US20160208070A1 - Foamable resin composition for foam sheet, foam sheet, process for preparing particulate polylactic acid and process for preparing foam sheet - Google Patents
Foamable resin composition for foam sheet, foam sheet, process for preparing particulate polylactic acid and process for preparing foam sheet Download PDFInfo
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- US20160208070A1 US20160208070A1 US14/913,994 US201414913994A US2016208070A1 US 20160208070 A1 US20160208070 A1 US 20160208070A1 US 201414913994 A US201414913994 A US 201414913994A US 2016208070 A1 US2016208070 A1 US 2016208070A1
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- polylactic acid
- foam sheet
- acid resin
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- spray nozzle
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
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- B29B9/10—Making granules by moulding the material, i.e. treating it in the molten state
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
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- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
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- B29C44/34—Auxiliary operations
- B29C44/36—Feeding the material to be shaped
- B29C44/46—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length
- B29C44/50—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length using pressure difference, e.g. by extrusion or by spraying
- B29C44/505—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length using pressure difference, e.g. by extrusion or by spraying extruding the compound through a flat die
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- 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
- C08J3/122—Pulverisation by spraying
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0004—Use of compounding ingredients, the chemical constitution of which is unknown, broadly defined, or irrelevant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
- B05B5/001—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means incorporating means for heating or cooling, e.g. the material to be sprayed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
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- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
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- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/25—Solid
- B29K2105/251—Particles, powder or granules
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Definitions
- the present disclosure relates to a foamable resin composition for a foam sheet, a foam sheet, a process for preparing a particulate polylactic acid resin, and a process for preparing a foam sheet.
- Products in which a polylactic acid is used are produced through multiple heat processes. It has been reported that a polylactic acid is sensitive to heat, and, therefore, a hydrolysis proceeds at a high temperature. Due to the property of the polylactic acid, a hydrolysis caused by heat during a process for preparing a polylactic acid product leads to a change of a molecular weight, which affects the state of the end product produced.
- One embodiment of the present disclosure provides a foamable resin composition for a foam sheet, which can produce a foam sheet including a polylactic acid resin and having an improved shelf-life.
- Another embodiment of the present disclosure provides a process for preparing a polylactic acid resin of microparticles, included in the foamable resin composition.
- Still another embodiment of the present disclosure provides a process for preparing a foam sheet, using the foamable resin composition for a foam sheet.
- a foamable resin composition for a foam sheet comprising polylactic acid resin particles, each of the particles having a particle size of about 1 ⁇ m to about 100 ⁇ m, is provided.
- a foam sheet prepared by molding the composition may comprise a polylactic acid resin having a weight average molecular weight of about 100,000 to about 200,000.
- the composition may be a suspension in which the polylactic acid resin particles are dispersed in a liquid solvent.
- a foam sheet comprising polylactic acid resin particles, each of the particles having a particle size of about 1 ⁇ m to 100 ⁇ m, is provided.
- the foam sheet may comprise a polylactic acid resin having a weight average molecular weight of about 100,000 to about 200,000.
- a process for preparing a particulate polylactic acid resin comprises: introducing a polylactic acid resin and then forming a molten polylactic acid spray solution; and spraying the molten polylactic acid spray solution by a melt spray method and simultaneously cooling the molten polylactic acid spray solution to obtain a particulate polylactic acid.
- the polylactic acid resin may be introduced into an extruder, and then transferred to an spray nozzle and heated in the spray nozzle to form the molten polylactic acid spray solution.
- the polylactic acid resin n the form of pellet or powder may be introduced into the extruder.
- the molten polylactic acid spray solution may be introduced into the spray nozzle together with an air and then discharged.
- a temperature of the air that is introduced into the spray nozzle may be of about 300° C. to about 500° C.
- a pressure of the air that is injected into the spray nozzle may be of about 100 psi to about 1,000 psi
- an injection speed of the air that is injected into the spray nozzle may be of about 10 m/s to about 50 m/s.
- a temperature of the spray nozzle may be of about 200° C. to about 400° C.
- a pressure of the spray nozzle may be of about 10 psi to about 1,000 psi.
- a diameter of the spray nozzle may be of about 0.5 mm to about 3.0 mm.
- the molten polylactic acid spray solution may comprise at least one additive selected from the group consisting of a lubricant, a plasticizer, and a combination thereof.
- the molten polylactic acid spray solution may have a viscosity of about 1,500 cps to about 2,000 cps at 250° C.
- a voltage of about 2,000 V to about 50,000 V may be applied to the spray nozzle to carry out a melt electrostatic spray deposition.
- the particulate polylactic acid resin may have an average particle size of about 1 ⁇ m to about 100 ⁇ m.
- a process for preparing a foam sheet comprising a polylactic acid foam layer comprising: mixing a particulate polylactic acid resin having an average particle size of 1 ⁇ m to 100 ⁇ m, a foam resin, and an additive to form a foamable resin composition, and then applying the foamable resin composition to form a layer; and allowing the resultant layer to foam and consequently forming a foam layer is provided.
- the particulate polylactic acid resin is obtained by a melt spray method.
- the foam sheet prepared by the process may comprise a polylactic acid resin having a weight average molecular weight of about 100,000 to about 200,000.
- a foam sheet prepared by using the microparticulate polylactic acid resin has excellent durability and surface property and improved shelf-life.
- FIG. 1 schematically shows a process flow diagram of a process for preparing a foam sheet according to one embodiment of the present disclosure
- FIG. 2 schematically shows a process flow diagram of a process for preparing a foam sheet.
- polylactic acid resin particles having an average particle size of about 1 ⁇ m to about 100 ⁇ m are provided.
- the polylactic acid resin particles having the particle size range may be prepared by a melt spray method. Further, more uniform polylactic acid particles may be obtained by introducing an air having a high temperature and a high pressure together to an spray nozzle during performing the melt spray method.
- the melt spray method may be carried out by a melt electrostatic spray deposition (melt ESD) applying a voltage during performing the melt spray method.
- a process according to another embodiment of the present disclosure for preparing polylactic acid resin particles having an average particle size of about 1 ⁇ m to about 100 ⁇ m comprises: introducing a polylactic acid resin and then forming a molten polylactic acid spray solution; and spraying the molten polylactic acid spray solution by a melt spray method and simultaneously cooling the molten polylactic acid spray solution to obtain a particulate polylactic acid.
- the process for preparing a particulate polylactic acid resin has advantages to easily control the size of the polylactic acid resin particles formed by applying the melt spray method and to make a distribution of the particle size uniform.
- ploylactic acid resin particles having an average particle size of about 1 ⁇ m to about 100 ⁇ m may be prepared by the process for preparing a particulate polylactic acid resin.
- a polylactic acid in the form of pellet or powder is introduced into an extruder equipped with an spray nozzle, and then the polylactic acid is melted in the high temperature spray nozzle to form a molten polylactic acid spray solution.
- molten polylactic acid spray solution is sprayed in the form of a liquid droplet in micrometers.
- spraying is performed in a cooling chamber, allowing the liquid droplet to be cooled to form microparticles of the polylactic acid resin.
- the melt spray method is optionally carried out by a melt electrostatic spray deposition applying a voltage to the spray nozzle.
- the molten polylactic acid spray solution is introduced into the spray nozzle together with an air and then discharged.
- the size and shape of a liquid droplet of the molten polylactic acid spray solution discharged may be controlled, whereby the particle size of a polylactic acid resin to be finally obtained may be controlled.
- a temperature of the air that is introduced into the spray nozzle may be of about 300° C. to about 500° C.
- a pressure of the air may be of about 10 psi to about 1,000 psi
- an injection speed of the air may be of about 10 m/s to about 50 m/s.
- a viscosity of the melted polylactic acid may be controlled to be sprayed as a liquid droplet in micrometers.
- To control the viscosity of the melted polylactic acid resin may be achieved by a method, such as adjusting the temperature of the spray nozzle, adding an additive, such as a lubricant, a plasticizer, or the like, together with the polylactic acid resin, to the extruder to be compounded, or introducing a gas such as CO 2 to the polylactic acid resin in the form of pellet, and the like.
- a method such as adjusting the temperature of the spray nozzle, adding an additive, such as a lubricant, a plasticizer, or the like, together with the polylactic acid resin, to the extruder to be compounded, or introducing a gas such as CO 2 to the polylactic acid resin in the form of pellet, and the like.
- a diameter of the spray nozzle may be of about 0.5 mm to about 3.0 mm.
- a viscosity of the molten polylactic acid spray solution may be of about 1,500 cps to about 2,000 cps at about 250° C.
- a coating solution having the above viscosity range a microparticulate polylactic acid resin may be formed.
- Process conditions of the melt spray method are not particularly limited, and the known process conditions, for example, a pressure of the spray nozzle of about 100 psi to about 1,000 psi may be applied.
- melt spray method should be carried out at a temperature range in which the polylactic acid melts.
- a temperature of the spray nozzle may be of about 200° C. to about 400° C.
- a diameter of the spray nozzle may be of about 0.5 mm to about 3.0 mm in order to form the microparticulate polylactic acid resin as described above.
- the melt spray method may be carried out, for example, by a melt electrostatic spray deposition applying a voltage of about 2,000 V to about 50,000 V to the spray nozzle.
- microparticulate polylactic acid resin which may be prepared by the process can be advantageously applied to a preparation of a foam sheet.
- a foam sheet comprising polylactic acid resin particles, each of the particles having a particle size of about 1 ⁇ m to about 100 ⁇ m.
- the foam sheet may be prepared by using the polylactic acid resin particles having a small particle size in micrometers, in accordance with a process for preparing a foam sheet as mentioned below, and the thus prepared foam sheet minimizes the number of heat processes to minimize the degradation of the polylactic acid resin, allowing the maintenance of higher molecular weight.
- the foam sheet may comprise a polylactic acid resin having a weight average molecular weight of about 100,000 to about 200,000.
- FIG. 2 shows a process flow diagram of an exemplary process for preparing a foam sheet.
- a foam sheet applied with a polylactic acid resin has been produced through a variety of processes. More specifically, a lubricant, an additive, a stabilizer, or the like is firstly added to a polylactic acid resin in the form of powder or pellet, followed by blending, kneading and T-die extrusion, and then lamination with paper and foaming process. In general, until a foam sheet is prepared by the processes, approximately at least three or four heat processes are performed.
- a polylactic acid resin is known to be sensitive to heat treatment since it is hydrolyzed at a high temperature. Due to the property of the polylactic acid resin, the hydrolysis of the foam sheet, applied with the polylactic acid resin, by heat during a process affects the molecular weight of the polylactic acid resin to result in the degradation of a product.
- a process for preparing a foam sheet capable of reducing the number of heat processes by using a microparticulate polylactic acid resin, is provided.
- a process for preparing a foam sheet comprising a polylactic acid foam layer comprising: mixing a particulate polylactic acid resin having an average particle size of about 1 ⁇ m to about 100 ⁇ m, a foam resin, and an additive to form a foamable resin composition, and then applying the foamable resin composition to form a layer; and allowing the resultant layer to foam and consequently forming a foam layer is provided.
- the foamable resin composition allows the polylactic acid resin to be mixed in a microparticle size to form a suspension.
- the foamable resin composition in the form of sol-gel may foams to form a polylactic acid foam layer.
- FIG. 1 shows a process flow diagram of a process for preparing a foam sheet according to one embodiment of the present disclosure.
- a powder of polylactic acid particles having a micro size is firstly prepared by applying a melt spray method ( FIG. 1 , MELT ESD step); a suspension is prepared by mixing a foamable resin composition comprising the powder of polylactic acid particles having a micro size ( FIG. 1 , MIXING (PREPARING SOL) step); a coating layer is formed by coating the suspension on a substrate ( FIG. 1 , SOL COATING step); and, subsequently, the coating layer foams ( FIG. 1 , FOAMING step) to form a foam layer, whereby a foam sheet may be prepared.
- a melt spray method FIG. 1 , MELT ESD step
- MIXING PREPARING SOL
- a foam sheet comprising a polylactic acid foam layer comprising the above polylactic acid resin particles having an average particle size of about 1 ⁇ m to about 100 ⁇ m may be prepared.
- the foam resin may be a material used in preparing a foam layer of a foam sheet, such as PVC, polyurethane, and the like, without being limited thereto.
- the microparticles of the polylactic acid resin are evenly dispersed. Since the polylactic acid resin is evenly dispersed, the surface property of the product, the foam sheet finally produced, may be improved, whereby the durability of the foam sheet is enhanced.
- the process for preparing a foam sheet may reduce the number of heat processes, compared with the well-known processes for preparing a foam sheet, the damage resulting from a hydrolysis of a polylactic acid resin may be remarkably lowered, whereby the loss of the molecular weight by the hydrolysis of the polylactic acid resin may be inhibited. Therefore, the foam sheet prepared by the above process unexpectedly improves the product degradation by heat processes to result in an extended shelf-life.
- the molecular weight of the microparticulate polylactic acid resin may be maintained without a remarkable loss resulting from a hydrolysis.
- the foam sheet produced by the above process for preparing a foam sheet may comprise a polylactic acid resin having a weight average molecular weight of about 100,000 to about 200,000.
- the foam sheet produced by the above process for preparing a foam sheet may comprise a polylactic acid resin having a weight average molecular weight of about 100,000 or more.
- particles having an average particle size of 50 ⁇ m were prepared by a melt electrostatic spray deposition.
- a temperature of an spray nozzle was 250° C.
- a pressure of the spray nozzle was 500 psi
- a diameter of the spray nozzle was 1 mm
- a voltage of 20,000 V was applied to the spray nozzle
- a viscosity of a molten polylactic acid spray solution was 2,000 cps at 250° C.
- the resulting polylactic acid particles, and additives including a plasticizer, a stabilizer, a lubricant and the like were added and blended to prepare a polylactic acid resin-containing sol.
- the resulting polylactic acid resin-containing sol was subjected to a sol-gel coating on a substrate, followed by drying (foaming) to obtain a foam sheet sample having a thickness of about 0.5 mm.
- Additive including a plasticizer, a stabilizer, a lubricant and the like was added to a polylactic acid resin in the form of pellet as in Example 1 and mixed to prepare a polylactic acid resin-containing mixture composition.
- the polylactic acid resin-containing mixture composition was kneaded at 150° C. with a Banbury mixer, and the first and the second mixing were conducted with two roll mill at 150° C.
- the thus prepared mixing materials were subjected to calendering process and foaming process to obtain a foam sheet having a thickness of about 0.5 mm.
- Example 1 With respect to the foam sheet samples prepared in Example 1 and Comparative Example 1, the weight average molecular weights thereof were determined with the GPC (gel permeation chromatography) (e2695, Waters), and shown in Table 1.
- GPC gel permeation chromatography
- Example 1 Each of the foam sheets prepared in Example 1 and Comparative Example 1 was determined for its impact resistance according to the ASTM D256 method, and results are shown in Table 1.
- Example 1 The surface property of each of the foam sheets prepared in Example 1 and Comparative Example 1 were visually determined, and shown in Table 1.
- the evaluation criteria are visual assessment and the surface property was scored from 5 (excellent) to 1 (NG) using a 5-point scale.
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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US15/874,632 US10508176B2 (en) | 2013-08-29 | 2018-01-18 | Foamable resin composition for foam sheet, foam sheet, process for preparing particulate polylactic acid and process for preparing foam sheet |
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KR10-2013-0103466 | 2013-08-29 | ||
KR1020130103466A KR101762996B1 (ko) | 2013-08-29 | 2013-08-29 | 발포 시트용 발포성 수지 조성물, 발포 시트, 입자상의 폴리락트산 수지의 제조 방법 및 발포 시트의 제조 방법 |
PCT/KR2014/008058 WO2015030516A1 (ko) | 2013-08-29 | 2014-08-29 | 발포 시트용 발포성 수지 조성물, 발포 시트, 입자상의 폴리락트산 수지의 제조 방법 및 발포 시트의 제조 방법 |
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PCT/KR2014/008058 A-371-Of-International WO2015030516A1 (ko) | 2013-08-29 | 2014-08-29 | 발포 시트용 발포성 수지 조성물, 발포 시트, 입자상의 폴리락트산 수지의 제조 방법 및 발포 시트의 제조 방법 |
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US20160208070A1 true US20160208070A1 (en) | 2016-07-21 |
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US14/913,994 Abandoned US20160208070A1 (en) | 2013-08-29 | 2014-08-29 | Foamable resin composition for foam sheet, foam sheet, process for preparing particulate polylactic acid and process for preparing foam sheet |
US15/874,632 Expired - Fee Related US10508176B2 (en) | 2013-08-29 | 2018-01-18 | Foamable resin composition for foam sheet, foam sheet, process for preparing particulate polylactic acid and process for preparing foam sheet |
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US (2) | US20160208070A1 (zh) |
EP (1) | EP3040378B1 (zh) |
JP (1) | JP6466453B2 (zh) |
KR (1) | KR101762996B1 (zh) |
CN (1) | CN105492529B (zh) |
WO (1) | WO2015030516A1 (zh) |
Cited By (1)
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US11001677B2 (en) | 2017-03-09 | 2021-05-11 | Lg Hausys, Ltd. | Thermoplastic polymer particles having low impurity content |
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US7776503B2 (en) * | 2005-03-31 | 2010-08-17 | Ricoh Company, Ltd. | Particles and manufacturing method thereof, toner and manufacturing method thereof, and developer, toner container, process cartridge, image forming method and image forming apparatus |
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-
2014
- 2014-08-29 JP JP2016538855A patent/JP6466453B2/ja not_active Expired - Fee Related
- 2014-08-29 EP EP14839916.5A patent/EP3040378B1/en not_active Not-in-force
- 2014-08-29 WO PCT/KR2014/008058 patent/WO2015030516A1/ko active Application Filing
- 2014-08-29 CN CN201480047646.3A patent/CN105492529B/zh active Active
- 2014-08-29 US US14/913,994 patent/US20160208070A1/en not_active Abandoned
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11001677B2 (en) | 2017-03-09 | 2021-05-11 | Lg Hausys, Ltd. | Thermoplastic polymer particles having low impurity content |
US11066527B2 (en) | 2017-03-09 | 2021-07-20 | Lg Hausys, Ltd. | Polylactic acid particles and manufacturing method therefor |
US11118019B2 (en) | 2017-03-09 | 2021-09-14 | Lg Hausys, Ltd. | Thermoplastic polyurethane particles having low impurity content and manufacturing method therefor |
US11149120B2 (en) | 2017-03-09 | 2021-10-19 | Lg Hausys, Ltd. | Method for manufacturing thermoplastic polymer particles |
US11542372B2 (en) | 2017-03-09 | 2023-01-03 | Lg Hausys, Ltd. | Thermoplastic polymer particles having a peak of cold crystallization temperature |
Also Published As
Publication number | Publication date |
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KR20150025494A (ko) | 2015-03-10 |
EP3040378B1 (en) | 2019-05-15 |
WO2015030516A1 (ko) | 2015-03-05 |
CN105492529B (zh) | 2018-07-03 |
JP2016536420A (ja) | 2016-11-24 |
CN105492529A (zh) | 2016-04-13 |
JP6466453B2 (ja) | 2019-02-06 |
EP3040378A1 (en) | 2016-07-06 |
US10508176B2 (en) | 2019-12-17 |
KR101762996B1 (ko) | 2017-07-28 |
US20180142069A1 (en) | 2018-05-24 |
EP3040378A4 (en) | 2016-08-31 |
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