WO2010101134A1 - ポリアミド粒子及びその製造方法 - Google Patents
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- WO2010101134A1 WO2010101134A1 PCT/JP2010/053309 JP2010053309W WO2010101134A1 WO 2010101134 A1 WO2010101134 A1 WO 2010101134A1 JP 2010053309 W JP2010053309 W JP 2010053309W WO 2010101134 A1 WO2010101134 A1 WO 2010101134A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to polyamide particles and a method for producing the same.
- Polyamide particles are applied to a wide range of fields such as cosmetics, additives such as paints and waxes, lubricants, adhesives, and anti-tacking agents.
- nylon 12 polyamide 12
- dipropylene glycol are mixed, heated, dissolved to form a uniform solution, and cooled to precipitate spherical particles of nylon 12
- Patent Document 1 a method for producing polyamide porous particles in which methanol and water, which are non-solvents of the polyamide, are mixed in a polyamide phenol solution (Patent Document 2), and the polyamide is heated and dissolved in ethylene glycol and cooled.
- Patent Document 3 Patent Document 4
- Patent Document 2 describes that porous particles were obtained as described above
- Patent Document 4 describes that “particles having a porous surface” were obtained (paragraph 0048 and the like).
- the shape of the hole takes a specific shape and form depending on the manufacturing method, it may not be satisfactory for various applications.
- the polyamide particles obtained in Patent Document 4 are fine particles having a particle size of about 12 to 15 ⁇ m, the oil absorption is 140 mL / g or less and does not have sufficient porosity.
- An object of the present invention is to provide novel porous polyamide particles. Another object of the present invention is to provide a method for producing polyamide particles in which the removal of the solvent used and the drying of the polyamide particles are easy in the production of polyamide particles.
- the present inventor can produce novel porous polyamide particles by dissolving polyamide in a cyclic amide by heating and cooling the polyamide amide. It has been found that residual polyamide amide as a solvent can be suppressed by washing high quality polyamide particles with liquid or supercritical carbon dioxide and drying.
- a polyamide particle characterized in that the appearance of the particle is substantially spherical, and is a spongy shape having a through hole in the outer surface and an independent hole in the inner surface.
- the polyamide particles according to item 1 having a number average particle diameter of 60 to 130 ⁇ m.
- the polyamide particles according to item 1 wherein the BET specific surface area is 15 m 2 / g or more. 4).
- the polyamide particles according to item 1, wherein the maximum pore diameter by a mercury porosimeter is 1 ⁇ m or less. 6).
- the polyamide particles according to item 1 wherein the median pore diameter measured by a mercury porosimeter is 0.5 ⁇ m or less. 7).
- DSC differential scanning calorimetry
- Item 9 is characterized in that the polyamide particles obtained by heating and dissolving the polyamide in a cyclic amide to obtain a homogeneous solution and cooling are washed with carbon dioxide in a liquid state or a supercritical state and dried.
- the manufacturing method of the polyamide particle of description is characterized in that the polyamide particles obtained by heating and dissolving the polyamide in a cyclic amide to obtain a homogeneous solution and cooling are washed with carbon dioxide in a liquid state or a supercritical state and dried.
- a polyamide can be heated and dissolved in a cyclic amide, and a novel polyamide particle can be produced by cooling the polyamide.
- the resulting novel polyamide particle is converted into a liquid state or a supercritical carbon dioxide.
- the residual cyclic amide polyamide particles as a solvent can be suppressed.
- a cyclic amide that dissolves in liquid or supercritical carbon dioxide is used as a solvent, the recovery and recycling of the solvent becomes simple, which is suitable as an industrial production method.
- the obtained polyamide particles were analyzed by SEM (Scanning Electron Microscope) and found to be spongy porous (see FIGS. 3 and 4). In addition, it was found from other analyzes that it has the characteristic physical properties shown in the above-mentioned items 1 to 8 and has properties superior to conventional products in the scrub feeling.
- the polyamide particles are effective as a raw material for various cosmetics because of their good slipperiness with the skin, and are excellent in oil absorption because they are porous.
- polyamide particles having a spheroidal shape in which the appearance of the particles is substantially spherical, having a through hole in the outer surface and an independent hole in the inner surface.
- the shape of the polyamide particles of the present invention is a spongy structure as seen in the scanning electron micrographs (SEM photographs) shown in FIGS. 1 and 2, and has through holes on the outer surface and independent holes on the inside. Yes. Since the through holes are concentrated on the outer surface, it is possible to develop a large specific surface area even though the particle diameter is large as shown below.
- the appearance of the particles is mainly a spherical fine particle shape such as a spherical shape or an elliptical shape.
- the number average particle size of the polyamide particles is in the range of 10 to 250 ⁇ m, particularly in the range of 20 to 200 ⁇ m, and further in the range of 60 to 130 ⁇ m, and the particle size can be controlled by the polyamide concentration and the cooling rate.
- the other physical properties of the polyamide particles of the present invention are as follows.
- the BET specific surface area is usually 15 m 2 / g or more, preferably 15 to 50 m 2 / g.
- General porous particles tend to have a specific surface area that decreases as the particle size increases.
- the polyamide particles of the present invention have a large specific surface area even though the particle diameter is around 100 ⁇ m.
- the specific surface area is small, it is not preferable when the catalyst or the like is supported because the supporting ability is lowered.
- the size is too large, the mechanical strength of the polyamide particles tends to be low, and the treatment for supporting the catalyst or the like tends to be difficult.
- the cumulative specific surface area is usually 80 m 2 / g or more, preferably 80 to 200 m 2 / g.
- the maximum pore diameter by a mercury porosimeter is usually 1 ⁇ m or less. This indicates that there are no pores having a diameter larger than 1 ⁇ m on the particle. Furthermore, since it has a high BET specific surface area of 15 m 2 / g or more, it can be said that very many fine pores exist on the polyamide particles. This feature slows the desorption rate of the adsorbed substance. This is very useful in applications where particles need to absorb maximum auxiliaries and do not release rapidly but rather slowly, such as cosmetics, paints, drugs and other applications. is there.
- the median pore diameter measured by a mercury porosimeter is usually 0.5 ⁇ m or less.
- the boiled linseed oil absorption amount is usually 170 ml / g or more.
- the degree of crystallinity measured by DSC is usually 45% or more.
- the crystallinity of polyamide can be determined by X-ray analysis, DSC measurement, or density. The DSC measurement is preferred.
- Polyamides crystallized from ordinary melts have a high crystallinity of about 30%. If the crystallinity is lower than 40%, the porous particles become unstable due to heat, which is not preferable.
- the polyamide particles of the present invention preferably have a crystallinity of 45% or more. It is particularly preferable that the crystallinity is higher than 50%.
- the polyamide particles of the present invention have a large number of independent pores inside as seen in the scanning electron micrographs shown in FIGS.
- the independent holes of the present invention are holes (encapsulated holes) that are not exposed on the surface of the polyamide particles and are encapsulated by the polyamide.
- the through hole is a hole that is not completely wrapped in polyamide and communicates with the surface.
- the shape of the hole may be in various forms, and the wall surface (cross section) may be linear, or may be irregularly winding, for example.
- Whether the hole is a through hole or an independent hole can be determined by observing a cured cross section with a scanning electron microscope after embedding and fixing polyamide particles with an epoxy resin.
- an epoxy resin that can be used is the main agent (Epok 812 manufactured by Oken Shoji Co., Ltd., viscosity 160CPS at 25 ° C., specific gravity 1.24 at 25 ° C.), curing agent (anhydrous methylnadic acid anhydride), polymerization accelerator (DMP-30). : 2,4,6-tris (dimethylaminomethyl) phenol) prepared according to the Lucas method, which can be cured at 70 ° C. for 12 hours, for example. Not only this epoxy resin but the thing with a similar viscosity and hardening conditions can also be used.
- the ratio of the independent holes to the through-holes of the polyamide particles of the present invention (the ratio of the cross-sectional area by the cross-sectional observation described above) varies depending on the manufacturing conditions, but is about 10:90 to 30:70.
- fragrances and antibacterial agents can be carried in these independent holes. It is also possible to change the elasticity of the particles themselves by changing the type of substance to be included.
- polyamide particles having a particle diameter of about 100 ⁇ m have a relatively smooth surface, so the amount of oil absorption is low.
- the polyamide particles of the present invention have a rough surface and are high Has oil absorption.
- it When used as a body wash, it also has the advantage of giving the skin a comfortable, scrubbing, and refreshing feel with moderate skin irritation, and the possibility of creating an unprecedented new body wash. have.
- polyamide particles are precipitated by heating and dissolving polyamide in a cyclic amide to form a uniform solution and cooling the solution.
- the polyamide particles are advantageous for washing with carbon dioxide in a liquid state or supercritical state and drying, and as a result, the residual cyclic amide as a solvent can be reduced.
- the polyamide used as a raw material in the method for producing polyamide particles of the present invention is a high molecular compound having an acid amide (—CONH—) bond as a repeating unit, and (1) by ring-opening polymerization of lactam according to the polymerization mode, (2 ) By polycondensation of aminocarboxylic acid, and (3) by polycondensation of diamine and dibasic acid.
- polyamide 6 polyamide 6
- polyamide 66 nylon 66
- polyamide 11 polyamide 12
- polyamide 46 polyamide 610
- polyamide 612 and other aliphatic polyamides
- poly (metaxylene azimuth) Pamid poly (hexamethylene terephthalamide), poly (hexamethylene isophthalamide), and other aliphatic-aromatic polyamides, copolymers thereof, and further, 2-methylpentamethylenediamine and adipine in its skeleton
- bio-based polyamide examples include polyamide 1010 (PA1010), polyamide 610 (PA610), polyamide 11 (PA11), and polyamide 4 (PA4).
- PA1010, PA610, and PA11 commercially available products can be used, and PA4 can be synthesized from 2-pyrrolidone, for example, based on the description in JP-A-2009-159840.
- the cyclic amide used in the present invention preferably has 4 to 18 carbon atoms constituting the ring.
- Specific examples include 2-pyrrolidone, piperidone, N-methylpyrrolidone, ⁇ -caprolactam, N-methylcaprolactam, ⁇ -lauryl lactam, and the like.
- the cycloalkylidene ring may have a substituent that does not inhibit the reaction, and examples of the substituent include an acyclic or cyclic alkyl group such as a methyl group, an ethyl group, and a cyclohexyl group, a vinyl group, Examples include acyclic or cyclic alkenyl groups such as cyclohexenyl group, aryl groups such as phenyl group, alkoxy groups such as methoxy group, alkoxycarbonyl groups such as methoxycarbonyl group, and halogen groups such as chloro group. Unsubstituted 2-pyrrolidone and ⁇ -caprolactam are preferable.
- the heating may be performed at a temperature at which the polyamide is dissolved in the cyclic amide.
- heating more than necessary may cause deterioration of the polyamide, discoloration, and the like.
- the time from the start of addition of polyamide to the cyclic amide to the formation of a homogeneous solution is usually in the range of 0.1 second to 120 minutes, preferably in the range of 1 second to 90 minutes, particularly preferably in the range of 1 second to The range is 60 minutes.
- the amount of polyamide used is 2% to 30% by weight, preferably 3% to 20% by weight, based on the total weight of polyamide and cyclic amide. If the amount of polyamide used is low, the crystal growth is unidirectional, so that it tends to be fibrous, and if the amount used is high, a part or the whole tends to be agglomerated, and the particle shape may not be obtained.
- the cooling is generally in the range of 5 to 100 ° C., preferably in the range of 10 to 80 ° C.
- the standing time of the uniform solution of polyamide and cyclic amide is usually 5 minutes or more, preferably 120 minutes or more after the uniform solution is formed.
- the cooling rate is not particularly limited, but typically ranges from 1.5 to 100 ° C./min.
- the polyamide particles precipitated in a uniform solution of polyamide and cyclic amide can be separated by a usual method such as centrifugation, decantation, or filtration.
- a low specific gravity solvent such as methanol, isopropanol or water
- the polyamide particles may be separated by a method such as centrifugation or decantation.
- the precipitated polyamide particles may be further washed several times with methanol, acetone or the like and then separated by a method such as centrifugation or decantation.
- the polyamide particles separated from the mixed solution can be dried by an ordinary method such as vacuum drying or a spray dryer.
- the obtained polyamide particles are spongy porous when analyzed by SEM (Scanning Electron Microscope) (see FIGS. 3 and 4).
- the present inventor has found that the cyclic amide used in the present invention has a property of being dissolved with liquid carbon dioxide or supercritical carbon dioxide, and thus polyamide particles obtained from a uniform solution of polyamide and cyclic amide are obtained. It has been found that by washing with liquid carbon dioxide or supercritical carbon dioxide and drying, the polyamide particles can be separated and dried in a single step, and polyamide particles in which almost no cyclic amide as a solvent remains can be produced.
- Polyamide particles precipitated from a homogeneous solution of polyamide and cyclic amide by the above method are added together with the solution to an autoclave equipped with a stirrer, a filter and a pressure control valve, and the system is pressurized to 5-10 MPa with carbon dioxide.
- carbon dioxide is circulated with a pump.
- the cyclic amide and carbon dioxide as the solvent are discharged from the pressure regulating valve.
- the system pressure is reduced to normal pressure, and then released to obtain dried polyamide particles.
- Carbon dioxide has a critical temperature of 31 ° C. and a critical pressure of 7.38 MPa. For example, when it is 8 MPa, it is liquid at 20 ° C. and supercritical at 50 ° C.
- the residual solvent can be controlled to 0.01% by weight or less and 100 ppm or less.
- the polyamide particles obtained by the production method of the present invention can be used as cleansing masks, foundations, UV care, antiperspirants, facial cleansers, shower gels, cosmetic raw materials such as detergent additives, and chromatographic fillers. It can also be used as a carrier or adsorbent for various catalysts in the food industry and the medical field, and can be used as a toner for electrophotography by loading a colorant on polyamide particles, or as an electronic material for display devices, etc. You can also Furthermore, it can also be used for water-based inks, HD abrasives, organic EL, adhesives, electrostatic coating applications, powder coating applications, and prototype fabrication by laser sintering.
- Sample amount About 0.2g Sample cell: Small cell (10mm ⁇ ⁇ 3cm) Measurement range: Whole area measurement range: Pore diameter 400 ⁇ m ⁇ 0.0036 ⁇ m Calculation range: Pore diameter 400 ⁇ m to 0.0036 ⁇ m Mercury contact angle: 140 deg Mercury surface tension: 480 dyn / cm Measurement cell volume: 0.5cc Number of measurements: 1 time
- Measurement was performed using a high-speed specific surface area / pore diameter distribution measuring device NOVA-1200 (manufactured by Quanta Chrome Co.). The following are the conditions. Pretreatment conditions: A sample was placed in a measurement cell and degassed for 30 minutes at 100 ° C. under vacuum.
- ⁇ Measurement principle Constant volume method (blank correction type)
- ⁇ Detection method Relative pressure; Ratio of adsorption equilibrium pressure and saturated vapor pressure in the sample cell by pressure transducer
- Item Specific surface area and number of measurements by BET multipoint method: Measured twice with the same sample.
- the crystallinity of the polyamide fine particles was measured by DSC (differential scanning calorimeter). Flow rate 40 ml / min. In a nitrogen stream, the heat of crystal fusion is calculated from the area of the endothermic peak at a rate of temperature increase of 5 ° C./min and a temperature range of 120 to 230 ° C. The degree of crystallinity is determined from the ratio between the calculated heat of fusion and the heat of crystal fusion of the polyamide constituting the polyamide fine particles. When the polyamide constituting the polyamide fine particles was polyamide 6, the heat of crystal melting was 189 J / g, and when the polyamide 12 was polyamide 12, the heat of crystal melting was 209 J / g.
- Measurement was performed using a laser diffraction / scattering particle size distribution analyzer LA-910 (manufactured by Horiba, Ltd.). The following are the conditions.
- ⁇ Measurement mode Manual flow cell measurement
- ⁇ Measurement range 0.02 ⁇ m to 1000 ⁇ m
- Dispersion medium 200 cc of 2-propanol Refractive index: 1.28-0.001
- Sample pretreatment A sample and a dispersion medium were placed in a sample tube and ultrasonically dispersed for 10 minutes.
- -Number of measurements The sample was changed and measured twice.
- Example 1 Production of polyamide 6 particles using 2-pyrrolidone as a solvent
- a mixing vessel equipped with a stirrer in which 2-pyrrolidone was mixed with 20% by weight of polyamide 6 pellets with nitrogen.
- the mixture was stirred at 200 ° C. for about 60 minutes until the polyamide 6 was completely dissolved.
- the obtained homogeneous solution was cooled to room temperature at a cooling rate of 1.5 ° C./min.
- 2-Propanol was added to this mixture, and the solvent was roughly separated by washing and filtration, followed by drying to obtain polyamide 6 spherical particles.
- Observation of the obtained spherical particles with a microscope revealed spherical particles having a particle size of 130 to 200 ⁇ m (see FIG. 1).
- the median diameter of the spherical particles was 154.8 ⁇ m.
- the spherical particles had a BET specific surface area of 30.6 square meters / g.
- the heat of crystal fusion was 103 J / g.
- the crystallinity was 54%.
- the cumulative specific surface area was 91 square meters (m 2 ) / g, the mercury maximum pore diameter was 0.03 ⁇ m, and the median pore diameter was 0.03 ⁇ m.
- the boiled linseed oil absorption amount was 195 ml / g.
- Table 1 shows the measurement results of the particle size distribution of polyamide 6 particles produced using 2-pyrrolidone. Further, the polyamide particles were mixed with epoxy resin (main agent (Epok Corporation, Epok 812, viscosity 160 CPS at 25 ° C., specific gravity 1.24 at 25 ° C.), curing agent (anhydrous methyl nadic acid), polymerization accelerator (DMP-30). : 2,4,6-tris (dimethylaminomethyl) phenol) was added according to the Lucas method (Luft JH: Improvments in epoxies resin embedding methods, J Biophys Biochem Cytol, 9: 409-414, 1961). Then, what was cured at 70 ° C.
- epoxy resin main agent (Epok Corporation, Epok 812, viscosity 160 CPS at 25 ° C., specific gravity 1.24 at 25 ° C.
- curing agent anhydrous methyl nadic acid
- DMP-30 polymerization accelerator
- Example 2 Production of polyamide 6 particles using 2-pyrrolidone as a solvent
- the cooling rate of the solution was set to 100 ° C / min.
- spherical particles of polyamide 6 were obtained. Similar to Example 1, the observation or measurement results are as follows.
- Example 3 Production of polyamide 6 particles using 2-pyrrolidone as a solvent The same procedure as in Example 1 was repeated except that the amount of polyamide 6 pellets used was 15% by weight. Spherical particles were obtained. Similar to Example 1, the observation or measurement results are as follows.
- Example 4 Production of polyamide 6 particles using ⁇ -caprolactam as a solvent
- the solvent was changed from 2-pyrrolidone to ⁇ -caprolactam
- the spherical shape of polyamide 6 was changed. Particles were obtained. Similar to Example 1, the observation or measurement results are as follows.
- Example 5 Production of polyamide 6 particles using ⁇ -caprolactam as a solvent
- the solvent was changed from 2-pyrrolidone to ⁇ -caprolactam, and the cooling rate of the solution was set to 100 ° C / min.
- Spherical particles of polyamide 6 were obtained in the same manner as in Example 1 except that it was cooled to the ice temperature. Similar to Example 1, the observation or measurement results are as follows.
- Example 6 Production of polyamide 12 particles using 2-pyrrolidone as a solvent In the same manner as in Example 1 except that polyamide 6 was changed to polyamide 12, spherical particles of polyamide 12 were obtained. . Similar to Example 1, the observation or measurement results are as follows.
- Example 2 a sample cured by injecting an epoxy resin into polyamide particles was observed with a scanning electron microscope. This is shown in FIGS. As is apparent from the SEM image, the through hole exists in the outer surface portion, and the independent hole exists in the inside. The ratio of the through hole and the independent hole was 8: 2.
- Example 7 Production of polyamide 12 particles using 2-pyrrolidone as a solvent In Example 6, except that the solution was cooled to the ice temperature at a cooling rate of 100 ° C / min. Thus, spherical particles of polyamide 12 were obtained. Similar to Example 1, the observation or measurement results are as follows.
- Example 8 Production of polyamide 12 particles using 2-pyrrolidone as a solvent The same procedure as in Example 6 was repeated except that the amount of polyamide 12 pellets used was 15 wt%. Spherical particles were obtained. Similar to Example 1, the observation or measurement results are as follows.
- Example 9 Production of polyamide 66 particles using 2-pyrrolidone as a solvent Mixing tank equipped with a stirrer in which 2-pyrrolidone was mixed with 5% by weight of polyamide 66 pellets with nitrogen. The mixture was stirred at 230 ° C. for about 60 minutes until the polyamide 66 was completely dissolved. The resulting homogeneous solution was cooled to ice temperature at a rate of 100 ° C./min. 2-Propanol was added to this mixture, and the solvent was roughly separated by washing and filtration, followed by drying to obtain polyamide 66 spherical particles. Similar to Example 1, the observation or measurement results are as follows.
- Example 10 Cleaning and drying of polyamide particles using carbon dioxide Mixture of polyamide particles obtained in Example 6 (polyamide 12 particles and 2) in a 50 mL stainless steel autoclave equipped with a stirrer, a filter and a pressure control valve -Pyrrolidone mixture) was added in an amount of 10 g, and the pressure in the system was increased to 8 MPa with carbon dioxide. Next, after heating to a temperature of 30 ° C., carbon dioxide was passed through the pump at 3 mL / min for 4 hours. At this time, 2-pyrrolidone and carbon dioxide used as a solvent were discharged from the pressure regulating valve. After reducing the internal pressure to normal pressure, the polyamide particles were opened and dried to obtain polyamide particles. Similar to Example 1, the observation or measurement results are as follows.
- the 2-pyrrolidone remaining in the spherical particles was measured by gas chromatography and found to be 97 ppm.
- Example 11 Production of polyamide 1010 particles using ⁇ -caprolactam as a solvent Mixing tank equipped with a stirrer in which a mixture obtained by mixing 15 wt% of polyamide 1010 pellets with ⁇ -caprolactam was replaced with nitrogen The mixture was stirred at 200 ° C. for about 60 minutes until the polyamide 1010 was completely dissolved. The resulting homogeneous solution was cooled to room temperature at a rate of 1.5 ° C./min. Then, it processed like Example 1 and obtained the spherical particle of the polyamide 1010. Similar to Example 1, the observation or measurement results are as follows.
- Example 12 Production of polyamide 11 particles using ⁇ -caprolactam as a solvent Mixing tank equipped with a stirrer in which a mixture obtained by mixing 15 wt% of pellets of polyamide 11 with ⁇ -caprolactam was replaced with nitrogen The mixture was stirred for about 60 minutes at 200 ° C. until the polyamide 11 was completely dissolved. The resulting homogeneous solution was cooled to room temperature at a rate of 1.5 ° C./min. Then, it processed like Example 1 and obtained the spherical particle of the polyamide 11. Similar to Example 1, the observation or measurement results are as follows.
- Example 13 Production of polyamide 610 particles using ⁇ -caprolactam as a solvent Mixing tank equipped with a stirrer in which a mixture obtained by mixing 15 wt% of pellets of polyamide 610 with ⁇ -caprolactam was replaced with nitrogen The mixture was stirred at 200 ° C. for about 60 minutes until the polyamide 610 was completely dissolved. The resulting homogeneous solution was cooled to room temperature at a rate of 1.5 ° C./min. Thereafter, the same treatment as in Example 1 was performed to obtain spherical particles of polyamide 610. Similar to Example 1, the observation or measurement results are as follows.
- Example U-1 Manufacture of liquid detergent containing polyamide particles Potassium laurate, potassium myristate, glycerin, propylene glycol, hydroxypropylcellulose, and coconut oil fatty acid diethanolamine were added to ion-exchanged water in the amounts shown in Table 2. It mix
- Example U-2 A liquid detergent containing polyamide particles was produced in the same manner as in Example U-1, except that the polyamide particles obtained in Example 6 were used.
- Example U-1 A liquid detergent containing polyamide particles was produced in the same manner as in Example U-1, except that general-purpose polyamide 12 true spherical particles (SP-500 manufactured by Toray Industries, Inc.) were used as the polyamide particles.
- SP-500 manufactured by Toray Industries, Inc.
- FIG. 9 is an image obtained by observing, with a scanning electron microscope, a sample obtained by injecting an epoxy resin into polyamide particles and curing the same as in Example 1.
- Example U-2 A liquid detergent containing polyamide particles was produced in the same manner as in Example U-1, except that general-purpose polyamide 12 porous non-spherical particles (Orgasol 2002 UD NAT COS manufactured by Atofina) were used as the polyamide particles.
- general-purpose polyamide 12 porous non-spherical particles Orgasol 2002 UD NAT COS manufactured by Atofina
- FIG. 14 is an image obtained by observing, with a scanning electron microscope, a sample obtained by injecting an epoxy resin into polyamide particles and curing the same as in Example 1.
- Example U-3 A liquid detergent containing polyamide particles was produced in the same manner as in Example U-1, except that general-purpose polyamide 6 porous particles (TR-1 manufactured by Metal Color) were used as the polyamide particles.
- FIG. 17 is an image obtained by observing, with a scanning electron microscope, a sample obtained by injecting an epoxy resin into polyamide particles and curing the same as in Example 1.
- the average value of each of these evaluation items was calculated and judged according to the following criteria.
- the evaluation was performed twice by 10 panelists. 2.5 points or more and 3.0 points or less: ⁇ 2.0 points or more and less than 2.5 points: ⁇ 1.5 points or more and less than 2.0 points: 1.0 point or more and less than 1.5 point: ⁇
- Examples U-1 and U-2 using the polyamide particles obtained in Examples 1 and 6 had high scrub feeling and high safety against the skin. In addition, it has a high detergency and was extremely effective in removing dirt on skin details.
- Comparative Examples U-1, U-2, and U-3 did not have much scrub feeling and had a slightly high cleaning effect.
- the polyamide particles of the present invention can be used in cosmetics, paints, chemicals, catalysts, and other various fields by utilizing at least one of the various characteristics described above.
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Abstract
Description
1. 粒子の外観形状が略球形であり、外表部に貫通孔、内部に独立孔を有する海綿状であることを特徴とするポリアミド粒子。
2. 数平均粒子径が60~130μmである第1項に記載のポリアミド粒子。
3. BET比表面積が15m2/g以上である第1項に記載のポリアミド粒子。
4. 累積比表面積が80m2/g以上である第1項に記載のポリアミド粒子。
5. 水銀ポロシメータによる極大細孔直径が1μm以下である第1項に記載のポリアミド粒子。
6. 水銀ポロシメータによるメジアン細孔直径が0.5μm以下である第1項に記載のポリアミド粒子。
7. JIS K 5101に準拠する方法で測定した煮亜麻仁油吸油量が170ml/g以上である第1項に記載のポリアミド粒子。
8. 示差走査熱量測定(DSC:Differential scanning calorimetry)で測定された結晶化度が45%以上である第1項に記載のポリアミド粒子。
9. ポリアミドを環状アミドに加熱溶解させ、均一溶液とし、これを冷却することによって、ポリアミド粒子を析出させる第1項に記載のポリアミド粒子の製造方法。
10. ポリアミドの濃度が、ポリアミドと環状アミドとの重量和に対して2重量%から30重量%であることを特徴とする第9項に記載のポリアミド粒子の製造方法。
11. ポリアミドが、ポリアミド6(ナイロン6)、ポリアミド66(ナイロン66)、又はポリアミド12(ナイロン12)であることを特徴とする第9項に記載のポリアミド粒子の製造方法。
12. 環状アミドが、2-ピロリドン、N-メチルピロリドン、ε-カプロラクタム、N-メチルカプロラクタム、又はω-ラウリルラクタムであることを特徴とする第9項に記載のポリアミド粒子の製造方法。
13. ポリアミドを環状アミドに加熱溶解させ、均一溶液とし、これを冷却することによって得られたポリアミド粒子を、液体状態または超臨界状態の二酸化炭素で洗浄し、乾燥することを特徴とする第9項に記載のポリアミド粒子の製造方法。
ポリアミド粒子の吸油量は、JIS K 5101に従って、煮亜麻仁油の吸油量を測定した。
水銀圧入式細孔径分布測定装置PoreMaster60GT(Quanta chrome .Co製)を用い、測定を行なった。以下はその条件である。
サンプル量 :約0.2g
サンプルセル:スモールセル(10mmΦ×3cm)
測定レンジ :全域
測定範囲 :細孔直径 400μm ~ 0.0036μm
計算範囲 :細孔直径 400μm ~ 0.0036μm
水銀接触角 :140deg
水銀表面張力:480dyn/cm
測定セル容積:0.5cc
測定回数 :1回
高速比表面積・細孔径分布測定装置 NOVA-1200(Quanta chrome .Co製)を用い、測定を行なった。以下はその条件である。
・前処理条件:試料を測定セルに入れ、100℃真空下で30分間脱気した。
・測定原理 :定容法(ブランク補正型)
・検出法 :相対圧力;圧力トランデューサによるサンプルセル内の吸着平衡圧力と飽和蒸気圧の比
吸着ガス量;圧力トランデューサによる圧力検出とサーミスタによるマニホールド 温度検出から理想気体での注入ガス量を計算
セルサイズ:スモール・ペレット・セル
・吸着ガス :窒素ガス
・測定範囲 :0.01m2/g以上
・測定項目 :P/P0=0.1、0.2、0.3の吸着側3点
・解析項目 :BET多点法による比表面積
・測定回数 :同一試料で2回測定した。
ポリアミド微粒子の結晶化度は、DSC(示差走査熱量計)で測定した。流速40ml/min.窒素気流中で、昇温速度5℃/min、温度範囲120~230℃の吸熱ピークの面積から結晶融解熱量を算出する。結晶化度は、算出した融解熱量とポリアミド微粒子を構成するポリアミドの結晶融解熱量との比から求める。ポリアミド微粒子を構成するポリアミドがポリアミド6の場合、結晶融解熱を189J/g、ポリアミド12の場合、結晶融解熱を209J/gとした。
レーザー回折/散乱式粒度分布測定装置LA-910(堀場製作所(株)製)を用い、測定した。以下はその条件である。
・測定モード:マニュアルフロー式セル測定
・測定範囲 :0.02μm ~ 1000μm
・分散媒 :2-プロパノール 200cc
・屈折率 :1.28 ― 0.001
・試料前処理:試料と分散媒をサンプル管に入れ、10分間超音波分散した。
・測定回数 :試料を替えて2回測定した。
2-ピロリドンにポリアミド6のペレットを20重量%混合し得られた混合物を、窒素で置換した撹拌機がついた混合槽内で、200℃にてポリアミド6が完全に溶解するまで約60分間撹拌した。得られた均一溶液を1.5℃/分の冷却速度で室温まで冷却した。 この混合物に2-プロパノールを添加し、洗浄、ろ過によって溶媒を粗分離後、乾燥してポリアミド6の球状粒子を得た。得られた球状粒子を顕微鏡にて観察したところ粒径が130~200μmの球状粒子が確認された(図1参照)。また得られた粒子の粒径とその分布を粒度分布測定器を用いて確認した結果、この球状粒子のメジアン径は154.8μmであった。また、この球状粒子のBET比表面積は、30.6平方メートル/gであった。
実施例1において、溶液の冷却速度を100℃/分の速度として、氷温まで冷却した以外は、実施例1と同様にして、ポリアミド6の球状粒子を得た。実施例1と同様に、観察または測定した結果は次のとおりである。
メジアン径:28.1μm
BET比表面積:10.9m2/g
粒度分布測定結果:表1に示す。
実施例1において、使用したポリアミド6ペレットの量を15重量%とした以外は、実施例1と同様にして、ポリアミド6の球状粒子を得た。実施例1と同様に、観察または測定した結果は次のとおりである。
メジアン径:107.8μm
BET比表面積:11.9m2/g
粒度分布測定結果:表1に示す。
実施例1において、溶媒を2-ピロリドンからε-カプロラクタムに変更した以外は、実施例1と同様にして、ポリアミド6の球状粒子を得た。実施例1と同様に、観察または測定した結果は次のとおりである。
メジアン径:102.2μm
BET比表面積:23.3m2/g
粒度分布測定結果:表1に示す。
実施例1において、溶媒を2-ピロリドンからε-カプロラクタムに変更し、また溶液の冷却速度を100℃/分の速度として、氷温まで冷却した以外は、実施例1と同様にして、ポリアミド6の球状粒子を得た。実施例1と同様に、観察または測定した結果は次のとおりである。
メジアン径:61.0μm
BET比表面積:19.9m2/g
粒度分布測定結果:表1に示す。
実施例1において、ポリアミド6をポリアミド12に変更した以外は、実施例1と同様にして、ポリアミド12の球状粒子を得た。実施例1と同様に、観察または測定した結果は次のとおりである。
BET比表面積:8.7m2/g
結晶融解熱:108J/g
結晶化度:52%
累積比表面積:92m2/g
水銀極大細孔直径:0.18μm
メジアン細孔直径:0.12μm
煮亜麻仁油吸油量:180ml/g
粒度分布測定結果:表1に示す。
実施例6において、溶液の冷却速度を100℃/分の速度として、氷温まで冷却した以外は、実施例6と同様にして、ポリアミド12の球状粒子を得た。実施例1と同様に、観察または測定した結果は次のとおりである。
メジアン径:86.9μm
BET比表面積:16.7m2/g
粒度分布測定結果:表1に示す。
実施例6において、使用したポリアミド12ペレットの量を15重量%とした以外は、実施例6と同様にして、ポリアミド12の球状粒子を得た。実施例1と同様に、観察または測定した結果は次のとおりである。
メジアン径:119.6μm
BET比表面積:11.2m2/g
粒度分布測定結果:表1に示す。
2-ピロリドンにポリアミド66のペレットを5重量%混合して得られた混合物を、窒素で置換した撹拌機がついた混合槽内で、230℃にてポリアミド66が完全に溶解するまで約60分間撹拌した。得られた均一溶液を100℃/分の速度で氷温まで冷却した。この混合物に2-プロパノールを添加し、洗浄、ろ過によって溶媒を粗分離後、乾燥してポリアミド66の球状粒子を得た。実施例1と同様に、観察または測定した結果は次のとおりである。
メジアン径:96.5μm
BET比表面積:3.3m2/g
粒度分布測定結果:表1に示す。
攪拌機、フィルター、圧力調整弁を備え持つ容積50mLのステンレス製オートクレーブに実施例6で得られたポリアミド粒子含有混合物(ポリアミド12粒子と2-ピロリドンの混合物)を10g添加し、系内を二酸化炭素で8MPaまで昇圧した。次に加熱して温度30℃にしてから、二酸化炭素をポンプで3mL/minで4時間流通させた。このとき圧力調整弁からは、溶媒として使用した2-ピロリドンと二酸化炭素が排出された。常圧まで系内圧力を低下させた後、開放して乾燥したポリアミド粒子を得た。実施例1と同様に、観察または測定した結果は次のとおりである。
メジアン径:133.3μm
BET比表面積:8.8m2/g
粒度分布測定結果:表1に示す。
エチレングリコールにポリアミド12のペレットを10重量%混合して得られた混合物を、窒素で置換した撹拌機がついた混合槽内で、190℃にてポリアミド12が完全に溶解するまで約60分間撹拌した。得られた均一溶液を1.5℃/分の速度で室温まで冷却してポリアミド粒子含有混合物を得た。
ε-カプロラクタムにポリアミド1010のペレットを15重量%混合して得られた混合物を、窒素で置換した撹拌機がついた混合槽内で、200℃にてポリアミド1010が完全に溶解するまで約60分間撹拌した。得られた均一溶液を1.5℃/分の速度で室温まで冷却した。その後、実施例1と同様に処理して、ポリアミド1010の球状粒子を得た。実施例1と同様に、観察または測定した結果は次のとおりである。
メジアン径:110μm
BET比表面積:8.1m2/g
ε-カプロラクタムにポリアミド11のペレットを15重量%混合して得られた混合物を、窒素で置換した撹拌機がついた混合槽内で、200℃にてポリアミド11が完全に溶解するまで約60分間撹拌した。得られた均一溶液を1.5℃/分の速度で室温まで冷却した。その後、実施例1と同様に処理して、ポリアミド11の球状粒子を得た。実施例1と同様に、観察または測定した結果は次のとおりである。
メジアン径:105μm
BET比表面積:9.3m2/g
ε-カプロラクタムにポリアミド610のペレットを15重量%混合して得られた混合物を、窒素で置換した撹拌機がついた混合槽内で、200℃にてポリアミド610が完全に溶解するまで約60分間撹拌した。得られた均一溶液を1.5℃/分の速度で室温まで冷却した。その後、実施例1と同様に処理して、ポリアミド610の球状粒子を得た。実施例1と同様に、観察または測定した結果は次のとおりである。
メジアン径:108μm
BET比表面積:8.5m2/g
次に、本発明のポリアミド粒子の使用実施例を示す。
表2に示す配合量にてイオン交換水にラウリン酸カリウム、ミリスチン酸カリウム、グリセリン、プロピレングリコール、ヒドロキシプロピルセルロース、及びヤシ油脂肪酸ジエタノールアミンを配合し、60℃で加熱溶解した。これにジステアリン酸エチレングリコールを表2に示す配合量で添加し、実施例1で得られたポリアミド粒子を表2に記載の配合量だけ添加し、均一に混合した。これを30℃まで冷却し、白色不透明のポリアミド粒子入り液体洗浄剤を製造した。
実施例6で得られたポリアミド粒子を用いた以外は、実施例U-1と同様にして、ポリアミド粒子入り液体洗浄剤を製造した。
ポリアミド粒子として、汎用のポリアミド12真球状粒子(東レ製 SP-500)を使用した以外は、実施例U-1と同様にして、ポリアミド粒子入り液体洗浄剤を製造した。
比表面積:1.2m2/g
累積比表面積:21.7m2/g
極大細孔直径:2.02μm
メジアン細孔直径:1.83μm
煮亜麻仁油吸油量:80mL/100g
ポリアミド粒子として、汎用のポリアミド12多孔質非球状粒子(アトフィナ製 Orgasol 2002 UD NAT COS)を使用した以外は、実施例U-1と同様にして、ポリアミド粒子入り液体洗浄剤を製造した。
比表面積:8.2m2/g
累積比表面積:30.1m2/g
極大細孔直径:1.88μm
メジアン細孔直径:1.68μm
煮亜麻仁油吸油量:80mL/100g
ポリアミド粒子として、汎用のポリアミド6多孔質粒子(メタルカラー製 TR-1)を使用した以外は、実施例U-1と同様にして、ポリアミド粒子入り液体洗浄剤を製造した。
比表面積:2.5m2/g
累積比表面積:34.7m2/g
極大細孔直径:5.36μm
メジアン細孔直径:5.05μm
煮亜麻仁油吸油量:130mL/100g
十分強い :3点
ふつう :2点
少し物足りない :1点
(スクラブの落ち易さ)
非常に落ち易い :3点
ふつう :2点
少し落ちにくい :1点
(ヒリヒリ感)
なし :3点
少しある :2点
ある :1点
2.5点以上3.0点以下:◎
2.0点以上2.5点未満:○
1.5点以上2.0点未満:△
1.0点以上1.5点未満:×
カーボンブラックを手のひらに2mg/cm2塗布し、乾燥後、実施例U-1~2、比較例U-1~3で得られた液体洗浄剤をつけて指による摩擦洗浄を一定回数行い、さらに、水洗、乾燥後、手のひら1cm2当たりに残ったカーボンブラックの度合いを実体顕微鏡で観察した。
なお、評価は下記の5段階とした。
5:洗浄力高い(皮膚細部の汚れがほぼ全量除去)
4:洗浄力高い(皮膚細部の汚れが8~9割程度除去)
3:洗浄力中位(皮膚細部の汚れが6~7割程度除去)
2:洗浄力中位(皮膚細部の汚れが4~5割程度除去)
1:洗浄力低い(皮膚細部の汚れが2~3割程度除去)
実施例1、6で得られたポリアミド粒子を用いた実施例U-1、U-2は、高いスクラブ感を有し、皮膚に対する高い安全性を有しているという結果であった。また、洗浄力も高く皮膚細部の汚れ除去にも極めて有効であった。
Claims (13)
- 粒子の外観形状が略球形であり、外表部に貫通孔、内部に独立孔を有する海綿状であることを特徴とするポリアミド粒子。
- 数平均粒子径が60~130μmである請求項1に記載のポリアミド粒子。
- BET比表面積が15m2/g以上である請求項1に記載のポリアミド粒子。
- 累積比表面積が80m2/g以上である請求項1に記載のポリアミド粒子。
- 水銀ポロシメータによる極大細孔直径が1μm以下である請求項1に記載のポリアミド粒子。
- 水銀ポロシメータによるメジアン細孔直径が0.5μm以下である請求項1に記載のポリアミド粒子。
- JIS K 5101に準拠する方法で測定した煮亜麻仁油吸油量が170ml/g以上である請求項1に記載のポリアミド粒子。
- 示差走査熱量測定で測定された結晶化度が45%以上である請求項1に記載のポリアミド粒子。
- ポリアミドを環状アミドに加熱溶解させ、均一溶液とし、これを冷却することによって、ポリアミド粒子を析出させる請求項1に記載のポリアミド粒子の製造方法。
- ポリアミドの濃度が、ポリアミドと環状アミドとの重量和に対して2重量%から30重量%であることを特徴とする請求項9に記載のポリアミド粒子の製造方法。
- ポリアミドが、ポリアミド6、ポリアミド66、又はポリアミド12であることを特徴とする請求項9に記載のポリアミド粒子の製造方法。
- 環状アミドが、2-ピロリドン、N-メチルピロリドン、ε-カプロラクタム、N-メチルカプロラクタム、又はω-ラウリルラクタムであることを特徴とする請求項9に記載のポリアミド粒子の製造方法。
- ポリアミドを環状アミドに加熱溶解させ、均一溶液とし、これを冷却することによって得られたポリアミド粒子を、液体状態または超臨界状態の二酸化炭素で洗浄し、乾燥することを特徴とする請求項9に記載のポリアミド粒子の製造方法。
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Cited By (9)
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JP2011116976A (ja) * | 2009-11-05 | 2011-06-16 | Sanyo Chem Ind Ltd | 樹脂粒子の製造方法 |
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Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005054153A (ja) * | 2003-08-07 | 2005-03-03 | Ube Ind Ltd | ポリアミド多孔質粒子の製造方法 |
JP2006169373A (ja) | 2004-12-15 | 2006-06-29 | Metal Color:Kk | ナイロン12球状粒子粉末の製造方法 |
WO2006082908A1 (ja) * | 2005-02-02 | 2006-08-10 | Ube Industries, Ltd. | 多孔質球状ポリアミド粒子の製造方法 |
JP2006328173A (ja) | 2005-05-25 | 2006-12-07 | Metal Color:Kk | ポリアミド球状粒子粉末の製造方法 |
JP2007056085A (ja) | 2005-08-23 | 2007-03-08 | Toray Ind Inc | ポリカプロアミド樹脂微粒子およびそれを含む化粧品 |
JP2007106895A (ja) * | 2005-10-14 | 2007-04-26 | Sumika Enviro-Science Co Ltd | 球状ポリアミド粒子の製造方法 |
JP2007515500A (ja) * | 2003-06-26 | 2007-06-14 | ロディア・ポリアミド・インターミーディエッツ | ポリアミドから作られた球形粒子の製造方法 |
JP2007204767A (ja) * | 2000-06-14 | 2007-08-16 | Ube Ind Ltd | ポリアミド多孔質粒子の製造方法 |
JP2008038037A (ja) | 2006-08-07 | 2008-02-21 | Ube Ind Ltd | 多孔質ポリアミド粉末の製造方法 |
JP2008088296A (ja) * | 2006-10-02 | 2008-04-17 | Ube Ind Ltd | 着色ポリアミド微粒子およびその製造方法 |
JP2008086874A (ja) * | 2006-09-29 | 2008-04-17 | Ube Ind Ltd | 吸放湿材料 |
JP2008127495A (ja) * | 2006-11-22 | 2008-06-05 | Teijin Ltd | 全芳香族ポリアミド粒子の製造方法 |
JP2008189895A (ja) * | 2007-02-08 | 2008-08-21 | Gantsu Kasei Kk | 球状ポリアミド粒子の製造方法 |
JP2009159840A (ja) | 2007-12-28 | 2009-07-23 | National Institute Of Advanced Industrial & Technology | バイオマスからの2−ピロリドン乃至ポリアミド4、n−メチル−2−ピロリドン、ポリビニルピロリドンの合成方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2958677A (en) * | 1955-05-10 | 1960-11-01 | Phillips Petroleum Co | Purification of polymers of the polyamide type |
US5128125A (en) * | 1988-02-16 | 1992-07-07 | Barnes Arthur C | Method for preparing finely divided nylon-4 complex with iodine and antiseptic preparation made therefrom |
CA2044787A1 (en) * | 1990-10-31 | 1992-05-01 | Shahid P. Qureshi | Fiber-reinforced composites toughened with porous resin particles |
US5268223A (en) | 1991-05-31 | 1993-12-07 | Amoco Corporation | Toughened fiber-reinforced composites |
JP2005239575A (ja) * | 2004-02-24 | 2005-09-08 | Ube Ind Ltd | ポリアミド多孔質粒子を含有する皮膚用及び毛髪用の化粧料組成物 |
WO2007069694A1 (ja) * | 2005-12-14 | 2007-06-21 | Ube Industries, Ltd. | 無機化合物担持ポリアミド多孔質粒子からなる粉末 |
-
2010
- 2010-03-02 CN CN201080016142.7A patent/CN102388088B/zh not_active Expired - Fee Related
- 2010-03-02 EP EP10748729.0A patent/EP2404955A4/en not_active Withdrawn
- 2010-03-02 US US13/254,026 patent/US8822555B2/en not_active Expired - Fee Related
- 2010-03-02 WO PCT/JP2010/053309 patent/WO2010101134A1/ja active Application Filing
- 2010-03-02 JP JP2011502755A patent/JP5652389B2/ja not_active Expired - Fee Related
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007204767A (ja) * | 2000-06-14 | 2007-08-16 | Ube Ind Ltd | ポリアミド多孔質粒子の製造方法 |
JP2007515500A (ja) * | 2003-06-26 | 2007-06-14 | ロディア・ポリアミド・インターミーディエッツ | ポリアミドから作られた球形粒子の製造方法 |
JP2005054153A (ja) * | 2003-08-07 | 2005-03-03 | Ube Ind Ltd | ポリアミド多孔質粒子の製造方法 |
JP2006169373A (ja) | 2004-12-15 | 2006-06-29 | Metal Color:Kk | ナイロン12球状粒子粉末の製造方法 |
WO2006082908A1 (ja) * | 2005-02-02 | 2006-08-10 | Ube Industries, Ltd. | 多孔質球状ポリアミド粒子の製造方法 |
JP2006328173A (ja) | 2005-05-25 | 2006-12-07 | Metal Color:Kk | ポリアミド球状粒子粉末の製造方法 |
JP2007056085A (ja) | 2005-08-23 | 2007-03-08 | Toray Ind Inc | ポリカプロアミド樹脂微粒子およびそれを含む化粧品 |
JP2007106895A (ja) * | 2005-10-14 | 2007-04-26 | Sumika Enviro-Science Co Ltd | 球状ポリアミド粒子の製造方法 |
JP2008038037A (ja) | 2006-08-07 | 2008-02-21 | Ube Ind Ltd | 多孔質ポリアミド粉末の製造方法 |
JP2008086874A (ja) * | 2006-09-29 | 2008-04-17 | Ube Ind Ltd | 吸放湿材料 |
JP2008088296A (ja) * | 2006-10-02 | 2008-04-17 | Ube Ind Ltd | 着色ポリアミド微粒子およびその製造方法 |
JP2008127495A (ja) * | 2006-11-22 | 2008-06-05 | Teijin Ltd | 全芳香族ポリアミド粒子の製造方法 |
JP2008189895A (ja) * | 2007-02-08 | 2008-08-21 | Gantsu Kasei Kk | 球状ポリアミド粒子の製造方法 |
JP2009159840A (ja) | 2007-12-28 | 2009-07-23 | National Institute Of Advanced Industrial & Technology | バイオマスからの2−ピロリドン乃至ポリアミド4、n−メチル−2−ピロリドン、ポリビニルピロリドンの合成方法 |
Non-Patent Citations (2)
Title |
---|
LUFT JH: "Improvements in epoxy resin embedding methods", J BIOPHYS BIOCHEM CYTOL, vol. 9, 1961, pages 409 - 414 |
See also references of EP2404955A4 * |
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JP2011116976A (ja) * | 2009-11-05 | 2011-06-16 | Sanyo Chem Ind Ltd | 樹脂粒子の製造方法 |
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JP2016186068A (ja) * | 2015-03-19 | 2016-10-27 | 株式会社リコー | ポリアミド粒子及びその製造方法 |
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WO2017195705A1 (ja) * | 2016-05-10 | 2017-11-16 | 株式会社クレハ | ポリアミド微粒子およびその製造方法ならびにポリアミド微粒子組成物 |
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JP7142653B2 (ja) | 2018-02-08 | 2022-09-27 | 株式会社 資生堂 | 粉末含有組成物、水系溶媒用粉末、及び水系溶媒用粉末の製造方法 |
Also Published As
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US20110311821A1 (en) | 2011-12-22 |
JP5652389B2 (ja) | 2015-01-14 |
EP2404955A4 (en) | 2013-07-03 |
US8822555B2 (en) | 2014-09-02 |
EP2404955A1 (en) | 2012-01-11 |
CN102388088A (zh) | 2012-03-21 |
CN102388088B (zh) | 2015-11-25 |
JPWO2010101134A1 (ja) | 2012-09-10 |
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