WO2015123960A1 - 一种发泡热塑性聚氨酯粒子及其制备方法和应用 - Google Patents

一种发泡热塑性聚氨酯粒子及其制备方法和应用 Download PDF

Info

Publication number
WO2015123960A1
WO2015123960A1 PCT/CN2014/082594 CN2014082594W WO2015123960A1 WO 2015123960 A1 WO2015123960 A1 WO 2015123960A1 CN 2014082594 W CN2014082594 W CN 2014082594W WO 2015123960 A1 WO2015123960 A1 WO 2015123960A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoplastic polyurethane
foamed
foamed thermoplastic
parts
polyurethane particle
Prior art date
Application number
PCT/CN2014/082594
Other languages
English (en)
French (fr)
Inventor
黄波
王仁鸿
王光阜
张生
赵玮
Original Assignee
山东美瑞新材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 山东美瑞新材料有限公司 filed Critical 山东美瑞新材料有限公司
Priority to EP14883292.6A priority Critical patent/EP3109280B1/en
Priority to MX2016010762A priority patent/MX2016010762A/es
Priority to ES14883292T priority patent/ES2748163T3/es
Priority to US15/120,083 priority patent/US10519289B2/en
Priority to KR1020167025522A priority patent/KR102100655B1/ko
Publication of WO2015123960A1 publication Critical patent/WO2015123960A1/zh

Links

Classifications

    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • 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
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • 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
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B29K2105/048—Expandable particles, beads or granules
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0066—≥ 150kg/m3
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/046—Unimodal pore distribution
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/26—Elastomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2427/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C08J2431/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
    • C08J2431/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
    • C08J2431/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • 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
    • C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
    • C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers

Definitions

  • thermoplastic poly-S ester particle Foamed thermoplastic poly-S ester particle and preparation method and application thereof
  • the invention relates to a foamed thermoplastic polyurethane particle, a preparation method and application thereof, and belongs to the field of foaming materials. Background technique
  • a plastic foam is used to fill a large amount of air bubbles inside the plastic by physical or chemical means to obtain a polymer foamed material.
  • Foam materials have a wide range of advantages such as low density, thermal insulation, high specific strength, and cushioning. Therefore, they are widely used in the packaging industry, industry, agriculture, transportation, military industry, aerospace industry, and daily necessities. Commonly used foam types are polyurethane (PU) soft and rigid foam, polystyrene (PS) foam, polyethylene (PE) foam, polypropylene (PP) foam and the like.
  • PS polystyrene
  • PE polyethylene
  • PP polypropylene
  • polyurethane foams tend to remain isocyanate during the foaming process, which is harmful to the human body, and the foamed material cannot be recycled. Styrofoam products are difficult to degrade and are prone to "white pollution" problems.
  • the UN Environment Organization has decided to stop using PS foam products. Polyethylene foams have poor high temperature resistance and are not suitable for use in high temperature
  • Thermoplastic polyurethane elastomer has a wide range of hardness, excellent wear resistance, mechanical strength, water resistance, oil resistance, chemical resistance, mold resistance, environmental friendliness, and recycling.
  • a molded foamed article can be obtained by filling foamed thermoplastic polyurethane particles into a mold and performing heat molding using steam.
  • the product has excellent resilience, shape diversity, low density and can be used over a wide temperature range.
  • TPU foaming materials have a very wide application prospect in many industrial fields (automotive industry, packaging materials) and daily life (shoe materials, pillows, mattresses). Moldable foam beads based on thermoplastic polyurethanes have been disclosed in WO2007/082838.
  • the reported foamed thermoplastic polyurethane beads have the disadvantage that the cell structure is relatively large in size, "wrinkles" appear on the surface of the particles, and the product yield is low.
  • the thermoplastic polyurethane resin used has a narrow melting temperature range, a high melt viscosity, and a soft segment and a hard segment in the polymer chain are mixed, and the hard segment is
  • the hydrogen bonding effect between the molecular chains produces hard-stage crystallization, which is a semi-crystalline material, and subsequent molding processes need to be softened to an appropriate degree in a semi-molten state. Therefore, the size of the molded foamed article shrinks, and the deformation phenomenon is affected by factors such as the viscosity of the melt of the resin, the degree of crystallinity, and the activity of the polymer chain during semi-melting.
  • the present inventors have attempted to control the shrinkage and deformation of the expanded particles and the product by adjusting the crystallinity of the resin, the molecular weight of the soft segment, and the molecular weight distribution, but various problems occur in the production of the particles and the molding of the product.
  • the technical problem to be solved by the present invention is to provide a foamed thermoplastic polyurethane particle having a uniform cell size and a high product yield, and a preparation method thereof, and at the same time, when a foamed article is obtained by a lower pressure steam molding, even if After the subsequent shrinkage of the product, the deformation is restored after the ripening Under the shorter process conditions, it is also possible to obtain a foamed article having a small deformation, a small dimensional shrinkage ratio with respect to the mold, excellent dimensional stability, and an aesthetically pleasing appearance.
  • a foamed thermoplastic polyurethane particle consisting of the following parts by weight: 100 parts of thermoplastic polyurethane particles, 1 to 10 parts of cell size stabilizer, 1 to 35 parts of melt viscosity Conditioner.
  • the present invention can also be improved as follows.
  • the foamed thermoplastic polyurethane particles have a melt viscosity of 8000 ° at 180 ° C.
  • the melt viscosity of the thermoplastic polyurethane resin is substantially unchanged during the foaming process, and therefore the melt viscosity of the foamed thermoplastic polyurethane particles in the present invention at 180 ° C can be obtained by adjusting the thermoplastic polyurethane resin.
  • the foamed thermoplastic polyurethane particles have a melt viscosity at 180 ° C of from 8,000 to 15,000 poise, preferably from 10,000 to 13,000 poise.
  • thermoplastic polyurethane particles have a Shore hardness of 55 to 95 ⁇ and a preferred Shore hardness of 60 to 90 Ao.
  • Shore hardness test method Insert the material to be tested with a Shore hardness tester, The pointer on the disc is connected to a lancet by a spring, and the needle is inserted into the surface of the object to be tested. The value displayed on the dial is the hardness value.
  • thermoplastic polyurethane particles have a melt flow rate (Ml) of 5 to 50 g/10 min, preferably 10 to 45 g/10 min.
  • ASTM refers to the American Society for Testing and aterials'AST (formerly known as the International Association for Testing Materials, IAT% in the 19th century, to solve the purchase and sale of buyers and suppliers)
  • ASTM aims to promote Public health and safety, improving the quality of life; Providing dependable raw materials, products, systems and services; Promoting national, regional and international economies ASTM-1238 is the standard of the American Materials Association for testing plastic melt flow rates.
  • the cell size stabilizer is dihydroxypropyl octadecanoate (GMS sorbitan lauric acid monoester, sorbitan palmitic acid monoester, sorbitan stearic acid monoester, fatty acid a mixture of one or more of sucrose esters.
  • GMS sorbitan lauric acid monoester sorbitan palmitic acid monoester
  • sorbitan stearic acid monoester fatty acid a mixture of one or more of sucrose esters.
  • the foaming agent is unevenly distributed inside the resin during the foaming process, and the cell size distribution of the foamed particles is coarse. Not uniform.
  • the foamed thermoplastic polyurethane particles of the present invention have a cell diameter of 500 um to 800 um.
  • the cell size stabilizer facilitates the entry of the volatile blowing agent into the interior of the thermoplastic polyurethane particles and is evenly distributed.
  • the cell size stabilizer is added in an amount of from 1 to 10 parts by weight, preferably from 2 to 8 parts by weight.
  • the melt viscosity modifier is an ethylene-vinyl acetate copolymer (EVA X polyvinyl chloride (PVC X polypropylene-butadiene-styrene resin (ABS polystyrene-polyethylene-polybutylene-polyphenylene) A mixture of one or more of ethylene (SBS).
  • EVA X polyvinyl chloride PVC X polypropylene-butadiene-styrene resin (ABS polystyrene-polyethylene-polybutylene-polyphenylene)
  • SBS ethylene-ethylene
  • thermoplastic polyurethane resin has sufficient strength during production and processing, and is less prone to strain that causes shrinkage, that is, the polymer chain is free when the cell wall is expanded. Extending the exhibition.
  • the melt processing temperature range is expanded, and the movement ability of the polymer chain in the melt state is improved.
  • the melt viscosity modifier is added in an amount of from 1 to 35 parts by weight, preferably from 5 to 30 parts by weight.
  • the amount thereof is less than 5 parts by weight, the effect of improving the melt viscosity of the thermoplastic polyurethane is not obvious.
  • the amount is more than 30 parts by weight, the viscosity loss of the TPU melt is large, and the foam is easily caused in the preparation of the foamed particles. Broken, it is difficult to obtain closed-cell cells.
  • thermoplastic polyurethane foaming process it may be melt-processed into a thermoplastic polyurethane bead of a desired shape by an extruder in advance.
  • the following method is generally employed: 100 parts by weight of thermoplastic polyurethane particles, 1 to 10 parts by weight of cell size stabilizer, 1 to 35 parts by weight of melt viscosity modifier using a high speed mixer or masterbatch mixer (antioxidant may also be added) , anti-yellowing agent, antistatic agent, etc.) are mixed evenly, and then put into the extruder for melting.
  • the extruded lines are cooled and shaped in the water tank and then cut or after the melt is extruded from the die, and then granulated underwater.
  • thermoplastic polyurethane beads obtained in the step (1) to the pressure-resistant container with a volatile foaming agent and water, and raising the temperature to 1 15 to 18 ° C (i.e., near the softening point of the thermoplastic polyurethane), the pressure resistant container
  • the internal pressure was maintained at 18 bar to 26 bar.
  • the suspension in the pressure vessel was discharged to the atmosphere to obtain foamed thermoplastic polyurethane beads.
  • the foamed thermoplastic polyurethane particles obtained in the present invention have a density of 0.08 to 0.2 g/cm 3 .
  • the volatile blowing agent is a mixture of one or more of propane, n-butane, isobutane, n-pentane, and isopentane, and is added in an amount of 1 to 40 parts by weight.
  • the invention further comprises the use of a foamed thermoplastic polyurethane particle for producing a thermoplastic polyurethane foamed article, wherein the thermoplastic polyurethane foamed article is expanded and sintered by using 1 to 3 bar of water vapor for the foamed thermoplastic polyurethane particle.
  • the molded article obtained afterwards.
  • the foamed thermoplastic polyurethane molded article is obtained by expanding and sintering the expanded particles under a steam of 1 bar to 3 bar.
  • a foamed article excellent in performance can be obtained even at a molding pressure as low as 1 bar to 1.5 bar.
  • the invention has the beneficial effects that the foamed thermoplastic polyurethane particles prepared by the invention have uniform cell size and high product yield, and the foamed thermoplastic polyurethane particles have good sintering performance even under a low water vapor pressure.
  • the obtained molded foamed article has a small deformation, a small dimensional shrinkage ratio with respect to the mold, excellent dimensional stability, and an aesthetically pleasing surface.
  • thermoplastic polyurethane elastomer particles For the preparation of raw material thermoplastic polyurethane elastomer particles, it is usually produced by mixing isocyanate, an active hydrogen compound having a molar mass of 500 to 10000 g/mol, and a chain extender having a molar mass of 50 to 500 g/mol, and a catalyst is added in the production.
  • Isocyanates include aliphatic, alicyclic, aromatic, and araliphatic groups. Preferred are diisocyanates such as toluene diisocyanate (TDI), diphenylmethane-2,2'-diisocyanate (MDI) (where 2,2'- can be replaced by 2,4'- or 4,4'-), 3-Iocyanate-methylene-3,5,5-trimethylcyclohexyl isocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), 1,5-na Isocyanate ( NDI ) , p-phenylene diisocyanate ( PPDI ) , 1 ,4-cyclohexyl Alkyl diisocyanate (CHDI), cyclohexane dimethylene diiso
  • TDI toluene diisocyanate
  • MDI diphenylmethane
  • the chain agent includes an aliphatic, aromatic or alicyclic diol compound having a molar mass of from 50 to 500 g/mol.
  • catalysts are triethylenediamine, dimethylcyclohexylamine, triethylamine, (N, N, N', N'-tetraethyl Methylenediamine), 1,4-dimethylpiperazine, dibutyltin dilaurate, potassium isooctoate, tetrabutyl titanate, tetraisopropyl titanate.
  • thermoplastic polyurethane elastomer particles are continuously produced by a conventional method, such as using an extrusion reaction type extruder, or by a one-pot method or a prepolymer method.
  • thermoplastic polyurethane bead type and the ratio of addition of each component used in the examples and comparative examples are shown in Table 1.
  • T1 20 100 Dihydroxypropyl octadecanoate 5 EVA 10
  • T2 25 100 sorbitan lauric acid monoester 3
  • PVC 15 100 fatty acid sucrose ester 2 ABS 10
  • T4 20 100 Dihydroxypropyl octadecanoate 5 - -
  • TPU pellets of 20 g/10 min of Ml, 5 parts by weight of dihydroxypropyl octadecanoate, and 10 parts by weight of EVA were uniformly mixed by a high-speed mixer and then subjected to twin-screw extrusion for melt-kneading.
  • the melt-kneaded product was extruded into a strip from a die having an extruder diameter of 2 mm, and then cooled and set in a water bath, and cut with a pelletizer to obtain thermoplastic polyurethane beads.
  • thermoplastic polyurethane beads obtained above and 400 parts by weight of water were placed in a 10 L autoclave, and 30 parts by weight of a n-butane blowing agent was added while stirring.
  • the autoclave was heated to 18 ° C, and then at this temperature for 20 minutes, the bottom end discharge valve of the autoclave was opened, and the mixed liquid in the autoclave was discharged to the atmosphere to obtain foamed thermoplastic polyurethane particles.
  • the obtained foamed thermoplastic polyurethane beads had a density of 0.16 g/cm 3 and a cell diameter of 550 um.
  • the foamed thermoplastic polyurethane particles obtained above were filled in a mold having a length of 300 mm x a width of 250 mm x a thickness of 50 mm.
  • the particles were bonded by molding with water vapor of 1.4 bar in the thickness direction of the mold to form a foamed thermoplastic polyurethane molded foam article.
  • the obtained foamed product was allowed to stand at 50 ° C x 50% RH for 2 hours, dried in a constant temperature room at 80 ° C for 2 hours, and finally placed at 25 ° C x 50% RH for 2 hours, and its performance was evaluated as shown in Table 2. Show.
  • the foamed thermoplastic polyurethane particles and the foamed thermoplastic were obtained in the same manner as in Example 1 except that dihydroxypropyl octadecanoate was added as a cell size stabilizer to 100 parts of TPU particles of 20 g/10 min.
  • the polyurethane molded foam article was evaluated as shown in Table 2.
  • a foamed thermoplastic polyurethane particle and a foamed thermoplastic polyurethane molded foam article were obtained in the same manner as in Example 2 except that 100 parts of M1 was 25 g/10 min of TPU was added as a melt viscosity modifier, and the performance evaluation was as follows. 2 is shown.
  • a foamed thermoplastic polyurethane particle and a foamed thermoplastic polyurethane molded foam article were obtained in the same manner as in Example 1 except that 100 parts of M1 was 20 g/10 min of TPU particles without adding a cell size stabilizer and a melt viscosity modifier.
  • the performance evaluation is shown in Table 2.
  • the appearance of the molded foamed article was visually observed, in which a foamed article in which shrinkage and wrinkles (stripes of 1 cm or more) were hardly observed was evaluated as o, and a foamed article in which only wrinkles were observed but shrinkage was not observed was evaluated as ⁇ , a foam molded body having many wrinkles and irregular shapes was evaluated as x.
  • the surface of the molded foam article was observed, and the average number of interstitial spaces of the expanded beads of 1 cm 2 or more per 10 cm 2 area was calculated, and the following was determined:
  • the foamed thermoplastic polyurethane beads prepared in Examples 1 to 3 had uniform cell sizes and high product yield.
  • the molded foam articles obtained in Examples 1 to 3 were small in deformation with respect to Comparative Examples 1 to 3, and shrinkage and wrinkles (streaks of 1 cm or more) were not observed at all, and the gap between the expanded beads was small, and shrinkage was observed. Low rate, excellent dimensional stability and beautiful surface.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Emergency Medicine (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明涉及一种发泡热塑性聚氨酯粒子及其制备方法和应用，所述发泡热塑性聚氨酯粒子，由以下重量份的成分组成：100份热塑性聚氨酯颗粒，1～10份泡孔尺寸稳定剂，1～35份熔体粘度调节剂。本发明还公开了此种发泡热塑性聚氨酯粒子的制备方法，这些粒子是通过采用挥发性发泡剂将包含泡孔尺寸稳定剂与熔体粘度调节剂的热塑性聚氨酯珠粒浸渍在水悬浮液中，然后发泡来生产。利用本发明的发泡热塑性聚氨酯粒子可制备发泡制品。本发明制备的发泡热塑性聚氨酯粒子泡孔尺寸均匀，产品收率高，同时发泡热塑性聚氨酯粒子即使在较低的水蒸气压力下也具有良好的熔结性能，所得到的模塑泡沫制品形变小，相对于模具的尺寸收缩率低，尺寸稳定性优异，表面美观。

Description

一种发泡热塑性聚 S酯粒子及其制备方法和应用 技术领域
本发明涉及一种发泡热塑性聚氨酯粒子及其制备方法和应用 ，属于发泡 材料领域。 背景技术
以塑料为基体，通过物理或化学方法在塑料内部填充大量气泡，得到聚 合物发泡材料。 泡沫材料具有密度低、 隔热隔音、 比强度高、 缓冲等一列优 点，因此在包装业、 工业、 农业、 交通运输业、 军事工业、 航天工业以及日 用品等领域得到广泛应用。 常用的泡沫塑料品种有聚氨酯（ PU )软质和硬 质泡沫塑料、 聚苯乙烯（ PS )泡沫塑料、 聚乙烯（ PE )泡沫塑料、 聚丙烯 ( PP )泡沫塑料等。 但是聚氨酯泡沫塑料在发泡过程中容易残留异氰酸酯， 对人体有害，并且发泡材料无法回收利用。聚苯乙烯泡沫塑料产品降解困难， 易产生" 白色污染" 问题，联合国环境组织已决定停止使用 PS泡沫塑料产 品。 聚乙烯泡沫塑料耐高温性能较差，不适合在高温领域内应用。
热塑性聚氨酯弹性体（ TPU )具有较宽泛的硬度范围 ，优异的耐磨性、 机械强度、 耐水、 耐油、 耐化学腐蚀、 耐霉菌，对环境友好，可回收利用等 优点。通过将发泡热塑性聚氨酯粒子填充到模具中 ，利用水蒸气进行加热成 型可得到模塑发泡制品。此种制品在保留原基体优异的性能之外，同时拥有 优异的回弹性，形状多样性，低密度，可以在较宽的温度范围内使用。 基于 上述优点， TPU发泡材料在许多工业领域（汽车工业、 包装材料）以及日常 生活领域（鞋材、 枕头、 床垫）具有非常广泛的应用前景。 基于热塑性聚氨酯的可模塑泡沫珠粒在 WO2007/082838 中已经被公 开。但是该报道的发泡热塑性聚氨酯珠粒的缺点是泡孔结构尺寸较粗，颗粒 表面出现" 皱纹" ，产品收率低。
另一方面，针对发泡热塑性聚氨酯粒子及其模塑制品而言，所采用的热 塑性聚氨酯树脂熔融温度范围较窄，熔体粘度较高，高分子链中软段与硬段 混合存在，硬段由于分子链之间的氢键效应，会产生硬段结晶，属于半结晶 材料，后续成型加工需要将其软化至适当程度的半熔融状态下进行。 因此， 模塑发泡制品的尺寸收縮，变形现象会受到树脂熔体粘度、 结晶度、 半熔融 时高分子链的活动能力等因素的影响。特别对于高发泡倍率的制品，更易受 到上述因素影响。本发明人曾尝试通过调整树脂结晶性，软段分子量以及分 子量分布等方法对发泡粒子以及制品的收縮、 变形进行控制，但在粒子生产 以及制品成型过程中 ，会产生各种问题。
此外，在用于日常生活领域（鞋材、 枕头、 床垫），休闲场所（如地板 涂层 缓冲包装材料等用途时，使用者大多重视模塑发泡制品的表观性。 由于发泡制品是采用水蒸气加热使发泡粒子之间相互熔结来制备的，因此发 泡粒子之间的熔结面处可能会产生细缝、 孔、 皱纹或龟甲纹的痕迹。 为了解 决上述问题，往往通过采用提高成型水蒸气压力的方法，促使发泡粒子之间 的熔结。 但是，提高成型水蒸气的压力涉及到要消耗更多的能耗，进而导致 成型加工成本的增加。 此外，相应的需要更高耐压的模具，设备成本也会随 之增加。 发明内容
本发明 所要解决的技术问题是提供 一种具有均勻泡孔尺寸、 产品收率 高的发泡热塑性聚氨酯粒子及其制备方法，同时采用较低压力的水蒸气模塑 成型得到发泡制品时，即使在后续使制品的收縮，变形得以恢复的后熟化时 间较短的工艺条件下，也可以获得形变小，相对于模具的尺寸收縮率低，尺 寸稳定性优异，表面美观的发泡制品。
本发明解决上述技术问题的技术方案如下： 一种发泡热塑性聚氨酯粒 子， 由以下重量份的成分组成： 100份热塑性聚氨酯颗粒， 1 ~ 10份泡孔尺 寸稳定剂， 1 ~ 35份熔体粘度调节剂。
在上述技术方案的基础上，本发明还可以做如下改进。
进一步 ，所述发泡热塑性聚氨酯粒子在 180°C的熔融粘度为 8000 ~
15000泊。
熔融黏度意思是在给定条件下加热熔化或融解状态的黏度，由粘度计或 黏度仪测定，直接影响树脂的流动性，比如薄制品，黏度小更容易注入流动 成型，粘度单位厘斯与厘泊 ，厘斯 (est)是运动粘度的最小单位,厘泊（ cP ) 是动力粘度的最小单位， 1厘泊等于 0.01泊 ，即 1cP=0.01 Po
热塑性聚氨酯树脂的熔融粘度在发泡过程中基本没有变化，因此在本发 明中的发泡热塑性聚氨酯粒子在 180°C的熔融粘度可通过调整热塑性聚氨酯 树脂来获得。 其中 ，所述的发泡热塑性聚氨酯粒子在 180°C的熔融粘度为 8000 ~ 15000泊 ，优选的为 10000 ~ 13000泊之间。
进一步，所述热塑性聚氨酯颗粒的邵氏硬度为 55 ~ 95Α ,优选的邵氏硬 度为 60 ~ 90Ao
硬度是物质受压变形程度或抗刺穿能力的一种物理度量方式。硬度可分 相对硬度和绝对硬度。 绝对硬度一般在科学界使用 ，生产实践中很少用到。 我们通常使用硬度体系为相对的硬度，常用有以下几种标示方法：肖氏（也 叫邵氏，邵尔，英文 SH〇RE)、 洛氏、 布氏三种。 邵氏一般用于橡胶类材料 上。 邵氏硬度也称肖氏（ SHORE )硬度，常用于度量塑料，橡胶的表面抵 抗坚硬物体压入的能力。 肖氏硬度（ HS )和布氏硬度 （ BHN )换算关系为 HS=BHN/10 +12。 邵氏硬度的测试方法：用邵氏硬度计插入被测材料，表 盘上的指针通过弹簧与一个刺针相连，用针刺入被测物表面，表盘上所显示 的数值即为硬度值。
进一步，所述热塑性聚氨酯颗粒的熔体流动速率（ Ml )为 5 ~ 50g/10 分钟，优选的 10 ~ 45g/10分钟。
上述数值是根据 ASTM-1238在 180°C施加 5Kg的重量测得。 ASTM指 美国村料与试验协会 ( American Society for Testing and aterials'AST ) 前身是国际 ¾料试验协会 ( International Association for Testing Materials, IAT % 19世纪 80年优 ,为解决采购商与供货商在购销工业材料过程中产 生的意见和分歧 ,有人提出違立技术委员会制度，由技术委员会组织各方面 的代表参加技术座谈会，讨论解决有关材料规范、 试验程序等方面的争议问 题。 ASTM 的宗旨就是促进公共健康与安全，提高生活质量； 提供值得信 赖的原料、产品、体系和服务； 推动国家、地区、乃至国际经济。 ASTM-1238 是测试塑料熔体流动速率的美国材料协会的标准。
进一步，所述泡孔尺寸稳定剂为二羟基丙基十八烷酸酯（ GMS 失水 山梨醇月桂酸单酯、 失水山梨醇棕榈酸单酯、 失水山梨醇硬脂酸单酯、 脂肪 酸蔗糖酯中一种或几种的混合。
由于所使用的热塑性聚氨酯树脂分子内部存在硬段与软段相分离结构， 会导致在发泡过程中发泡剂在树脂内部分布不均勻，最终发泡粒子的泡孔尺 寸分布较粗，泡孔不均勻。 本发明的发泡热塑性聚氨酯粒子的泡孔直径为 500um - 800um。所述的泡孔尺寸稳定剂有利于挥发性发泡剂进入热塑性聚 氨酯颗粒内部，并且能够均勻地分布。 所述的泡孔尺寸稳定剂加入量为 1 ~ 10重量份，优选的为 2 ~ 8重量份。
进一步，所述熔体粘度调节剂为乙烯-醋酸乙烯共聚物（ EVA X 聚氯乙 烯（ PVC X 聚丙烯-丁二烯 -苯乙烯树脂（ ABS 聚苯乙烯-聚乙烯 -聚丁烯- 聚苯乙烯（ SBS )中一种或几种的混合。 发泡热塑性聚氨酯粒子以及水蒸汽模塑发泡制品需要加热使其在软化 状态下进行，由于热塑性聚氨酯树脂内部硬段存在结晶 ，泡孔壁在膨胀定型 时会产生应变，从而导致发泡珠粒表面出现褶皱或是发泡制品强度不够，尺 寸收縮严重。 为了避免发泡制品尺寸收縮以及发泡粒子表面褶皱，须保证在 生产以及加工过程中热塑性聚氨酯树脂具有足够的强度，并且不易发生导致 收縮的应变，即保证泡孔壁膨胀时高分子链可以自由地延展。 热塑性聚氨酯 树脂中添加熔体粘度调节剂后，扩大了其熔体加工温度范围 ，提高了高分子 链在熔体状态下的运动能力。 所述熔体粘度调节剂的加入量为 1 ~ 35 重量 份，优选的为 5 ~ 30重量份。 当其加入量低于 5重量份时，对热塑性聚氨酯 熔体粘度改善效果不明显，当加入量高于 30重量份时， TPU熔体粘度损失 较大，在制备发泡粒子时易导致泡孔破裂，难以得到闭孔泡孔。
本发明解决上述技术问题的另一技术方案如下：一种发泡热塑性聚氨酯 粒子的制备方法，包括以下步骤：
( 1 )通常为了方便后续热塑性聚氨酯发泡工艺操作，可预先采用挤出 机将其熔融加工成所需形状的热塑性聚氨酯珠粒。通常采用下述方法：采用 高速混合机或母料混合机将 100重量份热塑性聚氨酯颗粒、 1 ~ 10重量份泡 孔尺寸稳定剂、 1 ~ 35重量份熔体粘度调节剂（还可以加入抗氧化剂、 抗黄 变剂、 抗静电剂等）混合均勻，然后投入挤出机进行熔融，挤出的线条在水 槽中冷却定型后进行切割或在熔体从模头挤出后进行水下造粒，得到热塑性 聚氨酯珠粒；
( 2 )将步骤（ 1 )得到的热塑性聚氨酯珠粒与挥发性发泡剂和水加入到 耐压容器中 ，升温至 1 15 ~ 1 18°C (即热塑性聚氨酯软化点附近），耐压容器 内压力保持在 18bar ~ 26bar，在保持耐压容器内温度、压力恒定 20分钟后， 将压力容器内悬浮液排放到大气环境中 ，从而制得发泡热塑性聚氨酯珠粒。 在本发明中所得到的发泡热塑性聚氨酯粒子密度为 0.08 ~ 0.2g/cm3。 进一步，所述挥发性发泡剂为丙烷、 正丁烷、 异丁烷、 正戊烷、 异戊烷 中一种或几种的混合，其加入的量为 1 ~ 40重量份。
本发明还包括了一种述发泡热塑性聚氨酯粒子在制作热塑性聚氨酯发 泡制品中的应用 ，该热塑性聚氨酯发泡制品为所述发泡热塑性聚氨酯粒子采 用 1 ~ 3bar的水蒸气进行膨胀和熔结后得到的模塑制品。
所述的发泡热塑性聚氨酯模塑制品，是将发泡粒子在 1 bar ~ 3bar的水 蒸气加热下进行膨胀和熔结得到。对于本发明的发泡热塑性聚氨酯粒子，即 使在 1 bar ~ 1.5bar如此低的成型压力同样可以得到性能优异的发泡制品。
本发明的有益效果是：本发明制备的发泡热塑性聚氨酯粒子泡孔尺寸均 勻，产品收率高，同时发泡热塑性聚氨酯粒子即使在较低的水蒸气压力下也 具有良好的熔结性能，所得到的模塑泡沫制品形变小，相对于模具的尺寸收 縮率低，尺寸稳定性优异，表面美观。 具体实施方式
以下对本发明的原理和特征进行描述，所举实例只用于解释本发明 ，并 非用于限定本发明的范围。
对于原料热塑性聚氨酯弹性体颗粒的制备：通常是采用异氰酸酯，摩尔 质量为 500 ~ 10000g/mol 的含有活性氢化合物以及摩尔质量为 50 ~ 500g/mol的扩链剂混合来生产，生产中加入催化剂。
下面举例描述在本发明中优选生产热塑性聚氨酯颗粒的起始原料： 异氰酸酯包括脂肪族、 脂环族、 芳香族以及芳脂族。 优选二异氰酸酯， 例如甲苯二异氰酸酯（ TDI ) ,二苯基甲烷 -2,2' -二异氰酸酯（ MDI ) (其中 2,2' -可替换为 2,4' -或 4,4' - ) , 3-异氰酸酯基亚甲基 -3,5,5-三甲基环己基 异氰酸酯（ IPDI ) ,六亚甲基二异氰酸酯（ HDI ) ,二环己基甲烷二异氰酸酯 ( HMDI ) , 1 ,5-奈二异氰酸酯（ NDI ) ,对苯二异氰酸酯（ PPDI ) , 1 ,4-环己 烷二异氰酸酯（ CHDI ),环己烷二亚甲基二异氰酸酯（ HXDI ),特别优选二 苯基甲烷 -4,4' 二异氰酸酯（ MDI )b 含有活性氢化合物包括聚酯多元醇，聚醚多元醇以及聚碳酸酯多元醇。 优选摩尔质量为 800-1200g/mol的聚酯多元醇与摩尔质量为 500-2000g/mol 聚醚多元醇，特别优选聚醚多元醇；其平均官能度为 1.8~2.5，优选在 1.9~ 2.0 ,特别优选为 2；例如：聚己二酸乙二醇酯二醇（ PEA),聚己二酸二甘 醇酯二醇（ PDA ) ,聚己二酸丁二醇酯二醇（ PBA ) ,聚己二酸丙二醇酯二醇 ( PPA ) ,聚氧化丙烯二醇，聚四氢呋喃多元醇（ PTMEG )；特别优选聚己 二酸丁二醇酯二醇（ PBA )与聚四氢呋喃多元醇（ PTMEG )b 扩链剂包括摩尔质量为 50~500g/mol的脂肪族、 芳香族或脂环族二醇 化合物。例如，乙二醇（ EG ), 1.4-丁二醇（ BD〇）， 1,2-丙二醇（ PG ), 1,6- 己二醇（ HD ) ,氢醌双（ 2-羟乙基）醚（ HQEE ) ,间苯二醇双（羟乙基）醚 ( HER), —縮二丙二醇（ DPG ), 1,4-二羟甲基环己烷（ CHDM );特别优 选 1.4-丁二醇（ BD〇 )b 催化剂促进异氰酸酯基团与羟基的反应速率，常用的催化剂有三亚乙基 二胺，二甲基环己胺，三乙胺，（ N , N , N' , N' -四乙基甲二胺）， 1,4-二 甲基哌嗪，二月桂酸二丁基锡，异辛酸钾，钛酸四丁酯，钛酸四异丙酯。
通过常规方法连续生产热塑性聚氨酯弹性体颗粒，如使用挤出反应型挤 出机，或者通过一锅法或预聚物方法。
在实施例与对比例中所使用热塑性聚氨酯珠粒类型与各组分添加比例 如表 1所示。
表 1
TPU 泡孔尺寸稳定剂 熔体粘度调节剂 珠粒类型
Ml (g/10min) 加入量 类型 加入量 类型 加入量
T1 20 100 二羟基丙基十八垸酸酯 5 EVA 10
T2 25 100 失水山梨醇月桂酸单酯 3 PVC 15 T3 30 100 脂肪酸蔗糖酯 2 ABS 10
T4 20 100 二羟基丙基十八垸酸酯 5 - -
Τ5 25 100 - - PVC 15
Τ6 20 100 - - - - 实施例 1
将 100份 Ml为 20g/10min 的 TPU颗粒、 5重量份二羟基丙基十八烷 酸酯、 10重量份 EVA通过高速混合机混合均勻后投入双螺杆挤出中进行熔 融混炼。 将熔融混炼物从挤出机直径为 2mm的模头中挤出成条状，然后在 水槽中冷却定型，用造切粒机进行切割，从而得到热塑性聚氨酯珠粒。
将上述得到的热塑性聚氨酯珠粒 100重量份、水 400重量份加入到 10L 高压反应釜中 ，在进行搅拌的同时添加 30重量份正丁烷发泡剂。 将高压反 应釜升温至 1 18°C ,然后在此温度下保证 20分钟，打开高压釜底端放料阀 门，使高压反应釜内混合液排放到大气环境中 ，从而得到发泡热塑性聚氨酯 粒子。所得到发泡热塑性聚氨酯珠粒密度为 0.16g/cm3，气泡直径为 550um。
将上述得到的发泡热塑性聚氨酯粒子填充到长 300mmx宽 250mmx厚 50mm的模具中。 采用 1.4bar的水蒸气沿模具厚度方向压縮 10%使粒子粘 结成型，最终得到发泡热塑性聚氨酯模塑泡沫制品。将所得到的泡沫制品在 50°Cx50%RH下放置 2小时之后，在 80°C的恒温室内进行 2小时干燥，最 后在 25°Cx50%RH放置 2小时后，评价其性能，如表 2所示。
实施例 2
通过在 100份 Ml为 25g/10min 的 TPU加入失水山梨醇月桂酸单酯作 为泡孔尺寸稳定定， PVC作为熔体粘度调节剂，将发泡温度设定为 1 16°C , 采用正戊烷作为发泡剂。 除此之外，按照与实施例 1相同的方法获得发泡热 塑性聚氨酯粒子与发泡热塑性聚氨酯模塑泡沫制品，性能评价如表 2所示。
实施例 3
通过在 100份 Ml为 30g/10min 的 TPU加入脂肪酸蔗糖酯作为泡孔尺 寸稳定定， ABS作为熔体粘度调节剂 ，将发泡温度设定为 1 15°C ,采用正丁 烷作为发泡剂，水蒸气成型压力为 1.2bar。 除此之外，按照与实施例 1相同 的方法获得发泡热塑性聚氨酯粒子与发泡热塑性聚氨酯模塑泡沫制品，性能 评价如表 2所示。
对比例 1
除单独在 100份 Ml为 20g/10min 的 TPU颗粒中添加二羟基丙基十八 烷酸酯作为泡孔尺寸稳定剂外，按照与实施例 1相同的方法获得发泡热塑性 聚氨酯粒子与发泡热塑性聚氨酯模塑泡沫制品，性能评价如表 2所示。
对比例 2
除单独在 100份 Ml为 25g/10min 的 TPU加入 PVC作为熔体粘度调节 剂外，按照与实施例 2相同的方法获得发泡热塑性聚氨酯粒子与发泡热塑性 聚氨酯模塑泡沫制品，性能评价如表 2所示。
对比例 3
除了在 100份 Ml为 20g/10min 的 TPU颗粒不添加泡孔尺寸稳定剂与 熔体粘度调节剂外，按照与实施例 1相同的方法获得发泡热塑性聚氨酯粒子 与发泡热塑性聚氨酯模塑泡沫制品，性能评价如表 2所示。
发泡热塑性聚氨酯粒子的生产工艺条件，物性以及模塑发泡制品的性能 评价如表 2所示。
表 2
Figure imgf000010_0001
各种评价按下述方法实施。
1.泡沫制品变形
对于模塑成型泡沫制品的外观进行了肉眼观察，其中将基本观察不到收 縮与皱纹（ 1 cm以上的条纹）的泡沫制品评价为 o ,将仅仅存在皱纹但观察 不到收縮的泡沫制品评价为△ ，将皱纹多，形状整体不规则的泡沫成形体评 价为 x。
2.泡沫制品表面性评价
对模塑成型泡沫制品的表面进行观察 ， 计算出每 10cm2面积中出现 1 cm2以上发泡珠粒间间隙的平均个数，并对此进行如下判定：
少于 100个计为 o ；
100个以上计为 χ。
由以上实例和对比例可以看出 ，实施例 1至 3制备的发泡热塑性聚氨酯 珠粒泡孔尺寸均勻，产品收率高。 相对于对比例 1至 3 ,实施例 1至 3所得 到的模塑泡沫制品形变小，基本观察不到收縮与皱纹（ 1 cm以上的条纹）， 而且发泡珠粒间间隙也很少，收縮率低，尺寸稳定性优异，表面美观。
以上所述仅为本发明的较佳实施例，并不用以限制本发明 ，凡在本发明 的精神和原则之内 ，所作的任何修改、 等同替换、 改进等，均应包含在本发 明的保护范围之内。

Claims

权 利 要 求 书
1. 一种发泡热塑性聚氨酯粒子，其特征在于， 由以下重量份的成分组 成： 100份热塑性聚氨酯颗粒， 1 ~ 10份泡孔尺寸稳定剂， 1 ~ 35份熔体粘 度调节剂。
2. 根据权利要求 1 所述发泡热塑性聚氨酯粒子，其特征在于，所述发 泡热塑性聚氨酯粒子在 180°C的熔融粘度为 8000 ~ 15000泊。
3. 根据权利要求 1 所述发泡热塑性聚氨酯粒子，其特征在于，所述热 塑性聚氨酯颗粒的邵氏硬度为 55 ~ 95A。
4. 根据权利要求 1 所述发泡热塑性聚氨酯粒子，其特征在于，所述热 塑性聚氨酯颗粒的熔体流动速率为 5 ~ 50g/10分钟。
5. 根据权利要求 1至 4任一项所述发泡热塑性聚氨酯粒子，其特征在 于，所述泡孔尺寸稳定剂为二羟基丙基十八烷酸酯、失水山梨醇月桂酸单酯、 失水山梨醇棕榈酸单酯、 失水山梨醇硬脂酸单酯、 脂肪酸蔗糖酯中一种或几 种的混合。
6. 根据权利要求 1至 4任一项所述发泡热塑性聚氨酯珠粒，其特征在 于，所述熔体粘度调节剂为乙烯 -醋酸乙烯共聚物、 聚氯乙烯、 聚丙烯 -丁二 烯-苯乙烯树脂、 聚苯乙烯-聚乙烯-聚丁烯 -聚苯乙烯中一种或几种的混合。
7. —种发泡热塑性聚氨酯粒子的制备方法，其特征在于，包括以下步
( 1 )将 100重量份热塑性聚氨酯颗粒、 1 ~ 10重量份泡孔尺寸稳定剂、 1 ~ 35重量份熔体粘度调节剂混合均勻，然后投入挤出机进行熔融，挤出的 线条在水槽中冷却定型后进行切割或在熔体从模头挤出后进行水下造粒，得 到热塑性聚氨酯珠粒；
( 2 )将步骤（ 1 )得到的热塑性聚氨酯珠粒与挥发性发泡剂和水加入到 耐压容器中 ，升温至 1 15 ~ 1 18°C,耐压容器内压力保持在 18 ~ 26bar ,在保 持耐压容器内温度、 压力恒定 20分钟后，将压力容器内悬浮液排放到大气 环境中 ，从而制得发泡热塑性聚氨酯粒子。
8. 根据权利要求 7所述发泡热塑性聚氨酯粒子的制备方法，其特征在 于，所述挥发性发泡剂为丙烷、 正丁烷、 异丁烷、 正戊烷、 异戊烷中一种或 几种的混合，其加入的量为 1 ~ 40重量份。
9. 一种如权利要求 1至 6任一项所述发泡热塑性聚氨酯粒子在制作热 塑性聚氨酯发泡制品中的应用。
10.—种热塑性聚氨酯发泡制品 ，其特征在于，所述发泡制品为如权利 要求 1至 6任一项所述发泡热塑性聚氨酯粒子采用 1 ~ 3bar的水蒸气进行膨 胀和熔结后得到的模塑制品。
PCT/CN2014/082594 2014-02-18 2014-07-21 一种发泡热塑性聚氨酯粒子及其制备方法和应用 WO2015123960A1 (zh)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP14883292.6A EP3109280B1 (en) 2014-02-18 2014-07-21 Foamed thermoplastic polyurethane particle, and use thereof
MX2016010762A MX2016010762A (es) 2014-02-18 2014-07-21 Esferas de poliuretano termoplastico expandido y metodo de preparacion y aplicacion de las mismas.
ES14883292T ES2748163T3 (es) 2014-02-18 2014-07-21 Partícula de poliuretano termoplástico espumado y uso de la misma
US15/120,083 US10519289B2 (en) 2014-02-18 2014-07-21 Expanded thermoplastic polyurethane beads and preparation method and application thereof
KR1020167025522A KR102100655B1 (ko) 2014-02-18 2014-07-21 팽창된 열가소성 폴리우레탄 비드 및 이의 제조 방법 및 적용

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410054599.7A CN103804889B (zh) 2014-02-18 2014-02-18 一种发泡热塑性聚氨酯粒子及其制备方法和应用
CN201410054599.7 2014-02-18

Publications (1)

Publication Number Publication Date
WO2015123960A1 true WO2015123960A1 (zh) 2015-08-27

Family

ID=50702306

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/082594 WO2015123960A1 (zh) 2014-02-18 2014-07-21 一种发泡热塑性聚氨酯粒子及其制备方法和应用

Country Status (8)

Country Link
US (1) US10519289B2 (zh)
EP (1) EP3109280B1 (zh)
KR (1) KR102100655B1 (zh)
CN (1) CN103804889B (zh)
ES (1) ES2748163T3 (zh)
MX (1) MX2016010762A (zh)
PT (1) PT3109280T (zh)
WO (1) WO2015123960A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3181620A1 (en) * 2015-12-17 2017-06-21 Sunko Ink Co., Ltd. Microwave molded article and manufacturing method thereof
WO2019237280A1 (zh) * 2018-06-13 2019-12-19 三晃股份有限公司 发泡热塑性聚氨基甲酸酯及其微波成型体
CN110791059A (zh) * 2019-11-12 2020-02-14 常州市顺祥新材料科技股份有限公司 一种热塑性聚酯弹性体发泡颗粒的低压釜式制备方法

Families Citing this family (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103804889B (zh) * 2014-02-18 2016-01-27 山东美瑞新材料有限公司 一种发泡热塑性聚氨酯粒子及其制备方法和应用
CN104149253B (zh) * 2014-06-25 2016-12-07 裕克施乐塑料制品（太仓）有限公司 一种热塑型聚氨酯弹性体发泡材料成型装置及方法
CN104231592B (zh) * 2014-09-12 2017-02-15 美瑞新材料股份有限公司 一种发泡型热塑性聚氨酯粒子及其制备方法
EP3305837B1 (en) * 2015-06-01 2022-07-06 Jsp Corporation Expanded thermoplastic polyurethane particles and expanded thermoplastic polyurethane particle molded article
TW201736423A (zh) * 2015-09-11 2017-10-16 三晃股份有限公司 發泡熱塑性聚氨基甲酸酯及其微波成型體
KR102307784B1 (ko) 2015-10-02 2021-10-05 더 케무어스 컴퍼니 에프씨, 엘엘씨 소수성 화합물이 혼합되어 있는 고체 중합체 물품
WO2018003316A1 (ja) * 2016-06-29 2018-01-04 株式会社ジェイエスピー 熱可塑性ポリウレタン発泡粒子成形体及びその製造方法、並びに熱可塑性ポリウレタン発泡粒子
CN106189103A (zh) * 2016-08-24 2016-12-07 深圳市传佳新材料有限公司 一种热塑性聚酯弹性体发泡颗粒及制备方法
JP6346919B2 (ja) * 2016-09-08 2018-06-20 株式会社ジェイエスピー 熱可塑性ポリウレタン発泡粒子の製造方法
WO2018061859A1 (ja) * 2016-09-28 2018-04-05 日本ゼオン株式会社 塩化ビニル樹脂組成物、塩化ビニル樹脂成形体、及び積層体
CN106589908B (zh) * 2016-11-22 2019-01-04 茂泰(福建)鞋材有限公司 一种低压缩变形的发泡鞋底及其制备方法
JP6782152B2 (ja) * 2016-11-25 2020-11-11 株式会社ジェイエスピー 熱可塑性ポリウレタン発泡粒子及び熱可塑性ポリウレタン発泡粒子成形体
JP6371821B2 (ja) * 2016-11-28 2018-08-08 株式会社ジェイエスピー 熱可塑性ポリウレタン発泡粒子及び熱可塑性ポリウレタン発泡粒子成形体
KR101911790B1 (ko) * 2017-01-18 2018-10-26 코스파 주식회사 차음용 적층체
CN106967286A (zh) * 2017-03-27 2017-07-21 盛嘉伦橡塑(深圳）股份有限公司 用于制备发泡型热塑性弹性体的组合物及其制备方法、发泡型热塑性弹性体及其制备方法
EP3424973A1 (en) * 2017-07-04 2019-01-09 Covestro Deutschland AG Article comprising expanded tpu and a coating
JP6912317B2 (ja) * 2017-08-03 2021-08-04 株式会社ジェイエスピー ウレタン系熱可塑性エラストマー発泡粒子
CN107446343B (zh) * 2017-08-04 2019-03-08 南通德亿新材料有限公司 一种可降解防污热塑性微气囊聚合物弹性体材料及其制备
CN107298847B (zh) * 2017-08-04 2019-01-18 南通德亿新材料有限公司 一种热塑性微气囊聚合物弹性体材料及其制备方法
BR112020021105A2 (pt) * 2018-04-20 2021-02-17 Basf Se espuma de esferas, processos de produção de corpos moldados, corpo moldado, calçado e uso de espuma de esferas
EP3781617A1 (de) 2018-04-20 2021-02-24 Basf Se Schaumstoffe auf basis thermoplastischer elastomere
CN108530876A (zh) * 2018-04-23 2018-09-14 福建万聚福体育科技有限公司 一种弹性减震透孔垫层、加工方法及施工工艺
CN108948411A (zh) * 2018-05-23 2018-12-07 贵州理工学院 一种聚乳酸模塑珠粒发泡材料的制备方法
KR102317520B1 (ko) * 2018-09-07 2021-10-26 (주)엘엑스하우시스 열가소성 폴리우레탄 입자 및 이의 제조방법
FR3088845B1 (fr) * 2018-11-26 2022-04-01 Tesca France Procédé de réalisation d’une matelassure de siège de véhicule automobile
CN109535696A (zh) * 2018-12-12 2019-03-29 深圳麦德利宇航材料科技有限公司 一种航空座椅的泡沫生产工艺
CN112622392B (zh) * 2019-09-20 2023-03-10 美瑞新材料股份有限公司 一种具有表面涂层的热塑性聚氨酯泡沫制品及其制备方法
CN112940488B (zh) * 2019-11-26 2024-06-11 美瑞新材料股份有限公司 一种高平整度的热塑性聚氨酯泡沫制品及其制备方法和应用
CN110922629B (zh) * 2019-12-03 2021-01-26 成都玉瓶科技有限公司 可逆动态大孔弹性体聚合物材料及其制备方法和应用
CN111171364A (zh) * 2020-01-21 2020-05-19 翁秋梅 一种力响应聚合物泡沫颗粒及其制备方法
CN111253610A (zh) * 2020-01-21 2020-06-09 翁秋梅 一种动态聚合物泡沫复合材料
CN111171365A (zh) * 2020-01-21 2020-05-19 翁秋梅 一种力响应聚合物泡沫复合材料
KR102397310B1 (ko) 2020-04-08 2022-05-12 에이치디씨현대이피 주식회사 용매를 사용하지 않는 고발포 폴리우레탄 폼 제조방법 및 이 제조방법에 의해 제조된 폴리우레탄 폼
CN114456433B (zh) * 2022-01-29 2022-09-13 浙江环龙新材料科技有限公司 一种高硬度热塑性聚氨酯发泡卷材及其半连续制备方法
CN116004136A (zh) * 2022-12-24 2023-04-25 烟台德邦科技股份有限公司 一种锂电池封装用膨胀胶带及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007091840A (ja) * 2005-09-28 2007-04-12 Sekisui Plastics Co Ltd 発泡性熱可塑性樹脂粒子、熱可塑性樹脂予備発泡粒子とその製造方法、発泡成形品
WO2007082838A1 (de) * 2006-01-18 2007-07-26 Basf Se Schaumstoffe auf basis thermoplastischer polyurethane
CN101821326A (zh) * 2007-10-11 2010-09-01 株式会社钟化 聚丙烯类树脂预发泡颗粒及其制造方法
CN102070841A (zh) * 2011-01-21 2011-05-25 北京工商大学 采用复合发泡剂的聚丙烯泡沫片材及其生产方法
CN103642200A (zh) * 2013-12-20 2014-03-19 烟台开发区新龙华包装材料有限公司 一种发泡热塑性聚氨酯珠粒及其制备方法
CN103804889A (zh) * 2014-02-18 2014-05-21 山东美瑞新材料有限公司 一种发泡热塑性聚氨酯粒子及其制备方法和应用

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882191A (en) 1973-03-29 1975-05-06 Uniroyal Ltd Blend of thermoplastic polyurethane elastomer, polyvinyl chloride resin and chlorinated polyethylene
JPH11124532A (ja) * 1997-10-22 1999-05-11 Mc Industries Ltd 熱可塑性プラスチックシート付ポリウレタンフォーム成形品の製造法
WO2002032986A1 (fr) * 2000-10-18 2002-04-25 Mitsui Chemicals, Inc. Mousse a base d"une composition d"elastomere d"urethane thermoplastique et son procede de preparation
US7770691B2 (en) * 2004-08-18 2010-08-10 Schabel Polymer Technology, Llc Lightweight pelletized materials
EP2109637B1 (de) * 2007-01-16 2018-07-25 Basf Se Hybridsysteme aus geschäumten thermoplastischen elastomeren und polyurethanen
US9456326B2 (en) * 2008-07-24 2016-09-27 Cable Television Laboratories, Inc. Method and system of supporting continuous access to content transmitted over two or more networks
WO2010010010A1 (de) * 2008-07-25 2010-01-28 Basf Se Thermoplastische polymer blends auf der basis von thermoplastischem polyurethan und styrolpolymerisat, daraus hergestellte schaumstoffe und zugehörige herstellungsverfahren
CN103408922B (zh) * 2013-08-13 2015-04-29 泉州三盛橡塑发泡鞋材有限公司 一种热塑性聚氨酯弹性体发泡材料及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007091840A (ja) * 2005-09-28 2007-04-12 Sekisui Plastics Co Ltd 発泡性熱可塑性樹脂粒子、熱可塑性樹脂予備発泡粒子とその製造方法、発泡成形品
WO2007082838A1 (de) * 2006-01-18 2007-07-26 Basf Se Schaumstoffe auf basis thermoplastischer polyurethane
CN101821326A (zh) * 2007-10-11 2010-09-01 株式会社钟化 聚丙烯类树脂预发泡颗粒及其制造方法
CN102070841A (zh) * 2011-01-21 2011-05-25 北京工商大学 采用复合发泡剂的聚丙烯泡沫片材及其生产方法
CN103642200A (zh) * 2013-12-20 2014-03-19 烟台开发区新龙华包装材料有限公司 一种发泡热塑性聚氨酯珠粒及其制备方法
CN103804889A (zh) * 2014-02-18 2014-05-21 山东美瑞新材料有限公司 一种发泡热塑性聚氨酯粒子及其制备方法和应用

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3181620A1 (en) * 2015-12-17 2017-06-21 Sunko Ink Co., Ltd. Microwave molded article and manufacturing method thereof
WO2019237280A1 (zh) * 2018-06-13 2019-12-19 三晃股份有限公司 发泡热塑性聚氨基甲酸酯及其微波成型体
CN112166157A (zh) * 2018-06-13 2021-01-01 三晃股份有限公司 发泡热塑性聚氨基甲酸酯及其微波成型体
CN112166157B (zh) * 2018-06-13 2021-10-29 三晃股份有限公司 发泡热塑性聚氨基甲酸酯及其微波成型体
US11993689B2 (en) 2018-06-13 2024-05-28 Sunko Ink Co., Ltd. Foamed thermoplastic polyurethane and microwave molded body thereof
CN110791059A (zh) * 2019-11-12 2020-02-14 常州市顺祥新材料科技股份有限公司 一种热塑性聚酯弹性体发泡颗粒的低压釜式制备方法
CN110791059B (zh) * 2019-11-12 2022-01-28 常州市顺祥新材料科技股份有限公司 一种热塑性聚酯弹性体发泡颗粒的低压釜式制备方法

Also Published As

Publication number Publication date
EP3109280A4 (en) 2017-07-19
CN103804889A (zh) 2014-05-21
PT3109280T (pt) 2019-10-24
KR20160124821A (ko) 2016-10-28
US10519289B2 (en) 2019-12-31
CN103804889B (zh) 2016-01-27
ES2748163T3 (es) 2020-03-13
KR102100655B1 (ko) 2020-04-14
US20170218154A1 (en) 2017-08-03
EP3109280B1 (en) 2019-09-04
EP3109280A1 (en) 2016-12-28
MX2016010762A (es) 2017-02-02

Similar Documents

Publication Publication Date Title
WO2015123960A1 (zh) 一种发泡热塑性聚氨酯粒子及其制备方法和应用
US9346929B2 (en) Hybrid foam
CN109952331B (zh) 膨胀热塑性聚氨酯颗粒、其制备方法及模塑品的制备方法
JP6279576B2 (ja) 複合フォーム
CN103642200B (zh) 一种发泡热塑性聚氨酯珠粒及其制备方法
CN104231592B (zh) 一种发泡型热塑性聚氨酯粒子及其制备方法
CN107828205B (zh) 一种可硫化交联的发泡聚氨酯混炼胶粒子及其制备方法和成型工艺
KR20000077134A (ko) 특성이 개선된 지방족 소결가능한 열가소성 폴리우레탄성형 조성물
CN101522742A (zh) 制备粘弹性聚氨酯泡沫材料的方法
JP2023029384A (ja) 熱可塑性ポリウレタン
US20190202087A1 (en) Method for producing expanded granular material
CN113490706A (zh) 由热塑性聚氨酯组成的软丸粒泡沫
TW202239842A (zh) 由具有２０ｄ至９０ｄ之間之蕭氏硬度之ｔｐｅ構成之粒子泡沫
CN112004870A (zh) 基于热塑性弹性体的泡沫
CN112004869A (zh) 基于热塑性弹性体的泡沫
CN113260649B (zh) 由芳族聚酯-聚氨酯多嵌段共聚物组成的颗粒泡沫
CN112088181B (zh) 包含热塑性多异氰酸酯加聚产物的制剂、其制备方法及其用途
CN113950497A (zh) 新的颗粒泡沫
CN118119652A (zh) 热塑性弹性体粉末、其制备工艺以及制备3d制品的方法
CN112004868A (zh) 基于热塑性弹性体的泡沫

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14883292

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 15120083

Country of ref document: US

Ref document number: MX/A/2016/010762

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: IDP00201605596

Country of ref document: ID

ENP Entry into the national phase

Ref document number: 20167025522

Country of ref document: KR

Kind code of ref document: A

REEP Request for entry into the european phase

Ref document number: 2014883292

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2014883292

Country of ref document: EP