JP6091947B2 - Thermoplastic urethane (urea) resin particle composition for slush molding - Google Patents

Description

  The present invention relates to thermoplastic urethane (urea) resin particles for slush molding.

  Slush molded products are used for instrument panels for automobile interior parts. Until now, soft polyvinyl chloride powder has been mainly used as a material for slush molding (for example, Patent Document 1). However, since the softened polyvinyl chloride contains a large amount of low molecular weight plasticizer, there is a problem that the soft feeling disappears below the freezing point of the plasticizer. On the other hand, a polyurethane-based resin molding material that has a soft feeling even at low temperatures has been proposed (for example, Patent Document 2). However, in the conventional polyurethane resin molding material, if the heat resistance is to be imparted, the meltability of the particles is lowered and the molding can be performed only at a high temperature of about 250 ° C. On the other hand, resin particles made of a resin having specific esters, polyisocyanates and polyamines as structural units are proposed as slush molding materials that have excellent meltability and can be molded at low temperatures (for example, Patent Document 3). .

JP-A-5-279485 JP-A-10-259369 JP 2011-132500 A

However, in recent years, the shape of the instrument panel has been complicated to improve the design, and the shape of the mold for slush molding has also been complicated, and conventional slash molding as described in Patent Documents 1 to 3 When the material is molded with such a mold, there is a problem in that particles do not reach the convex portion of the molded product, and pinholes, undercuts and the like are likely to occur in the convex portion.
An object of the present invention is to provide a slush molding material that has a soft feeling even at low temperatures and is excellent in the moldability of the convex portions of the slush molded product and the heat resistance of the molded product.

  As a result of intensive studies to solve the above problems, the present inventor has reached the present invention. That is, the present invention contains a urethane (urea) resin (U) having a residue (j) obtained by removing a hydroxyl group from a trivalent or higher aromatic polycarboxylic acid and having a volume average particle size of 50 to 500 μm. (Urea) resin particles (D) and a thermoplastic resin and / or a thermosetting resin having a thermal softening point higher than the thermal softening point of the urethane (urea) resin (U), and having a volume average particle size of 0. It is a thermoplastic urethane (urea) resin particle composition (P) for slush molding comprising resin fine particles (E) having a diameter of 0.01 to 5 μm.

  The thermoplastic urethane (urea) resin particle composition (P) for slush molding of the present invention has a soft feeling even at low temperatures, and is excellent in the moldability of convex portions of the slush molded product and the heat resistance of the molded product.

  The thermoplastic urethane (urea) resin particle composition (P) for slush molding of the present invention comprises urethane (urea) resin particles (D) containing a thermoplastic urethane (urea) resin (U) and the heat of (U). It contains a thermoplastic resin and / or resin fine particles (E) containing a thermosetting resin having a heat softening point higher than the softening point.

<Urethane (urea) resin particles (D)>
The urethane (urea) resin particle (D) contains a urethane (urea) resin (U) having a covalently bonded residue (j) obtained by removing a hydroxyl group from a trivalent or higher valent aromatic polycarboxylic acid, (U ) And a residue (j) obtained by removing a hydroxyl group from a trivalent or higher valent aromatic polycarboxylic acid is hydrogen-bonded. By having the hydrogen bond in (U) constituting (D), it is possible to impart excellent performance over all three of the meltability of (D), the heat resistance of the molded product of (D), and the mechanical properties. it can. In the present invention, the urethane (urea) resin (U) represents a urethane resin and / or a urethane urea resin.

  (U) preferably has a structural unit (x) represented by the following general formula (1).

  When the structural unit (x) represented by the general formula (1) is obtained by reacting, for example, a urethane (urea) resin (U) with an active hydrogen component (A) and an isocyanate component (B), the active hydrogen component As a part of (A), it can introduce | transduce into (U) by using the active hydrogen containing compound (C) represented by General formula (2).

R ¹ in the general formulas (1) and (2) represents a monovalent group or a hydroxyl group obtained by removing one active hydrogen from a monovalent or polyvalent active hydrogen-containing compound (R ¹ H). When there are a plurality of R ^{1 s} , they may be the same or different. R ² represents a divalent group obtained by removing two active hydrogens from a divalent active hydrogen-containing compound (R ² H), and when there are a plurality of R ^{2 s} , R ² may be the same or different. Y represents a trivalent or higher group obtained by removing all carboxyl groups from a trivalent or higher aromatic polycarboxylic acid. The aromatic ring of Y is composed of carbon atoms, and a substituent other than a carboxyl group and / or a halogen atom may be bonded to the carbon atom, and at least one of the carbon atoms is bonded to a substituent. A represents an integer of 1 or more, b represents an integer of 0 or more, and satisfies 3 ≦ a + b ≦ d−1. However, d is the number of hydrogen atoms bonded to the carbon atoms constituting the aromatic ring when all the substituents including the carboxyl group of the aromatic polycarboxylic acid are substituted with hydrogen atoms, that is, can be substituted on the aromatic ring. Represents the number of sites.

The active hydrogen-containing compound (R ¹ H) has 1 to 30 carbon atoms, and is a hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, a thiol group-containing compound, and a phosphate compound; And a compound having an active hydrogen-containing functional group.

Examples of the hydroxyl group-containing compound include monohydric alcohols, divalent to octavalent polyhydric alcohols, phenols and polyhydric phenols. Specifically, monohydric alcohols having 1 to 12 carbon atoms such as methanol, ethanol, butanol, octanol, benzyl alcohol, naphthylethanol; ethylene glycol, propylene glycol, 1,3 and 1,4-butanediol, 1,6 -Divalent alcohols such as hexanediol, 1,10-decanediol, diethylene glycol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, 1,4-bis (hydroxymethyl) cyclohexane and 1,4-bis (hydroxyethyl) benzene Trivalent alcohols such as glycerin and trimethylolpropane; pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, full 4- to 8-valent alcohols such as toose, methyl glucoside and derivatives thereof; phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1, Phenols such as 3,6,8-tetrahydroxynaphthalene, anthrol, 1,4,5,8-tetrahydroxyanthracene and 1-hydroxypyrene; polybutadiene polyol; castor oil-based polyol; hydroxyalkyl (meth) acrylate ( Co) polymers and polyfunctional polyols (for example, 2 to 100 functional groups) such as polyvinyl alcohol, condensates (novolaks) of phenol and formaldehyde, and polyphenols described in US Pat. No. 3,265,641 Among these, monohydric alcohols having 1 to 12 carbon atoms are particularly preferable from the viewpoints of productivity and compatibility between the low-temperature meltability of molded articles and mechanical properties (elongation and tensile strength) and heat resistance. Is benzyl alcohol.
(Meth) acrylate means methacrylate and / or acrylate, and the same applies hereinafter.

  Examples of the amino group-containing compound include amines, polyamines and amino alcohols. Specifically, ammonia; monoamines such as C1-C20 alkylamine (butylamine and the like) and aniline; aliphatic polyamines such as ethylenediamine, hexamethylenediamine and diethylenetriamine; heterocyclics such as piperazine and N-aminoethylpiperazine Polyamines; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; aromatic polyamines such as phenylenediamine, tolylenediamine and diphenylmethanediamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and dicarboxylic acids Polyamide polyamine obtained by condensation with excess polyamine; polyether polyamine; hydrazine (such as hydrazine and monoalkylhydrazine), dihydrazide ( Etc. Haq acid dihydrazide and dihydrazide terephthalate), guanidine (butyl guanidine and 1-cyanoguanidine, etc.); dicyandiamide; and the like.

  Examples of the carboxyl group-containing compound include aliphatic monocarboxylic acids such as acetic acid and propionic acid; aromatic monocarboxylic acids such as benzoic acid; aliphatic dicarboxylic acids such as succinic acid, fumaric acid, sebacic acid and adipic acid; phthalic acid, Isophthalic acid, terephthalic acid, trimellitic acid, naphthalene-1,4 dicarboxylic acid, naphthalene-2,3,6 tricarboxylic acid, pyromellitic acid, diphenic acid, 2,3-anthracene dicarboxylic acid, 2,3,6-anthracene Examples thereof include aromatic polycarboxylic acids such as tricarboxylic acid and pyrene dicarboxylic acid; polycarboxylic acid polymers (functional group number: 2 to 100) such as (co) polymer of acrylic acid.

  Examples of the thiol group-containing compound include monofunctional phenylthiol, alkanethiol and polythiol compounds. Examples of the polythiol include divalent to octavalent polyvalent thiols. Specific examples include ethanedithiol and 1,6-hexanedithiol.

  Examples of phosphoric acid compounds include phosphoric acid, phosphorous acid, and phosphonic acid.

The active hydrogen-containing compound (R ¹ H) also includes compounds having two or more active hydrogen-containing functional groups (hydroxyl group, amino group, carboxyl group, thiol group, phosphate group, etc.) in the molecule.

The active hydrogen-containing compound (R ¹ H) also includes a compound obtained by adding alkylene oxide (hereinafter abbreviated as AO) to the active hydrogen-containing compound.

  As AO to be added, AO having 2 to 6 carbon atoms such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propylene oxide, 1,2 Examples include butylene oxide and 1,4-butylene oxide. Of these, PO, EO, and 1,2-butylene oxide are preferable from the viewpoints of properties and reactivity. When two or more types of AO are used (for example, PO and EO), block addition or random addition may be used, or a combination thereof may be used.

Furthermore, as the active hydrogen-containing compound (R ¹ H), an active hydrogen-containing compound (polyester compound) obtained by a condensation reaction between a diol and a dicarboxylic acid (aliphatic dicarboxylic acid or aromatic dicarboxylic acid) can be used. . In the condensation reaction, one type of active hydrogen-containing compound and polycarboxylic acid may be used, or two or more types may be used in combination.

  Aliphatic dicarboxylic acids include C2-C10 aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, maleic acid and fumaric acid.

  Aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 2,2'-bibenzyldicarboxylic acid, hemimellitic acid, trimesic acid, and naphthalene-1,4 dicarboxylic acid, diphenic acid, 2,3-anthracene Examples thereof include aromatic polycarboxylic acids having 8 to 18 carbon atoms such as dicarboxylic acid and pyrene dicarboxylic acid.

  Moreover, when performing condensation reaction of dicarboxylic acid and diol, the anhydride and lower alkyl ester of polycarboxylic acid can also be used.

Examples of the active hydrogen-containing compound (R ² H) include divalent active hydrogen-containing compounds among the above (R ¹ H).

  Specific examples of the divalent hydroxyl group-containing compound include ethylene glycol, 1,2- or 1,3-propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, 1, Divalent alcohols such as 10-decanediol, diethylene glycol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, 1,4-bis (hydroxymethyl) cyclohexane and 1,4-bis (hydroxyethyl) benzene, and their carbon number of 2 ˜6 AO adducts.

  Specific examples of the divalent amino group-containing compound include aliphatic diamines such as ethylenediamine and hexamethylenediamine; alicyclic diamines such as dicyclohexylmethanediamine and isophoronediamine; phenylenediamine, tolylenediamine, and diphenylmethanediamine. Aromatic diamines may be mentioned.

  Specific examples of the divalent carboxyl group-containing compound include aliphatic dicarboxylic acids having 2 to 10 carbon atoms such as succinic acid, fumaric acid, sebacic acid and adipic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene- Examples thereof include aromatic dicarboxylic acids having 8 to 18 carbon atoms such as 1,4 dicarboxylic acid and 2,3-anthracene dicarboxylic acid.

  Specific examples of the divalent thiol group-containing compound include ethanedithiol and 1,6-hexanedithiol.

The divalent active hydrogen-containing compound (R ² H) is preferably a divalent active hydrogen-containing compound (R ² H) from the viewpoint of compatibility between low-temperature meltability and mechanical properties (elongation, tensile strength) and heat resistance of a urethane (urea) resin molded product. A hydroxyl group-containing compound and a divalent amino group-containing compound are more preferable, and glycols having 2 to 10 carbon atoms, poly (n = 2 to 5) ethylene glycol, poly (n = 2 to 5) (1,2 -Propylene) glycol and diamines having 2 to 6 carbon atoms (ethylenediamine, butylenediamine, hexamethylenediamine, etc.), particularly preferred are ethylene glycol, 1,2-propylene glycol, ethylenediamine and butylenediamine, most preferred Is ethylene glycol.

  Y represents a residue obtained by removing all carboxyl groups from a trivalent or higher aromatic polycarboxylic acid. The atoms constituting the aromatic ring of Y are only carbon atoms. What is directly bonded to the aromatic ring may be a hydrogen atom or a substituent, but at least one is a hydrogen atom. That is, the aromatic ring of Y has at least one hydrogen atom bonded to the carbon atom constituting the aromatic ring.

  Substituents include alkyl groups, vinyl groups, allyl groups, cycloalkyl groups, halogen atoms, amino groups, carbonyl groups, carboxyl groups, hydroxyl groups, hydroxyamino groups, nitro groups, phosphino groups, thio groups, thiol groups, and aldehydes. Group, ether group, aryl group, amide group, cyano group, urea group, urethane group, sulfone group, ester group and azo group. From the viewpoint of improving mechanical properties (elongation, tensile strength, compression hardness) and cost, the substituent is preferably an alkyl group, a vinyl group, an allyl group, an amino group, an amide group, a urethane group or a urea group.

The arrangement of substituents on Y is preferably the following structure from the viewpoint of improving mechanical properties.
In the case of a trivalent aromatic polycarboxylic acid; a structure in which two carbonyl groups are adjacent and a hydrogen atom is arranged between the third carbonyl group and the first or second carbonyl group is preferred.
In the case of an aromatic polycarboxylic acid having a valence of 4 or more; a structure in which two carbonyl groups are adjacent and a hydrogen atom is arranged between the third and subsequent carbonyl groups and the first or second carbonyl group is preferable.

  As trivalent or higher aromatic polycarboxylic acid (YH) constituting Y, benzene polycarboxylic acid (trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid, etc.), and polycyclic aromatic polycarboxylic acid Examples thereof include aromatic polycarboxylic acids having 8 to 18 carbon atoms (such as naphthalene-1,2,4 tricarboxylic acid).

  Of the trivalent or higher aromatic polycarboxylic acids (YH), benzene polycarboxylic acid is preferred. When the benzene polycarboxylic acid has 3 carboxyl groups, the carboxyl group substitution position is 1,2,4-position (trimellitic acid). When the carboxyl group has 4 carboxyl groups, the carboxyl group substitution position is 1, The 2,4,5-position (pyromellitic acid) or the 1,2,3,5-position is preferred.

a and b are integers in which a represents an integer of 1 or more, b represents an integer of 0 or more, and satisfies 3 ≦ a + b ≦ d−1. Where d is the number of hydrogen atoms bonded to the carbon atoms constituting the aromatic ring when all the substituents including the carboxyl group of the aromatic polycarboxylic acid are substituted with hydrogen atoms, that is, the sites that can be substituted on the aromatic ring Represents the number of For example, the number of hydrogen atoms bonded to the ring carbon of a compound such as benzene or naphthalene is meant. 6 for benzene and 8 for naphthalene.
The active hydrogen-containing compound (C), which will be described later, has a general formula of a divalent active hydrogen-containing compound (R ² H) or an active hydrogen-containing compound (R ¹ H) to a trivalent or higher aromatic polycarboxylic acid (YH). Instead of dehydrating condensation reaction at a ratio satisfying a and b specified in (2) or dehydrating condensation reaction of (R ² H), an alkylene oxide (ethylene oxide, propylene oxide, etc.) is added to a carboxyl group. Can also be obtained. Further, instead of using (R ¹ H), it is preferable to obtain (C) by dehydrochlorinating a monochloride having an organic group having 1 to 30 carbon atoms from the viewpoint of reaction temperature.
As the monochloride, a monochloride having a chloromethylene group is more preferable, and benzyl chloride is particularly preferable.

  (U) is a structural unit (x) represented by the general formula (1) in (U) from the viewpoint of both the meltability of urethane (urea) resin particles and the mechanical strength and heat resistance of the molded product. Is preferably contained in an amount of 0.1 to 30% by weight based on the weight of (U), more preferably 0.5 to 20% by weight, and most preferably 1.0 to 10.0% by weight. preferable.

  In (U), from the viewpoint of the meltability of urethane (urea) resin particles, it is preferable that a in formulas (1) and (2) is 1 or 2 in (U). From the viewpoint of achieving both mechanical strength and heat resistance of the product, it is more preferable that a is 1, that is, the structural unit (x) is present at the molecular end of the urethane (urea) resin (U).

  (U) is a urethane (urea) resin (U1) having a structural unit (x1) where a is 1 in the general formulas (1) and (2) at the end of the molecule; From the viewpoint of both strength and heat resistance, the structural unit (x1) is preferably contained in an amount of 0.1 to 5% by weight based on the weight of (U1), and is preferably contained in an amount of 0.5 to 4% by weight. More preferably, it is most preferably contained in an amount of 1 to 3% by weight.

  (U) is a urethane (urea) resin (U2) having a structural unit (x2) in which a is 2 in the general formulas (1) and (2), meltability and mechanical strength and heat resistance of the molded product In view of the above, the structural unit (x2) is preferably contained in an amount of 0.1 to 3% by weight, more preferably 0.1 to 2% by weight, based on the weight of (U2), Most preferably, it is contained in an amount of ˜1% by weight.

  In the urethane (urea) resin (U), the active hydrogen component (A) other than the active hydrogen-containing compound (C) represented by the general formula (2) has a number average molecular weight (hereinafter abbreviated as Mn) of 500 or more. High molecular diol (a1), low molecular diamine (a2), low molecular diol (a3) having a Mn of less than 500, monool (a4), and the like.

  In addition, Mn of the diol in this invention is a value computed from the hydroxyl group of the diol measured based on JISK1557-1.

  Examples of the polymer diol (a1) having a Mn of 500 or more include polyester diol, polyether diol, polyether ester diol, and the like.

  Examples of the polyester diol include (1) condensation polymerization of a low molecular diol (a3) described later and a dicarboxylic acid or an ester-forming derivative thereof [an acid anhydride, a lower alkyl (carbon number 1 to 4) ester, an acid halide, etc.]. (2) Ring-opening polymerization of a lactone monomer using a low molecular diol (a3) described later as an initiator; and a mixture of two or more of these.

  Specific examples of the dicarboxylic acid or ester-forming derivatives thereof include aliphatic dicarboxylic acids having 4 to 15 carbon atoms [succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.], carbon 8-12 aromatic dicarboxylic acids [terephthalic acid, isophthalic acid, etc.], ester-forming derivatives thereof [acid anhydrides, lower alkyl esters (dimethyl esters, diethyl esters, etc.), acid halides (acid chlorides, etc.)] And mixtures of two or more thereof.

  Examples of the lactone monomer include γ-butyrolactone, ε-caprolactone, γ-valerolactone, and a mixture of two or more thereof.

  Specific examples of the polyester diol include polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyneopentylene adipate diol, poly 3-methylpentylene adipate diol, polycaprolactone diol, polyvalerolactone diol, polyhexamethylene carbonate Diol etc. are mentioned.

Examples of the polyether diol include compounds having a structure in which an alkylene oxide is added to two hydroxyl group-containing compounds (for example, the low molecular diol, divalent phenols, etc.). Examples of the divalent phenols 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 EO to dihydric phenols.

  As the polyether ester diol, the polyester diol using the polyether diol instead of the raw material low molecular diol, for example, one or more of the polyether diols and the dicarboxylic acid exemplified as the raw material of the polyester diol or its Examples thereof include those obtained by condensation polymerization with one or more ester-forming derivatives. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.

  As the polymer diol (a1), it is preferable to use a polyester diol from the viewpoint of heat resistance and light resistance.

  Examples of the low molecular diamine (a2) include alicyclic diamines having 6 to 18 carbon atoms [4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4′-diaminodicyclohexylmethane, diaminocyclohexane, isophoronediamine. Etc.]; C2-C12 aliphatic diamine [ethylenediamine, propylenediamine, hexamethylenediamine, etc.]; C8-C15 aromatic aliphatic diamine [xylylenediamine, α, α, α ′, α′-tetra Methylxylylenediamine etc.] and mixtures of two or more thereof. Of these, preferred are alicyclic diamines and aliphatic diamines, and particularly preferred are isophorone diamine and hexamethylene diamine.

  As the low molecular diol (a3) having a Mn of less than 500, aliphatic diols having 2 to 8 carbon atoms [linear diols (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 [C6-C15 alicyclic group-containing diol {1,4-bis (hydroxymethyl) Cyclohexane, hydrogenated bisphenol A, etc.], aromatic ring-containing diol having 8 to 20 carbon atoms (m- or p-xylylene glycol, etc.) Oxyalkylene ethers of bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.), oxyalkylene ethers of polynuclear phenols (dihydroxynaphthalene, etc.), bis (2-hydroxyethyl) terephthalate, etc.]; these alkylene oxide adducts (molecular weight) Less than 500) and mixtures of two or more thereof. Among the low molecular diols, preferred are aliphatic diols and alicyclic group-containing diols.

  As monool (a4), 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)]; monools having a cyclic group having 6 to 10 carbon atoms [alicyclic group-containing monools (cyclohexanol etc.), carbon number 7 -12 aromatic ring-containing monools (such as benzyl alcohol and naphthylethanol) and the like, and mixtures of two or more thereof. Among these, preferred are aliphatic monools and aromatic ring-containing monools. Moreover, high molecular monools, such as polyester monool, polyether monool, and polyether ester monool, and the compound whose a is 1 in General formula (1) can also be used as monool (a4).

As the isocyanate component (B) constituting the urethane (urea) resin (U),
(I) C2-C18 aliphatic diisocyanate [ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethyl] (excluding carbon in NCO group, the same applies hereinafter) Hexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanate Natohexanoate, etc.];
(Ii) C4-C15 alicyclic diisocyate [isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene and the like];
(Iii) C8-15 araliphatic diisocyanate [m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI) etc.]; aroma Specific examples of the group polyisocyanates include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and / Or 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4 '-Diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, 4,4', 4 "-triphenylmethane triisocyanate DOO, m- and p- isocyanatophenyl sulfonyl isocyanate;
(Iv) Modified products of these diisocyanates (diisocyanate modified products having a carbodiimide group, a uretdione group, a uretoimine group, a urea group, etc.); and a mixture of two or more of these. Of these, preferred are aliphatic diisocyanates or alicyclic diisocyanates, and particularly preferred are HDI, IPDI, and hydrogenated MDI.

Examples of the method for synthesizing the urethane (urea) resin (U) include the following methods.
(1) A mixture of a polymer diol (a1), an active hydrogen-containing compound (C) and a monool (a6) and a diisocyanate component (B) in the presence or absence of an organic solvent, and a hydroxyl group and diisocyanate in the mixture. The urethane prepolymer (G) having an isocyanate group at the terminal obtained is reacted with water and dispersed so that the molar ratio of the isocyanate group of the component (B) is 1: 1.2 to 1: 4.0. A method in which an extension reaction is carried out with a low molecular diamine (a2) or a low molecular diol (a3) in the presence of a stabilizer. As the low molecular diamine, a blocked linear aliphatic diamine (for example, ketimine compound) can be used.
(2) A method in which the urethane prepolymer (G) is subjected to an extension reaction with a low molecular diamine (a2) or a low molecular diol (a3) in the presence of a nonpolar organic solvent and a dispersion stabilizer.
(3) A method in which the diisocyanate component (B) and the active hydrogen component (A) are reacted in one shot.

The reaction temperature at the time of producing the urethane prepolymer (G) may be the same as that usually employed for urethanization, and is usually 20 ° C to 100 ° C when a solvent is used, and the solvent is not used. In the case, it is usually 20 ° C to 140 ° C, preferably 80 ° C to 130 ° C.
In the urethanization reaction, a catalyst usually used for polyurethane can be used as necessary to accelerate the reaction. Examples of the catalyst include amine catalysts [triethylamine, N-ethylmorpholine, triethylenediamine, etc.], tin catalysts [trimethyltin laurate, dibutyltin dilaurate, dibutyltin malate, etc.] and the like.

  The storage elastic modulus at −20 ° C. of the urethane (urea) resin (U) is preferably 0.2 to 10 MPa, more preferably 0.5 to 5 MPa from the viewpoint of soft feeling.

  By using urethane (urea) resin (U) as urethane (urea) resin particles (D), application to not only slush molding powder but also hot-melt adhesive is possible. The urethane (urea) resin particles (D) are obtained, for example, as an emulsification / dispersion in the production of the urethane (urea) resin (U), and then solid-liquid separation and drying, or a block or urethane (urea) ) It can be obtained by a production method such as grinding the resin (U).

  Examples of the method for obtaining the urethane (urea) resin particles (D) as a dispersion include the method described in International Publication No. 2011/070784.

  The emulsifying / dispersing apparatus is not particularly limited as long as it is generally marketed as an emulsifying machine or dispersing machine. For example, a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (Primix) Batch emulsifiers, etc., Ebara Milder (Ebara Seisakusho), TK Fillmix, TK Pipeline Homomixer (Primics), Colloid Mill (Shinko Pantech), Thrasher, Trigonal Wet Fine Grinding Continuous emulsifiers such as machine (Nippon Coke Kogyo Co., Ltd.), Capitolon (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Kiko Co., Ltd.), Microfluidizer (Mizuho Kogyo Co., Ltd.) High pressure emulsifiers such as APV Gaurin (manufactured by Gaurin), membrane emulsifiers (manufactured by Chilling Industries), etc. Emulsifier, Vibro Mixer (Hiyaka Kogyo) vibrating emulsifier such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix and TK pipeline homomixer are preferable from the viewpoint of particle size distribution.

  As a method for producing the lump or pellet urethane (urea) resin (U), for example, a batch kneader such as a kneader, a screw extruder with a side feeder, or the like can be used. Subsequently, it is cooled with liquid nitrogen or the like and pulverized with an impact pulverizer such as a turbo mill, whereby urethane (urea) resin particles (D) can be obtained.

  The volume average particle diameter of the urethane (urea) resin particles (D) of the present invention is preferably 50 to 500 μm, more preferably 70 to 300 μm. Further, the urethane (urea) resin particles (D) may be spherical or non-spherical.

  The volume average particle size in the present invention is measured using, for example, a Microtrac HRA particle size analyzer 9320-X100 (manufactured by Nikkiso Co., Ltd.).

<Resin fine particles (E)>
Examples of the resin fine particles (E) include thermoplastic resin fine particles (E1) and thermosetting resin fine particles (E2).

  Examples of (E1) include fine particles containing a polyurethane (urea) resin, a poly (meth) acrylate resin, a maleimide copolymer, and the like, and the heat softening point of these resins is a thermoplastic urethane (urea) resin (U). Must be higher than the thermal softening point.

The thermal softening point in the present invention refers to a temperature at which a resin is heated at a constant speed under the following conditions using a flow tester CFT-500 manufactured by Shimadzu Corporation and the resin starts to soften.
Load: 5kg
Die: 0.5mmΦ-1mm
Temperature increase rate: 5 ° C./min.

  Examples of (E2) include fine particles containing a thermosetting polyurethane (urea) resin, a guanamine resin, an epoxy resin, a poly (meth) acrylate resin having a crosslinked structure, a maleimide copolymer having a crosslinked structure, and the like. .

  From the viewpoint of moldability of the convex portions of the urethane (urea) resin particle composition (P), (E) is preferably one that does not melt at 160 ° C. (E2) is preferred as one that does not melt at 160 ° C., a maleimide copolymer having a crosslinked structure and a poly (meth) acrylate resin having a crosslinked structure are more preferred, and N-cyclohexylmaleimide and 2-hydroxyethyl are particularly preferred. A copolymer of (meth) acrylate crosslinked with hexamethylene diisocyanate and / or isophorone diisocyanate (described in JP-A-2005-126534), and poly (meth) acrylate of alkyl (meth) acrylate and polyhydric alcohol And a poly (meth) acrylate resin having a cross-linked structure (described in International Publication No. 2005-097901).

The volume average particle diameter of the resin fine particles (E) is preferably 0.01 to 5 μm, more preferably 0.05 to 4 μm, and most preferably 0.1 to 3 μm.
The amount of (E) is preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight, based on the total weight of the urethane (urea) resin particles (D) and (E).

<Thermoplastic urethane (urea) resin particle composition for slush molding (P)>
As a method for producing the urethane (urea) resin particle composition (P), a method of mixing the urethane (urea) resin particles (D) and the resin fine particles (E) is preferable. The mixing method may be either dry blend or wet blend, but is preferably dry blend.

  As a mixing device used when the resin particle composition (P) is mixed and produced, a known powder mixing device can be used, and a container rotating mixer, a fixed container mixer, a fluid motion mixer Either of these can be used. For example, as a fixed vessel 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 dry blending method using a machine (Nauta Mixer (registered trademark) or the like) is well known. Among these methods, it is preferable to use a double-shaft paddle type mixer, a low speed mixing device (planetary mixer or the like), and a conical screw mixer (Nauta mixer (registered trademark, hereinafter omitted) or the like).

The urethane (urea) resin particles (D) may contain an additive (F) in addition to the urethane (urea) resin (U). Moreover, the thermoplastic urethane (urea) resin particle composition (P) for slush molding may contain (F) in addition to (D) and (E). Examples of the additive (F) include inorganic fillers, pigments, plasticizers, mold release agents, stabilizers, and dispersants.
The amount of the additive (F) added is preferably 0 to 50% by weight, more preferably 1 to 30% by weight, based on the weight of the urethane (urea) resin (U).

  Additive (F) is added at any stage after the production of urethane prepolymer (G) and after the production of urethane (urea) resin particles (D) in the raw material before production of urethane (urea) resin particles (D). May be. Moreover, when an additive (F) is a plasticizer or a mold release agent, the method of adding after urethane (urea) resin particle (D) manufacture is preferable.

  Inorganic fillers include 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. Of these, 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 size (μm) of the inorganic filler is preferably 0.1 to 30, more preferably 1 to 20, and particularly preferably 5 to 10 from the viewpoint of dispersibility in the thermoplastic resin.
The added amount of the inorganic filler is preferably 0 to 40% by weight, more preferably 1 to 20% by weight based on the weight of the urethane (urea) resin (U).

It does not specifically limit as a pigment, A well-known organic pigment and / or an inorganic pigment can be used, (U) 100 weight part is normally 10 weight part or less, Preferably 0.01-5 weight part is mix | blended. . Examples of the organic pigment include insoluble or soluble azo pigments, copper phthalocyanine pigments, quinacridone pigments, and inorganic pigments include chromates, 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. Although there is no limitation in particular about the average particle diameter of a pigment, it is 0.2-5.0 micrometers normally, Preferably it is 0.5-1 micrometer.
The added amount of the pigment is preferably 0 to 5% by weight, more preferably 1 to 3% by weight based on the weight of the urethane (urea) resin (U).

Examples of 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 (trimellitic acid tri-2-ethylhexyl and trimellitic acid trioctyl); fatty acid ester (such as butyl oleate); aliphatic phosphoric acid ester (trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri- 2-ethylhexyl phosphate and tributoxy phosphate); aromatic phosphates (triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xyleni Diphenyl phosphate, 2-ethylhexyl diphenyl phosphate and tris (2,6-dimethylphenyl) phosphate, etc.); halogen aliphatic phosphate ester (tris (chloroethyl) phosphate, tris (β-chloropropyl) phosphate, tris (dichloropropyl) phosphate and tris (Tribromoneopentyl) phosphate, etc.); and mixtures of two or more thereof.
The addition amount of the plasticizer is preferably 0 to 50% by weight, more preferably 5 to 20% by weight, based on the weight of the urethane (urea) resin (U).

As the mold release agent, known mold release agents can be used, and fluorine compound type mold release agents (triperfluoroalkyl phosphate (8 to 20 carbon atoms) ester such as triperfluorooctyl phosphate and triperfluorododecyl phosphate). Etc.); silicone compound mold release agents (dimethylpolysiloxane, amino-modified dimethylpolysiloxane, carboxyl-modified dimethylpolysiloxane, etc.), fatty acid ester mold release agents (mono- or polyhydric alcohol esters of fatty acids having 10 to 24 carbon atoms, For example, butyl stearate, hydrogenated castor oil, ethylene glycol monostearate, etc .; 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 of the release agent is preferably 0 to 1% by weight, more preferably 0.1 to 0.5% by weight, based on the weight of the urethane (urea) resin (U).

Stabilizers include carbon-carbon double bonds (such as ethylene bonds which may have a substituent) in the molecule (excluding double bonds in aromatic rings), carbon-carbon triple bonds (with substituents). 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, the same shall apply hereinafter). , Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol tri (meth) acrylate); esters of (meth) allyl alcohol and divalent to hexavalent polycarboxylic acids (diallyl phthalate) And trimellitic acid triallyl ester); poly (meth) allyl ether of polyhydric alcohol Ritol (meth) allyl ether, etc.); Polyhydric alcohol polyvinyl ether (ethylene glycol divinyl ether, etc.); Polyhydric alcohol polypropenyl ether (ethylene glycol dipropenyl ether, etc.); Polyvinylbenzene (divinylbenzene etc.) and these 2 A mixture of seeds or more may be mentioned. Among these, from the viewpoint of stability (radical polymerization rate), 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 of the stabilizer is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, based on the weight of the urethane (urea) resin (U).

  The volume average particle size of the resin particle composition (P) is preferably in the range of 50 to 500 μm, more preferably 70 to 300 μm.

The resin particle composition (P) is a JIS K6720-2 (1999) bulky urethane (urea) resin particle composition (P) having a volume of 100 cm ^{3 at} a temperature of 23 ° C. and a relative humidity of 50% from the viewpoint of moldability of the convex portion. The time for flowing down the bulk specific gravity measuring device defined by the specific gravity measurement is preferably 13 seconds or less, more preferably 12.5 seconds or less. The flow time can be adjusted to the above range by optimizing the mixing ratio of the urethane (urea) resin particles (D) and the resin fine particles (E) and the mixing time thereof.

The resin particle composition (P) can be molded by, for example, a slush molding method to produce a urethane (urea) resin molded product such as a skin. As the slush molding method, the box containing the powder composition of the present invention and a heated mold are both oscillated and rotated, the powder is melted and flowed in the mold, cooled and solidified, and a skin is manufactured. Can be mentioned.
The mold temperature is preferably 200 to 300 ° C, more preferably 200 to 250 ° C.

The skin thickness formed with the resin particle composition (P) is preferably 0.3 to 1.5 mm.
The resin particle composition (P) can be molded in a relatively low temperature region, and the molding temperature can be 200 to 250 ° C.

The molded skin can be set as a resin molded product by setting the surface to be in contact with the foaming mold, pouring urethane foam, and forming a foamed layer of 5 mm to 15 mm on the back surface.
The resin molded product molded with the resin particle composition (P) is suitably used for automobile interior materials such as instrument panels and door trims.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. In the following, “parts” represents parts by weight, and “%” represents% by weight.

Production Example 1
Production of MEK ketimine product of diamine Hexamethylenediamine and excess MEK (methyl ethyl ketone; 4-fold molar amount with respect to diamine) were refluxed at 80 ° C. for 24 hours, and the generated water was removed from the system. Thereafter, unreacted MEK was removed under reduced pressure to obtain a MEK ketiminate.

Production Example 2
Production of active hydrogen-containing compound (C-1) Trimellitic anhydride (192 parts) and benzyl alcohol (216 parts) are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and produced at 180 ° C. The reaction was carried out for 5 hours while distilling off the water to be produced, and then ethylene glycol (62 parts) was reacted at 140 ° C. for 5 hours while distilling off the water produced to remove the active hydrogen-containing compound (C-1). It was 434 as a result of measuring the hydroxyl value of the obtained active hydrogen containing compound (C-1), and calculating molecular weight.

Production Example 3
Production of active hydrogen-containing compound (C-2) Trimellitic anhydride (192 parts) and ethylene glycol (186 parts) are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube and produced at 140 ° C. The reaction was carried out for 5 hours while distilling off the water, and the active hydrogen-containing compound (C-2) was taken out. It was 342 as a result of measuring the hydroxyl value of the obtained active hydrogen containing compound (C-2), and calculating molecular weight.

Production Example 4
Production of active hydrogen-containing compound (C-3) Pyromellitic anhydride (218 parts) and benzyl alcohol (216 parts) are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and produced at 180 ° C. The reaction is allowed to proceed for 5 hours while distilling off the water, and then ethylene glycol (124 parts) is added, and the reaction is carried out for 5 hours while distilling off the water generated at 140 ° C. It was. It was 558 as a result of measuring the hydroxyl value of the obtained active hydrogen containing compound (C-3), and calculating molecular weight.

Comparative production example 1
Production of Comparative Active Hydrogen-Containing Compound (C-1 ′) Into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, phthalic anhydride (148 parts) and benzyl alcohol (108 parts) are placed at 180 ° C. After reacting for 5 hours while distilling off the produced water, ethylene glycol (62 parts) was added, and the reaction was conducted for 5 hours while distilling off the produced water at 140 ° C. to obtain an active hydrogen-containing compound (C-1 ′) Was taken out. The comparative active hydrogen-containing compound (C-1 ′) is monoethylene glycol monobenzyl ester of phthalic acid. It was 300 as a result of measuring the hydroxyl value of the obtained active hydrogen containing compound (C-1 '), and calculating molecular weight.

Production Example 5
Production of prepolymer solution (G-1) Polyethylene isophthalate diol (278.1 parts) with Mn of 2300 and polybutylene adipate diol with Mn of 1000 in a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube (417.2 parts), active hydrogen-containing compound (C-1) (16.0 parts), benzyl alcohol (5.3 parts) were charged, and the atmosphere was purged with nitrogen. And cooled to 50 ° C. Subsequently, methyl ethyl ketone (150.0 parts) and hexamethylene diisocyanate (132.0 parts) were added and reacted at 90 ° C. for 6 hours to obtain a prepolymer solution (G-1). The NCO content of the obtained prepolymer solution was 1.63%.

Production Example 6
Production of prepolymer solution (G-2) In a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, polyethylene isophthalate diol (271.3 parts) with Mn of 2300 and polybutylene adipate diol with Mn of 1000 (406.9 parts) and an active hydrogen-containing compound (C-1) (38.1 parts) were charged and purged with nitrogen, then heated to 110 ° C. with stirring and melted, and cooled to 50 ° C. Subsequently, methyl ethyl ketone (150.0 parts) and hexamethylene diisocyanate (132.4 parts) were added and reacted at 90 ° C. for 6 hours to obtain a prepolymer solution (G-2). The NCO content of the obtained prepolymer solution was 1.63%.

Production Example 7
Production of prepolymer solution (G-3) In a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, polyethylene isophthalate diol (282.5 parts) with Mn of 2300 and polybutylene adipate diol with Mn of 1000 (423.7 parts), active hydrogen-containing compound (C-2) (0.7 parts), benzyl alcohol (9.2 parts) were charged, and the atmosphere was purged with nitrogen. And cooled to 50 ° C. Subsequently, methyl ethyl ketone (150.0 parts) and hexamethylene diisocyanate (132.5 parts) were added and reacted at 90 ° C. for 6 hours to obtain a prepolymer solution (G-3). The NCO content of the obtained prepolymer solution was 1.63%.

Production Example 8
Production of prepolymer solution (G-4) In a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, polyethylene isophthalate diol (278.1 parts) with Mn of 2300 and polybutylene adipate diol with Mn of 1000 (417.2 parts), active hydrogen-containing compound (C-3) (16.0 parts), and benzyl alcohol (5.3 parts) were charged, and the atmosphere was purged with nitrogen. And cooled to 50 ° C. Subsequently, methyl ethyl ketone (150.0 parts) and hexamethylene diisocyanate (132.0 parts) were added and reacted at 90 ° C. for 6 hours to obtain a prepolymer solution (G-4). The NCO content of the obtained prepolymer solution was 1.63%.

Comparative production example 2
Production of prepolymer solution (G-1 ′) Polyethylene isophthalate diol (282.9 parts) with Mn of 2300 and polybutylene adipate with Mn of 1000 in a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube Diol (424.4 parts) and benzyl alcohol (9.34 parts) were charged and purged with nitrogen, then heated to 110 ° C. with stirring and melted, and cooled to 50 ° C. Subsequently, methyl ethyl ketone (150.0 parts) and hexamethylene diisocyanate (132.0 parts) were added and reacted at 90 ° C. for 6 hours to obtain a prepolymer solution (G-1 ′). The NCO content of the obtained prepolymer solution was 1.63%.

Comparative production example 3
Production of prepolymer solution (G-2 ′) Polyethylene isophthalate diol (280.2 parts) with Mn of 2300 and polybutylene adipate with Mn of 1000 in a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube Diol (420.3 parts) and benzyl alcohol (9.25 parts) were charged and purged with nitrogen, then heated to 110 ° C. with stirring and melted, and cooled to 50 ° C. Subsequently, methyl ethyl ketone (150.0 parts) and hexamethylene diisocyanate (138.9 parts) were added and reacted at 90 ° C. for 6 hours to obtain a prepolymer solution (G-2 ′). The NCO content of the obtained prepolymer solution was 2.03%.

Comparative production example 4
Production of prepolymer solution (G-3 ′) Polyethylene isophthalate diol (278.1 parts) with Mn of 2300 and polybutylene adipate with Mn of 1000 in a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube A diol (417.2 parts), a comparative active hydrogen-containing compound (C-1 ′) (16.0 parts), and benzyl alcohol (3.5 parts) were charged, purged with nitrogen, and heated to 110 ° C. with stirring. And then cooled to 50 ° C. Subsequently, methyl ethyl ketone (150.0 parts) and hexamethylene diisocyanate (132.0 parts) were added and reacted at 90 ° C. for 6 hours to obtain a prepolymer solution (G-3 ′). The NCO content of the obtained prepolymer solution was 1.63%.

Production Examples 9-12 and Comparative Production Examples 5-7
Production of Resin Particles (D-1) to (D-4) and (D-1 ′) to (D-3 ′) In a reaction vessel, a prepolymer solution and a stabilizer [Irganox 1010 manufactured by BASF Japan Ltd. ], Carbon black, MEK ketimine product of Production Example 1 was added and mixed, and the solid content concentration of polycarboxylic acid type anionic surfactant [Sansu Pearl PS-8 manufactured by Sanyo Chemical Industries, Ltd.] was 2% by weight. The aqueous solution was added and mixed for 1 minute at a rotation speed of 6000 rpm using an ultradisperser manufactured by Yamato Scientific Co., Ltd. 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. for 10 hours with stirring. After completion of the reaction, filtration and drying were performed to produce resin particles (D-1) to (D-4) and (D-1 ′) to (D-3 ′). In addition, the addition amount of each mixed component was described in Table 1.

Production Example 13
Production of resin particles (D-5) To a reaction vessel, a mixture of a polycarboxylic acid type anionic surfactant [Sanyo Pearl Industry Co., Ltd. Sanspear PS-8] having a solid content concentration of 5% by weight and methyl ethyl ketone was added, Hexamethylenediamine was added with stirring at a peripheral speed of 23 m / s (rotation speed: 10,000 rpm) using an ultradisperser manufactured by Yamato Scientific Co., Ltd. and mixed for 1 minute. Subsequently, the prepolymer solution (G-1) was added and mixed in 15 seconds, and mixed at a peripheral speed of 23 m / s for 2 minutes. 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. for 10 hours with stirring. After completion of the reaction, filtration and drying were performed to produce resin particles (D-5). In addition, the addition amount of each mixed component was described in Table 1.

Examples 1-6 and Comparative Examples 1-5
Next, in the Nauta mixer, resin particles (D), polyethylene glycol dibenzoate [manufactured by Sanyo Chemical Industries, Ltd .; Sunflex EB300], radical polymerizable unsaturated group-containing compound dipentaerythritol pentaacrylate [Sanyo Chemical Industries DA600], UV stabilizer bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (Mixture) [trade name: TINUVIN 765, manufactured by BASF Japan Ltd.] was added and impregnated at 70 ° C. for 4 hours. After 4 hours of impregnation, dimethylpolysiloxane [manufactured by Nippon Unicar Co., Ltd .; Kei L45-1000], carboxyl-modified silicon [manufactured by Shin-Etsu Chemical Co., Ltd .; X-22-3710], which are two types of internally added release agents Were mixed for 1 hour, and then cooled to room temperature. Finally, resin particle composition (P) was obtained by charging and mixing resin fine particles (E). The amount of each component added to (D) and the particle sizes of (D) and (E) are shown in Table 2.

Example 7
Carbon black and polyethylene glycol dibenzoate [manufactured by Sanyo Chemical Industries, Ltd .; Sunflex EB300] were premixed to prepare a colorant mixture. Radical polymerizable unsaturated group-containing compound dipentaerythritol pentaacrylate [manufactured by Sanyo Chemical Industries, Ltd .; DA600], UV stabilizer bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (mixture) [trade name: TINUVIN 765, manufactured by BASF Japan Ltd.] Dimethylpolysiloxane [Nihon Unicar Co., Ltd.] ); Kei L45-1000] and carboxyl-modified silicon [manufactured by Shin-Etsu Chemical Co., Ltd .; X-22-3710] were premixed to prepare an additive mixture. Next, the resin particles (D), the colorant mixture, and the additive mixture were put into a Nauta mixer and mixed for 2 hours. Finally, resin particle composition (P) was obtained by charging and mixing resin fine particles (E). The amount of each component added to (D) and the particle sizes of (D) and (E) are shown in Table 2.

In addition, commercially available polyvinyl chloride particles were used as (P-4 ′).
The following resin fine particles (E) were used.
(E-1); Methyl methacrylate / ethylene glycol dimethacrylate copolymer particles [copolymerization ratio 95: 5 (weight ratio), manufactured by Ganz Kasei Co., Ltd .; Ganzpearl PM030]
(E-2); Methyl methacrylate / ethylene glycol dimethacrylate copolymer particles [copolymerization ratio 95: 5 (weight ratio), manufactured by Ganz Kasei Co., Ltd .; Ganzpearl PM010J]
(E-3); N-cyclohexylmaleimide polymer particles having a crosslinked structure [DIC Corporation; POLYTON ASSISTER TPU-9527]

<Volume average particle diameter measuring method>
The particle diameters of resin particles (D-1) to (D-5), (D-1 ′) to (D-4 ′) and (E-1) to (E-3) were measured using a Microtrac HRA particle size analyzer. It measured using 9320-X100 (made by Nikkiso Co., Ltd.).

<Flow time>
Resin particle compositions (P-1) to (P-7) and (P-1 ′) to (P-5 ′) having a volume of 100 cm ³ are JIS K6720-2 (1999) at a temperature of 23 ° C. and a relative humidity of 50%. Year) The time for flowing down a bulk specific gravity measuring device (manufactured by Tokyo Kurochi Scientific Instruments) specified by bulk specific gravity measurement was measured.

<Production of epidermis>
The resin particle compositions (P-1) to (P-7) and (P-1 ′) to (P-5 ′) for slush molding are applied to a Ni electromold having a grain pattern preheated to 230 ° C. After filling, the excess resin particle composition was discharged after 10 seconds. After 60 seconds, it was cooled with water to prepare a skin (thickness 1 mm).

<Soft feeling at low temperatures>
A molded skin with a thickness of 1 mm was cut into a size of 30 mm length and 5 mm width, and the storage elastic modulus was measured. The storage elastic modulus was measured in the range from −80 ° C. to 100 ° C. at a frequency of 11 Hz using a viscoelasticity measuring device, Rheogel E4000 (manufactured by UBM). The lower the storage modulus, the higher the soft feeling.

<Moldability>
Form an indentation with a depth of 1 mm and a width of 0.5 mm on a Ni electroforming mold with a texture pattern (the side and bottom of the indent intersect at right angles), and apply the epidermis (thickness 1 mm) under the same conditions as the preparation of the above-mentioned epidermis. Since the epidermis which was produced and entered into the indented portion has a protrusion shape, the shape was visually observed.
Evaluation was made according to the following criteria.
○: There is a corner in the protrusion.
(Triangle | delta): The part with a corner | angular part and the part with a corner | corner are mixed in a projection part.
X: The protrusion has no corners.
In addition, the angle | corner in the above means the angle | corner (edge) of the protrusion part of an outer skin formed in the part which the side surface and bottom face of the hollow of Ni electroforming mold intersect, and this corner reproduces the shape of the hollow in Ni electroforming mold. The more it is formed, the better the moldability of the convex part.

<Heat resistance (heat fusion test)>
A 1 mm thick molded skin is cut into a size of 60 mm in length and 95 mm in width, and a depth of 0.4 to 0. 0 is formed on the back surface of the sheet at a right angle to the surface with a cold cutter (blade thickness 0.3 mm). A cut of 6 mm and a length of 60 mm was made. Put the molding skin between the release paper and put the iron plate with the weight of 95-100g from the top of the release paper and the dimensions (vertical, horizontal, height) 100mm vertical x 100mm horizontal x 1.2mm thick so that the release paper is hidden in the air Then, after standing at 130 ° C. under normal pressure for 100 hours and 200 hours, it was visually observed whether or not the cuts of the sheet were fused.
Evaluation was made according to the following criteria.
○: Cutter cuts are not fused at all.
Δ: The cut line of the cutter is partially fused.
X: The cut of the cutter is fused.

  A molded article, for example, a skin formed from the thermoplastic urethane (urea) resin particle composition of the present invention is suitably used as a skin for automobile interior materials, for example, instrument panels and door trims.

Claims (4)

Urethane (urea) resin particles containing a thermoplastic urethane (urea) resin (U) having a residue (j) obtained by removing a hydroxyl group from a trivalent or higher aromatic polycarboxylic acid and having a volume average particle size of 50 to 500 μm (D) and a resin containing a thermoplastic resin and / or a thermosetting resin having a melting temperature higher than the melting temperature of the urethane (urea) resin (U) and having a volume average particle size of 0.01 to 5 μm The thermoplastic urethane (urea) resin (U) contains fine particles (E) and has a structural unit (x) represented by the general formula (1). When the aromatic polycarboxylic acid is benzene polycarboxylic acid and the number of carboxyl groups is 3, the substitution position of the carboxyl group is 1,2,4-position, and when the number of carboxyl groups is 4, the substitution of the carboxyl group Position is 1, 2 , 4,5-position or 1,2,3,5-position thermoplastic urethane (urea) resin particle composition (P) for slush molding.

[In the formula, R ¹ represents a monovalent or polyvalent monovalent group or hydroxyl group from the active hydrogen-containing compound except one active hydrogen is a hydroxyl group-containing compound; R ¹ each identical when a plurality But it may be different; R ² represents a divalent group from divalent active hydrogen-containing compound is a hydroxyl group-containing compound obtained by removing two active hydrogen, or different from each R ² when there are a plurality of identical Y represents a trivalent or higher group obtained by removing all carboxyl groups from a trivalent or higher aromatic polycarboxylic acid; the aromatic ring of Y is composed of a carbon atom, and the carbon atom has a carboxyl group Other substituents and / or halogen atoms may be bonded, but at least one of them is not bonded to a substituent; a represents an integer of 1 or more, and b represents an integer of 0 or more. And 3 ≦ a + b ≦ -1 is satisfied; d is the number of hydrogen atoms bonded to the carbon atoms constituting the aromatic ring when all the substituents including the carboxyl group of the aromatic polycarboxylic acid are replaced with hydrogen atoms, that is, on the aromatic ring This represents the number of sites that can be substituted. ] Claims wherein the urethane (urea) resins (U), the resulting formula (2) an active hydrogen-containing compound represented by the active hydrogen component containing (A) and the isocyanate component (B) and (C) are reacted Item 4. The urethane (urea) resin particle composition according to Item 1 .

[In the formula, R ¹ represents a monovalent or polyvalent monovalent group or hydroxyl group from the active hydrogen-containing compound except one active hydrogen is a hydroxyl group-containing compound; R ¹ each identical when a plurality But it may be different; R ² represents a divalent group from divalent active hydrogen-containing compound is a hydroxyl group-containing compound obtained by removing two active hydrogen, or different from each R ² when there are a plurality of identical Y represents a trivalent or higher group obtained by removing all carboxyl groups from a trivalent or higher aromatic polycarboxylic acid; the aromatic ring of Y is composed of a carbon atom, and the carbon atom has a carboxyl group Other substituents and / or halogen atoms may be bonded, but at least one of them is not bonded to a substituent; a represents an integer of 1 or more, and b represents an integer of 0 or more. And 3 ≦ a + b ≦ -1 is satisfied; d is the number of hydrogen atoms bonded to the carbon atoms constituting the aromatic ring when all the substituents including the carboxyl group of the aromatic polycarboxylic acid are replaced with hydrogen atoms, that is, on the aromatic ring This represents the number of sites that can be substituted. ] The content of the structural unit represented by the general formula (1) (x) is a urethane (urea) according to claim 1 or 2 wherein the weight of the weight of the resin (U) is 0.1 to 30% by weight based thermoplastic urethane (urea) resin particles composition. The thermoplastic urethane (urea) resin particle composition according to any one of claims 1 to 3, wherein the resin fine particles (E) are thermosetting resin fine particles.