Classifications

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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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  • C08G18/40—High-molecular-weight compounds
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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  • C08G18/40—High-molecular-weight compounds
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/2815—Monohydroxy compounds
  • C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
  • C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4202—Two or more polyesters of different physical or chemical nature
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
  • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
  • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
  • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
  • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
  • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
  • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
  • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
  • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
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  • C08G2140/00—Compositions for moulding powders
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  • C08G2170/00—Compositions for adhesives
  • C08G2170/20—Compositions for hot melt adhesives

Definitions

• the present invention relates to a thermoplastic urethane resin.
• thermomechanical analysis penetration method in order to improve the adhesion to the interlining, water wash resistance, and dry cleaning resistance, the difference between the softening start temperature and the softening end temperature by the thermomechanical analysis penetration method, and the softening start temperature are within a specific range.
• a hot-melt adhesive made of a thermoplastic polyurethane resin has been proposed, and it is stated that this can also be used for a slush molding material.
• resin particles that can be melted at low temperatures by adjusting the crystallinity, melting point, and molecular weight have been proposed for resin particles used in powder coatings, electrophotographic toners, and electrostatic recording toners. It is stated that it is also used for materials.
• Patent Documents 2 and 3 for resin particles used in powder coatings, electrophotographic toners, and electrostatic recording toners. It is stated that it is also used for materials.
• slush molding materials particularly materials that can be suitably applied to automobile interiors, satisfy the conditions such as excellent meltability during slush molding and excellent tensile strength and elongation of molded products.
• a slush molding material that sufficiently satisfies all of these characteristics is not yet known.
• An object of the present invention is to provide a slush molding material that is excellent in low-temperature meltability and excellent in tensile strength and elongation of a molded product.
• the present invention is a thermoplastic urethane resin obtained by reacting a polymer diol (A) with a diisocyanate (B), and the polymer diol (A) has a glass transition temperature of 0 to 70 ° C.
• thermoplastic urethane resin (D) containing; Thermoforming thermoplastic urethane resin particle (K) containing thermoplastic thermoplastic resin (D) for thermoforming; Thermoplastic urethane resin particle (K) for thermoforming ) And an additive (F) containing urethane resin particle composition (P) for slush molding; thermoplastic urethane resin particles (K) for thermoforming or ureta for slush molding
• Resin particle composition (P) is a urethane resin molded product obtained by thermoforming.
• the slush molding urethane resin particle composition (P) containing the thermoplastic urethane resin (D) for thermoforming of the present invention is excellent in low-temperature meltability and excellent in tensile strength and elongation of the molded product.
• thermoplastic urethane resin for thermoforming (D) of the present invention is a thermoplastic urethane resin obtained by reacting a polymer diol (A) with a diisocyanate (B).
• the polymer diol (A) has a polyester diol (A1) having a glass transition temperature of 0 to 70 ° C., and a solubility parameter 1.2 to 3.0 lower than the solubility parameter of the (A1) And a high molecular diol (A2) having a glass transition temperature of ⁇ 40 to ⁇ 75 ° C.
• the polyester diol (A1) has a glass transition temperature of 0 to 70 ° C.
• Examples of the polyester diol (A1) include those obtained by polycondensation of an aliphatic diol having 2 to 4 carbon atoms and an aromatic dicarboxylic acid.
• Examples of the aliphatic diol having 2 to 4 carbon atoms include ethylene glycol, 1,3-propanediol and 1,4-butanediol. Of these, ethylene glycol is preferable.
• aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, orthophthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and the like.
• polyester diol (A11) having at least one phthalic acid (G) selected from the group consisting of terephthalic acid, isophthalic acid and orthophthalic acid and ethylene glycol as essential components, and (G) and tetramethylene Examples thereof include polyester diol (A12) containing glycol as an essential component.
• (A11) is preferable from the viewpoint of tensile strength and elongation of the molded product.
• phthalic acid represents at least one selected from the group consisting of terephthalic acid, isophthalic acid, and orthophthalic acid.
• the polyester diol (A1) is an aliphatic diol having 2 to 4 carbon atoms and an aromatic dicarboxylic acid or an ester-forming derivative thereof [an acid anhydride (for example, phthalic anhydride), a lower alkyl ester (for example, dimethyl terephthalate), Acid halide (for example, phthalic acid chloride)].
• the aromatic dicarboxylic acid component contained in the polyester diol may be a single component or may be composed of two or more components.
• the acid component is two components, there may be mentioned a mixture of terephthalic acid / isophthalic acid, terephthalic acid / orthophthalic acid, isophthalic acid / orthophthalic acid, and the molar ratio is usually 50/50.
• Tg of the polyester diol (A1) When the glass transition temperature (hereinafter sometimes referred to as Tg) of the polyester diol (A1) is lower than 0 ° C., the heat resistance of the urethane resin (D) is deteriorated, and when it is higher than 70 ° C., the polymer diol ( The melting point of A) becomes high and the urethanization reaction becomes difficult.
• the Tg of (A1) is preferably 10 to 60 ° C., more preferably 20 to 50 ° C.
• the number average molecular weight of the polyester diol (A1) is preferably 800 to 5000, more preferably 800 to 4000, and most preferably 900 to 3000.
• the polymer diol (A2) has an SP value 1.2 to 3.0 lower than the solubility parameter of the polyester diol (A1) (hereinafter sometimes referred to as SP value), preferably 1.5. Has an SP value of ⁇ 2.5. Since the urethane resin (D) of the present invention has a large difference in SP value between the polyester diol (A1) and the polymer diol (A2), they are microphase-separated so that (A1) is an elastomer hard segment, ( A2) is considered to form a soft segment. [SP value of (A1)]-[SP value of (A2)] is represented by ⁇ SP.
• the polymer diol (A2) has a Tg of ⁇ 40 to ⁇ 75 ° C. When it exceeds ⁇ 40 ° C., the low temperature (eg, ⁇ 35 ° C.) tensile physical properties of the urethane resin (D) deteriorate. A normal thermoplastic urethane resin having a Tg lower than ⁇ 75 ° C. cannot be obtained.
• polymer diol (A2) a polyester diol (A21) obtained by polycondensation of an aliphatic diol and an aliphatic dicarboxylic acid, a polyester diol (A22) synthesized from a lactone monomer, a polyether diol (A23), and And polyether ester diol (A24).
• the aliphatic diol is preferably an aliphatic diol having 2 to 10 carbon atoms, specifically, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6- Examples include hexane glycol and 1,10-decanediol.
• the aliphatic dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 4 to 15 carbon atoms, and specific examples include succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid and maleic acid.
• polyester diol (A22) examples of the lactone monomer include polyester diols obtained by polymerizing lactones having 4 to 12 carbon atoms such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, and mixtures of two or more thereof. It is done.
• polyether diol (A23) examples include compounds in which an alkylene oxide is added to two hydroxyl group-containing compounds (for example, the low molecular diol, divalent phenols, etc.).
• divalent phenols examples include bisphenols [bisphenol A, bisphenol F, bisphenol S, etc.], monocyclic phenols [catechol, hydroquinone, etc.], and the like. Of these, preferred are those obtained by adding alkylene oxide to dihydric phenols, and more preferred are those obtained by adding ethylene oxide (hereinafter referred to as EO) to divalent phenols.
• EO ethylene oxide
• polyether ester diol (A24) examples include those obtained by using the above-mentioned polyether diol in place of the low-molecular diol as a raw material in the polyester diol, for example, one or more of the above polyether diols and the dicarboxylic compounds exemplified as the raw material for the polyester diol Examples thereof include those obtained by condensation polymerization of one or more acids.
• Specific examples of the polyether diol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
• the polymer diol (A2) preferably does not contain an ether bond from the viewpoint of heat resistance and light resistance.
• a polyester diol composed of ethylene glycol and an aliphatic dicarboxylic acid having 6 to 15 carbon atoms and a polyester diol composed of an aliphatic diol having 4 to 10 carbon atoms and an aliphatic dicarboxylic acid having 4 to 15 carbon atoms are preferable.
• polyethylene adipate, polytetramethylene adipate, polyhexamethylene adipate, and polyhexamethylene isophthalate are preferable.
• the number average molecular weight of the polyester diol (A2) is preferably 800 to 5000, more preferably 800 to 4000, and particularly preferably 900 to 3000.
• the glass transition temperature is measured by differential scanning calorimetry (DSC).
• Equipment RDC220 robot DSC [manufactured by Seiko Instruments Inc.] Measurement conditions: sample amount 5 mg.
• the temperature is raised from ⁇ 100 ° C. to 100 ° C. at a temperature rising rate of 20 ° C./min, and kept at 100 ° C. for 10 minutes.
• Cool from 100 ° C. to ⁇ 100 ° C. at a cooling rate of ⁇ 90 ° C./min and hold at ⁇ 100 ° C. for 10 minutes.
• the temperature is increased from ⁇ 100 ° C. to 100 ° C. at a temperature increase rate of 20 ° C./min.
• Analysis method The intersection of the tangents of the peaks of the DSC curve at the second temperature rise is defined as the glass transition temperature.
• the solubility parameter is calculated by the Fedors method.
• the solubility parameter can be expressed by the following formula.
• SP value ( ⁇ ) ( ⁇ H / V) 1/2
• ⁇ H represents the heat of molar evaporation (cal / mol)
• V represents the molar volume (cm 3 / mol).
• ⁇ H and V are “POLYMER”.
• ENGINEERING AND FEBRUARY, 1974, Vol. 14, no. 2, ROBERT F. FEDORS. (151 to 153) can be used as the total molar heat of vaporization ( ⁇ H) and the total molar volume (V).
• Those having a close numerical value are easy to mix with each other (high compatibility), and those having a close numerical value are indices that indicate that they are difficult to mix.
• the polymer diol (A) contains a polyester diol (A1) and a polymer diol (A2), but when (A2) is a polyester diol (A21), it may further contain the following polyester diol (A3). preferable.
• Polyester diol (A3) at least one phthalic acid (G) selected from the group consisting of ethylene glycol, an aliphatic diol having 4 to 10 carbon atoms, terephthalic acid, isophthalic acid, and orthophthalic acid, and 4 to 15 carbon atoms Polyester diol containing an aliphatic dicarboxylic acid as an essential component
• the polyester diol (A1) and the polyester diol (A21) are preferably obtained by transesterification at 160 to 220 ° C.
• (A1) / (A21) is preferably 0.5 to 5.
• the content of (A3) is preferably 5 to 100% by weight, more preferably 5 to 70% by weight, and most preferably 5 to 50% by weight based on the weight of (A1).
• the diisocyanate (B) constituting the urethane resin (D) of the present invention includes (i) an aliphatic diisocyanate having 2 to 18 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter) [ethylene diisocyanate, tetramethylene diisocyanate, Hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2- Isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc.]; (ii) alicyclic diisocyanate having 4 to 15 carbon atoms [isophorone diisocyanate (IPDI), dicyclohexy
• the urethane resin (D) of the present invention can be obtained by reacting the polymer diol (A) with the diisocyanate (B), but it is preferable to further react the low molecular diamine or the low molecular diol (C).
• Specific examples of the low molecular diamine or the low molecular diol (C) are as follows.
• aliphatic diamines examples include alicyclic diamines having 6 to 18 carbon atoms [4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4′-diaminodicyclohexylmethane, diaminocyclohexane, isophoronediamine, etc.]
• An aliphatic diamine having 2 to 12 carbon atoms [ethylene diamine, propylene diamine, hexamethylene diamine, etc.]; an araliphatic diamine having 8 to 15 carbon atoms [xylylenediamine, ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylyl] Range amine and the like] and mixtures of two or more thereof.
• preferred are alicyclic diamines and aliphatic diamines, and particularly preferred are isophorone diamine and hexamethylene diamine.
• the low molecular weight diol include aliphatic diols having 2 to 8 carbon atoms [linear diol (ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc.), branched diols (propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,2- , 1,3- or 2,3-butanediol, etc.]; diols having a cyclic group [aliphatic group-containing diol having 6 to 15 carbon atoms [1,4-bis (hydroxymethyl) cyclohexane, hydrogenated bisphenol] A and the like], aromatic ring-containing diol having 8 to 20 carbon atoms (m- or p-xyly
• the weight ratio of the polyester diol (A1) to the polymer diol (A2) is preferably 5/95 to 80/20, more preferably 10/90 to 50/50, from the viewpoint of achieving both tensile strength and elongation. 20/80 to 40/60 is most preferable.
• (A1) functions as a hard segment similar to a urethane group or urea group, high physical properties are exhibited, and the urea group or urethane group concentration, which greatly affects the meltability of the thermoplastic urethane resin, can be lowered. Therefore, it is considered that the meltability is improved and the compatibility with the physical properties is possible.
• the combination of the polyester diol with high cohesive force with high solubility parameter and the polymer diol with low solubility parameter makes it possible to achieve both the solubility characteristic of the urethane resin of the present invention and the tensile strength, elongation and wear resistance. It becomes possible. This characteristic is particularly apparent when the weight ratio between the two is (A1) / (A2) of 5/95 to 80/20.
• the number average molecular weight of the urethane resin (D) is 1.0 to 40,000, and preferably from 1.2 to 35,000, more preferably from 1.5 to 40,000 from the viewpoint of low temperature meltability and high tensile strength. 3 million.
• a method of adjusting the molecular weight of the urethane resin (D) it can be adjusted by partially blocking the isocyanate group of the isocyanate group-terminated urethane prepolymer with a monofunctional alcohol.
• Examples of the monool include aliphatic monools having 1 to 8 carbon atoms [linear monool (methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, etc.), monool having a branched chain (isopropyl alcohol, Neopentyl alcohol, 3-methyl-pentanol, 2-ethylhexanol, etc.]; monools having a cyclic group with 6 to 10 carbon atoms [alicyclic group-containing monools (cyclohexanol, etc.), aromatic ring-containing monools (Benzyl alcohol etc.) etc.] and a mixture of two or more thereof. Of these, preferred are aliphatic monools.
• Examples of the polymer monool include polyester monool, polyether monool, polyether ester monool, and a mixture of two or more thereof.
• Examples of the method for producing the urethane resin (D) of the present invention include the following methods. (1) A polymer prepolymer (U) containing a mixture of a polyester diol (A1) and a polymer diol (A2) in advance and a diisocyanate (B) are reacted to form a polyurethane prepolymer (U) having an isocyanate group at the terminal. A method of producing a urethane resin by mixing and extending the prepolymer (U) and a low molecular diamine or low molecular diol (C) if necessary.
• the polyurethane prepolymer (U) is mixed in water, and the isocyanate group of the terminal of a polyurethane prepolymer (U) and water are made to react, and it is a urethane resin.
• a method in which (A), (B) and, if necessary, (C) are mixed and reacted in one shot can be used.
• the reaction temperature at the time of producing the urethane resin (D) may be the same as that usually employed for urethanization, and is usually 20 to 100 ° C. when a solvent is used, and when the solvent is not used. Usually, it is 20 to 140 ° C., preferably 80 to 130 ° C.
• a catalyst usually used for polyurethane can be used if necessary to accelerate the reaction.
• the catalyst include amine-based catalysts [triethylamine, N-ethylmorpholine, triethylenediamine, etc.], tin-based catalysts [trimethyltin laurate, dibutyltin dilaurate, dibutyltin malate, etc.].
• the melt viscosity at 190 ° C. of the urethane resin (D) is preferably 500 to 2000 Pa ⁇ s, more preferably 500 to 1000 Pa ⁇ s ° C., from the viewpoint that the low temperature meltability of the urethane resin (D) is good.
• the storage elastic modulus G ′ at 130 ° C. of (D) is preferably 2.0 ⁇ 10 6 to 1.0 ⁇ 10 8 dyn / cm 2 from the viewpoint of heat resistance, and more preferably 5.0 ⁇ 10 6 to 5.0 ⁇ 10 7 dyn / cm 2 .
• (D) is preferably 1.0 ⁇ 10 3 to 1.0 ⁇ 10 5 dyn / cm 2 , more preferably 5.0 ⁇ 10 3 from the viewpoint of low temperature meltability. ⁇ 5.0 ⁇ 10 4 dyn / cm 2 .
• thermoplastic urethane resin particles (K) for thermoforming include those obtained by the following production method. (1) After the polyester diol (A1) and the polymer diol (A2) are melt-mixed, the molar ratio of these hydroxyl groups to the isocyanate groups of the diisocyanate (B) is 1: 1.2 to 1: 4.0.
• (E) is produced by a method in which the urethane prepolymer (U) obtained by the reaction in the above manner is subjected to an extension reaction with a low-molecular diol or a low-molecular diamine (C) if necessary in the presence of water and a dispersion stabilizer.
• a low-molecular diamine a blocked linear aliphatic diamine (C) (for example, a ketimine compound) can be used.
• (E) can be produced by a method in which the urethane prepolymer (U) is subjected to an extension reaction with a low molecular diol or a low molecular diamine (C) in the presence of a nonpolar organic solvent and a dispersion stabilizer.
• (3) A lump of thermoplastic polyurethane resin is obtained by reacting diisocyanate (B), polymer diol (A), and low molecular diol or low molecular diamine (C).
• (E) can be produced by a method of pulverizing (for example, freezing and pulverizing, a method of cutting through pores in a molten state).
• the volume average particle diameter of the urethane resin particles (K) is preferably 10 to 500 ⁇ m, more preferably 70 to 300 ⁇ m.
• the urethane resin particles (K) of the present invention are obtained by adding an additive (F) in addition to the urethane resin (D) to obtain a urethane resin particle composition (P) for slush molding [hereinafter, urethane resin particle composition (P). And abbreviation].
• the additive (F) include inorganic fillers, pigments, plasticizers, mold release agents, organic fillers, antiblocking agents, stabilizers, and dispersants.
• Inorganic fillers are kaolin, talc, silica, titanium oxide, calcium carbonate, bentonite, mica, sericite, glass flake, glass fiber, graphite, magnesium hydroxide, aluminum hydroxide, antimony trioxide, barium sulfate, zinc borate , Alumina, magnesia, wollastonite, zonotlite, whisker, metal powder and the like.
• kaolin, talc, silica, titanium oxide and calcium carbonate are preferable from the viewpoint of promoting crystallization of the thermoplastic resin, and kaolin and talc are more preferable.
• the volume average particle diameter ( ⁇ m) of the inorganic filler is preferably from 0.1 to 30, more preferably from 1 to 20, particularly preferably from 5 to 10, from the viewpoint of dispersibility in the thermoplastic resin.
• the addition amount (% by weight) of the inorganic filler is preferably 0 to 40, more preferably 1 to 20 with respect to the weight of (D).
• the pigment particles are not particularly limited, and known organic pigments and / or inorganic pigments can be used, and (D) is usually 10 parts by weight or less, preferably 0.01 to 5 parts by weight per 100 parts by weight.
• the examples of the organic pigment include insoluble or soluble azo pigments, copper phthalocyanine pigments, quinacridone pigments, and inorganic pigments include chromate, ferrocyan compounds, metal oxides (titanium oxide, iron oxide, Zinc oxide, aluminum oxide, etc.), metal salts [sulfates (barium sulfate, etc.), silicates (calcium silicate, magnesium silicate, etc.), carbonates (calcium carbonate, magnesium carbonate, etc.), phosphates (calcium phosphate, magnesium phosphate, etc.) Etc.], metal powder (aluminum powder, iron powder, nickel powder, copper powder, etc.), carbon black, and the like.
• the average particle size of the pigment is not particularly limited, but is usually 0.05 to 5.0 ⁇ m, preferably 0.02 to 1 ⁇ m.
• the addition amount (% by weight) of the pigment particles is preferably 0 to 5, more preferably 1 to 3, with respect to the weight of (D).
• plasticizers include phthalate esters (dibutyl phthalate, dioctyl phthalate, dibutylbenzyl phthalate, diisodecyl phthalate, etc.); aliphatic dibasic acid esters (di-2-ethylhexyl adipate, 2-ethylhexyl sebacate, etc.) ); Trimellitic acid ester (tri-2-ethylhexyl trimellitic acid and trioctyl trimellitic acid); fatty acid ester (such as butyl oleate); aliphatic phosphoric acid ester (trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri- 2-ethylhexyl phosphate, tributoxy phosphate, etc.); aromatic phosphates (triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl
• mold release agent known mold release agents can be used, and fluorine compound type mold release agents (triperfluoroalkyl phosphate (carbon number 8 to 20) ester such as triperfluorooctyl phosphate and triperfluorododecyl phosphate).
• fluorine compound type mold release agents triperfluoroalkyl phosphate (carbon number 8 to 20) ester such as triperfluorooctyl phosphate and triperfluorododecyl phosphate).
• Silicone compound type release agents (dimethylpolysiloxane, amino-modified dimethylpolysiloxane, carboxyl-modified dimethylpolysiloxane, etc.), fatty acid ester type release agents (mono- or polyhydric alcohol esters of fatty acids having 10 to 24 carbon atoms, For example, butyl stearate, hydrogenated castor oil and ethylene glycol monostearate); aliphatic acid amide type mold release agents (mono- or bisamides of fatty acids having 8 to 24 carbon atoms, such as oleic acid amide, palmitic acid amide, stearic acid) Of amide and ethylenediamine Metal soap (such as magnesium stearate and zinc stearate); natural or synthetic wax (such as paraffin wax, microcrystalline wax, polyethylene wax and polypropylene wax); and mixtures of two or more thereof Is mentioned.
• the addition amount (% by weight) of the release agent is preferably 0 to 1 and more preferably 0.1
• a stabilizer is a carbon-carbon double bond (such as an ethylene bond which may have a substituent) in the molecule (except for a double bond in an aromatic ring), a carbon-carbon triple bond (a substituent is A compound having an acetylene bond which may be present can be used, and an ester (ethylene glycol di (meth) acrylate) of (meth) acrylic acid and a polyhydric alcohol (2- to 10-valent polyhydric alcohol; hereinafter the same).
• an ester of (meth) acrylic acid and a polyhydric alcohol is preferable, and trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and more preferably Dipentaerythritol penta (meth) acrylate.
• the added amount (% by weight) of the stabilizer is preferably 0 to 20, more preferably 1 to 15 with respect to the weight of (D).
• the urethane resin particle composition (P) of the present invention may contain a known inorganic antiblocking agent, organic antiblocking agent and the like as a powder flowability improver and an antiblocking agent.
• the inorganic blocking inhibitor include silica, talc, titanium oxide and calcium carbonate.
• Organic blocking inhibitors include thermosetting resins with a particle size of 10 ⁇ m or less (thermosetting polyurethane resins, guanamine resins, epoxy resins, etc.) and thermoplastic resins with a particle size of 10 ⁇ m or less (thermoplastic polyurethane urea resin and poly ( (Meth) acrylate resin, etc.).
• the addition amount (% by weight) of the anti-blocking agent (fluidity improver) is preferably 0 to 5, more preferably 0.5 to 1, with respect to the weight of (D).
• a known powder mixing device can be used, and a container rotating type mixer, a fixed container type mixer, Any of the fluid motion mixers can be used.
• a fixed container type mixer a high-speed flow type mixer, a double-shaft paddle type mixer, a high-speed shear mixing device (Hensiel mixer (registered trademark), etc.), a low-speed mixing device (planetary mixer, etc.), or a conical screw mixer
• a method of dry blending using a machine (Nauta-Mixer (registered trademark), etc.) is well known.
• a double-shaft paddle type mixer a low-speed mixing device (planetary mixer, etc.), and a conical screw mixer (Nauta-mixer (registered trademark, hereinafter omitted), etc.).
• the volume average particle size of the urethane resin particle composition (P) is preferably 10 to 500 ⁇ m, more preferably 70 to 300 ⁇ m.
• thermoplastic urethane resin particles (K) for thermoforming of the present invention examples include injection molding, extrusion molding, blow molding, vacuum molding, and slush molding.
• the preferred molding method is a slush molding method from the viewpoint that the design shape and the like can be freely and faithfully shaped.
• the urethane resin particle composition (P) of the present invention can be molded by, for example, a slush molding method to produce a urethane resin molded product such as a skin.
• a slush molding method include a method in which a box containing the particle composition and a heated mold are both oscillated and rotated to melt and flow the powder in the mold, and then cooled and solidified to produce a skin. Can do.
• the mold temperature is preferably 200 to 300 ° C, more preferably 210 to 280 ° C.
• the skin thickness formed with the urethane resin particle composition (P) of the present invention is preferably 0.3 to 1.5 mm.
• (P) can be molded in a relatively low temperature region, and the molding temperature can be 200 to 250 ° C.
• the molded skin is set so that the surface is in contact with the foaming mold, the urethane foam is poured, and a foamed layer of 5 mm to 15 mm is formed on the back surface, so that a resin molded product can be obtained.
• the resin molded product molded with the urethane resin particle composition (P) of the present invention is suitably used for automobile interior materials such as instrument panels and door trims.
• the melt viscosity at 190 ° C. of the urethane resin particle composition (P) of the present invention is preferably from 100 to 500 Pa ⁇ s, more preferably from 100 to 300 Pa ⁇ s ° C., from the viewpoint of good low temperature meltability.
• the storage elastic modulus G ′ at 130 ° C. of the urethane resin particle composition (P) of the present invention is preferably 1.0 ⁇ 10 6 to 5.0 ⁇ 10 7 dyn / cm 2 and more preferably from the viewpoint of heat resistance. Is 5.0 ⁇ 10 6 to 5.0 ⁇ 10 7 dyn / cm 2 .
• the storage elastic modulus G ′ of the urethane resin particle composition (P) of the present invention is preferably 1.0 ⁇ 10 3 to 1.0 ⁇ 10 5 dyn / cm 2 from the viewpoint of low-temperature meltability, Preferably, it is 5.0 ⁇ 10 3 to 5.0 ⁇ 10 4 dyn / cm 2 .
• a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe
• 393 parts of terephthalic acid 393 parts of isophthalic acid
• ethylene glycol 606 The reaction was carried out for 5 hours while distilling off the water produced at 210 ° C. under a nitrogen stream, followed by reaction under reduced pressure of 5 to 20 mmHg, so that polyethylene phthalate diol (A1-1) was allowed to react at a predetermined softening point. I took it out.
• the recovered ethylene glycol was 245 parts.
• the glass transition temperature was 20 ° C.
• a polyethylene phthalate diol (A1-2) having a Mn of 2500 was obtained by adjusting the pressure reduction time by the same production method.
• the recovered ethylene glycol was 270 parts.
• the glass transition temperature was 50 ° C.
• a polyethylene phthalate diol (A1-3) having a Mn of 5000 was obtained by adjusting the pressure reduction time by the same production method.
• the recovered ethylene glycol was 305 parts.
• the glass transition temperature was 65 ° C.
• Production Example 4 Production of polyethylene phthalate (terephthalic acid alone) (A1-5) 786 parts of terephthalic acid and 606 parts of ethylene glycol were placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, at 210 ° C under a nitrogen stream. The reaction was carried out for 5 hours while distilling off the generated water, and then the reaction was carried out under reduced pressure of 5 to 20 mmHg, and polyethylene phthalate diol (A1-5) was taken out at a predetermined softening point. The recovered ethylene glycol was 245 parts. It was 900 as a result of measuring the hydroxyl value of the obtained polyethylene phthalate diol, and calculating Mn.
• the glass transition temperature was 25 ° C.
• polyethylene phthalate diol (A1-6) having Mn of 900 was obtained.
• the glass transition temperature was 15 ° C.
• polyethylene phthalate diol (A1-7) having Mn of 900 was obtained.
• the glass transition temperature was 5 ° C.
• a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe 181 parts of terephthalic acid, 181 parts of isophthalic acid, 338 parts of adipic acid, 166 parts of ethylene glycol and 256 parts of butylene glycol were added and reacted at 210 ° C. for 5 hours while distilling off the water produced in a nitrogen stream.
• the hydroxyl value of the obtained (A3-1) was measured and Mn was calculated to be 950.
• (A1-1) / (A2-1) corresponds to 1 from the charged amount.
• a transesterification product (A3-3) of polyethylene phthalate (terephthalic acid / isophthalic acid 50/50) (A1-1) and Mn 915 of polybutylene adipate (A2-1) of Mn 1000 was taken out. The hydroxyl value of the obtained (A3-3) was measured, and Mn was calculated to be 965. In (A3-3), (A1-1) / (A2-1) corresponds to 5 from the charged amount.
• a prepolymer solution (U-2) was obtained in the same manner as in Production Example 9 except that the raw materials for the prepolymer solution (U-2) were charged as follows.
• the NCO content of the obtained prepolymer solution was 1.2%.
• Polyester diol (A1-2) (759 parts) Polybutylene adipate with Mn of 1000 [polymer diol (A2-1)] (glass transition temperature-60 ° C.) (759 parts) 1-octanol (26.4 parts) Hexamethylene diisocyanate (245.8 parts) Tetrahydrofuran (317 parts) Stabilizer [Irganox 1010] (2.7 parts) Carbon black (1 part)
• Production Example 15 Production of Prepolymer Solution (U-7) A prepolymer solution (U-7) was obtained in the same manner as in Production Example 9 except that the raw materials were charged as follows.
• the NCO content of the obtained prepolymer solution was 1.82%.
• Polyester diol (A1-5) (380 parts) Polymer diol (A2-1) (1139 parts) 1-octanol (26.4 parts) Hexamethylene diisocyanate (362 parts) Tetrahydrofuran (273 parts) Stabilizer [Irganox 1010] (3.0 parts) Carbon black (1 part)
• the prepolymer solution (U-8) was produced in the same manner as in Production Example 9 except that the raw materials were charged as described below to obtain a prepolymer solution prepolymer solution (U-8).
• the NCO content of the obtained prepolymer solution was 1.82%.
• Polyester diol (A1-6) (380 parts) Polymer diol (A2-1)] (1139 parts) 1-octanol (26.4 parts) Hexamethylene diisocyanate (362 parts) Tetrahydrofuran (273 parts) Stabilizer [Irganox 1010] (3.0 parts) Carbon black (1 part)
• Production Example 17 Production of Prepolymer Solution (U-9) A prepolymer solution (U-9) was obtained in the same manner as in Production Example 9 except that the raw materials were charged as follows.
• the NCO content of the obtained prepolymer solution was 1.82%.
• Polyester diol (A1-7) (380 parts) Polymer diol (A2-1) (1139 parts) 1-octanol (26.4 parts) Hexamethylene diisocyanate (362 parts) Tetrahydrofuran (273 parts) Stabilizer [Irganox 1010] (3.0 parts) Carbon black (1 part)
• the transesterification product (A3-3) (319 parts) of polybutylene adipate (A2-1) with (A1-1) was charged, heated to 100 ° C., and then polybutylene adipate with a Mn of 1000 [high Molecular diol (A2-1)] (glass transition temperature-60 ° C) (895 parts) and 1-octanol (27.6 parts) were charged, and the atmosphere was purged with nitrogen. Cooled to 60 ° C. Subsequently, hexamethylene diisocyanate (313.8 parts) was added and reacted at 85 ° C. for 6 hours.
• Example 1 A prepolymer solution (U-1) (100 parts) obtained in Production Example 9 and a MEK ketimine compound (2.1 parts) are charged into a reaction vessel for producing thermoplastic urethane resin particles (K-1). 300 parts of an aqueous solution in which a polycarboxylic acid type anionic surfactant (Sunspear PS-8 (30 parts) manufactured by Sanyo Chemical Industries Co., Ltd.) was dissolved was added at 6000 rpm using an ultradisperser manufactured by Yamato Scientific Co., Ltd. The mixture was mixed for 1 minute at the rotation speed. This mixture was transferred to a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, purged with nitrogen, and then reacted at 50 ° C.
• a polycarboxylic acid type anionic surfactant (Sunspear PS-8 (30 parts) manufactured by Sanyo Chemical Industries Co., Ltd.) was dissolved was added at 6000 rpm using an ultradisperser manufactured by Yamato Scientific Co.
• urethane resin particles K-1
• Mn of (K-1) was 18,000, and the volume average particle diameter was 143 ⁇ m.
• (K-1) has a melt viscosity at 190 ° C. of 510 Pa ⁇ s, a storage elastic modulus at 130 ° C. of 4.5 ⁇ 10 6 dyn / cm 2 , and a storage elastic modulus at 180 ° C. of 3.0 ⁇ 10 4 dyn / cm. 2 .
• thermoplastic urethane resin particles (K-1) (100 parts), radical polymerizable unsaturated group-containing compound dipentaerythritol pentaacrylate [manufactured by Sanyo Chemical Industries, Ltd .; DA600] (4. 0 parts), UV stabilizers bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (mixture) [trade name : TINUVIN 765, manufactured by Ciba] (0.3 parts) was added and impregnated at 70 ° C. for 4 hours.
• (P-1) has a melt viscosity at 190 ° C. of 100 Pa ⁇ s, a storage elastic modulus at 130 ° C. of 3.6 ⁇ 10 6 dyn / cm 2 , and a storage elastic modulus at 180 ° C. of 8.0 ⁇ 10 3 dyn / cm. 2 .
• Example 2 Example 1 except that the prepolymer solution (U-2) (100 parts) was used instead of the prepolymer solution (U-1) in Example 1 and the amount of the MEK ketimine compound was changed to 3.2 parts.
• the urethane resin particles (K-2) were produced in the same manner as described above. Mn of (K-2) was 18,000, and the volume average particle size was 152 ⁇ m.
• (K-2) has a melt viscosity at 190 ° C. of 850 Pa ⁇ s, a storage elastic modulus at 130 ° C. of 1.0 ⁇ 10 7 dyn / cm 2 , and a storage elastic modulus at 180 ° C. of 4.5 ⁇ 10 4 dyn / cm. 2 .
• Example 2 the same procedure was followed as in Example 1 except that the urethane resin particles (K-2) were used instead of the urethane resin particles (K-1) to obtain a urethane resin particle composition (P-2).
• the volume average particle diameter of (P-2) was 153 ⁇ m.
• (P-2) has a melt viscosity at 190 ° C. of 140 Pa ⁇ s, a storage elastic modulus at 130 ° C. of 8.0 ⁇ 10 6 dyn / cm 2 , and a storage elastic modulus at 180 ° C. of 1.5 ⁇ 10 4 dyn / cm. 2 .
• Examples 3 to 11 Except that the prepolymer solutions (U-3) to (U-11) (100 parts) were used instead of the prepolymer solution (U-1) in Example 1, and the amount of the MEK ketimine compound was changed to the following: The same operation as in Example 1 was performed to produce urethane resin particles (K-3) to (K-11). The Mn and volume average particle size of (K-3) to (K-11) are shown below. The melt viscosity at 190 ° C., the storage elastic modulus at 130 ° C. and the storage elastic modulus at 180 ° C. of (K-3) to (K-11) are shown in Table 1.
• Example 1 the same operation as in Example 1 was performed except that the urethane resin particles (K-3) to (K-11) were used instead of the urethane resin particles (K-1), and the urethane resin particle composition (P- 3) to (P-11) were obtained.
• the volume average particle diameters of (P-3) to (P-11) are shown below.
• the melt viscosity at 190 ° C., the storage elastic modulus at 130 ° C. and the storage elastic modulus at 180 ° C. of (P-3) to (P-11) are shown in Table 1.
• Example 3 MEK ketimine compound amount: 3.0 parts (K-3) of Mn: 18,000, volume average particle size: 144 ⁇ m Volume average particle diameter of (P-3): 145 ⁇ m
• Example 4 MEK ketimine compound amount: 7.7 parts (K-4) of Mn: 18,000, volume average particle size: 144 ⁇ m Volume average particle diameter of (P-4): 145 ⁇ m
• Example 5 MEK ketimine compound amount: 6.1 parts (K-5) of Mn: 18,000, volume average particle size: 144 ⁇ m Volume average particle diameter of (P-5): 145 ⁇ m
• Example 6 MEK ketimine compound amount: 4.7 parts (K-6) of Mn: 20,000, volume average particle size: 147 ⁇ m Volume average particle diameter of (P-6): 148 ⁇ m
• Example 7 MEK ketimine compound amount: 4.7 parts (K-7) of Mn: 20,000, volume average particle size: 150 ⁇ m Volume average particle diameter of (P-7): 151
• Example 12 Urethane resin particles (K-12) were produced in the same manner as in Example 2, except that the polyester diol (A1-1) (13 parts) was used instead of the MEK ketimine compound in Example 2. Mn of (K-12) was 18,000, and the volume average particle size was 155 ⁇ m. Table 2 shows the melt viscosity at 190 ° C., the storage elastic modulus at 130 ° C., and the storage elastic modulus at 180 ° C. of (K-12). Further, the same procedure was followed as in Example 1 except that the urethane resin particles (K-12) were used instead of the urethane resin particles (K-1) to obtain a urethane resin particle composition (P-12).
• the volume average particle diameter of (P-12) was 157 ⁇ m.
• the melt viscosity at 190 ° C., the storage elastic modulus at 130 ° C. and the storage elastic modulus at 180 ° C. of (P-12) are shown in Table 2.
• Example 13 Urethane resin particles (K-13) were produced in the same manner as in Example 2 except that instead of the MEK ketimine compound in Example 2, 1.4-butanediol (1.3 parts) was used. . Mn of (K-10) was 18,000, and the volume average particle size was 144 ⁇ m. The melt viscosity at 190 ° C., the storage elastic modulus at 130 ° C. and the storage elastic modulus at 180 ° C. of (K-13) are shown in Table 2. Further, a thermoplastic urethane resin particle composition (P-13) was obtained in the same manner as in Example 1 except that the urethane resin particles (K-13) were used instead of the urethane resin particles (K-1). It was.
• the volume average particle diameter of (P-13) was 145 ⁇ m.
• the melt viscosity at 190 ° C., the storage elastic modulus at 130 ° C. and the storage elastic modulus at 180 ° C. of (P-13) are shown in Table 2.
• Examples 14-17 Except that the prepolymer solutions (U-12) to (U-15) (100 parts) were used instead of the prepolymer solution (U-1) in Example 1, the same operation as in Example 1 was performed, Urethane resin particles (K-14) to (K-17) were produced. The Mn and volume average particle size of (K-14) to (K-17) are shown below. Table 2 shows the melt viscosity at 190 ° C., the storage elastic modulus at 130 ° C., and the storage elastic modulus at 180 ° C. of (K-14) to (K-17).
• Example 1 the same operation was carried out except that the urethane resin particles (K-14) to (K-17) were used in place of the urethane resin particles (K-1), and the urethane resin particle composition (P- 14) to (P-17) were obtained.
• the volume average particle diameters of (P-14) to (P-17) are shown below.
• the melt viscosity at 190 ° C., the storage elastic modulus at 130 ° C. and the storage elastic modulus at 180 ° C. of (P-14) to (P-17) are shown in Table 2.
• Example 14 Mn of (K-14): 2 million, volume average particle diameter: 152 ⁇ m Volume average particle size of (P-14): 144 ⁇ m
• Example 15 Mn of (K-15): 2 million, volume average particle diameter: 145 ⁇ m Volume average particle diameter of (P-15): 146 ⁇ m
• Example 16 Mn of (K-16): 2 million, volume average particle size: 147 ⁇ m Volume average particle diameter of (P-16): 148 ⁇ m
• Example 17 Mn of (K-17): 2 million, volume average particle diameter: 152 ⁇ m Volume average particle diameter of (P-17): 152 ⁇ m
• the volume average particle diameter was 141 ⁇ m, and the melt viscosity at 190 ° C., the storage elastic modulus at 130 ° C. and the storage elastic modulus at 180 ° C. of (K-1 ′) are shown in Table 2. Further, the same operation as in Example 1 was performed to obtain a urethane resin particle composition (P-1 ′). The volume average particle diameter of (P-1 ′) was 142 ⁇ m. The melt viscosity at 190 ° C., the storage elastic modulus at 130 ° C. and the storage elastic modulus at 180 ° C. of (P-1 ′) are shown in Table 2.
• Mn of (K-2 ′) was 18,000, and the volume average particle size was 144 ⁇ m.
• the melt viscosity at 190 ° C., the storage elastic modulus at 130 ° C. and the storage elastic modulus at 180 ° C. of (K-2 ′) are shown in Table 2. Further, the same operation as in Example 1 was performed to obtain a thermoplastic urethane resin particle composition (P-2 ′). The volume average particle diameter of (P-2 ′) was 145 ⁇ m.
• the melt viscosity at 190 ° C., the storage elastic modulus at 130 ° C. and the storage elastic modulus at 180 ° C. of (P-2 ′) are shown in Table 2.
• Table 2 shows the melt viscosity at 190 ° C., the storage elastic modulus at 130 ° C., and the storage elastic modulus at 180 ° C. of (K-3 ′). Further, the same operation as in Example 1 was performed to obtain a thermoplastic urethane resin particle composition (P-3 ′). The volume average particle diameter of (P-3 ′) was 148 ⁇ m. The melt viscosity at 190 ° C., the storage elastic modulus at 130 ° C. and the storage elastic modulus at 180 ° C. of (P-3 ′) are shown in Table 2.
• thermoplastic urethane resin particle composition (P-4 ′)
• the volume average particle diameter of (P-4 ′) was 148 ⁇ m.
• the melt viscosity at 190 ° C., the storage elastic modulus at 130 ° C. and the storage elastic modulus at 180 ° C. of (P-4 ′) are shown in Table 2.
• Tables 1 and 2 show the SP values of the polymer diol (A) used in Examples 1 to 17 and Comparative Examples 1 to 4.
• Thermoplastic urethane resin particle compositions (P-1) to (P-17) for slush molding of Examples 1 to 17 and resin particle compositions for slush molding (P-1 ′) of Comparative Examples 1 to 4 (P-4 ′) was used to form skins with a thickness of 1.0 mm and 0.5 mm at 210 ° C. by the method shown below, and the backside meltability of the skin with a thickness of 1.0 mm, 25 ° C. tensile strength 25 ° C. elongation, 25 ° C. skin thickness breaking stress of 0.5 mm, ⁇ 35 ° C. elongation, 25 ° C. tensile strength after the heat resistance test shown below, and elongation were measured.
• the results are shown in Tables 1 and 2.
• thermoplastic urethane resin particle composition (P-1) to (P-17), (P-1 ′) ) To (P-4 ′), and after 10 seconds, the excess resin particle composition was discharged. After 60 seconds, it was cooled with water to prepare a skin (thickness 1 mm). Further, a skin having a thickness of 0.5 mm was prepared in the same manner as described above except that the time after filling was changed to 6 seconds.
• the storage elastic modulus G ′ at 130 ° C. and 180 ° C. was measured using a dynamic viscoelasticity measuring device “RDS-2” (manufactured by Rheometric Scientific) under a frequency of 1 Hz. After setting the measurement sample on the jig of the measuring device, the temperature is raised to 200 ° C., and is melted by allowing it to stand between the jigs at 200 ° C. for 1 minute. Then, the sample is cooled and solidified to be brought into close contact with the jig. The measurement was performed. The measurement temperature range is 50 to 200 ° C.
• thermoplastic urethane resin particle compositions (P-1) to (P-17) for slush molding of Examples 1 to 17 were compared with (P-1 ′) to (P-4 ′) of Comparative Examples 1 to 4.
• it is excellent in all of the backside meltability of 210 ° C, 25 ° C tensile strength, 25 ° C elongation, -35 ° C elongation, 25 ° C tensile strength and 25 ° C elongation after the heat resistance test.
• the breaking stress of 0.5 mm is excellent, the molded skin can be made thin. Accordingly, (P-1) to (P-17) are particularly excellent as a material for an instrument panel because they are compatible with low-temperature meltability, tensile strength and elongation at a high level.
• a molded product for example, a skin formed from the thermoplastic urethane resin particle composition of the present invention, is suitably used as a skin for automobile interior materials, for example, instrument panels and door trims.

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