JP2013241573A - Urethane (urea) resin particle composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic polyurethane (urea) resin excellent in mechanical properties of a molding, excellent in thermal aging resistance and light aging resistance or the like and excellent in sense of touch after thermal aging.SOLUTION: A thermoplastic urethane (urea) resin particle composition (P) includes: a urethane (urea) resin particle (D) that contains a thermoplastic urethane (urea) resin (U) that has a residue (j) that excludes a hydroxyl group from an at least trivalent aromatic polycarboxylic acid; and a compound (E) that contains at least two radically polymerizable unsaturated groups in a molecule, wherein the (E) exists in the (D) and/or in an outside of the (D).

Description

  The present invention relates to a urethane (urea) resin particle composition.

As a polyurethane resin-based slush molding material with excellent heat aging resistance, photo-aging resistance, etc., instead of the soft polyvinyl chloride powder conventionally used in the slush molding method, radical polymerizable unsaturated groups are A polyurethane resin powder containing a compound containing two or more compounds has been proposed (for example, Patent Documents 1 and 2).
However, even in this method, there is a problem that although the resin strength is deteriorated after heat aging, coloring (fading) with time, and gloss increase are small, the skin after heat aging becomes hard and the feel is poor.
In addition, there is a need to reduce the weight of automobile parts for the purpose of improving fuel efficiency, and as a means for reducing the weight of automobile interior materials, a means for thinning a slush molded product can be considered. However, since the mechanical properties of the molded product are lowered by making the film thinner, it is necessary to provide stronger mechanical properties.

JP 2001-192549 A Japanese Patent Laid-Open No. 2004-204242

  An object of the present invention is to provide a thermoplastic polyurethane (urea) resin having excellent mechanical properties of a molded product, excellent heat aging resistance, photoaging resistance, and the like, and excellent tactile sensation after heat aging.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention. That is, the present invention includes urethane (urea) resin particles (D) 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, A thermoplastic urethane (urea) resin particle composition comprising a compound (E) containing two or more radically polymerizable unsaturated groups in the molecule, wherein (E) is the one in (D) And / or a thermoplastic urethane (urea) resin particle composition (P) present outside (D).

  The molded product obtained from the thermoplastic urethane (urea) resin particle composition (P) of the present invention is excellent in mechanical properties, excellent in heat aging resistance, photoaging resistance, etc., and excellent in touch after heat aging. .

  The thermoplastic urethane (urea) resin particle composition (P) of the present invention has a urethane (urea) resin particle (D) containing a thermoplastic urethane (urea) resin (U) and a radical polymerizable unsaturated group. And a compound (E) containing two or more thereof.

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

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

  The structural unit (x) represented by the general formula (1) is activated when, for example, a thermoplastic urethane (urea) resin (U) is obtained by reacting an active hydrogen component (A) and an isocyanate component (B). By using the active hydrogen-containing compound (C) represented by the general formula (2) as part of the hydrogen component (A), it can be introduced into (U).

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 a carbon atom, 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 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) includes a hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, a thiol group-containing compound, and a phosphate compound having 1 to 30 carbon atoms; Compounds having hydrogen-containing functional groups are included.

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, methylglucoside and derivatives thereof; phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8 Phenols such as tetrahydroxynaphthalene, anthrol, 1,4,5,8-tetrahydroxyanthracene and 1-hydroxypyrene; polybutadiene polyols; castor oil-based polyols; (co) polymers of hydroxyalkyl (meth) acrylates and polyvinyl alcohol, etc. Polyfunctional polyols (for example, having 2 to 100 functional groups) polyol, condensates of phenol and formaldehyde (novolak), and polyphenols described in US Pat. No. 3,265,641. Among these, monovalent alcohols having 1 to 12 carbon atoms are preferred from the viewpoints of productivity, low-temperature meltability and mechanical properties (elongation, tensile strength) and heat aging resistance of molded products, and particularly preferred are 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; dicarboxylic acids and excess polyamines Polyamines obtained by condensation with polyamines; polyether polyamines; hydrazines (such as hydrazine and monoalkylhydrazines), dihydrazides ( Etc. Haq acid dihydrazide and dihydrazide terephthalic acid), 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, naphthalene-1,4-dicarboxylic acid, diphenic acid, 2,3-anthracene Examples thereof include aromatic dicarboxylic acids having 8 to 18 carbon atoms such as dicarboxylic acids and pyrene dicarboxylic acids.

  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 divalent from the viewpoint of achieving both low-temperature meltability of urethane (urea) resin molding, mechanical properties (elongation, tensile strength) and heat aging resistance. And more preferable are 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, Preference is given to 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.

  As the arrangement of substituents on Y, from the viewpoint of improving mechanical properties, in the case of a trivalent aromatic polycarboxylic acid, two carbonyl groups are adjacent to each other, and the third carbonyl group is combined with the first or second carbonyl group. A structure in which a hydrogen atom is arranged between carbonyl groups is preferable, and in the case of an aromatic polycarboxylic acid having a valence of 4 or more, two carbonyl groups are adjacent to each other, and the third and subsequent carbonyl groups are combined with the first or second carbonyl group. A structure in which a hydrogen atom is arranged between carbonyl groups 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 trivalent or higher valent aromatic polycarboxylic acid (YH), a divalent active hydrogen-containing compound (R ² H), and an active hydrogen-containing compound (R ¹ H). It can also be obtained by subjecting AO such as EO and PO to a carboxyl group instead of dehydrating condensation reaction at a ratio satisfying a and b specified in (2) or dehydrating condensation reaction of (R ² H). It is possible. 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.

  The content of the structural unit (x) represented by the general formula (1) in (U) is from the viewpoint of compatibility between the meltability of the urethane (urea) resin particles, the mechanical strength of the molded product, and the heat aging resistance ( Based on the weight of U), it is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and particularly preferably 1.0 to 10.0% by weight.

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

  In the case where (U) is a urethane (urea) resin (U1) having a structural unit (x1) where a is 1 in the general formulas (1) and (2), the meltability and the mechanical strength of the molded product From the viewpoint of coexistence of heat aging resistance, the content of the structural unit (x1) in (U) is preferably 0.1 to 5% by weight on the basis of the weight of (U1), more preferably 0.8. 5 to 4% by weight, particularly preferably 1 to 3% by weight.

  When (U) is a urethane (urea) resin (U2) having a structural unit (x2) in which a is 2 in the general formulas (1) and (2), the meltability, the mechanical strength of the molded product, and the heat aging resistance From the viewpoint of coexistence, the content of the structural unit (x2) in (U) is preferably 0.1 to 3% by weight, more preferably 0.1 to 2% by weight, based on the weight of (U2). %, Particularly preferably 0.1 to 1% by weight.

  In the thermoplastic 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). Examples include 500 or more high molecular diols (a1), low molecular diamines (a2), low molecular diols (a3) having a Mn of less than 500, and monools (a4).

  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 AO is added to two hydroxyl group-containing compounds (for example, the low molecular diol, divalent phenols and the like). 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 AO to dihydric phenols, and more preferred are those obtained by adding EO to divalent 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, and polytetramethylene glycol.

  As the polymer diol (a1), it is preferable to use a polyester diol from the viewpoint of heat aging resistance and photoaging 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, alicyclic diamines and aliphatic diamines are preferred, and isophorone diamine and hexamethylene diamine are particularly preferred.

  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 AO adducts (molecular weight 500) Less) 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. Of 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 thermoplastic 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. Among these, preferred are aliphatic diisocyanates or alicyclic diisocyanates, and particularly preferred are HDI, IPDI, and hydrogenated MDI.

Examples of the method for synthesizing the thermoplastic 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-based catalysts [triethylamine, N-ethylmorpholine, triethylenediamine and the like], tin-based catalysts [trimethyltin laurate, dibutyltin dilaurate, dibutyltin malate, and the like].

The melt viscosity at 190 ° C. of the thermoplastic urethane (urea) resin (U) is preferably 500 to 2000 Pa · s, more preferably from the viewpoint of good meltability of the urethane (urea) resin particles (D). 500 to 1000 Pa · s. The melt viscosity is measured by, for example, using a flow tester CFT-500 manufactured by Shimadzu Corporation and raising the temperature at a constant speed under the following conditions.
Load: 5kg ・ f
Die: hole diameter 0.5mm, length 1.0mm
Temperature increase rate: 5 ° C / min

The storage elastic modulus G ′ at 130 ° C. of the thermoplastic urethane (urea) resin (U) is preferably 0.2 to 10 MPa, more preferably from the viewpoint of good heat aging resistance and good meltability of the urethane resin particles. Is 0.5 to 2 MPa. The storage elastic modulus G ′ is measured by the following operation under the condition of a frequency of 1 Hz using, for example, a dynamic viscoelasticity measuring device “RDS-2” (manufactured by Rheometric Scientific).
After setting the measurement sample on the jig of the measuring device (the diameter of the jig: 8 mm), the temperature is raised to 200 ° C., melted at 200 ° C. for 1 minute, and then cooled and solidified to be in close contact with the jig and measured. To start. The measurement temperature range is 50 to 200 ° C., and by measuring the melt viscoelasticity between these temperatures, curves of temperature-G ′ and temperature-G ″ can be obtained. The storage elastic modulus G ′ at 130 ° C. is , Read from the curve of temperature-G ′.

  By using the thermoplastic urethane (urea) resin (U) as the urethane (urea) resin particles (D), application to not only a slush molding powder but also a hot-melt adhesive or the like becomes possible. The urethane (urea) resin particles (D) are obtained, for example, as an emulsion / dispersion when producing a thermoplastic urethane (urea) resin (U), and are then solid-liquid separated and dried, or are in the form of a lump or pellet. It can be obtained by a production method such as grinding thermoplastic urethane (urea) resin (U).

The method for obtaining the urethane (urea) resin particles (D) as a dispersion is not particularly limited. For example, the method (1) in the method for synthesizing the thermoplastic urethane (urea) resin (U), more specifically, Examples include the methods described in International Publication No. 2011/070784 and International Publication No. 2013/018747.

  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.), Nanomizer (Nanomizer Co., Ltd.), High pressure emulsifiers such as APV Gaurin (manufactured by Gaurin), membrane emulsifiers (manufactured by Chilling Industries) Emulsifier, Vibro Mixer (Hiyaka Kogyo) vibrating emulsifier such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Preferable from the viewpoint of the inner particle size distribution is APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer.

  As a method for producing the bulk or pellet thermoplastic urethane (urea) resin (U), for example, a batch type kneader such as a kneader, a screw type 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 10 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 the value when the cumulative amount is 50% in the relative cumulative particle size distribution curve measured using a laser diffraction type particle size distribution measuring apparatus [for example, “Microtrac MT3000II” manufactured by Nikkiso Co., Ltd.]. Means particle size (d ₅₀ ).

<Compound (E) containing two or more radically polymerizable unsaturated groups in the molecule>
As the compound (E) containing two or more radically polymerizable unsaturated groups in the molecule used in the present invention, (meth) acrylic acid and polyhydric alcohols (2 to 10 or higher polyhydric alcohols). And the like, etc.] [Ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc.]]; (meth) allyl alcohol and Esters with 2 to 6 or more polyvalent carboxylic acids [eg diallyl phthalate, trimellitic acid triallyl ester, etc.]; poly (meth) allyl ethers of polyhydric alcohols [eg pentaerythritol tri (meth) allyl ether] Etc.]; Polyvinyl alcohol of polyhydric alcohols Le [such as ethylene glycol divinyl ether, etc.]; polyhydric alcohols Polypropylene ether-[such as ethylene glycol dipropionate propenyl ether, etc.] of; polyvinyl benzenes [such as divinylbenzene, etc.], and mixtures of two or more thereof.

  Among these, preferred are esters of (meth) acrylic acid and polyhydric alcohols in terms of radical polymerization rate, and particularly preferred are trimethylolpropane tri (meth) acrylate and pentaerythritol tetra (meth). Acrylate and dipentaerythritol penta (meth) acrylate.

  (E) The number of unsaturated groups (non-conjugated double bonds) in one molecule is usually 2 to 10, preferably 3 to 6. If the number of functional groups is less than 2, the molded skin fades over time and gloss increases, and if it exceeds 10, the compound (E) has a high molecular weight, resulting in a high viscosity and difficult handling. (E) captures radicals generated when the thermoplastic urethane (urea) resin (U) is deteriorated by light (ultraviolet rays) or heat, and (E) itself is polymerized. It has the effect of suppressing a decrease in resin strength, fading over time, and an increase in gloss.

  The amount of (E) used in the present invention is preferably 0.1 to 10% by weight, more preferably 0.5 to 8% by weight, based on the weight of the urethane (urea) resin particles (D). When the number of added parts is 0.1% by weight or more, the decrease in resin strength after the heat aging test is small.

  When (E) is a liquid, by mixing urethane (urea) resin particles (D) and (E), (E) is soaked in (D), and (E) is impregnated in (D). A thermoplastic urethane (urea) resin particle composition (P) is obtained.

  As a mixing device used when impregnating or mixing a compound (E) containing two or more radically polymerizable unsaturated groups in the molecule with urethane (urea) resin particles (D), a known powder mixing device is used. Any of a container rotation type mixer, a fixed container type mixer, and a fluid motion type mixer can be used. For example, as a fixed container type mixer, a high-speed flow type mixer, a double-shaft paddle type mixer, a high-speed shear mixer [Hensiel mixer (registered trademark), etc.], a low-speed mixer (planetary mixer, etc.), and a conical screw mixer [Nauta mixer (registered trademark, omitted below), etc.] are preferable, and among these, a double-shaft paddle type mixer, a low speed mixing device (planetary mixer, etc.) and a conical screw mixer (Nauta mixer, etc.) are preferable. It is.

  The urethane (urea) resin particles (D) may contain a compound (E) and an additive (F) in addition to the thermoplastic urethane (urea) resin (U). Further, the thermoplastic urethane (urea) resin particle composition (P) may contain (F) in addition to (D) and (E).

Examples of the additive (F) include inorganic fillers, pigments, plasticizers, mold release agents, anti-rocking agents (powder fluidity improvers), antioxidants and ultraviolet absorbers.
The addition amount of the additive (F) is preferably 0 to 50% by weight, more preferably 1 to 30% by weight, based on the weight of the thermoplastic 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). However, when the additive (F) is a plasticizer, a release agent or an anti-blocking agent (powder fluidity improver), it is preferably added after the production of the urethane (urea) resin particles (D).

  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 diameter of the inorganic filler is preferably 0.1 to 30 μm, more preferably 1 to 20 μm, and particularly preferably 5 to 10 μm, from the viewpoint of dispersibility in the thermoplastic resin.
The addition 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 thermoplastic 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. 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 addition amount of the pigment is usually 10% by weight or less, preferably 0.01 to 5% by weight, more preferably 1 to 3% by weight, based on the weight of the thermoplastic 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, tributoxy phosphate, etc.); aromatic phosphate ester [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 thermoplastic urethane (urea) resin (U).

As the mold release agent, a known mold release agent or the like can be used. Fluorine compound type mold release agents [Triperfluoroalkyl phosphate (carbon number: 8 to 20) 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) Amide and ethylenediamine diste 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 amount of the release agent added is preferably 0 to 1% by weight, more preferably 0.1 to 0.5% by weight, based on the weight of the thermoplastic urethane (urea) resin (U).

As an anti-blocking agent (powder fluidity improver), known inorganic anti-blocking agents, organic anti-blocking agents and the like can be used. Examples of the inorganic blocking inhibitor include silica, talc, titanium oxide and calcium carbonate. Examples of the organic blocking inhibitor include thermosetting resins having a particle size of 10 μm or less (thermosetting polyurethane resin, guanamine-based resin, epoxy resin, etc.) and thermoplastic resins having a particle size of 10 μm or less [thermoplastic polyurethane urea resin and poly ( Meth) acrylate resin etc.].
The addition amount of the antiblocking agent (fluidity improver) is preferably 0 to 5% by weight, more preferably 0.5 to 1% by weight, based on the weight of the thermoplastic urethane (urea) resin (U). .

  Antioxidants include phenolic [2,6-di-t-butyl-p-cresol and butylated hydroxyanisole, etc.]; bisphenol [2,2′-methylenebis (4-methyl-6-t-butylphenol) Etc.]; phosphorus-based [triphenyl phosphite and diphenylisodecyl phosphite etc.] and the like.

  Examples of the ultraviolet absorber include benzophenone [2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone and the like]; benzotriazole [2- (2′-hydroxy-5′-methylphenyl) benzotriazole and the like]; Salicylic acid type [phenyl salicylate and the like]; hindered amine type [bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like] and the like.

  The addition amount of the antioxidant and the ultraviolet absorber is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, based on the weight of the thermoplastic urethane (urea) resin (U).

  As a mixing device when the urethane (urea) resin particles (D) are obtained and then mixed with the additive (F), the urethane (urea) resin particles (D) have two radically polymerizable unsaturated groups in the molecule. The thing similar to what was illustrated as a mixing apparatus used when impregnating or mixing the compound (E) contained above is mentioned, A preferable thing is also the same.

  The volume average particle diameter of the thermoplastic urethane (urea) resin particle composition (P) is preferably 10 to 500 μm, more preferably 70 to 300 μm.

The thermoplastic urethane (urea) resin particle composition (P) of the present invention is particularly useful as a material for producing a urethane (urea) resin molded product such as a skin by a slush molding method. 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 of the thermoplastic urethane (urea) resin particle composition (P) is preferably 0.3 to 1.5 mm.
The thermoplastic urethane (urea) 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 thermoplastic urethane (urea) 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
Preparation of methyl ethyl ketone (hereinafter abbreviated as MEK) ketimine product of diamine Hexamethylenediamine and excess MEK (4 times molar amount with respect to diamine) were refluxed at 80 ° C. for 24 hours to remove the generated water out of 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) Ethyl acetate (384 parts) was charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and then trimellitic anhydride (192 parts), ethylene glycol (62 parts) and triethylamine (202 parts) were added and reacted at 80 ° C. for 2 hours, and then benzyl chloride (252 parts) was added and reacted at 70 ° C. for 2 hours. Thereafter, liquid separation and solvent removal were performed to obtain an active hydrogen-containing compound (C-1). As a result of measuring the hydroxyl value of the active hydrogen-containing compound (C-1) and calculating the molecular weight, it was 434. The structure of (C-1) [a and b in the general formula (2)] is shown in Table 1. The following (C-2) to (C-4) are also described in Tables 1-2.

Production Example 3
Production of active hydrogen-containing compound (C-2) Trimellitic anhydride (192 parts) and benzyl alcohol (216 parts) are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 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 for 5 hours while distilling off the water produced at 140 ° C. to obtain an active hydrogen-containing compound (C-2). As a result of measuring the hydroxyl value of the active hydrogen-containing compound (C-2) and calculating the molecular weight, it was 434.

Production Example 4
Production of active hydrogen-containing compound (C-3) In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, trimellitic anhydride (192 parts) and benzyl alcohol (108 parts) were added 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 produced at 140 ° C. to obtain an active hydrogen-containing compound (C-3). It was. It was 388 as a result of measuring the hydroxyl value of the obtained active hydrogen containing compound (C-3), and calculating molecular weight.

Production Example 5
Production of active hydrogen-containing compound (C-4) Pyromellitic anhydride (254 parts) and ethylene glycol (248 parts) were placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and produced at 140 ° C. The reaction was carried out for 5 hours while distilling off the water to obtain an active hydrogen-containing compound (C-4). It was 430 as a result of measuring the hydroxyl value of the obtained active hydrogen containing compound (C-4), and calculating molecular weight.

Production Example 6
Production of prepolymer solution (G-1) Polyethylene isophthalate diol (93.1 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 (349.6 parts), active hydrogen-containing compound (C-1) (6.0 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 (400.3 parts), hexamethylene diisocyanate (112.9 parts) and isophorone diisocyanate (3.8 parts) were added and reacted at 90 ° C. for 6 hours. Subsequently, after cooling to 70 degreeC, antioxidant [BASF Japan Co., Ltd. product Irganox 1010] (2.7 parts) was added, and it mixed uniformly, and obtained the prepolymer solution (G-1). The NCO content of the obtained prepolymer solution was 1.26%.

Production Example 7
Production of prepolymer solution (G-2) 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-2) (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. Subsequently, after cooling to 70 degreeC, antioxidant [BASF Japan Co., Ltd. product Irganox 1010] (1.4 parts) was added, and it mixed uniformly, and obtained the prepolymer solution (G-2). The NCO content of the obtained prepolymer solution was 1.63%.

Production Example 8
Production of prepolymer solution (G-3) In a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, polyethylene isophthalate diol (281.2 parts) with Mn of 2300 and polybutylene adipate diol with Mn of 1000 (421.8 parts), an active hydrogen-containing compound (C-3) (3.5 parts), and benzyl alcohol (9.2 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 (132.9 parts) were added and reacted at 90 ° C. for 6 hours. Subsequently, after cooling to 70 degreeC, antioxidant [BASF Japan Co., Ltd. product Irganox 1010] (1.4 parts) was added, and it mixed uniformly, and obtained the prepolymer solution (G-3). The NCO content of the obtained prepolymer solution was 1.63%.

Production Example 9
Production of prepolymer solution (G-4) In a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, polyethylene isophthalate diol (192.7 parts) with Mn of 2300 and polybutylene adipate diol with Mn of 1000 (289.0 parts), active hydrogen-containing compound (C-3) (178.2 parts) and 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 (179.6 parts) were added and reacted at 90 ° C. for 6 hours. Subsequently, after cooling to 70 degreeC, antioxidant [BASF Japan Co., Ltd. product Irganox 1010] (1.4 parts) was added, and it mixed uniformly, and obtained the prepolymer solution (G-4). The NCO content of the obtained prepolymer solution was 1.63%.

Production Example 10
Production of prepolymer solution (G-5) In a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, polyethylene isophthalate diol (273.1 parts) with Mn of 2300 and polybutylene adipate diol with Mn of 1000 (409.7 parts), active hydrogen-containing compound (C-4) (0.45 parts), and benzyl alcohol (13.07 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 (140.9 parts) were added and reacted at 90 ° C. for 6 hours. Subsequently, after cooling to 70 degreeC, antioxidant [BASF Japan Co., Ltd. product Irganox 1010] (1.4 parts) was added, and it mixed uniformly, and obtained the prepolymer solution (G-5). The NCO content of the obtained prepolymer solution was 1.63%.

Comparative production example 1
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. Subsequently, after cooling to 70 degreeC, antioxidant [BASF Japan Co., Ltd. product Irganox 1010] (1.4 parts) was added, and it mixed uniformly, and obtained the prepolymer solution (G-1 '). . The NCO content of the obtained prepolymer solution was 1.63%.

Example 1
Production of thermoplastic urethane urea resin particle composition (P-1) In a reaction vessel, prepolymer solution (G-1) obtained in Production Example 6 (100 parts), carbon black (1 part), MEK of Production Example 1 Ketimine compound (3.2 parts) was added and mixed, and a 2% by weight aqueous solution (300 parts) of a solid content concentration of polycarboxylic acid type anionic surfactant [Sanspear PS-8 manufactured by Sanyo Chemical Industries, Ltd.] was added. In addition, it was 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 carried out to produce urethane urea resin particles (D-1). Mn of (D-1) was 20,000, and the volume average particle diameter was 145 μm.

  Next, in a Nauta mixer, urethane urea resin particles (D-1) (100 parts), polyethylene glycol dibenzoate [manufactured by Sanyo Chemical Industries, Ltd .; Sunflex EB-300] (8 parts), radical polymerizability Dipentaerythritol pentaacrylate (E-1) as a compound containing two or more unsaturated groups in the molecule (manufactured by Sanyo Chemical Industries, Ltd .; Neomer DA-600) (1.0 part), as an ultraviolet absorber Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidylsebacate (mixture) [trade name: TINUVIN 765, BASF Japan Co., Ltd.] (0.3 parts) was added and impregnated at 70 ° C. for 4 hours. Subsequently, dimethylpolysiloxane [made by Nippon Unicar Co., Ltd .; L45-1000] (0.06 parts), carboxyl-modified silicon [made by Shin-Etsu Chemical Co., Ltd .; 3710] (0.05 parts) was added, mixed for 1 hour, and then cooled to room temperature. Finally, a crosslinked urethane polymethylmethacrylate [Gantz Kasei Co., Ltd .; Gantz Pearl PM-030S] (0.5 part) as an antiblocking agent is added and mixed to form a thermoplastic urethane urea resin particle composition (P-1). Got. The volume average particle size of (P-1) was 148 μm.

  In addition, Mn of the urethane urea resin in an Example was measured by the gel permeation chromatography using "HLC-8120" by Tosoh Corporation. Tetrahydrofuran was used as the solvent, polystyrene was the standard substance, the sample concentration was 0.25% by weight, two “TSK GEL GMH6” manufactured by Tosoh Corporation were used as the column stationary phase, and the column temperature was 40 ° C. It was.

Example 2
Production of Thermoplastic Urethane Urea Resin Particle Composition (P-2) Thermoplastic urethane in the same manner as in Example 1 except that the number of added parts of dipentaerythritol pentaacrylate (E-1) was changed to 0.1 part. A urea resin particle composition (P-2) was obtained. The volume average particle size of (P-2) was 148 μm.

Example 3
Production of thermoplastic urethane urea resin particle composition (P-3) A thermoplastic urethane urea resin in the same manner as in Example 1 except that the number of added parts of dipentaerythritol pentaacrylate (E-1) was changed to 10 parts. A particle composition (P-3) was obtained. The volume average particle size of (P-3) was 148 μm.

Example 4
Production of Thermoplastic Urethane Urea Resin Particle Composition (P-4) Urethane urea was produced in the same manner as in Example 1 except that the prepolymer solution (G-2) was used instead of the prepolymer solution (G-1). Resin particles (D-2) were produced. Mn of (D-2) was 20,000, and the volume average particle diameter was 145 μm.
Furthermore, a thermoplastic urethane urea resin particle composition (P-4) was obtained in the same manner as in Example 1 except that (D-2) was used instead of the urethane urea resin particles (D-1). The volume average particle size of (P-4) was 148 μm.

Example 5
Production of Thermoplastic Urethane Urea Resin Particle Composition (P-5) Urethane urea was produced in the same manner as in Example 1 except that the prepolymer solution (G-3) was used instead of the prepolymer solution (G-1). Resin particles (D-3) were produced. Mn of (D-3) was 20,000, and the volume average particle diameter was 158 μm.
Furthermore, instead of urethane urea resin particles (D-1), (D-3) is used instead of dipentaerythritol pentaacrylate (E-1), trimethylolpropane triacrylate (E-2) [Daicel Cytec Co., Ltd. Thermoplastic urethane urea resin particle composition (P-5) was obtained in the same manner as in Example 1 except for using TMPTA]. The volume average particle diameter of (P-5) was 160 μm.

Example 6
Production of thermoplastic urethane urea resin particle composition (P-6) The same operation as in Example 1 was carried out except that the prepolymer solution (G-4) was used instead of the prepolymer solution (G-1). Urethane urea resin particles (D-4) were produced. Mn of (D-4) was 20,000, and the volume average particle size was 152 μm.
Furthermore, urethane urea resin particles (D-4) are used instead of urethane urea resin particles (D-1), and trimethylolpropane triacrylate (E-2) is used instead of dipentaerythritol pentaacrylate (E-1). Except for the above, the same operation as in Example 1 was performed to obtain a thermoplastic urethane urea resin particle composition (P-6). The volume average particle diameter of (P-6) was 154 μm.

Example 7
Production of thermoplastic urethane urea resin particle composition (P-7) The same operation as in Example 1 was carried out except that the prepolymer solution (G-5) was used instead of the prepolymer solution (G-1). Urethane urea resin particles (D-5) were produced. Mn of (D-5) was 26,000, and the volume average particle diameter was 146 μm.
Further, the same operation as in Example 1 was carried out except that the urethane urea resin particles (D-5) were used in place of the urethane urea resin particles (D-1), and a thermoplastic urethane urea resin particle composition (P-7) was obtained. ) The volume average particle diameter of (P-7) was 148 μm.

Example 8
Production of Thermoplastic Urethane Urea Resin Particle Composition (P-8) In a reaction vessel, a polycarboxylic acid type anionic surfactant [Sansu Pearl PS-8 manufactured by Sanyo Chemical Industries Co., Ltd.] aqueous solution with a solid content concentration of 5% by weight ( 236 parts) and MEK (70.5 parts) were added, and hexamethylenediamine (2.2) was stirred with an ultradisperser manufactured by Yamato Scientific Co., Ltd. under a peripheral speed of 23 m / s (rotation speed: 10,000 rpm). Part) was added and mixed for 1 minute. Subsequently, the prepolymer solution (G-1) (100 parts) was added and mixed in 15 seconds, and mixed at a peripheral speed of 23 m / s for 2 minutes. The mixture was transferred to a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen blowing tube, purged with nitrogen, and reacted at 50 ° C. for 10 hours with stirring. After completion of the reaction, filtration and drying were performed to produce urethane urea resin particles (D-6). Mn of (D-6) was 20,000, and the volume average particle diameter was 165 μm.
Next, carbon black (1 part) and polyethylene glycol dibenzoate [manufactured by Sanyo Chemical Industries, Ltd .; Sunflex EB-300] (8 parts) were premixed to prepare a colorant mixture. Dipentaerythritol pentaacrylate (E-1) as a compound containing two or more radically polymerizable unsaturated groups in the molecule [manufactured by Sanyo Chemical Industries, Ltd .; Neomer DA-600] (1.0 part), Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidylsebacate (mixture) as UV absorbers [trade name : TINUVIN 765, manufactured by BASF Japan Ltd.] (0.3 parts), dimethylpolysiloxane [manufactured by Nippon Unicar Co., Ltd .; L45-1000] (0.06 parts) Carboxyl-modified silicon [manufactured by Shin-Etsu Chemical Co., Ltd .; X-22-3710] (0.05 parts) was premixed to prepare an additive mixture. Next, urethane urea resin particles (D-6) (100 parts), a colorant mixture and an additive mixture were charged into a Nauta mixer and mixed for 2 hours. Finally, a crosslinked urethane polymethylmethacrylate [Gantz Kasei Co., Ltd .; Gantz Pearl PM-030S] (0.5 part) as an antiblocking agent is added and mixed to form a thermoplastic urethane urea resin particle composition (P-8). Got. The volume average particle diameter of (P-8) was 175 μm.

Comparative Example 1
Production of Thermoplastic Urethane Urea Resin Particle Composition (P-1 ′) The same operation as in Example 1 was conducted except that dipentaerythritol pentaacrylate (E-1) was not used, and the thermoplastic urethane urea resin particle composition ( P-1 ′) was obtained. The volume average particle diameter of (P-1 ′) was 148 μm.

Comparative Example 2
Production of thermoplastic urethane urea resin particle composition (P-2 ′) The same operation as in Example 1 was conducted except that the prepolymer solution (G-1 ′) was used instead of the prepolymer solution (G-1). And urethane urea resin particles (D-1 ′) were produced. The Mn of (D-1 ′) was 20,000.
Further, the same operation as in Example 1 was carried out except that the urethane urea resin particles (D-1 ′) were used instead of the urethane urea resin particles (D-1), and a thermoplastic urethane urea resin particle composition (P— 2 ′) was obtained. The volume average particle diameter of (P-2 ′) was 148 μm.

  The thermoplastic urethane urea resin particle compositions (P-1) to (P-8) of Examples 1 to 8 and the thermoplastic urethane urea resin particle compositions (P-1 ') to (P-) of Comparative Examples 1 to 2 2 '), the skin was prepared by the method described below, and the tensile strength, elongation at break and tensile strength at break were measured. Moreover, the foam molding (henceforth a pad material) which has a skin layer was produced with the method shown below using these skins, and Asker C hardness and gloss were measured. Furthermore, the pad material was allowed to stand for 600 hours in a circulating drier whose temperature was adjusted to 130 ° C. to test the heat aging resistance. After heat aging test, measure or evaluate the Asker C hardness, gloss, fading and feel of the pad material that was allowed to stand at 25 ° C. for 24 hours, as well as the tensile strength and cutting of the skin obtained by removing the foam layer from the pad material. The elongation at break and the tensile force at break were measured. The results are shown in Tables 1 and 2.

<Production of epidermis>
For the purpose of low temperature molding, a thermoplastic urethane urea resin particle composition (P-1) to (P-8), (P-1) ') Was filled, and after 5 seconds, the excess resin particle composition was discharged. After 60 seconds, it was cooled with water to prepare a skin (thickness: 0.3 mm). In addition, using (P-2 ′), a skin having a thickness of 1.0 mm was produced in the same manner as described above except that the time after filling was changed to 10 seconds.

<Measurement method of tensile strength, elongation at break and tensile force at break>
The measurement was performed according to JIS K 6251: 2010. That is, three JIS K 6251: 2010 tensile test piece dumbbells No. 1 were punched from the molded skin to form test pieces, and marked lines were drawn at 40 mm intervals in the center. For the thickness, a minimum value of 5 points between the marked lines was adopted. The test piece was attached to an autograph in an atmosphere of 25 ° C., and pulled at a speed of 200 mm / min, and the tensile strength, elongation at break and tensile strength at break were measured. Here, the tensile force at the time of cutting means the tensile force at the time of cutting, and the tensile strength at the time of cutting is calculated by dividing this by the initial cross-sectional area of the test piece.

<Production of pad material>
Each skin produced by the above method is set in a mold, on which a urethane foam-forming component [95 parts of EO chipped polypropylene triol (Mn = 5,000), 5 parts of triethanolamine, 2.5 parts of water, triethylamine 1 part, consisting of 61.5 parts of polymeric MDI] was added and foam-adhered to obtain each pad material.

<Measurement of Asker C hardness>
Using an Asker C hardness meter [manufactured by Kobunshi Keiki Co., Ltd.], the hardness of the pad material surface was measured in accordance with JIS K7312.

<Gross measurement>
Using a gloss meter (portable gloss meter GMX-202: manufactured by Murakami Color Research Laboratory), the gloss of the pad material surface was measured. The higher the gloss value, the glossier.

<Confirmation of fading>
Before and after the heat aging test, the skin of the pad material was directly visually observed and evaluated according to the following criteria.
○: No color change △: Color change ×: Significant color change

<Evaluation of tactile sensation>
The surface of the pad material was touched with a finger and evaluated according to the following criteria.
○: There is no difference in the hardness of the pad material before and after the heat aging test.
X: Before and after the heat aging test, the pad material feels stiff.

  The molded skins of Examples 1 to 8 can maintain high tensile strength and elongation at break even after heat aging compared to those of Comparative Example 1, and have less coloring (fading) and gloss increase over time. In addition, compared with Comparative Example 2, since it has a high tensile strength, the tensile force at the time of cutting is sufficiently high even after thinning, and the hardness of the pad material is sufficiently low even after heat aging, and the tactile sensation is excellent. It is excellent as a material for instrument panels.

  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, such as instrument panels and door trims.

Claims (9)

  Urethane (urea) resin particles (D) 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 radically polymerizable unsaturated It is a thermoplastic urethane (urea) resin particle composition comprising a compound (E) containing two or more groups in the molecule, wherein (E) is in (D) and / or ( D) Thermoplastic urethane (urea) resin particle composition (P) present outside. The thermoplastic urethane (urea) resin particle composition according to claim 1, wherein the thermoplastic urethane (urea) resin (U) has a structural unit (x) represented by the general formula (1).

[In the formula, R ¹ 1 represents a monovalent group or a hydroxyl group obtained by removing one active hydrogen from monovalent or polyvalent active hydrogen-containing compound; be different in R ¹ are each the same when a plurality R ² represents a divalent group obtained by removing two active hydrogens from a divalent active hydrogen-containing compound, and when there are a plurality of R ^{2 s} , they may be the same or different; Y is trivalent or more Represents a trivalent or higher group obtained by removing all carboxyl groups from the aromatic polycarboxylic acid of Y; the aromatic ring of Y is composed of carbon atoms, and the carbon atoms have substituents and / or halogen atoms other than carboxyl groups. It may be bonded, but at least one of the carbon atoms is not bonded to a substituent; a represents an integer of 1 or more, b represents an integer of 0 or more, and 3 ≦ a + b ≦ d-1 is satisfied; d is the aromatic polycarboxylic acid The number of hydrogen atoms bonded to all the substituents in the carbon atoms constituting the aromatic ring of the case of substituting a hydrogen atom containing carboxyl groups, i.e. represents the number of substitutable positions on the aromatic ring. ]   When the trivalent or higher valent 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 the number of carboxyl groups is 4 3. The thermoplastic urethane (urea) resin particle composition according to claim 1, wherein the carboxyl group substitution position is 1,2,4,5-position or 1,2,3,5-position. The thermoplastic urethane (urea) resin (U) is obtained by reacting an active hydrogen component (A) containing an active hydrogen-containing compound (C) represented by the general formula (2) with an isocyanate component (B). The thermoplastic urethane (urea) resin particle composition according to any one of claims 1 to 3.

[In the formula, R ¹ 1 represents a monovalent group or a hydroxyl group obtained by removing one active hydrogen from monovalent or polyvalent active hydrogen-containing compound; be different in R ¹ are each the same when a plurality R ² represents a divalent group obtained by removing two active hydrogens from a divalent active hydrogen-containing compound, and when there are a plurality of R ^{2 s} , they may be the same or different; Y is trivalent or more Represents a trivalent or higher group obtained by removing all carboxyl groups from the aromatic polycarboxylic acid of Y; the aromatic ring of Y is composed of carbon atoms, and the carbon atoms have substituents and / or halogen atoms other than carboxyl groups. It may be bonded, but at least one of the carbon atoms is not bonded to a substituent; a represents an integer of 1 or more, b represents an integer of 0 or more, and 3 ≦ a + b ≦ d-1 is satisfied; d is the aromatic polycarboxylic acid The number of hydrogen atoms bonded to all the substituents in the carbon atoms constituting the aromatic ring of the case of substituting a hydrogen atom containing carboxyl groups, i.e. represents the number of substitutable positions on the aromatic ring. ]   The content of the structural unit (x) represented by the general formula (1) is 0.1 to 30% by weight based on the weight of the thermoplastic urethane (urea) resin (U). The urethane (urea) resin particle composition according to any one of the above.   The thermoplastic urethane (urea) resin particle composition according to any one of claims 1 to 5, wherein the compound (E) is an ester of an unsaturated carboxylic acid and a polyhydric alcohol.   The thermoplastic urethane (urea) resin according to any one of claims 1 to 6, wherein the content of the compound (E) based on the weight of the urethane (urea) resin particles (D) is 0.1 to 10% by weight. Particle composition.   Any one of Claims 1-7 which further contains at least 1 sort (s) of additives (F) chosen from the group which consists of an inorganic filler, a pigment, a plasticizer, a mold release agent, an antiblocking agent, antioxidant, and a ultraviolet absorber. The thermoplastic urethane (urea) resin particle composition described.   The thermoplastic urethane (urea) resin particle composition according to any one of claims 1 to 8, which is used for slush molding.