WO2019143200A1 - Composition de polyuréthane thermoplastique pour moulage par embouage de poudre, son procédé de préparation, et matériau de revêtement intérieur d'automobile fabriqué à l'aide de ladite composition de polyuréthane thermoplastique - Google Patents

Composition de polyuréthane thermoplastique pour moulage par embouage de poudre, son procédé de préparation, et matériau de revêtement intérieur d'automobile fabriqué à l'aide de ladite composition de polyuréthane thermoplastique Download PDF

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Publication number
WO2019143200A1
WO2019143200A1 PCT/KR2019/000795 KR2019000795W WO2019143200A1 WO 2019143200 A1 WO2019143200 A1 WO 2019143200A1 KR 2019000795 W KR2019000795 W KR 2019000795W WO 2019143200 A1 WO2019143200 A1 WO 2019143200A1
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WIPO (PCT)
Prior art keywords
thermoplastic
weight
thermoplastic polyurethane
skin material
polyurethane resin
Prior art date
Application number
PCT/KR2019/000795
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English (en)
Korean (ko)
Inventor
전성모
김병민
송은호
홍민기
변재현
Original Assignee
주식회사 엘지하우시스
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.)
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Priority claimed from KR1020180133913A external-priority patent/KR102242483B1/ko
Application filed by 주식회사 엘지하우시스 filed Critical 주식회사 엘지하우시스
Priority claimed from KR1020190006980A external-priority patent/KR102226152B1/ko
Publication of WO2019143200A1 publication Critical patent/WO2019143200A1/fr

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Classifications

    • 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
    • B29B9/10—Making granules by moulding the material, i.e. treating it in the molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/18—Slush casting, i.e. pouring moulding material into a hollow mould with excess material being poured off
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen

Definitions

  • the present invention relates to a thermoplastic polyurethane composition for powder slush molding, a method for producing the same, and a skin material for an automobile interior material manufactured using the same, and more particularly, to a skin material for an automobile interior material by a powder slush molding method
  • the thermoplastic polyurethane composition is excellent in moldability, and the skin material for an automobile interior material formed using the thermoplastic polyurethane composition is excellent in scratch resistance, tensile strength, elongation at break, gloss change rate, weatherability,
  • the present invention relates to a thermoplastic polyurethane composition for slush molding, a method for producing the same, and a skin material for automobile interior materials manufactured using the same.
  • Thermoplastic polyurethane (TPU) resin which is widely used as an automobile interior material, can be molded in various forms in comparison with price and has good mechanical properties and is particularly suitable for instrument panel, door trim Door trims), automotive interior mat backing materials, and the like.
  • the skin material for automobile interior materials manufactured from the composition including the TPU resin is manufactured by a powder slush molding method having a high degree of design freedom and excellent emboss pattern retention as disclosed in Korean Patent Registration No. 10-1775199 ,
  • the TPU resin has a higher tackiness than other thermoplastic elastomers, and scratches are generated by the hands of the operator when the skin material is demolded from the mold after molding.
  • the scratch resistance of the TPU material is not good due to its inherent characteristics, it is not easy to satisfy the hardness or scratch resistance according to the level of the end user.
  • silicone oil, paraffin oil or paraffin wax is added to the composition to reduce stickiness between the mold and the resin to facilitate demoulding and to improve the scratch resistance.
  • the oil or wax having a small molecular weight is excessively transferred to the surface of the skin material to increase the gloss and the oil or wax transferred to the surface is volatilized and the scratch resistance can not be maintained. There is a problem that scratches are generated by the user of the final product applied.
  • the skin material formed using the TPU resin composition is excellent in moldability, and the thermoplastic polyurethane composition for powder slush molding is excellent in scratch resistance, tensile strength, elongation at break, weather resistance, And to develop a skin material for automobile interior materials manufactured using the same.
  • Patent Literature (Patent Document 1) KR 10-1775199 B (Notification: 2017.08.30)
  • the present invention relates to a thermoplastic polyurethane composition for powder slush molding, which is excellent in moldability, and a skin material for automobile interior materials manufactured using the same has low gloss change rate, scratch resistance, which is excellent in elongation at break, weather resistance, and feel, and a method for producing the same, and a skin material for automobile interior materials manufactured using the same.
  • the present invention relates to a thermoplastic resin composition
  • a thermoplastic resin composition comprising 100 parts by weight of a thermoplastic polyurethane resin
  • thermoplastic silicone vulcanizate 25 to 70 parts by weight of a thermoplastic silicone vulcanizate.
  • the present invention also relates to a thermoplastic silicone vulcanate production step (S1) for producing thermoplastic silicone vulcanizate (B);
  • thermoplastic silicone vulcanizate (B) in the step (S1) mixing 25-70 parts by weight of the thermoplastic silicone vulcanizate (B) in the step (S1) with 100 parts by weight of the thermoplastic polyurethane resin (A). ≪ / RTI >
  • the present invention also relates to a skin material for an automobile interior material manufactured using the thermoplastic polyurethane composition for powder slush molding.
  • thermoplastic polyurethane composition for powder slush molding of the present invention has an excellent moldability.
  • the skin material for automobile interior materials manufactured using the thermoplastic polyurethane composition for powder slush molding of the present invention has an excellent scratch resistance, tensile strength, elongation at break, gloss change rate, weather resistance, and touch.
  • thermoplastic polyurethane composition for powder slush molding of the present invention will be described in detail.
  • thermoplastic polyurethane composition for powder slush molding is excellent in moldability, and a skin material for an automobile interior material manufactured using the same has a small rate of change in gloss, and is excellent in scratch resistance, tensile strength, elongation at break, As a result of the efforts, it was confirmed that the above effect can be realized when the thermoplastic silicone vulcanizate is used within a certain amount range.
  • the present invention relates to a thermoplastic resin composition
  • a thermoplastic resin composition comprising 100 parts by weight of a thermoplastic polyurethane resin
  • thermoplastic silicone vulcanizate 25 to 70 parts by weight of a thermoplastic silicone vulcanizate.
  • the powder slush molding is performed by loading a thermoplastic polyurethane composition in the form of powder into an open container, combining the heated mold with the open container to form a closed system and rotating the mold, Means a method of producing a skin material for an automobile interior material by melting and applying the thermoplastic polyurethane composition.
  • thermoplastic polyurethane composition for powder slush molding each component contained in the thermoplastic polyurethane composition for powder slush molding will be described in detail.
  • thermoplastic polyurethane resin of the present invention has an ability to stretch beyond its original length and to shrink substantially to its original length when relaxed. Specifically, it is softened upon exposure to heat and substantially returned to its original state when cooled to room temperature Means the polyurethane coming from.
  • thermoplastic polyurethane resin (A) of the present invention may be an aliphatic thermoplastic polyurethane resin excellent in weather resistance without discoloration and aging due to ultraviolet rays.
  • thermoplastic polyurethane resin (A) can be produced by reacting an aliphatic diisocyanate with a polyol and a chain extender.
  • aliphatic diisocyanate examples include isophorone diisocyanate, 1,6 hexamethylene diisocyanate, 4,4-dicyclomethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,4-cyclohexyl Diisocyanate, decane-1,10-diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate.
  • the polyol may be at least one selected from the group consisting of a polyether polyol, a polyester polyol and a polycarbonate polyol.
  • the polyether polyol is a diol or a polyol having 2-15 carbon atoms, specifically, an alkyldiol or a glycol and an alkylene oxide having 2-6 carbon atoms, specifically, ethylene oxide or propylene oxide Lt; / RTI >
  • the polyester polyol may be formed by esterifying one or more glycols with one or more dicarboxylic acids or anhydrides thereof.
  • the glycol may be at least one selected from ethylene glycol, propylene glycol and glycerin
  • the dicarboxylic acid may be at least one selected from adipic acid, phthalic acid and maleic acid.
  • the polyester polyol may be formed by subjecting a lactone or a derivative thereof to ring-opening polymerization using a small amount of a diol, a triol or an amine as an initiator.
  • the polyester polyol may be polycaprolactone (PCL) synthesized by ring-opening polymerization using ⁇ -caprolactone (CL) with diethylene glycol as an initiator.
  • PCL polycaprolactone
  • CL ⁇ -caprolactone
  • the polycarbonate polyol may be derived from the reaction of a glycol and a carbonate.
  • the chain extender may be, for example, an aliphatic linear and branched chain diol having 2 to 10 carbon atoms in the chain, and specific examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, Hexanediol, cyclohexanediol, cyclohexanediol, diethylene glycol, dipropylene glycol monomethyl ether, cyclohexanedimethanol, cyclohexanediol, cyclohexanediol, cyclohexanediol, cyclohexanediol, cyclohexanediol, Glycol, ethanolamine, and N-methyldiethanolamine.
  • thermoplastic polyurethane resin (A) of the present invention may be at least one selected from the group consisting of a polyether-based polyurethane or a polycaprolactone-based polyurethane, and more specifically, a polyol having a hydrolyzable and heat- Caprolactone-based polyurethane.
  • the thermoplastic polyurethane resin (A) may have a particle size of 100-600 ⁇ ⁇ or 200-400 ⁇ ⁇ . If the amount is less than the above range, the dropping property of the thermoplastic polyurethane composition may be lowered, which may result in difficulty in the powder slush molding process. If the above range is exceeded, the thermoplastic polyurethane resin melts less at a molding temperature of 200-250 ° C Which may cause problems in moldability and may have a particle size within the above range.
  • the particle size can be inferred through particle size distribution analysis (dry or wet) using a sieve vibrator from FRITSCH.
  • the thermoplastic polyurethane resin (A) may have a Shore A hardness of 65-92 or 70-90. If it is less than the above range, the scratch resistance may be deteriorated. If it exceeds the above range, the soft touch feeling may be lowered as a skin material for automobile interior materials, and Shore A hardness within the above range can be obtained.
  • the Shore A hardness can be measured according to ISO 868.
  • the thermoplastic polyurethane resin (A) may have a tensile strength of 5-35 MPa or 10-30 MPa. If it is less than the above range, the tensile strength and elongation at break, which are required as the skin material for automobile interior materials, may not be satisfied, and if it exceeds the above range, the air bag may not be torn along the incision line during deployment, It can have strength.
  • the tensile strength can be measured according to ISO 527-2.
  • the thermoplastic polyurethane resin (A) may have a elongation at break of 300-520% or 350-480%. If it is less than the above range, the tensile strength and the elongation at break, which are required as the skin material for automobile interior materials, may not be satisfied. If it exceeds the above range, the air bag may not be torn along the incision line during deployment, It can be stretched.
  • the elongation at break can be measured in accordance with ISO 527-2.
  • the thermoplastic polyurethane resin (A) may have a Vicat softening point of 40-60 ° C or 45-55 ° C. If the temperature of the automobile is lower than the above range, the appearance of the automobile interior temperature may be changed and cracks may occur. If the temperature is above the above range, the skin softness may be deteriorated under low temperature conditions, have.
  • the Vicat softening point of the present invention can be measured according to ISO 306.
  • the melt flow index (MFI) of the thermoplastic polyurethane resin (A) may be 50-100 g / 10 min (185 ° C, 2.16 kg) or 60-85 g / 10 min (185 ° C, 2.16 kg) . If it is outside the above range, the processability may be deteriorated and the melt flow index within the above range may be obtained.
  • thermoplastic polyurethane composition of the present invention may include a thermoplastic silicone vulcanizate which is a thermoplastic elastomer in order to improve the scratch resistance of the skin material for an automobile interior material and impart soft touch and weatherability.
  • thermoplastic silicone vulcanizate (B) may be in the form of a crosslinked silicone rubber (B-2) dispersed in a thermoplastic polymer matrix (B-1).
  • thermoplastic polymer matrix (B-1) is at least one of polyamide, polypropylene, polyethylene, polyvinyl chloride, polyurethane, polyester, polycarbonate, Polysulfone, and polysulfone.
  • thermoplastic polyurethane resin (A) is excellent in compatibility with the thermoplastic polyurethane resin (A), and the thermoplastic polymer matrix (B-1) Urethane resin can be used.
  • thermoplastic polyurethane resin as the thermoplastic polyurethane resin (A) described above is used, and redundant description thereof is omitted.
  • the cross-linked silicone rubber (B-2) means that it is cured, vulcanized and / or catalyzed, and has excellent mechanical properties such as strength, elasticity or heat resistance as compared with the silicone rubber (C) It is possible to impart an improved scratch resistance and weather resistance to a skin material for an automobile interior material.
  • the crosslinked silicone rubber (B-2) means a fully-crosslinked silicone rubber.
  • the weight ratio of the thermoplastic polymer matrix (B-1) to the crosslinked silicone rubber (B-2) may be 90: 10-50: 50 or 85: 15-55: 45.
  • the amount of the crosslinked silicone rubber (B-2) is less than the above range, the effect of improving the scratch resistance of the skin material for automobile interior materials may be insignificant, and the tactile feeling and weather resistance may be deteriorated.
  • the dispersibility of the rubber (B-2) is lowered and the composition is poorly melted during the powder slush molding process, resulting in deterioration of the mechanical properties such as tensile strength and elongation at break of the skin material, B-2), the tactile sensation of the skin material may be deteriorated and may be included within the above range.
  • thermoplastic silicone vulcanizate (B) may have a Shore A hardness of 30-80 or 40-77. If the amount is less than the above range, the effect of improving the scratch resistance may be insignificant. If the above range is exceeded, the feeling of soft feeling may be lowered as the skin material for automobile interior materials.
  • the Shore A hardness can be measured according to ISO 868.
  • the thermoplastic silicone vulcanates (B) may have a tensile strength at break of 3-35 MPa, 4-30 MPa, or 4-20 MPa, and the elongation at break may be 600-750%, 610-740%, or 620-730% have. If it is less than the above range, the effect of improving the scratch resistance may be insignificant. If it exceeds the above range, the air bag may not be torn along the incision line when the air bag is deployed, so that the tensile strength and the elongation at break may be within the above range.
  • the tensile strength and elongation at break can be measured in accordance with ISO 37.
  • the thermoplastic silicone vulcanizate (B) may have a melt flow index (MFI) of 40-100 g / 10 min (190 ° C, 10 kg) or 45-95 g / 10 min (190 ° C, 10 kg).
  • MFI melt flow index
  • the amount is less than the above range, the composition may not flow well after melting, and the moldability may be deteriorated. If it exceeds the above range, the composition may not be maintained as a skin material after melting and flow down, .
  • the melt flow index can be measured in accordance with ISO 1133.
  • the thermoplastic silicone vulcanizate (B) may be contained in an amount of 25-70 parts by weight or 30-60 parts by weight based on 100 parts by weight of the thermoplastic polyurethane resin (A).
  • the amount is less than the above range, the slip property of the skin material for automobile interior materials is lowered and the effect of improving the de-moldability and improving the scratch resistance is small, and the tactile and weather resistance is decreased.
  • the dispersibility of the crosslinked silicone rubber (B-2) is lowered and the composition is poorly melted during the powder slush molding process, resulting in deterioration of the moldability.
  • mechanical properties such as tensile strength and elongation at break of the skin material deteriorate, -2), the tactile sensation of the skin material may be deteriorated and may be included within the above range.
  • thermoplastic polyurethane composition for powder slush molding of the present invention may optionally contain at least one additive selected from a flame retardant, a light stabilizer, a high heat stabilizer, a lubricant, an antioxidant, a heat resistant agent, an antistatic agent, an antibacterial agent, As shown in FIG.
  • the kind and content of the additive are not limited as long as the effect of the present invention is not impaired.
  • thermoplastic polyurethane composition for powder slush molding of the present invention may be in the form of a powder and the thermoplastic polyurethane composition in powder form may have an average particle size of 150-250 ⁇ ⁇ or 170-200 ⁇ ⁇ , The moldability can be excellent in the powder slush molding.
  • the average particle size can be measured using a mesh.
  • the dropping property of the powdery thermoplastic polyurethane composition is 10-15 seconds or 12-13 seconds, and the dropping property is within the above range, so that the moldability in powder slush molding can be excellent.
  • the castability can be measured by taking 100 ml of the powdery thermoplastic polyurethane composition into an apparent specific gravity measuring device funnel according to KS M 3002 and taking 100 ml of powder to fully escape from the funnel.
  • thermoplastic polyurethane composition for powder-slush molding of the present invention will be described.
  • thermoplastic silicone vulcanizate (B) in the step (S1) mixing 25-70 parts by weight of the thermoplastic silicone vulcanizate (B) in the step (S1) with 100 parts by weight of the thermoplastic polyurethane resin (A). ≪ / RTI >
  • thermoplastic silicon vulcanate production step (S1) The thermoplastic silicon vulcanate production step (S1)
  • the step (S1) is a step of mixing and dynamically vulcanizing a thermoplastic polymer, a silicone rubber (C), a curing agent and a catalyst so as to obtain a thermoplastic elastomer in the form of a silicone rubber (B-2) crosslinked in the thermoplastic polymer matrix (B- To produce a thermoplastic silicone vulcanizate (B).
  • the dynamic vulcanization process is a process in which a vulcanization process is carried out under the conditions of a high shear flow (for example, 150-300 rpm) and a high temperature (for example, 160-200 deg. C) Means a vulcanization process in which a polymer and at least one vulcanizable rubber are mixed.
  • This dynamic vulcanization step can be carried out simultaneously with mixing in an extruder as an example.
  • thermoplastic polymer may be present as a continuous matrix through the dynamic vulcanization step and the silicone rubber (C) may be crosslinked (that is, crosslinked silicone rubber (B-2)) as particles in the matrix.
  • thermoplastic polymer The properties of the thermoplastic polymer are the same as those described above, and it is particularly preferable to use the thermoplastic polyurethane resin (A) as the thermoplastic polymer for excellent compatibility with the thermoplastic polyurethane resin (A) described later.
  • the silicone rubber (C) may be prepared from an organopolysiloxane or by mixing a filler with an organopolysiloxane.
  • the organopolysiloxane may be a high consistency homopolymer or copolymer of di-organopolysiloxane gum (gum) containing two or more alkenyl groups of 2-20 carbon atoms in the molecule.
  • the alkenyl group having 2-20 carbon atoms may be, for example, at least one member selected from the group consisting of vinyl, allyl, butenyl, pentenyl, hexenyl, propenyl and decenyl.
  • the position of the alkenyl group is not critical, and it can be bonded at the molecular chain end, at the non-terminal position of the molecular chain, or at both of the above positions.
  • the alkenyl group is vinyl or hexenyl, and these groups may be included in the organopolysiloxane in an amount of 0.001-3 wt%, or 0.01-1 wt%.
  • the remaining (i.e., non-alkenyl) organic groups bonded to the silicon of the organopolysiloxane are independently selected from hydrocarbons or halogenated hydrocarbons that do not contain aliphatic unsaturation. Specifically, they may be an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a halogenated alkyl group having 1 to 20 carbon atoms.
  • the alkyl group having 1-20 carbon atoms includes, for example, methyl, ethyl, propyl, butyl, pentyl, and hexyl;
  • the cycloalkyl group can be exemplified by, for example, cyclohexyl and cycloheptyl.
  • Examples of the aryl group having 6-12 carbon atoms include phenyl, tolyl and xylyl.
  • the aralkyl group having 7 to 20 carbon atoms may be, for example, benzyl and phenethyl.
  • halogenated alkyl group having 1-20 carbon atoms examples include, for example, 3,3,3-trifluoropropyl and chloromethyl.
  • the viscosity of the organopolysiloxane at 25 ⁇ ⁇ is not less than 100 mPa ⁇ ⁇ , for example not less than 300 mPa ⁇ ⁇ , not more than 90000 mPa ⁇ ⁇ , or not more than 70000 mPa ⁇ ⁇ .
  • the filler is a finely divided filler known to enhance the organopolysiloxane and is, for example, selected from the group consisting of fumed silica, precipitated silica, silica aerosol and titanium dioxide having a specific surface area of at least 50 m 2 / g Fumed silica may be used as a specific example.
  • the filler may be used in an amount of 5-150 parts by weight or 20-100 parts by weight based on 100 parts by weight of the organopolysiloxane.
  • the curing agent for crosslinking the silicone rubber (C) may be an organopolysiloxane containing two or more hydrogen atoms bonded to silicon (Si) in a molecule, and the content thereof is preferably 0.2-2 wt% Or 0.5-1.7 wt%.
  • the curing agent may have a viscosity at 25 ° C of 0.5-1000 mPa ⁇ s or 2-500 mPa ⁇ s or 5-150 mPa ⁇ s.
  • the molar ratio of silicon-bonded hydrogen atoms of the curing agent to the silicon-bonded alkenyl of the organopolysiloxane may be 1 or more and less than 50, and may be 3 to 30 in one embodiment.
  • the catalyst may be a catalyst for accelerating the crosslinking of the silicone rubber (C).
  • a hydrosilylation catalyst may be used.
  • the hydrosilylation catalyst include platinum black, platinum supported on silica, carbon Platinum catalysts such as platinum, chloroplatinic acid, an alcohol solution of chloroplatinic acid, platinum / olefin complexes, platinum / alkenylsiloxane complexes, platinum / beta-diketone complexes, platinum / phosphine complexes and the like, rhodium chloride and rhodium chloride / Di (n-butyl) sulfide complexes and the like, and palladium catalysts such as palladium on carbon, palladium chloride and the like.
  • thermoplastic polymer and the silicone rubber (C) may be mixed in a weight ratio of 90-50: 10-50 or 85-55: 15-45, and when the content of the silicone rubber is less than the above range, If the amount exceeds the above range, the dispersibility of the silicone rubber (C) in the composition is lowered and the moldability of the composition is lowered. As a result, mechanical properties such as tensile strength and elongation at break of the finished skin material , So that they can be mixed at a weight ratio within the above range.
  • the curing agent may be added in an amount of 0.5-10 parts by weight or 1-5 parts by weight based on 100 parts by weight of the total amount of the thermoplastic polymer and the silicone rubber (C) Within the above range, the crosslinking of the silicone rubber is excellent, so that the skin material for automobile interior materials can be provided with improved scratch resistance, weather resistance and touch.
  • the catalyst may be contained in an amount of 0.05-10 parts by weight or 0.1-5 parts by weight based on 100 parts by weight of the total amount of the thermoplastic polymer and the silicone rubber (C), and the crosslinking of the silicone rubber can be promoted within the above range The production efficiency is excellent.
  • step (S1) may be performed at a temperature of 160-200 ⁇ ⁇ or 170-190 ⁇ ⁇ .
  • the thermoplastic polymer and the silicone rubber (C) are not sufficiently melted and the dispersibility of the silicone rubber (C) in the thermoplastic polymer is lowered, Mechanical properties such as tensile strength and elongation at break of the finished skin material may be deteriorated. If the temperature range is exceeded, the thermoplastic polymer is thermally decomposed to deteriorate physical properties such as tensile strength and elongation at break of the finished skin material. . ≪ / RTI >
  • the step (S1) may be carried out using a coupling agent, a softening mineral oil, a plasticizer, other mineral fillers, pigments, dyes, viscosity modifiers, stabilizers, lubricants and flexibilizers ), And the kind and content of the additive is not limited.
  • the present inventors have found that when a small amount of silicone rubber (C) is added during the production of the thermoplastic polyurethane composition for powder slush molding, the dispersibility of the silicone rubber (C) is lowered and the physical properties of the skin material formed using the silicone rubber (Step S1) of master batching the thermoplastic polymer (that is, the polyurethane resin) and the high-content silicone rubber (C) in advance as described above, The dispersibility of the composition (C) was improved, and the moldability of the composition was excellent, and the excellent physical properties of the skin material formed using the composition could be realized.
  • the master batch is prepared by first mixing a polymer material and a high-concentration additive in the form of a chip or a pellet when adding an additive to add functionality to a polymer material such as plastic And then adding it to the polymer material to use it.
  • the step (S3) may be a step of mixing 25 to 70 parts by weight or 30 to 60 parts by weight of the thermoplastic silicone vulcanizate (B) in the step (S1) with respect to 100 parts by weight of the thermoplastic polyurethane resin (A).
  • step (S3) the thermoplastic polyurethane resin (A) and the thermoplastic silicon vulcanizate (B) are placed in a Banbury mixer and heated at 150-170 ° C or 155-165 ° C for 3-10 minutes or 5 -7 minutes. At this time, the mixture of step (S3) may be heated to about 170-180 DEG C due to frictional heat.
  • the mixture of step (S3) may optionally contain at least one additive selected from a flame retardant, a light stabilizer, a high heat stabilizer, a lubricant, an antioxidant, a heat resistant agent, an antistatic agent, an antimicrobial agent, a processing aid, a metal deactivator, And the kind and content thereof are not limited unless they impair the desired effects of the present invention.
  • the method for producing a thermoplastic polyurethane composition for powder slush molding according to the present invention may further comprise: a pellet preparation step (S5) of producing a mixture of the mixing step (S3) as a pellet; And a powder preparation step (S7) of pulverizing the pellet to produce a powder; As shown in FIG.
  • the pellet preparation step (S5) may be a step of putting the mixture of step (S3) into an extruder and extruding the mixture at 160-190 ° C or 170-185 ° C to form pellets.
  • step (S3) If the temperature is less than the above range, the mixture of step (S3) is not sufficiently melted, and the mechanical properties such as tensile strength and elongation at break of the finished skin material deteriorate.
  • the thermoplastic polyurethane resin (A ) Is thermally decomposed to deteriorate physical properties such as tensile strength and elongation at break of the finished skin material.
  • the powder manufacturing step (S7) is a step of preparing the powdery thermoplastic polyurethane composition by freezing the pellet produced in the step (S5) and pulverizing the granulated product using the liquid nitrogen or by hydro-grinding .
  • thermoplastic polyurethane composition in the powder form may have an average particle size of 150-250 ⁇ ⁇ or 170-200 ⁇ ⁇ , and the flowability may be 10-15 seconds or 12-13 seconds.
  • thermoplastic polyurethane composition of the present invention in powder form prepared from the above-described method for producing a thermoplastic polyurethane composition for powder slush molding has an excellent dispersibility of silicone rubber in the composition and is excellent in powder-slush molding and moldability.
  • the present invention also relates to a skin material for an automobile interior material formed using the thermoplastic polyurethane composition for powder slush molding.
  • the skin material for an automobile interior material of the present invention can be manufactured through a powder slush molding process using the composition described above.
  • the powder slush molding process may be performed at a temperature of about 200-250 ° C, 210-250 ° C, or 220-240 ° C, in which case the skin moldability may be excellent.
  • the automobile interior material may be an instrument panel, a door trim, a console box, an armrest, a headrest, a pillar trim, a seat buckle, a headliner, a glove box, a trunk cover trim, an airbag cover or a steering wheel cover.
  • the skin material for an automobile interior material of the present invention comprises 50-84% by weight or 55-80% by weight of the thermoplastic polyurethane resin (A), 16-40% by weight or 18-38% by weight of the thermoplastic silicone vulcanizate (B) By weight, and is excellent in mechanical properties as well as excellent scratch resistance, touch, and weather resistance as a skin material for automobile interior materials.
  • the skin material is a thermoplastic polyurethane resin (A + , 82-90% by weight or 85-88% by weight of silicone rubber (C), 6.3-15% by weight, 6.4-14% by weight or 7-10% by weight of silicone rubber (C)
  • a skin material it has excellent mechanical properties and excellent dispersibility of the silicone rubber (C) in the composition, and has excellent properties such as scratch resistance, tensile strength and elongation at break of the skin material.
  • the skin material for automobile interior material of the present invention has an scratch resistance (JIS K 6718, g) of 300 g or more or 400 g or more, and has excellent scratch resistance in the above range.
  • the upper limit thereof is not limited, but may be, for example, 1500 g or less or 1300 g or less.
  • the surface scratch resistance was evaluated by scratching the surface of the surface of the skin with a Heidon scratch tester (SHINTO Co., HEIDON type 14FW) under a load of 100 mm / s at a speed of 100 mm / s in accordance with JIS K 6718, It is possible to measure the load when it exceeds 200 mu m.
  • the skin material for automobile interior materials of the present invention may have a tensile strength (ISO 5207-3) of 85-150 MPa, 90-140 MPa or 90-120 MPa, and is advantageous in expanding the airbag with excellent mechanical properties within the above range .
  • ISO 5207-3 tensile strength
  • the tensile strength may be measured using a universal testing machine (UTM) according to ISO 5207-3.
  • UTM universal testing machine
  • the skin material for automobile interior materials of the present invention may have a breaking elongation (ISO 5207-3) of 350-500%, 350-450%, or 400-450% There is an advantageous effect of expanding the airbag even though the mechanical properties are excellent within the above range.
  • the elongation at break may be measured using a universal testing machine (UTM) according to ISO 5207-3.
  • UTM universal testing machine
  • the skin material for an automobile interior material of the present invention may have a gloss change rate of -40% to + 40%, -20% to + 20%, or -7% to + 7% It is possible to satisfy the required gloss change rate.
  • the gloss change rate was measured by using a gloss meter (BYK Gardner GLOSS master 60) after irradiating ultraviolet ray (Xenon arc defined in ISO 105) in an amount of 126 MJ to a skin sample at an incident angle of 60 degrees according to ASTM D563, The glossiness before and after the ultraviolet irradiation can be measured and the rate of change thereof can be calculated.
  • the skin material for automobile interior material of the present invention may have weatherability of -30% to + 30%, -25% to + 25% or -20% to + 20% It is possible to satisfactorily satisfy the weatherability.
  • the weathering resistance was measured by irradiating ultraviolet ray (UV, Xenon arc specified in ISO 105) in the amount of 126 MJ to the skin sample and measuring tensile strength and / or elongation before and after aging using a universal testing machine (UTM) The rate of change can be calculated.
  • UV ultraviolet ray
  • UPM universal testing machine
  • thermoplastic polyurethane composition for powder-type powder-slush molding having an average particle size of 150-250 ⁇ ⁇ and a flowability of 10-15 seconds was prepared.
  • Example 1 Example 2
  • Example 3 Example 4 Comparative Example 1 Comparative Example 2 Reference Example 1 Reference Example 2 Reference Example 3 Reference Example 4
  • Thermoplastic polyurethane resin 100 100 100 100 100 100 100 100 100 100 Thermoplastic Silicon Vulcanide 1 30 50 - - - - 20 80 - - Thermoplastic Silicon Vulcanide 2 - - 30 50 - - - - 20 80 Thermoplastic vulcanizate - - - - - 30 - - - - Paraffin oil - - - - - 5 - - - - - - High heat stabilizer 6 6 6 6 6 6 6 6 6 Light stabilizer 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
  • Thermoplastic polyurethane resin particle size of 200 ⁇ ⁇ , Shore A hardness (ISO 868) of 88, tensile strength (ISO 527-2) of 26 MPa, elongation at break (ISO 527-2) of 415% (ISO 306) of 48 ⁇ ⁇ and a melt flow index (MFI) of 70 g / 10 min (185 ⁇ ⁇ , 2.16 kg)
  • Thermoplastic Silicon Vulcanide 1 A thermoplastic silicone vulcanizate in which 30% by weight of a crosslinked silicone rubber (B-2) is dispersed in 70% by weight of a thermoplastic polyurethane polymer matrix (B-1) (ISO 868) of 75, a tensile strength (ISO 37) of 12.1 MPa, a elongation at break (ISO 37) of 630% and a melt flow index (ISO 1133) of 60 g / 10 min
  • Thermoplastic Silicon Vulcanide 2 Thermoplastic silicone vulcanizate in which 40% by weight of a crosslinked silicone rubber (B-2) is dispersed in 60% by weight of a thermoplastic polyurethane polymer matrix (B-1) (ISO 868) of 48, a tensile strength (ISO 37) of 4.4 Mpa, a elongation at break (ISO 37) of 710% and a melt flow index (ISO 1133) of 55 g / 10 min
  • Thermoplastic vulcanizate a thermoplastic vulcanizate in which crosslinked EPDM rubber is dispersed in a thermoplastic polypropylene polymer matrix having a Shore A hardness (ISO 868) of 70, a tensile strength (ASTM D412) of 6.20 MPa, a elongation at break Thermoplastic vulcanizate (ExxonMobil, Santoprene TM 121-70M350) with a melt flow index (ISO 1133) of 5-10 g / 10 min (190 ° C, 10 kg).
  • Paraffin oil Paraffin oil having a weight average molecular weight of 400 g / mol (Kukdong Yufu Co., LP500).
  • thermoplastic polyurethane compositions used in Examples 1 to 4, Comparative Examples 1 and 2, and Reference Examples 1 to 4 were prepared by the following production methods.
  • Reference Example 7 for confirming the physical properties of the skin material and a thermoplastic polyurethane composition of Reference Example 8 for confirming the physical properties of the skin material when using non-crosslinked silicone gum other than thermoplastic silicon vulcanizate were further prepared .
  • thermoplastic silicon vulcanate production step (S1) The thermoplastic silicon vulcanate production step (S1)
  • thermoplastic silicone vulcanizate 1 6 parts by weight of the high heat-resistant stabilizer and 0.3 part by weight of the light stabilizer were added to a Banbury mixer at a temperature of 160 ° C for 5 minutes to 100 parts by weight of the thermoplastic polyurethane resin.
  • step (S3) was put into an extruder and extruded at a temperature of 180 ° C to form pellets.
  • the pellet was pulverized to prepare a thermoplastic polyurethane powder having a particle size of 150 to 250 ⁇ ⁇ and a flowability of 10 to 15 seconds.
  • thermoplastic silicone vulcanizate 1 50 parts by weight of the thermoplastic silicone vulcanizate 1, 6 parts by weight of the high heat-resistant stabilizer and 0.3 part by weight of the light stabilizer were added to a thermosetting polyurethane resin at a temperature of 160 ⁇ for 5 minutes.
  • thermoplastic silicon vulcanate production step (S1) The thermoplastic silicon vulcanate production step (S1)
  • thermoplastic polyurethane resin 60 parts by weight of a thermoplastic polyurethane resin, 40 parts by weight of a silicone rubber, 2.5 parts by weight of a curing agent and 0.1 part by weight of a catalyst were charged into a twin-screw extruder and subjected to dynamic vulcanization and mixing at a temperature of 150-300 rpm and 180 ° C to obtain a thermoplastic silicone vulcanizate 2 .
  • thermoplastic silicone vulcanizate 2 6 parts by weight of the high heat-resistant stabilizer and 0.3 part by weight of the light stabilizer were added to a Banbury mixer at a temperature of 160 ° C for 5 minutes to 100 parts by weight of the thermoplastic polyurethane resin.
  • thermoplastic silicone vulcanizate 2 50 parts by weight of the thermoplastic silicone vulcanizate 2, 6 parts by weight of the high heat-resistant stabilizer and 0.3 part by weight of the light stabilizer were added to a thermosetting polyurethane resin at a temperature of 160 DEG C for 5 minutes.
  • thermosetting polyurethane resin 5 parts by weight of paraffin oil, 6 parts by weight of a high heat stabilizer and 0.3 part by weight of a light stabilizer were added to a thermosetting polyurethane resin at a temperature of 160 DEG C for 5 minutes.
  • thermoplastic polyurethane resin 30 parts by weight of thermoplastic vulcanizate, 6 parts by weight of the high heat stabilizer and 0.3 part by weight of the light stabilizer were mixed in a Banbury mixer at a temperature of 160 DEG C for 5 minutes.
  • Thermoplastic Silicon Vulcanide Production Step (S1) The same procedure as in Example 1 was carried out.
  • thermoplastic silicone vulcanizate 1 20 parts by weight of the thermoplastic silicone vulcanizate 1, 6 parts by weight of the high heat stabilizer and 0.3 part by weight of the light stabilizer were added to a thermosetting polyurethane resin at a temperature of 160 ⁇ for 5 minutes.
  • Thermoplastic Silicon Vulcanide Production Step (S1) The same procedure as in Example 1 was carried out.
  • thermoplastic silicone vulcanizate 1 80 parts by weight of the thermoplastic silicone vulcanizate 1, 6 parts by weight of the high heat-resistant stabilizer and 0.3 part by weight of the light stabilizer were added to a thermosetting polyurethane resin at a temperature of 160 ⁇ for 5 minutes.
  • Thermoplastic Silicon Vulcanide Production Step (S1) The same procedure as in Example 3 was carried out.
  • thermoplastic silicone vulcanizate 2 20 parts by weight of the thermoplastic silicone vulcanizate 2, 6 parts by weight of the high heat-resistant stabilizer and 0.3 part by weight of the light stabilizer were added into a Banbury mixer at a temperature of 160 ⁇ for 5 minutes to 100 parts by weight of the thermoplastic polyurethane resin.
  • Thermoplastic Silicon Vulcanide Production Step (S1) The same procedure as in Example 3 was carried out.
  • thermoplastic silicone vulcanizate 2 80 parts by weight of the thermoplastic silicone vulcanizate 2, 6 parts by weight of the high heat-resistant stabilizer and 0.3 part by weight of the light stabilizer were added to a thermosetting polyurethane resin at a temperature of 160 ⁇ for 5 minutes.
  • thermoplastic silicon vulcanate production step (S1) The thermoplastic silicon vulcanate production step (S1)
  • thermoplastic polyurethane resin 95 parts by weight of a thermoplastic polyurethane resin, 5 parts by weight of a silicone rubber, 2.5 parts by weight of a curing agent and 0.1 part by weight of a catalyst were charged into a twin-screw extruder and subjected to dynamic vulcanization and mixing at a temperature of 150-300 rpm and 180 DEG C to obtain thermoplastic silicone vulcanizates .
  • Example 2 The procedure of Example 2 was repeated.
  • thermoplastic silicon vulcanate production step (S1) The thermoplastic silicon vulcanate production step (S1)
  • thermoplastic polyurethane resin 60 parts by weight of a silicone rubber, 2.5 parts by weight of a curing agent and 0.1 part by weight of a catalyst were charged into a twin-screw extruder and subjected to dynamic vulcanization and mixing at a temperature of 150-300 rpm and 180 DEG C to obtain thermoplastic silicone vulcanizates .
  • Example 2 The procedure of Example 2 was repeated.
  • unbridged silicon gum (Wacker chemical, Genioplast pellet S) containing 70% by weight of polydimethylsiloxane and 30% by weight of fumed silica and having a weight average molecular weight of 800,000 g / Respectively.
  • the powdery thermoplastic polyurethane composition prepared in the above (1) and (2) was subjected to a powder slush molding process at 230 ° C to prepare a skin material for automobile interior materials.
  • Example 1 Example 2 Example 3
  • Example 4 Comparative Example 1 Comparative Example 2 Reference Example 1 Reference Example 2 Reference Example 3 Reference Example 4
  • Skin material (% by weight)
  • Thermoplastic Silicon Vulcanide 1 22.0 32.0 - - - - 15.8 43.0 - -
  • thermoplastic polyurethane resin and the silicone rubber in the skin material for automobile interior materials including the thermoplastic polyurethane compositions of Reference Examples 5 to 8 are shown in Table 3 below.
  • Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Reference Example 1 Reference Example 2 Reference Example 3 Reference Example 4 Reference Example 5 Reference Example 6 Reference Example 7 Reference Example 8 Skin material (% by weight) Thermoplastic polyurethane resin 88.4 85.8 86.2 82.7 89.8 73.4 90.0 83.0 88.4 78.8 93.6 76.4 84.5 89.8 Silicone rubber 6.4 9.4 8.6 12.4 - - 4.6 12.6 6.2 16.7 1.5 18.7 10.1 -
  • Scratch resistance The surface of a skin sample for automobile interior material having a width of 5 cm and a length of 20 cm or more was subjected to a load of 100 mm / min using a Heidon scratch tester (SHINTO, HEIDON) according to JIS K 6718, After scratching 100 mm at a speed of s, the load was measured when the scratch width on the surface exceeded 200 ⁇ .
  • SHINTO Heidon scratch tester
  • Elongation at break The surface roughness of 5cm width and 20cm length was measured using universal testing machine (UTM) according to ISO 5207-3.
  • Gloss change rate (Gloss before ultraviolet irradiation - Gloss after ultraviolet irradiation) X 100 / (Gloss before ultraviolet irradiation)
  • Examples 1 to 4 according to the present invention are excellent in moldability of a composition including a specific amount of thermoplastic silicone vulcanizate, and the skin material formed using the silicone vulcanizate has a low rate of gloss change and scratch resistance , Tensile strength, elongation at break, weather resistance, and feel were all excellent.
  • Comparative Example 1 which is a skin material containing paraffin oil as the scratch-proofing agent, the weather resistance is lowered and the paraffin oil is eluted to the surface of the skin material as time elapses so that the gloss becomes excessive and buried in the user's hands. Scratch resistance can not be maintained.
  • the skin material of Comparative Example 1 has higher tensile strength and elongation at break than the skin materials of Examples 1 to 4, and thus it is confirmed that the skin material of Comparative Example 1 is not suitable for deploying the air bag.
  • Comparative Example 2 which is a skin material containing other thermoplastic vulcanizates than thermoplastic silicon vulcanizate, has a lower scratch resistance and feel than Examples 1 to 4, and also has a gloss change rate and weather resistance required as a skin material for automobile interior materials We can confirm that it is not satisfied.
  • Reference Examples 2 and 4 which are the skin materials containing the thermoplastic silicon vulcanizate in a specific content exceeding the specific content range, and Reference Example 6 in which the silicone rubber is excessively used in the production of the thermoplastic silicone vulcanizate, are poor in the dispersibility of the silicone rubber in the composition, And mechanical properties such as tensile strength and elongation at break of the skin material and feel are reduced.
  • Reference Example 7 in which a thermoplastic polyurethane resin and a silicone rubber were immediately mixed together without performing the step of producing a thermoplastic silicone vulcanized product as in Examples 1 to 4 is not preferable because the dispersibility of the silicone rubber in the composition is deteriorated, It was confirmed that the scratch resistance, the tensile strength, the elongation at break, the rate of change in gloss, the weatherability, and the touch were all lowered compared with the skin materials of Examples 1 to 4.
  • Reference Example 8 which is a skin material containing silicone gum which is not a crosslinked thermoplastic silicone vulcanizate but which is not crosslinked, has lower scratch resistance, rate of gloss change, weatherability, and feel as compared with Examples 1 to 4.

Abstract

La présente invention concerne une composition de polyuréthane thermoplastique pour moulage par embouage de poudre, son procédé de préparation, et un matériau de revêtement intérieur d'automobile fabriqué à l'aide de ladite composition de polyuréthane thermoplastique et, plus précisément : une composition de polyuréthane thermoplastique pour moulage par embouage de poudre, la composition de polyuréthane thermoplastique étant destinée à la fabrication d'un matériau de revêtement intérieur d'automobile au moyen d'un procédé de moulage par embouage de poudre, et présentant une excellente aptitude au formage, un matériau de revêtement intérieur d'automobile formé à l'aide de cette dernière présentant une excellente résistance aux rayures, une excellente résistance à la traction, un excellent allongement à la rupture, une excellente variation de brillance, une excellente résistance aux intempéries et une excellente sensation tactile ; un procédé de préparation de ladite composition de polyuréthane thermoplastique ; et un matériau de revêtement intérieur d'automobile fabriqué à l'aide de cette dernière.
PCT/KR2019/000795 2018-01-18 2019-01-18 Composition de polyuréthane thermoplastique pour moulage par embouage de poudre, son procédé de préparation, et matériau de revêtement intérieur d'automobile fabriqué à l'aide de ladite composition de polyuréthane thermoplastique WO2019143200A1 (fr)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
KR10-2018-0006793 2018-01-18
KR20180006793 2018-01-18
KR10-2018-0133912 2018-11-02
KR1020180133913A KR102242483B1 (ko) 2018-01-18 2018-11-02 자동차 내장재용 표피재 및 이의 제조방법
KR10-2018-0133913 2018-11-02
KR1020180133912A KR102242481B1 (ko) 2018-01-18 2018-11-02 분말 슬러쉬 몰딩용 열가소성 폴리우레탄 분말 및 이를 이용하여 제조된 표피재
KR10-2018-0152191 2018-11-30
KR1020180152191A KR20190088394A (ko) 2018-01-18 2018-11-30 분말 슬러쉬 몰딩용 열가소성 폴리우레탄 분말의 제조방법과 이로부터 제조된 열가소성 폴리우레탄 분말 및 이를 이용하여 형성된 표피재
KR1020190006980A KR102226152B1 (ko) 2018-01-18 2019-01-18 분말 슬러쉬 몰딩용 열가소성 폴리우레탄 조성물 및 이를 이용하여 제조된 자동차 내장재용 표피재
KR10-2019-0006980 2019-01-18
KR1020190006998A KR102226148B1 (ko) 2018-01-18 2019-01-18 분말 슬러쉬 몰딩용 열가소성 폴리우레탄 분말의 제조방법과 이로부터 제조된 열가소성 폴리우레탄 분말 및 이를 이용하여 형성된 자동차 내장재용 표피재
KR10-2019-0006998 2019-01-18

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112457655A (zh) * 2020-11-30 2021-03-09 宁海宏德新材料科技有限公司 一种减振耐磨材料及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050002881A (ko) * 2002-04-10 2005-01-10 산요가세이고교 가부시키가이샤 폴리우레탄수지계 슬러시 성형용 재료
KR100851786B1 (ko) * 2000-06-15 2008-08-13 차이나 페트로리움 앤드 케미컬 코포레이션 완전 가황된 열가소성 탄성중합체, 그의 제조 방법 및 용도
KR101347245B1 (ko) * 2013-07-24 2014-01-06 강남화성 (주) 스크래치 자기치유성 폴리우레탄계 수지조성물 및 이로부터 제조된 성형품
KR20150073093A (ko) * 2013-12-20 2015-06-30 이엠에스-패턴트 에이지 플라스틱 몰딩 조성물 및 이의 용도
KR20150073850A (ko) * 2013-12-20 2015-07-01 이엠에스-패턴트 에이지 플라스틱 몰딩 컴파운드 및 이의 용도

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100851786B1 (ko) * 2000-06-15 2008-08-13 차이나 페트로리움 앤드 케미컬 코포레이션 완전 가황된 열가소성 탄성중합체, 그의 제조 방법 및 용도
KR20050002881A (ko) * 2002-04-10 2005-01-10 산요가세이고교 가부시키가이샤 폴리우레탄수지계 슬러시 성형용 재료
KR101347245B1 (ko) * 2013-07-24 2014-01-06 강남화성 (주) 스크래치 자기치유성 폴리우레탄계 수지조성물 및 이로부터 제조된 성형품
KR20150073093A (ko) * 2013-12-20 2015-06-30 이엠에스-패턴트 에이지 플라스틱 몰딩 조성물 및 이의 용도
KR20150073850A (ko) * 2013-12-20 2015-07-01 이엠에스-패턴트 에이지 플라스틱 몰딩 컴파운드 및 이의 용도

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112457655A (zh) * 2020-11-30 2021-03-09 宁海宏德新材料科技有限公司 一种减振耐磨材料及其制备方法和应用

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