling, a resulting block material was added to the water with ion-exchanged, washed at a temperature of 60 degrees Celsius and filtered. By drying the filtered matter in a vacuum at 80 degrees Celsius for 10 hours, 21.0 g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the powder obtained was microparticles of polylactic acids that have a smooth surface microparticle format, which has an average particle diameter of 6.1 μm, which has a diameter distribution index particle size of 17.1, which has a sphericity of 94 and a flaxseed oil absorption of 56 ml / 100g. Additionally, the melting enthalpy of these polylactic acid microparticles was 38.8 J / g. A diagram of observation of these microparticles through the scanning electron microscope is shown in Figure 7. COMPARATIVE EXAMPLE 5
[0192] Polylactic acid-based resin microparticles were prepared according to a procedure disclosed in Patent Document 2 (JP-A-2004-269865). 24.0g of polylactic acid (L / D = 88/12, molecular weight (in terms of PMMA) = 150,000, melting enthalpy = 0 J / g, SP value = 23.14 (J / cm3) 1/2) , 40.0g of oligosaccharide (hydrogenated starch hydrolyzate PO-10 supplied by Mitsubishi Shoji Foodtech Co., Ltd.) and 16.0g of pentaerythritol were placed in a Labo-Plast Mill at a temperature of 200 degrees Celsius and massaged by 5 minutes at a speed of 50 revolutions per minute. After cooling, a resulting block material was added to the water with ion-exchanged, washed at a temperature of 60 degrees Celsius and filtered. By drying the filtered material in a vacuum at 80 degrees Celsius for 10 hours, 21.5 g of white solid were obtained in powder form. According to an observation with a scanning electron microscope, the obtained powder was microparticles of polylactic acids that include smooth-surface and fiber-shaped microparticles, which have an average particle diameter of 4.7 μm, which has an index of particle diameter distribution of 6.2, which has a sphericity of 79 and an absorption of linseed oil of 54 ml / 100g. In addition, the melting enthalpy of these polylactic acid microparticles was 0 J / g. An observation diagram of these microparticles through the scanning electron microscope is shown in Figure 8. COMPARATIVE EXAMPLE 6
[0193] Polylactic acid-based resin microparticles were prepared according to a procedure disclosed in Patent Document 3 (JP-UM-2005-002302). 1.4g of polylactic acid (L / D = 98.8 / 1.2, molecular weight (in terms of PMMA) 160,000, melting enthalpy = 31.1 J / g, SP value 23.14 (J / cm3) 1/2) were completely dissolved in 12.6g of 1,3-dioxolane and subsequently 7.0g of ethyl acetate was added to it. 21.0 g of water were dripped for 20 minutes by stirring with a homogenizer, however, it was not possible to obtain the microparticles due to the fact that a block material was formed instead. COMPARATIVE EXAMPLE 7
[0194] Polylactic acid-based resin microparticles were prepared according to a procedure disclosed in Patent Document 3 (JP-UM-2005-002302). 1.4 g of polylactic acid (L / D = 88/12, molecular weight (in terms of PMMA) 150,000, melting enthalpy = 0 J / g, SP value 23.14 (J / cm3) 1/2) were dissolved completely in 12.6 g of 1,3-dioxolane and subsequently 7.0 g of ethyl acetate were added to this. 21.0 g of water were dripped for 20 minutes by stirring with a homogenizer, however, it was not possible to obtain the microparticles due to the fact that a block material was formed instead. As for Examples 1 to 13 and Comparative Examples 1 to 7, the conditions of production processes are shown in Table 1 and the measurement results with respect to the polylactic acid-based resin microparticles obtained are shown in Table 2.

[TABLE 2]

EXAMPLE 14 (COSMETIC BASE)
[0195] A composite was prepared according to a prescription containing 5% by weight of the polylactic acid-based resin microparticles obtained in Example 2, 35% by weight of talc, 30% by weight of mica, 10% by weight of synthetic fluorflogopite, 5% by weight of titanium oxide, 3% by weight of aluminum hydroxide, 4% by weight of stearic acid, 3% by weight of iron oxide, 0.2% by weight of butyl paraben, 0 , 1% by weight of methyl paraben, 9% by weight of dimethicone, 1.7% by weight of methicone and 4% by weight or greater of trimethylsiloxysilicate. This composite had a good sliding ability and a soft touch feeling. EXAMPLE 15
[0196] A composite was prepared as in Example 14 except that the polylactic acid-based microparticles obtained in Example 3 were used. This composite had a good sliding ability and a soft touch feeling. EXAMPLE 16
[0197] A composite was prepared as in Example 14 except that the polylactic acid-based microparticles obtained in Example 4 were used. This composite had a good sliding ability and a soft touch feeling. EXAMPLE 17
[0198] A composite was prepared as in Example 14 except that the polylactic acid-based microparticles obtained in Example 5 were used. This composite had a good sliding ability and a soft touch feeling. COMPARATIVE EXAMPLE 8
[0199] A composite was prepared as in Example 14 except that in microparticles based on polylactic acid were used. This composite had a low sliding ability and a rough feel. EXAMPLE 18 (POWDER EYE SHADOW)
[0200] A composite was prepared according to a prescription containing 7% by weight of the polylactic acid-based resin in Example 9, 63.6% by weight of synthetic mica, 15% by weight of mica with a dioxide coating sodium, 6% by weight of glycerin, 4% by weight of scalene, 1.8% by weight of methicone, 0.2% by weight of silica, 2.0% by weight of overseas, 0.2% by weight of organic pigment and 0.2% by weight or more of ethyl paraben. This composite had a good sliding ability and was shiny in appearance. EXAMPLE 19 (COSMETIC BASE)
[0201] A composite was prepared according to a prescription containing 5% by weight of the polylactic acid-based resin microparticles obtained in Example 9, 35% by weight of talc, 30% by weight of mica, 10% by weight of synthetic fluorflogopite, 5% by weight of titanium oxide, 3% by weight of aluminum hydroxide, 4% by weight of stearic acid, 3% by weight of iron oxide, 0.2% by weight of butyl paraben, 0 , 1% by weight of methyl paraben, 9% by weight of dimethicone, 1.7% by weight of methicone and 4% by weight or more of trimethylsiloxysilicate. Due to the fact that of its sliding ability, the composite could be well spread, had a non-viscous touch feeling and was shiny in appearance. COMPARATIVE EXAMPLES 9 TO 10
[0202] Linseed oil absorptions of commercially available microparticles have been evaluated.
[0203] The results of the same and the results of Examples 2, 3, 4, 5 are shown in Table 3.
[0204] Microparticles that have been used COMPARATIVE EXAMPLE 9: SP-500 Nylon MICROPARTICLES (SUPPLYED BY TORAY INDUSTRIES, INC.) COMPARATIVE EXAMPLE 10: TR-1 Nylon MICROPARTICLES (SUPPLYED BY TORAY INDUSTRIES, INC.).

EXAMPLES 20 TO 23 AND COMPARATIVE EXAMPLES 11 TO 12 (EVALUATION AS BASE MATERIAL FOR TONER)
[0205] It has been assessed whether the polylactic acid resin microparticles prepared in Examples 9 to 12 can be used or not as a base material for toner that has low temperature fixation characteristics or from the point of view of powder flow capacity and features thermofusion at 80 degrees Celsius. Polylactic acid-based resin microparticles prepared in Example 2 and Comparative Example 2 were also evaluated. The evaluation results are shown in Table 4.
[0206] The polylactic acid-based resin microparticles of Examples 9 to 12 had good flowability and were formed in a film format. In Example 2, the resin microparticles based on polylactic acid did not have sufficient flow capacity and remained as a powder format. In Comparative Example 2, the microparticles lacked flow capacity due to the wide particle distribution and low sphericity and as for thermofusion characteristics, the microparticles fused and partially formed into a membrane format, but did not form a film format.
[0207] Dust flow capacity
[0208] An angle (angle of rest) formed between a plane and a boundary line of dripped powders from a powder funnel (made of polypropylene) was measured and an angle of 50 degrees or less was rated as "acceptable". In addition, the presence or absence of residues in the funnel was inspected and powders that had no residue were assessed as "excellent".
[0209] Thermofusion characteristics at 80 degrees Celsius
[0210] 100mg of powders were placed on a hot plate at 80 degrees Celsius for 5 minutes, powders that did not maintain the particle shape and formed a film format were rated as "acceptable" and the others were rated as "unacceptable"". TABLE 4
INDUSTRIAL APPLICABILITY
[0211] According to the present invention, the porous microparticles of resin based on polylactic acid which have small particle diameter and high absorption capacity of linseed oil and the smooth surface microparticles of resin based on polylactic acid which have spherical shapes and narrow particle diameter distribution are quite useful and practical for various uses in the industry. More specifically, these microparticles can be used for, for example, facial wash, sunscreen, cleaning agent, cosmetic water, lotion, cosmetic liquid, cream, cold cream, aftershave lotion, hair shaving soap, absorbent razor blade oil, various skin care agents such as moisturizer, foundation, powder foundation, liquid foundation, mask, face powder, Dohran, eyebrow pencil, mask, eye liner, eye shadow, eye shadow base, nose shadow, lipsticks , shine, cheek brushes, tooth wax, manicure, various cosmetics and various modifying agents such as finish, shampoo, dry shampoo, conditioner, rinse, shampoo that contains rinse ingredients, treatment, hair tonic, hair conditioner, hair oil, ointment, additives for various hair care products such as hair coloring agent, perfume, cologne, deodorant, baby powder, dental powder, mouthwash, lip balm, additives for various products of convenience such as soap, toner additive, various rheology enhancing agents used for paint and the like, diagnostic testing agents for medical purposes, agents for enhancing machine characteristics of molded products such as car materials and building materials , film, materials for enhancing fiber machine characteristics and the like, raw materials for resin molded products used in rapid prototype creation, rapid manufacturing and the like, rapid molding material, bulk resin for Plastic Sol, blocking agent powder, powder flow capacity enhancing agent, lubricant, rubber compound ingredient, polishing agent, viscosity enhancer, filler / filler compound, gelatin former, coagulation agent, paint additive, material oil absorbent, mold release agent, slip enhancement agent for films / foils p plastics, block anti-forming agent, gloss adjustment agent, matte finishing agent, light diffusing agent, surface hardness enhancing agent and malleability enhancing material, spacer for liquid crystal display equipment, cargo / carrier for chromatography, base material / cosmetic base additive, auxiliary for microcapsules, medical materials for drug delivery system / diagnostic reagents, perfume / pesticide support agent, catalyst / carrier for chemical reactions, gas adsorption agent, sintered material for ceramic processing, standard particle material for measurement / analysis, particle material for the food manufacturing industry, powder coating material, and toner for electrophotographic development.

权利要求:
Claims (12)
[0001]
1. PROCESS TO PRODUCE RESIN MICROPARTICLES, based on polylactic acid, characterized by comprising: a dissolution process to form a system, which can cause phase separation in two phases of a solution phase composed mainly of acid-based resin polylactic (A) and a solution phase composed mainly of polymer (B) different from resin based on polylactic acid, by dissolving said resin based on polylactic acid (A) and said polymer (B) different from resin based on polylactic acid in an ether-based organic solvent (C); an emulsion forming process to form an emulsion by applying a shear force to said system; and a microparticle forming process to precipitate microparticles of resin based on polylactic acid by putting said emulsion in contact with a weak solvent that has lower solubility of said resin based on polylactic acid (A) compared to said organic solvent based on ether (C).
[0002]
PROCESS according to claim 1, characterized in that said ether-based organic solvent (C) has a boiling point of 100 ° C or greater.
[0003]
PROCESS according to claim 2, characterized in that said organic solvent based on ether (C) is diethylene glycol dimethyl ether.
[0004]
PROCESS according to any one of claims 1 to 3, characterized in that said polymer (B) other than a resin based on polylactic acid is a polyvinyl alcohol, a hydroxypropylcellulose, a polyethylene oxide or a polyethylene glycol.
[0005]
PROCESS according to any one of claims 1 to 4, characterized in that said weak solvent is water.
[0006]
PROCESS according to any one of claims 1 to 5, characterized in that said resin based on polylactic acid (A) has a melting enthalpy of 5 J / g or greater.
[0007]
7. PROCESS, according to claim 6, characterized in that the contact temperature of said weak solvent is equal to or greater than the crystallization temperature of said resin based on polylactic acid (A).
[0008]
PROCESS according to any one of claims 1 to 5, characterized in that said resin based on polylactic acid (A) has a melting enthalpy less than 5 J / g.
[0009]
9. RESIN MICROPARTICLES, based on polylactic acid, characterized by said microparticles having an average number of particle diameter from 1 to 30 μm and a linseed oil absorption of 90 ml / 100g or greater, in which the oil absorption Linseed oil is defined by a volume of linseed oil absorbed in 100g of microparticles according to the “Pigment Test Method: Linseed Oil Refining Method” based on Japan Industrial Standards (JIS) K 5101.
[0010]
MICROPARTICLES according to claim 9, characterized in that said microparticles comprise a polylactic acid-based resin that has a melting enthalpy of 5 J / g or more.
[0011]
11. MICROPARTICLES according to any one of claims 9 to 10, characterized in that said microparticles have a particle diameter distribution index of 1 to 2, wherein the particle diameter distribution index is defined by the following equation with “ Ri ”as a particle diameter of the microparticle,“ n ”as 100,“ Dn ”as an average particle diameter number of the microparticles,“ Dv ”as an average particle diameter volume of the microparticles, and“ PDI ”as the particle diameter distribution index
[0012]
12. COSMETICS, characterized in that they comprise said resin microparticles based on polylactic acid, as defined in any of claims 9 to 11, used for bases, powder base, face powder in liquid form, mask, face powder, Dohran, pencil eyebrow, mask, eye liner, eye shadow, eye shadow base, nose shadow, lipsticks, gloss, cheek brushes, tooth wax, manicure and finishing.

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同族专利:

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公开号 | 公开日

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CA2824961C|2015-07-07|

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TW201237097A|2012-09-16|

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CN103937012A|2014-07-23|

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TWI412559B|2013-10-21|

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JPWO2012105140A1|2014-07-03|

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CN103201319B|2014-11-05|

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KR20130043240A|2013-04-29|

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CN103937012B|2016-08-24|

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BR112013018678A2|2016-10-18|

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US9017812B2|2015-04-28|

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ES2528961T3|2015-02-13|

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KR101382732B1|2014-04-08|

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US20150183928A1|2015-07-02|

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EP2660272A4|2013-11-06|

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US20130309497A1|2013-11-21|

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CN103201319A|2013-07-10|

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EP2660272A1|2013-11-06|

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法律状态:
2017-04-25| B27A| Filing of a green patent (patente verde)|

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2017-05-23| B27C| Request for a green patent denied|

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2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-04-28| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-11-03| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |

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2021-01-19| B16D| Grant of patent or certificate of addition of invention cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 16.1 NA RPI NO 2606 DE 15/12/2020 POR TER SIDO INDEVIDA. |

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2021-01-26| B09X| Decision of grant: republication|

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2021-04-13| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2011018041|2011-01-31|

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JP2011-018041|2011-01-31|

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JP2011-145913|2011-06-30|

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JP2011145913|2011-06-30|

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JP2011256061|2011-11-24|

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JP2011-256061|2011-11-24|

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PCT/JP2011/079776|WO2012105140A1|2011-01-31|2011-12-22|Method for producing microparticles of polylactic acid-based resin, microparticles of polylactic acid-based resin and cosmetic using same|

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