JP2012229396A - Urethane resin particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a slush molding material excellent in all of meltability, and heat resistance and mechanical properties of molded products.SOLUTION: The urethane resin particle (D) includes a urethane resin or urethaneurea resin (U) covalently bonded with a residue (j) obtained by subtracting a hydroxy group from an aromatic tri- or more hydric polycarboxylic acid. It is preferable that the urethane or urea group (u) is hydrogen-bonded with the residue (j), and the (U) is a thermoplastic resin. A thermoplastic urethane resin particle composition (P) including the urethane resin particle (D) and at least one kind of additive (F) selected from the group of inorganic filler, pigment, plasticizer, release agent, antiblocking agent and stabilizer is preferably used.

Description

  The present invention relates to urethane resin particles.

Conventionally, in order to improve the adhesion to the interlining, water wash resistance, and dry cleaning resistance, the difference between the softening start temperature and the softening end temperature by the thermomechanical analysis penetration method, and the softening start temperature are within a specific range. A hot melt adhesive comprising a thermoplastic polyurethane resin has been proposed, and it is stated that this can also be used for a slush molding material. (For example, see Patent Document 1)
In addition, regarding resin particles used in powder coatings, electrophotographic toners, and electrostatic recording toners, urethane resin particles that can be melted at low temperatures by adjusting the crystallinity, melting point, and molecular weight have been proposed. It is stated that it is also used for materials. (For example, see Patent Documents 2 and 3)

In recent years, slush molded products have been used for instrument panels for automobile interior parts. In order to reduce the cost of slush molding, increase the cycle, and extend the life of the mold, low temperature molding is desired. (For example, see Patent Document 4)
On the other hand, in order to deploy the airbag stored under the instrument panel, a cleavage opening is provided in the instrument panel. For the processing for the cleavage opening, a method of slitting the back surface of the slush molded product with a cutter is performed from the viewpoint of design. However, when the back slit is fused with heat in a high temperature area, the slit may disappear and the airbag may not open normally, and a slush molding material with excellent heat resistance is required. (For example, see Patent Documents 5 and 6)
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-A-10-259369 JP 2010-150535 A JP 2010-189633 A JP 2010-222477 A JP 2007-283865 A JP 2002-326241 A

Therefore, it is desirable that slush molding materials, particularly materials that can be suitably applied to automobile interiors, satisfy the conditions such as meltability during slush molding, heat resistance of slush molding, and excellent mechanical properties. When focusing on the material, no slush molding material that sufficiently satisfies all of these characteristics has been known yet.
An object of the present invention is to provide a slush molding material excellent in all of meltability, heat resistance of a molded product, and mechanical properties.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
The present invention relates to a urethane resin particle (D) containing a urethane resin or urethane urea resin (U) having a covalent bond to a residue (j) obtained by removing a hydroxyl group from an aromatic polycarboxylic acid having a valence of 3 or more. ); Slush molding containing the urethane resin particles (D) and an additive (F) which is at least one selected from the group consisting of inorganic fillers, pigments, plasticizers, mold release agents, antiblocking agents, and stabilizers. Is a thermoplastic urethane resin particle composition (P).

The thermoplastic urethane resin particle composition (P) for slush molding containing the urethane resin particles (D) of the present invention is excellent in all three of meltability, heat resistance of the molded product of (P), and mechanical properties. Has performance.

Infrared absorption spectrum measurement result (Example 10) Infrared absorption spectrum measurement result (Comparative Example 1)

<Urethane resin or urethane urea resin (U)>
The urethane resin particle (D) of the present invention contains a urethane resin or urethane urea resin (U) having a covalent bond to a residue (j) obtained by removing a hydroxyl group from an aromatic polycarboxylic acid having a valence of 3 or more. More preferably, the urethane group or urea group (u) in (U) and a residue (j) obtained by removing a hydroxyl group from an aromatic polycarboxylic acid having a valence of 3 or more are hydrogen-bonded. To do.
By introducing the hydrogen bond into (U) constituting (D), excellent performance is imparted over all three of (D) meltability, (D) molded product heat resistance, and mechanical properties. Can do.
The urethane group or urea group (u) in (U) and the residue (j) are hydrogen-bonded in the vicinity of 1680 to 1720 cm ^{−1 in} the infrared absorption spectrum (hereinafter sometimes referred to as IR spectrum). This can be confirmed by the appearance of absorption in.

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

In the general formula (1), R ¹ represents a residue or OH group obtained by removing one active hydrogen from a monovalent or polyvalent active hydrogen-containing compound (R ¹ H). The plurality of R ¹ may be the same or different. R ² represents a residue obtained by removing two active hydrogens from a divalent active hydrogen-containing compound (R ² H). A plurality of R ² may be the same or different. Y represents a residue obtained by removing all carboxyl groups from a trivalent or higher aromatic polycarboxylic acid. a and b are integers satisfying 1 ≦ a ≦ (number of substituents directly connectable to the aromatic ring−b), 0 ≦ b ≦ (number of substituents directly connectable to the aromatic ring−a), and 3 ≦ a + b ≦ 8.

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 such as methanol, ethanol, butanol, octanol, benzyl alcohol, naphthylethanol; ethylene glycol, propylene glycol, 1,3 and 1,4-butanediol, 1,6-hexanediol, 1, Dihydric alcohols such as 10-decanediol, diethylene glycol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, 1,4-bis (hydroxymethyl) cyclohexane and 1,4-bis (hydroxyethyl) benzene; glycerin and trimethylolpropane Trihydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methyl 4- to 8-valent alcohols such as lucoside and derivatives thereof; phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1, 3, 6 , 8-tetrahydroxynaphthalene, anthrol, phenols such as 1,4,5,8-tetrahydroxyanthracene and 1-hydroxypyrene; polybutadiene polyol; castor oil-based polyol; (co) heavy of hydroxyalkyl (meth) acrylate Examples thereof include polyfunctional (eg, 2-100 functional group) polyols such as coalesced and polyvinyl alcohol, condensates of phenol and formaldehyde (novolak), and polyphenols described in US Pat. No. 3,265,641. Of these, benzyl alcohol is preferred from the viewpoint of productivity.
(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, alkylthiol, and polythiol compounds. Examples of the polythiol include divalent to octavalent polyvalent thiols. Specific examples include ethylenedithiol and 1,6-hexanedithiol.

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

Examples of the active hydrogen-containing compound (R ¹ H) include 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 an alkylene oxide to the active hydrogen-containing compound.

The alkylene oxide to be added (hereinafter abbreviated as AO) includes AO having 2 to 6 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1, Examples include 3-propylene oxide, 1,2-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 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, propylene glycol, 1,3 and 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, diethylene glycol, neopentyl glycol. And dihydric alcohols such as cyclohexanediol, cyclohexanedimethanol, 1,4-bis (hydroxymethyl) cyclohexane and 1,4-bis (hydroxyethyl) benzene.

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 such as succinic acid, fumaric acid, sebacic acid and adipic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-1,4 dicarboxylic acid, Examples include aromatic dicarboxylic acids such as 2,3-anthracene dicarboxylic acid.

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

From the viewpoint of improving the mechanical properties (elongation and tensile strength) of the urethane resin molded product, the divalent active hydrogen-containing compound (R ² H) is preferably a divalent hydroxyl group-containing compound or a divalent amino group-containing compound. More preferably, ethylene glycol, propylene glycol, diethylamine, and dibutylamine are preferable. Most preferred is ethylene glycol.
Further, R ² in the general formulas (1) and (2) is —O (CH ₂ CH ₂ O) _n — (n is 1 ≦ n ≦ 5),
_{-O (CH 2 CHCH 3 O)} n - (n is 1 ≦ n ≦ 5) it is also preferred. These groups can be obtained by adding each EO and PO to a carboxyl group of an aromatic polycarboxylic acid having a valence of 3 or more.

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. The substituent of the aromatic ring may be a hydrogen atom or another substituent, but at least one substituent 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.

Other 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. Aldehyde 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 other substituents are preferably an alkyl group, a vinyl group, an allyl group, an amino group, an amide group, a urethane group and 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 hydrogen is arranged as a substituent between the third carbonyl group and the first or second carbonyl group is preferable.
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 hydrogen is arranged as a substituent between the third and subsequent carbonyl groups and the first or second carbonyl group. 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-2,3,6 tricarboxylic acid).

Of the trivalent or higher aromatic polycarboxylic acids (YH), benzene polycarboxylic acid is preferred. That is, the residue (j) obtained by removing the hydroxyl group from an aromatic polycarboxylic acid having a valence of 3 or more is preferably a residue obtained by removing the hydroxyl group from benzene polycarboxylic acid.
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 1,2,3,4-position is preferred.

a and b are integers satisfying 1 ≦ a ≦ (number of substituents directly connectable to the aromatic ring−b), 0 ≦ b ≦ (number of substituents directly connectable to the aromatic ring−a), and 3 ≦ a + b ≦ 8.
The number of substituents that can be directly bonded to an aromatic ring refers to the number of hydrogen atoms bonded to the ring carbon of an aromatic hydrocarbon having only an aromatic ring that forms an aromatic polycarboxylic acid, such as a compound such as benzene or naphthalene. And 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). It can be obtained by a dehydration condensation reaction at a ratio satisfying a and b defined in (2).
Further, instead of subjecting (R ² H) to a dehydration condensation reaction, it can also be obtained by subjecting AO (EO, PO, etc.) to a carboxyl group. Moreover, it is preferable to obtain (C) by dehydrochlorinating the monochloride which has a C1-C30 organic group from a viewpoint of reaction temperature instead of using (R < ¹ > H).
As the monochloride, a monochloride having a chloromethylene group is more preferable, and benzyl chloride is particularly preferable.

The urethane resin or urethane urea resin (U) is a polyurethane resin obtained by reacting an active hydrogen component (A) with an isocyanate component (B). As a part of the active hydrogen component (A), a general formula ( It is obtained by using the active hydrogen-containing compound (C) represented by 2).

In general formula (2), R ¹ , R ² , Y, a and b are the same as in general formula (1).

From the viewpoint of achieving both low-temperature meltability of urethane resin particles and tensile strength, elongation, and heat resistance of the molded product, R ^{2 in} the general formula (1) or (2) is represented by the following general formula (3) Is preferred.

In the formula, R ⁴ represents a divalent aliphatic hydrocarbon group having 2 to 10 carbon atoms, preferably 2 to ⁴ carbon atoms. More preferably, R ⁴ is an ethylene group.

From the viewpoint of compatibility between the low-temperature meltability of the urethane resin particles and the tensile strength, elongation, and heat resistance of the molded product, R ^{1 in} the general formula (1) or (2) is represented by the following general formula (4) Is preferred.

In the formula, R ⁵ represents a monovalent hydrocarbon group having 1 to 29 carbon atoms, and is preferably a phenyl group.

In (U), the structural unit (x) represented by the general formula (1) is (U) in (U) from the viewpoint of both the meltability of urethane resin particles and the mechanical strength and heat resistance of the molded product. ) To 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and most preferably 1.0 to 10.0% by weight.

(U) is preferably 1 or 2 in general formulas (1) and (2) in (U) from the viewpoint of the meltability of urethane resin particles.

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

(U) is a urethane resin or urethane urea resin (U2) having a structural unit (x2) in which a is 3 or 4 in the general formulas (1) and (2), and meltability and mechanical strength of the molded product From the viewpoint of heat resistance, 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, the content is 0.1 to 1% by weight.

  In the urethane resin or urethane urea resin (U), as the active hydrogen component (A) other than the active hydrogen-containing compound (C) represented by the general formula (2), polyester diol (A1), polyether diol (A2) And polyether ester diol (A3).

The polyester diol (A1) is, for example, (1) obtained by condensation polymerization of a low molecular diol and a dicarboxylic acid or an ester-forming derivative [an acid anhydride, a lower alkyl (carbon number of 1 to 4) ester, an acid halide, etc.]; 2) Ring-opening polymerization of a lactone monomer using a low-molecular diol as an initiator; and a mixture of two or more of these.

Specific examples of the low molecular diol include aliphatic diols [linear diols (ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol. ) Having a branched chain (propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,2-, 1,3- or 2,3-butanediol and the like]; diols having a cyclic group [for example, those described in JP-B No. 45-1474; diols containing aliphatic cyclic groups (1,4-bis (hydroxymethyl) cyclohexane, hydrogenated) Bisphenol A and the like, aromatic cyclic group-containing diol (m- and p-xylylene glycol) Alkylene oxide adduct of bisphenol A, alkylene oxide adduct of bisphenol S, alkylene oxide adduct of bisphenol F, alkylene oxide adduct of dihydroxynaphthalene, bis (2-hydroxyethyl) terephthalate, etc.)] and two or more of these A mixture is mentioned. Among these, preferred are aliphatic diols and diols having a cyclic group.

Specific examples of the dicarboxylic acid or ester-forming derivative 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.] C8-12 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.), 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 (A1) include polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyneopentylene adipate diol, poly-3-methylpentylene adipate diol, polycaprolactone diol, polyvalerolactone diol, poly Examples include hexamethylene carbonate diol.

Examples of the polyether diol (A2) 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 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 alkylene oxide to dihydric phenols, and more preferred are those obtained by adding EO to dihydric phenols.

As the polyether ester diol (A3), in the polyester diol, the above polyether diol is used instead of the raw low molecular diol, for example, one or more of the above polyether diols and the dicarboxylic compounds exemplified as the raw materials of the polyester diol. Examples thereof include those obtained by polycondensing an acid or one or more ester-forming derivatives thereof. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.

The active hydrogen component (A) other than the diol having the structural unit represented by the general formula (2) preferably does not contain an ether bond from the viewpoint of heat resistance and light resistance.

As the isocyanate component (B) constituting the urethane resin or 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.]; 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 Sulfonates, 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.

The urethane resin or urethane urea resin (U) is obtained by reacting an active hydrogen component (A), an isocyanate component (B), and a low molecular diamine or low molecular diol (K).
Specific examples of the low molecular diamine or low molecular diol (K) constituting the urethane resin or urethane urea resin (U) are as follows.

Aliphatic diamines having 6 to 18 carbon atoms [4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4′-diaminodicyclohexylmethane, diaminocyclohexane, isophoronediamine, etc.] An aliphatic diamine having 2 to 12 carbon atoms [ethylenediamine, propylenediamine, hexamethylenediamine and the like]; an araliphatic diamine having 8 to 15 carbon atoms [xylylenediamine, α, α, α ′, α′-tetramethylxylyl] Range amine and the like] 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.

Low molecular diols include 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.] ], An aromatic ring-containing diol having 8 to 20 carbon atoms (such as m- or p-xylylene glycol), bisphenol Oxyalkylene ethers of bisphenol A (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 a method of adjusting the molecular weight of the urethane resin or urethane urea resin (U), it can be adjusted by partially blocking the isocyanate group of the isocyanate group-terminated urethane prepolymer with a monofunctional alcohol. Examples of the monool include aliphatic monools having 1 to 8 carbon atoms [linear monool (methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, etc.), monool having a branched chain (isopropyl alcohol, Neopentyl alcohol, 3-methyl-pentanol, 2-ethylhexanol, etc.]; monools having a cyclic group having 6 to 10 carbon atoms [alicyclic group-containing monools (cyclohexanol etc.), aromatic ring-containing monools] (Such as benzyl alcohol)] and mixtures of two or more thereof. Of these, preferred are aliphatic monools and aromatic ring-containing monools. Examples of the polymer monool include polyester monool, polyether monool, polyether ester monool, and a mixture of two or more thereof.
In the general formula (1), even for a polyol having a of 1, the isocyanate group of the isocyanate group-terminated urethane prepolymer is partially blocked, so that the molecular weight can be adjusted.

Examples of the method for producing the urethane resin or urethane urea resin (U) include the following methods.
(1) The active hydrogen component (A) containing a mixture of the polyester diol (A1) and the active hydrogen-containing compound (C) represented by the general formula (3) in advance is reacted with the diisocyanate component (B), A method in which a urethane prepolymer (G) having an isocyanate group is produced, and then the prepolymer (G) and a low molecular diamine or low molecular diol (K) are mixed and elongated to obtain a urethane resin.
(2) A method in which (A), (B) and (K) are mixed and 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 prepolymerization reaction, a catalyst usually used for polyurethane can be used if necessary to accelerate the reaction. Examples of the catalyst include amine-based catalysts [triethylamine, N-ethylmorpholine, triethylenediamine, etc.], tin-based catalysts [trimethyltin laurate, dibutyltin dilaurate, dibutyltin malate, etc.].

The 190 ° C. melt viscosity of the urethane resin or urethane urea resin (U) is preferably 500 to 2000 Pa · s, more preferably 500 to 1000 Pa · s, from the viewpoint of good meltability of the urethane resin particles (D). It is.
The storage elastic modulus G ′ at 130 ° C. of (U) is preferably 0.2 to 10 MPa, more preferably 0.5 to 2 MPa, from the viewpoint of good heat resistance and good meltability of the urethane resin particles.

The urethane resin or urethane urea resin (U) is preferably a thermoplastic resin.
By using (U) as particles, in addition to powder for slush molding, application to hot melt adhesives and the like becomes possible. Examples of the urethane resin particles (D) include those obtained by the following production method.
(1) The active hydrogen component (A) and the diisocyanate component (B) containing a mixture of the polyester diol (A1) and the active hydrogen-containing compound (C) represented by the general formula (3) in advance are combined with the active hydrogen component (A ) And the isocyanate group of the diisocyanate component (B) are reacted so that the molar ratio is 1: 1.2 to 1: 4.0, and the urethane prepolymer (G) having an isocyanate group at the end is treated with water. In the presence of a dispersion stabilizer, urethane resin particles (D) can be produced by a method in which an extension reaction is performed with a low molecular diamine or a low molecular diol (K).
As the low-molecular diamine, a blocked linear aliphatic diamine (H1) (for example, a ketimine compound) can be used.
(2) Producing urethane resin particles (D) by a method in which the urethane prepolymer (G) is subjected to an extension reaction with a low molecular diamine or a low molecular diol (K) in the presence of a nonpolar organic solvent and a dispersion stabilizer. Can do.
(3) A lump of thermoplastic polyurethane resin is obtained by reacting the diisocyanate component (B), the high molecular diol (A), and the low molecular diol or low molecular diamine (K). Subsequently, the urethane resin particles (D) can be produced by pulverization (for example, freeze pulverization, a method of cutting through pores in a molten state).

The volume average particle diameter of the urethane resin particles (D) of the present invention is preferably in the range of 10 to 500 μm, more preferably 70 to 300 μm.

The urethane resin particle (D) of the present invention is obtained by adding an additive (F) in addition to the urethane resin or urethane urea resin (U) and the compound (E) to produce a thermoplastic urethane resin particle composition (P) for slush molding. It can be. Examples of the additive (F) include inorganic fillers, pigments, plasticizers, mold release agents, organic fillers, antiblocking agents, stabilizers, and dispersants.
0-50 are preferable with respect to the weight of a urethane resin or a urethane urea resin (U), and, as for the addition amount (weight%) of an additive (F), More preferably, it is 1-30.
The additive (F) may be added to the active hydrogen component (A), may be added during the production process of the urethane prepolymer (G), or may be added to the obtained (G).
Further, when the additive (F) is a plasticizer, a release agent, a fluidity modifier, or an anti-blocking agent, there is a method in which these additives are impregnated or mixed into a powder composed of urethane resin particles (D). 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 diameter (μm) of the inorganic filler is preferably from 0.1 to 30, more preferably from 1 to 20, particularly preferably from 5 to 10, from the viewpoint of dispersibility in the thermoplastic resin.
0-40 are preferable with respect to the weight of a urethane resin or a urethane urea resin (U), and, as for the addition amount (weight%) of an inorganic filler, 1-20 are more preferable.

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 chromate, ferrocyan compounds, metal oxides (titanium oxide, iron oxide, Zinc oxide, aluminum oxide, etc.), metal salts [sulfates (barium sulfate, etc.), silicates (calcium silicate, magnesium silicate, etc.), carbonates (calcium carbonate, magnesium carbonate, etc.), phosphates (calcium phosphate, magnesium phosphate, etc.) Etc.], metal powder (aluminum powder, iron powder, nickel powder, copper powder, etc.), carbon black, and the like. 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.
0-5 are preferable with respect to the weight of a urethane resin or a urethane urea resin (U), and, as for the addition amount (weight%) of a pigment, 1-3 are more preferable.

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); halogen aliphatic phosphate esters (tris (chloroethyl) phosphate, tris (β-chloropropyl) phosphate, tris (dichloropropyl) phosphate and tris (Tribromoneopentyl) phosphate, etc.); and mixtures of two or more thereof.
0-50 are preferable with respect to the weight of a urethane resin or a urethane urea resin (U), and, as for the addition amount (weight%) of a plasticizer, 5-20 are more preferable.

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.
0-1 are preferable with respect to the weight of a urethane resin or a urethane urea resin (U), and, as for the addition amount (weight%) of a mold release agent, 0.1-0.5 are more preferable.

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 applies 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, etc.); poly (meth) allyl ether of polyhydric alcohol (pentaeryth Toll (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.) 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.
0-20 are preferable with respect to the weight of a urethane resin or a urethane urea resin (U), and, as for the addition amount (weight%) of a stabilizer, 1-15 are more preferable.

The thermoplastic polyurethane resin particle composition (P) for slush molding of the present invention (hereinafter referred to as the resin particle composition (P)) is a known inorganic antiblocking agent as a powder flowability improver and an antiblocking agent. Moreover, an organic type antiblocking agent etc. can be used. Examples of the inorganic blocking inhibitor include silica, talc, titanium oxide and calcium carbonate. Organic blocking inhibitors include thermosetting resins with a particle size of 10 μm or less (thermosetting polyurethane resins, guanamine resins, epoxy resins, etc.) and thermoplastic resins with a particle size of 10 μm or less (thermoplastic polyurethane urea resin and poly ( (Meth) acrylate resin, etc.).
0-5 are preferable with respect to the weight of a urethane resin or a urethane urea resin (U), and, as for the addition amount (weight%) of an antiblocking agent (fluidity improver), 0.5-1 are more preferable.

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.) 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 volume average particle size of the resin particle composition (P) is preferably in the range of 10 to 500 μm, more preferably 70 to 300 μm.

The resin particle composition (P) can be molded by, for example, a slush molding method to produce a urethane 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.

The resin particle composition (P) has a melt viscosity at 190 ° C. of preferably 100 to 500 Pa · s, and more preferably 100 to 300 Pa · s.
When the melt viscosity at 190 ° C. of the resin particle composition (P) is 500 Pa · s or less, the low-temperature meltability of the resin particle composition is good.
The storage elastic modulus G ′ at 130 ° C. of the molded product molded from the resin particle composition (P) is preferably 0.1 to 5 MPa, more preferably 0.25 to 1 MPa for slush molding.
If the storage elastic modulus G ′ at 130 ° C. of the molded product is 0.1 MPa or more, the heat resistance is good. Moreover, if it is 5 MPa or less, the low-temperature meltability of the resin particle composition (P) is good.

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) 192 parts of trimellitic anhydride and 216 parts of benzyl alcohol are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and water produced at 180 ° C. is distilled. The reaction was allowed to proceed for 5 hours, and then 62 parts of ethylene glycol was reacted for 5 hours while distilling off the water produced at 140 ° C., and the active hydrogen-containing compound (C-1) was taken out. It was 434 as a result of measuring the hydroxyl value of the obtained active hydrogen containing compound (C-1), and calculating molecular weight. The structures of (C-1) {a and b in the general formula (2)} are shown in Tables 1 and 2. Hereinafter, (C-2) to (C-9) are also shown in Table 1 and Table 2.

Production Example 3
Production of active hydrogen-containing compound (C-2) 192 parts of trimellitic anhydride and 108 parts of benzyl alcohol were placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and the water produced at 180 ° C was distilled. After reacting for 5 hours while leaving, 124 parts of ethylene glycol was added, and the reaction was performed for 5 hours while distilling off the water produced at 140 ° C., and the active hydrogen-containing compound (C-2) was taken out. It was 388 as a result of measuring the hydroxyl value of the obtained active hydrogen containing compound (C-2), and calculating the molecular weight.

Production Example 4
Production of active hydrogen-containing compound (C-3) 192 parts of trimellitic anhydride and 186 parts of ethylene glycol were placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and water produced at 140 ° C was distilled. It was made to react for 5 hours, leaving, and the active hydrogen containing compound (C-3) was taken out. It was 342 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) 254 parts of pyromellitic anhydride and 248 parts of ethylene glycol were placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and water produced at 140 ° C was distilled. The reaction was carried out for 5 hours while leaving, and the active hydrogen-containing compound (C-4) was taken out. 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 active hydrogen-containing compound (C-5) 192 parts of trimellitic anhydride and 108 parts of benzyl alcohol are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and water produced at 180 ° C. is distilled. The reaction is allowed to proceed for 5 hours, 1 mol of 1,2,4-benzenetricarboxylic acid and 1 mol of benzyl alcohol are taken out, charged into a pressure reactor, and 59 parts of PO at 120 ° C. for 3 hours in the pressure reactor. It was made to react and the active hydrogen containing compound (C-5) was taken out. It was 416 as a result of measuring the hydroxyl value of the obtained active hydrogen containing compound (C-5), and calculating molecular weight.

Production Example 7
Production of active hydrogen-containing compound (C-6) 192 parts of trimellitic anhydride and 186 parts of dodecyl alcohol were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and water produced at 180 ° C was distilled. The reaction was allowed to proceed for 5 hours, and then 124 parts of ethylene glycol was added. The reaction was allowed to proceed for 5 hours while distilling off the water produced at 140 ° C., and the active hydrogen-containing compound (C-6) was taken out. It was 466 as a result of measuring the hydroxyl value of the obtained active hydrogen containing compound (C-6), and calculating molecular weight.

Production Example 8
Production of active hydrogen-containing compound (C-7) 384 parts of ethyl acetate was charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and then 192 parts of trimellitic anhydride, 62 parts of ethylene glycol, triethylamine After 202 parts were added and reacted at 80 ° C. for 2 hours, 252 parts of benzyl chloride was added and reacted at 70 ° C. for 2 hours. Then, liquid separation and solvent removal were performed, and the active hydrogen containing compound (C-7) was taken out. It was 434 as a result of measuring the hydroxyl value of the obtained active hydrogen containing compound (C-7), and calculating molecular weight.

Production Example 9
Production of active hydrogen-containing compound (C-8) 192 parts of trimellitic anhydride and 60 parts of ethylenediamine were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 80 ° C. for 2 hours. Then, 216 parts of benzyl alcohol was added and reacted for 5 hours while distilling off the water produced at 180 ° C., and the active hydrogen-containing compound (C-8) was taken out. It was 432 as a result of measuring the amine number of the obtained active hydrogen containing compound (C-8), and calculating molecular weight.

Production Example 10
Production of active hydrogen-containing compound (C-9) After charging 384 parts of ethyl acetate into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 192 parts of trimellitic anhydride, 62 parts of ethylene glycol, triethylamine After 202 parts were added and reacted at 80 ° C. for 2 hours, 252 parts of benzyl chloride was added and reacted at 70 ° C. for 2 hours. Then, liquid separation and solvent removal were performed, and the active hydrogen containing compound (C-9) was taken out. It was 434 as a result of measuring the hydroxyl value of the obtained active hydrogen containing compound (C-9), and calculating molecular weight.

Production Example 11
A reaction vessel equipped with a production thermometer, a stirrer, and a nitrogen blowing tube for the prepolymer solution (G-1) has a molecular weight (hereinafter referred to as Mn) calculated from a hydroxyl value of 2300, and is polyethylene isophthalate diol (278. 1 part), polybutylene adipate diol (417.2 parts) with Mn of 1000, active hydrogen-containing compound (C-1) (16.0 parts), benzyl alcohol (5.3 parts), and after nitrogen substitution The mixture was 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. Next, after cooling to 70 ° C., a stabilizer (1.4 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-1) was obtained. The NCO content of the obtained prepolymer solution was 1.63%.

Production Example 12
Preparation of prepolymer solution (G-2) A reaction vessel equipped with a thermometer, a stirrer, and a nitrogen blowing tube was added to a polyethylene isophthalate diol (281.8 parts) with Mn of 2300 and polybutylene adipate diol with Mn of 1000. (422.7 parts), an active hydrogen-containing compound (C-1) (4.0 parts), and benzyl alcohol (8.2 parts) were charged, 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 (131.9 parts) were added and reacted at 90 ° C. for 6 hours. Next, after cooling to 70 ° C., a stabilizer (1.4 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-2) was obtained. The NCO content of the obtained prepolymer solution was 1.63%.

Production Example 13
Preparation of prepolymer solution (G-3) A reaction vessel equipped with a thermometer, a stirrer, and a nitrogen blowing tube was added to a polyethylene isophthalate diol (271.3 parts) having an Mn of 2300 and a polybutylene adipate diol having an 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. Next, after cooling to 70 ° C., a stabilizer (1.4 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-3) was obtained. The NCO content of the obtained prepolymer solution was 1.63%.

Production Example 14
Production of prepolymer solution (G-4) A reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube was charged with polyethylene isophthalate diol (281.2 parts) with Mn of 2300 and polybutylene adipate diol with Mn of 1000. (421.8 parts), active hydrogen-containing compound (C-2) (3.5 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 (132.9 parts) were added and reacted at 90 ° C. for 6 hours. Next, after cooling to 70 ° C., a stabilizer (1.4 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-4) was obtained. The NCO content of the obtained prepolymer solution was 1.63%.

Production Example 15
Production of prepolymer solution (G-5) A reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube was added to a polyethylene isophthalate diol (192.7 parts) having an Mn of 2300 and a polybutylene adipate diol having an Mn of 1000. (289.0 parts), active hydrogen-containing compound (C-2) (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. Next, after cooling to 70 ° C., a stabilizer (1.4 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-5) was obtained. The NCO content of the obtained prepolymer solution was 1.63%.

Production Example 16
Production of prepolymer solution (G-6) A reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube was added to a 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-3) (0.7 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 (132.5 parts) were added and reacted at 90 ° C. for 6 hours. Next, after cooling to 70 ° C., a stabilizer (1.4 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-6) was obtained. The NCO content of the obtained prepolymer solution was 1.63%.

Production Example 17
Preparation of prepolymer solution (G-7) A reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube was added to a polyethylene isophthalate diol (273.1 parts) having an Mn of 2300 and a polybutylene adipate diol having an 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. Next, after cooling to 70 ° C., a stabilizer (1.4 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-7) was obtained. The NCO content of the obtained prepolymer solution was 1.63%.

Production Example 18
Preparation of prepolymer solution (G-8) A reaction vessel equipped with a thermometer, a stirrer, and a nitrogen blowing tube was added to a polyethylene isophthalate diol (264.9 parts) having an Mn of 2300 and a polybutylene adipate diol having an Mn of 1000. (397.3 parts), an active hydrogen-containing compound (C-5) (36.4 parts), and benzyl alcohol (9.3 parts) were charged, purged with nitrogen, and then heated to 110 ° C. with stirring to melt. And cooled to 50 ° C. Subsequently, methyl ethyl ketone (150.0 parts) and hexamethylene diisocyanate (140.7 parts) were added and reacted at 90 ° C. for 6 hours. Next, after cooling to 70 ° C., a stabilizer (1.4 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-8) was obtained. The NCO content of the obtained prepolymer solution was 1.63%.

Production Example 19
Preparation of prepolymer solution (G-9) A reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube was added to a polyethylene isophthalate diol (265.5 parts) with Mn of 2300 and polybutylene adipate diol with Mn of 1000. (398.2 parts), active hydrogen-containing compound (C-6) (36.5 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 (139.2 parts) were added and reacted at 90 ° C. for 6 hours. Next, after cooling to 70 ° C., a stabilizer (1.4 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-9) was obtained. The NCO content of the obtained prepolymer solution was 1.63%.

Production Example 20
Preparation of prepolymer solution (G-10) A reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube was added to a polyethylene isophthalate diol (93.1 parts) having a Mn of 2300 and a polybutylene adipate diol having a Mn of 1000. (349.6 parts), an active hydrogen-containing compound (C-7) (6.0 parts), and benzyl alcohol (5.3 parts) were charged, purged with nitrogen, heated to 110 ° C. with stirring and melted. 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 ° C., a stabilizer (2.7 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-10) was obtained. The NCO content of the obtained prepolymer solution was 1.26%.

Production Example 21
Preparation of prepolymer solution (G-11) A reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube was added to a polyethylene isophthalate diol (92.1 parts) with Mn of 2300 and polybutylene adipate diol with Mn of 1000. (338.5 parts), an active hydrogen-containing compound (C-7) (30.7 parts), and benzyl alcohol (0.45 parts) were charged, and the atmosphere was purged with nitrogen. And cooled to 50 ° C. Subsequently, methyl ethyl ketone (396.1 parts), hexamethylene diisocyanate (110.0 parts) and isophorone diisocyanate (3.7 parts) were added and reacted at 90 ° C. for 6 hours. Subsequently, after cooling to 70 ° C., a stabilizer (2.7 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-11) was obtained. The NCO content of the obtained prepolymer solution was 1.26%.

Production Example 22
Production of prepolymer solution (G-12) In a reaction vessel equipped with a thermometer, stirrer and nitrogen blowing tube, polyethylene isophthalate diol (92.1 parts) with Mn of 2300 and polybutylene adipate diol with Mn of 1000 (338.5 parts), an active hydrogen-containing compound (C-8) (30.6 parts), and benzyl alcohol (0.45 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 (396.1 parts), hexamethylene diisocyanate (110.0 parts) and isophorone diisocyanate (3.7 parts) were added and reacted at 90 ° C. for 6 hours. Subsequently, after cooling to 70 ° C., a stabilizer (2.7 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-12) was obtained. The NCO content of the obtained prepolymer solution was 1.26%.

Production Example 23
Production of prepolymer solution (G-13) In a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen blowing tube, polybutylene adipate (349.3) having Mn of 2300 polyethylene isophthalate (93.1 parts) and Mn of 1000. 6 parts), 1,4-butanediol (12.8 parts), active hydrogen-containing compound (C-9) (6.0 parts), benzyl alcohol (5.3 parts), and after purging with nitrogen, stirring While being heated to 110 ° C., the mixture was melted 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. Next, after cooling to 70 ° C., a stabilizer (2.7 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-13) was obtained. The NCO content of the obtained prepolymer solution was 1.26%.

Comparative production example 1
Production of prepolymer solution (G-1 ′) A reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube was added to a polyethylene isophthalate diol (282.9 parts) with Mn of 2300 and polybutylene adipate with Mn of 1000. 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. Next, after cooling to 70 ° C., a stabilizer (1.4 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-1 ′) was obtained. The NCO content of the obtained prepolymer solution was 1.63%.

Comparative production example 2
Production of prepolymer solution (G-2 ′) A reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube was added to a polyethylene isophthalate diol (280.2 parts) with Mn of 2300 and polybutylene adipate with Mn of 1000. 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. Next, after cooling to 70 ° C., a stabilizer (1.4 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-2 ′) was obtained. The NCO content of the obtained prepolymer solution was 2.03%.

Comparative production example 3
Production of comparative active hydrogen-containing compound (C-1 ′) In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 148 parts (1 mole) of phthalic anhydride, 108 parts (1 mole) of benzyl alcohol, ethylene 62 parts (1 mol) of glycol was reacted for 5 hours while distilling off water produced at 180 ° C., and the compound (C-1 ′) was taken out. The comparative active hydrogen-containing compound (C-1 ′) is monoethylene glycol monobenzyl ester of phthalic acid.

Comparative production example 4
Polyethylene isophthalate diol (278) having a molecular weight (hereinafter referred to as Mn) calculated from a hydroxyl value of 2300 in a reaction vessel equipped with a production thermometer, a stirrer and a nitrogen blowing tube for the prepolymer solution (G-3 ′). 0.1 part), polybutylene adipate diol (417.2 parts) with Mn of 1000, comparative active hydrogen-containing compound (C-1 ′) (16.0 parts), benzyl alcohol (3.5 parts), and nitrogen After the replacement, the mixture was heated to 110 ° C. with melting 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. Next, after cooling to 70 ° C., a stabilizer (1.4 parts) [Irganox 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.] and carbon black (1 part) were added and mixed uniformly to prepare a prepolymer solution ( G-3 ′) was obtained. The NCO content of the obtained prepolymer solution was 1.63%.

Example 1
The prepolymer solution (G-1) (100 parts) obtained in Production Example 11 and the MEK ketimine product (4.2 parts) of Production Example 1 are charged and mixed into the production reaction vessel of the resin particle composition (P-1). Then, 300 parts of an aqueous solution in which a polycarboxylic acid type anionic surfactant [Sansu Pearl PS-8 manufactured by Sanyo Chemical Industries Co., Ltd.] (30 parts) was dissolved was added, and an ultradispers manufactured by Yamato Scientific Co., Ltd. was used. And mixed for 1 minute at a rotation speed of 6000 rpm. 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 urethane resin particles (D-1). The number average molecular weight (hereinafter referred to as Mn) of (D-1) was 20,000, and the volume average particle diameter was 145 μm. The melt viscosity at 190 ° C. and the storage elastic modulus at 130 ° C. of (D-1) are shown in Table 1. The following examples and comparative examples are also shown in Tables 1-2.
Next, in a 100 L Nauta mixer, thermoplastic urethane resin particles (D-1) (100 parts), radical polymerizable unsaturated group-containing compound dipentaerythritol pentaacrylate [manufactured by Sanyo Chemical Industries, Ltd .; DA600] (1 0.0 part), UV stabilizers bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate (mixture) [ [Product name: TINUVIN 765, manufactured by Ciba] (0.3 parts) 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) (0.06 parts), carboxyl-modified silicon [manufactured by Shin-Etsu Chemical Co., Ltd .; X-22-3710] (0.05 parts) was added, mixed for 1 hour, and then cooled to room temperature. Finally, an antiblocking agent cross-linked polymethylmethacrylate [Ganz Kasei Co., Ltd .; Ganzpearl PM-030S] (0.5 part) was added and mixed to obtain a resin particle composition (P-1). The volume average particle size of (P-1) was 148 μm. The melt viscosity at 190 ° C. and the storage elastic modulus at 130 ° C. of (P-1) are shown in Table 1. The following examples and comparative examples are also shown in Tables 1-2.

Example 2
Production of Resin Particle Composition (P-2) Same as Example 1, except that the prepolymer solution (G-2) (100 parts) was used instead of the prepolymer solution (G-1) in Example 1. Then, urethane resin particles (D-2) were produced. Mn of (D-2) was 20,000, and the volume average particle size was 140 μm.
Furthermore, in Example 1, except having used the urethane resin particle (D-2) instead of the urethane resin particle (D-1), the same operation was performed and the resin particle composition (P-2) was obtained. The volume average particle diameter of (P-2) was 143 μm.

Example 3
Production of Resin Particle Composition (P-3) Same as Example 1 except that instead of the prepolymer solution (G-1) in Example 1, the prepolymer solution (G-3) (100 parts) was changed. Then, urethane resin particles (D-3) were produced. Mn of (D-3) was 15,000, and the volume average particle size was 148 μm.
Furthermore, in Example 1, except having used the urethane resin particle (D-3) instead of the urethane resin particle (D-1), the same operation was performed and the resin particle composition (P-3) was obtained. The volume average particle size of (P-3) was 150 μm.

Example 4
Production of Resin Particle Composition (P-4) Same as Example 1 except that the prepolymer solution (G-4) (100 parts) was used instead of the prepolymer solution (G-1) in Example 1. Then, urethane resin particles (D-4) were produced. Mn of (D-4) was 20,000, and the volume average particle size was 158 μm.
Furthermore, in Example 1, except having used the urethane resin particle (D-4) instead of the urethane resin particle (D-1), the same operation was performed and the resin particle composition (P-4) was obtained. The volume average particle diameter of (P-4) was 160 μm.

Example 5
Production of Resin Particle Composition (P-5) Same as Example 1, except that the prepolymer solution (G-5) (100 parts) was used instead of the prepolymer solution (G-1) in Example 1. Then, urethane resin particles (D-5) were produced. Mn of (D-5) was 20,000, and the volume average particle diameter was 152 μm.
Furthermore, in Example 1, except having used the urethane resin particle (D-5) instead of the urethane resin particle (D-1), the same operation was performed and the resin particle composition (P-5) was obtained. The volume average particle diameter of (P-5) was 154 μm.

Example 6
Production of Resin Particle Composition (P-6) Same as Example 1 except that the prepolymer solution (G-6) (100 parts) was used instead of the prepolymer solution (G-1) in Example 1. Then, urethane resin particles (D-6) were produced. Mn of (D-6) was 22,000, and the volume average particle size was 154 μm.
Further, in Example 1, a resin particle composition (P-6) was obtained by performing the same operation except that the urethane resin particles (D-6) were used instead of the urethane resin particles (D-1). The volume average particle diameter of (P-6) was 155 μm.

Example 7
Production of Resin Particle Composition (P-7) Same as Example 1 except that the prepolymer solution (G-7) (100 parts) was used instead of the prepolymer solution (G-1) in Example 1. Then, urethane resin particles (D-7) were produced. Mn of (D-6) was 26,000, and the volume average particle diameter was 146 μm.
Furthermore, in Example 1, except having used the urethane resin particle (D-7) instead of the urethane resin particle (D-1), the same operation was performed and the resin particle composition (P-7) was obtained. The volume average particle diameter of (P-7) was 148 μm.

Example 8
Production of Resin Particle Composition (P-8) Same as Example 1 except that the prepolymer solution (G-8) (100 parts) was used instead of the prepolymer solution (G-1) in Example 1. Then, urethane resin particles (D-8) were produced. Mn of (D-8) was 20,000, and the volume average particle size was 144 μm.
Furthermore, in Example 1, except having used the urethane resin particle (D-8) instead of the urethane resin particle (D-1), the same operation was performed and the resin particle composition (P-8) was obtained. The volume average particle diameter of (P-8) was 146 μm.

Example 9
Production of Resin Particle Composition (P-9) Same as Example 1 except that the prepolymer solution (G-9) (100 parts) was used instead of the prepolymer solution (G-1) in Example 1. Then, urethane resin particles (D-9) were produced. Mn of (D-9) was 20,000, and the volume average particle size was 145 μm.
Furthermore, in Example 1, except having used the urethane resin particle (D-9) instead of the urethane resin particle (D-1), the same operation was performed and the resin particle composition (P-9) was obtained. The volume average particle size of (P-9) was 148 μm.

Example 10
Production of Resin Particle Composition (P-10) In Example 1, instead of the prepolymer solution (G-1), the prepolymer solution (G-10) (100 parts) and the MEK ketimine compound (3.2 parts) were used. Except having changed, operation similar to Example 1 was performed and the urethane resin particle (D-10) was manufactured. Mn of (D-10) was 20,000, and the volume average particle diameter was 145 μm.
Furthermore, in Example 1, except having used the urethane resin particle (D-10) instead of the urethane resin particle (D-1), the same operation was performed and the resin particle composition (P-10) was obtained. The volume average particle diameter of (P-10) was 148 μm.

Example 11
Production Example 1 of Resin Particle Composition (P-11) Instead of the prepolymer solution (G-1) in Example 1, the prepolymer solution (G-11) (100 parts) and the MEK ketimine compound (3.2 parts) were used. Except having changed, the same operation as Example 1 was performed and urethane resin particles (D-11) were manufactured. Mn of (D-11) was 20,000, and the volume average particle diameter was 145 μm.
Furthermore, in Example 1, except having used the urethane resin particle (D-11) instead of the urethane resin particle (D-1), the same operation was performed and the resin particle composition (P-11) was obtained. The volume average particle diameter of (P-11) was 148 μm.

Example 12
Production of Resin Particle Composition (P-12) In Example 1, instead of the prepolymer solution (G-1), the prepolymer solution (G-12) (100 parts) and the MEK ketimine compound (3.2 parts) were used. Except having changed, operation similar to Example 1 was performed and the urethane resin particle (D-12) was manufactured. Mn of (D-12) was 20,000, and the volume average particle size was 150 μm.
Furthermore, in Example 1, except having used the urethane resin particle (D-12) instead of the urethane resin particle (D-1), the same operation was performed and the resin particle composition (P-12) was obtained. The volume average particle diameter of (P-12) was 152 μm.

Example 13
Production of Resin Particle Composition (P-13) In Example 1, instead of the prepolymer solution (G-1), the prepolymer solution (G-13) (100 parts) and the MEK ketimine compound (3.2 parts) were used. Except having changed, operation similar to Example 1 was performed and the urethane resin particle (D-13) was manufactured. Mn of (D-13) was 20,000, and the volume average particle diameter was 145 μm.
Furthermore, in Example 1, except having used the urethane resin particle (D-13) instead of the urethane resin particle (D-1), the same operation was performed and the resin particle composition (P-13) was obtained. The volume average particle diameter of (P-13) was 148 μm.

Comparative Example 1
Production Example 1 of Resin Particle Composition (P-1 ′) Example 1 except that the prepolymer solution (G-1 ′) (100 parts) was used instead of the prepolymer solution (G-1) in Example 1. The same operation was carried out to produce urethane resin particles (D-1 ′).
In Example 1, the same operation was performed except that the urethane resin particles (D-1 ′) were used instead of the urethane resin particles (D-1) to obtain a resin particle composition (P-1 ′). The volume average particle diameter of (P-1 ′) was 148 μm.

Comparative Example 2
Production of Resin Particle Composition (P-2 ′) In Example 1, instead of the prepolymer solution (G-1) (100 parts) and the MEK ketimine compound (4.2 parts), the prepolymer solution (G-2 ′) ) (100 parts) and the MEK ketimine compound (5.2 parts), except that the same operation as in Example 1 was performed to produce urethane resin particles (D-2 ′). Mn of (D-2 ′) was 20,000, and the volume average particle diameter was 145 μm.
Furthermore, in Example 1, except having used the urethane resin particle (D-2 ') instead of the urethane resin particle (D-1), the same operation was performed and the resin particle composition (P-2') was obtained. . The volume average particle diameter of (P-2 ′) was 148 μm.

Comparative Example 3
Production Example 1 of Resin Particle Composition (P-3 ′) Except that the prepolymer solution (G-3 ′) (100 parts) was replaced with the prepolymer solution (G-1) (100 parts) in Example 1. The same operations as in Example 1 were performed to produce urethane resin particles (D-3 ′). Mn of (D-3 ′) was 20,000, and the volume average particle diameter was 145 μm.
Furthermore, in Example 1, the same operation was performed except having used the urethane resin particle (D-3 ′) instead of the urethane resin particle (D-1) to obtain a resin particle composition (P-3 ′). . The volume average particle diameter of (P-3 ′) was 148 μm.

Resin particle compositions (P-1) to (P-13) for slush molding of Examples 1 to 13 and resin particle compositions (P-1 ′) to (P-3 ′) of Comparative Examples 1 to 3 , By using the following method to form a skin with a thickness of 1.0 mm and 0.3 mm at 210 ° C., the backside meltability of the skin with a thickness of 1.0 mm, 25 ° C. tensile strength, 25 ° C. elongation, The maximum load at the time of breaking at 25 ° C. of the skin having a thickness of 0.3 mm, the 25 ° C. tensile strength after the heat resistance test shown below, and the elongation were measured.
The results are shown in Tables 1-2.

In order to confirm the hydrogen bond of the residue (j) obtained by removing the hydroxyl group from the urethane group or urea group (u) in the urethane resin or urethane urea resin (U) and the aromatic polycarboxylic acid having a valence of 3 or more, As a result of measuring the IR spectrum of the resin particle composition (P-10) of Example 10, absorption was observed at 1686 cm ⁻¹ as shown in FIG. Moreover, as a result of measuring the IR spectrum of the resin particle composition (P-1 ′) of Comparative Example 1 in which the hydrogen bond of (u) and (j) does not exist, as shown in FIG. 2, around 1680 to 1720 cm ⁻¹ . Absorption was not observed.

<Creation of epidermis>
For the purpose of low temperature molding, resin particle compositions (P-1) to (P-13), (P-1 ′) to (S-1 P-3 ′) was filled, and after 10 seconds, the excess resin particle composition was discharged. After 60 seconds, it was cooled with water to prepare a skin (thickness 1 mm). In addition, a skin having a thickness of 0.3 mm was prepared in the same manner as described above except that the time after filling was changed to 5 seconds.

<Method of measuring 190 ° C. melt viscosity>
Using a flow tester CFT-500 manufactured by Shimadzu Corporation, the temperature was raised at a constant speed under the following conditions, and the melt viscosity at 190 ° C. was measured.
Load: 5kgf
Die: Hole diameter 0.5mm, length 1.0mm
Temperature increase rate: 5 ° C./min.

<Method for measuring storage elastic modulus at 130 ° C.>
The storage elastic modulus G ′ at 130 ° C. was measured using a dynamic viscoelasticity measuring device “RDS-2” (Rheometric Scientific) under a frequency of 1 Hz.
After setting the measurement sample on the jig of the measurement apparatus, the temperature was raised to 200 ° C., and the mixture was allowed to stand at 200 ° C. for 1 minute to be melted, and then cooled and solidified to be brought into close contact with the jig.
Thereafter, measurement was performed. The measurement temperature range is 50 to 200 ° C., and by measuring the melt viscoelasticity between these temperatures, it can be obtained as curves of temperature-G ′ and temperature-G ″.
The storage elastic modulus G ′ at 130 ° C. is read from the temperature-G ′ curve.
Jig diameter: 8mm

<Measuring method of number average molecular weight (Mn)>
The number average molecular weight (Mn) of the resin was measured under the following conditions using gel permeation chromatography (GPC).
Apparatus: “HLC-8120” [manufactured by Tosoh Corporation]
Column: 2 “TSK GEL GMH6” [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF (tetrahydrofuran) solution Solution injection amount: 100 μl
Detection device: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (molecular weight 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2,890,000) [manufactured by Tosoh Corporation]
For the measurement of molecular weight, a sample was dissolved in THF, and the insoluble matter was filtered off with a glass filter and used as the sample solution.

<Volume average particle diameter measuring method>
The particle size of 50% under the sieve, measured by a laser light scattering method, was measured using a Microtrac HRA particle size analyzer 9320-X100 (manufactured by Nikkiso Co., Ltd.).

<Backside meltability>
The center part of the back surface of the molded skin was visually observed for a 1 mm thick skin, and the meltability was evaluated according to the following criteria.
5: Uniform and glossy.
4: There is a partially unmelted powder, but it is glossy.
3: There are irregularities on the entire back surface and there is no gloss. There are no pinholes penetrating the surface.
2: There are irregularities in the form of powder on the entire back surface, and there are pinholes penetrating the surface.
1: The powder does not melt and does not become a molded product.

<Abrasion resistance>
A molded skin having a thickness of 1 mm is cut to a width of 30 mm and a length of 200 mm, and is attached to a flat surface wear tester (model number FR-T, Suga tester), and a white cotton cloth is placed on the friction element and fixed. The test piece was reciprocated 3000 times with a frictional load of 0.5 kgf, and an abrasion resistance test was performed.
Evaluation was made according to the following criteria.
A: No abnormality is recognized.
○: Slight abnormality is observed but not noticeable.
Δ: Abnormality is observed and clearly visible.
X: Remarkable abnormality is recognized.

<Tensile strength, elongation, maximum load measurement method at break>
Three JIS K 6400-5 tensile test piece dumbbells No. 1 were punched from a molded skin having a thickness of 1 mm, and marked lines were formed at intervals of 40 mm in the center. The plate thickness is the minimum of 5 points between marked lines. This was attached to an autograph in an atmosphere at 25 ° C., pulled at a speed of 200 mm / min, and the tensile strength and elongation until the test piece was broken were calculated.
Moreover, the same measurement was performed with a 0.3 mm skin, and the maximum load at the time of breaking until the test piece at the time of the above test was broken was calculated.

<25 ° C. tensile strength after heat test, elongation measurement method>
A molded skin having a thickness of 1 mm was left in a circulating dryer at 130 ° C. for 600 hours. Subsequently, the treated epidermis was allowed to stand at 25 ° C. for 24 hours. Subsequently, three JIS K 6400-5 tensile test piece dumbbells No. 1 were punched out and marked at intervals of 40 mm in the center. The plate thickness is the minimum of 5 points between marked lines. This was attached to an autograph in an atmosphere at 25 ° C., pulled at a speed of 200 mm / min, and the tensile strength and elongation until the test piece was broken were calculated.

<Thermal 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, it was visually observed whether or not the cut of the sheet was fused.
Evaluation was made according to the following criteria.
○: Cutter cuts are not fused at all.
X: The cut of the cutter is fused.

The resin particle compositions (P-1) to (P-13) for slush molding of Examples 1 to 13 are the resin particle compositions (P-1 ′) to (P-3 ′) of Comparative Examples 1 to 3, respectively. As compared with the above, it is excellent in wear resistance, 25 ° C. tensile strength, maximum load at break, 25 ° C. tensile strength after heat test, and 25 ° C. elongation after heat test.
In addition, (P-1) to (P-13) are superior to or equivalent to backside meltability, thermal fusion test, and 25 ° C. elongation compared to (P-1 ′) to (P-3 ′). It is.
Moreover, since the maximum load at the time of the break of 0.3 mm of (P-1) to (P-13) is superior to (P-1 ′) to (P-3 ′), the molded skin The film thickness can be reduced.
From this, the resin particle compositions (P-1) to (P-13) for slush molding of Examples 1 to 13 are all three of meltability, heat resistance of the molded product of (P), and mechanical properties. In particular, it has excellent performance as an instrument panel material.

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

Claims (16)

Urethane resin particles (D) comprising a urethane resin or urethane urea resin (U) having a covalent bond to a residue (j) obtained by removing a hydroxyl group from an aromatic polycarboxylic acid having a valence of 3 or more. The urethane group or urea group (u) in the urethane resin or urethane urea resin (U) and a residue (j) obtained by removing a hydroxyl group from an aromatic polycarboxylic acid having a valence of 3 or more are hydrogen bonded. 1. The urethane resin particle (D) according to 1. The urethane resin particles (D) according to claim 1 or 2, wherein the urethane resin or urethane urea resin (U) is a thermoplastic resin. The urethane resin particle (D) according to any one of claims 1 to 3, wherein the urethane resin or urethane urea resin (U) has a structural unit (x) represented by the general formula (1).

[In General Formula (1), R ¹ represents a residue or OH group obtained by removing one active hydrogen from a monovalent or polyvalent active hydrogen-containing compound. The plurality of R ¹ may be the same or different. R ² represents a residue obtained by removing two active hydrogens from a divalent active hydrogen-containing compound. A plurality of R ² may be the same or different. Y represents a residue obtained by removing all carboxyl groups from a trivalent or higher aromatic polycarboxylic acid. a and b are integers satisfying 1 ≦ a ≦ (number of substituents directly connectable to the aromatic ring−b), 0 ≦ b ≦ (number of substituents directly connectable to the aromatic ring−a), and 3 ≦ a + b ≦ 8. ] In the urethane resin or urethane urea resin (U), when the residue (j) obtained by removing the hydroxyl group from the aromatic polycarboxylic acid is the residue obtained by removing the hydroxyl group from the benzene polycarboxylic acid, and there are 3 carboxyl groups When the carboxyl group is substituted at the 1,2,4-position and the number of carboxyl groups is 4, the carboxyl group is substituted at the 1,2,4,5-position or 1,2,3,4-position. The urethane resin particle (D) according to any one of claims 1 to 4. The urethane resin or urethane urea resin (U) is a polyurethane resin obtained by reacting the active hydrogen component (A) with the isocyanate component (B), and the active hydrogen component (A) is represented by the general formula (2). The urethane resin particle (D) of any one of Claims 1-4 containing the active hydrogen containing compound (C) by which it is carried out.

[In General Formula (2), R ¹ , R ² , Y, a and b are the same as those in General Formula (1). ] The urethane resin particle (D) according to any one of claims 4 to 6, wherein in the general formula (1) or (2), R ² is represented by the general formula (3).

[Wherein, R ⁴ represents a divalent aliphatic hydrocarbon group having 2 to 10 carbon atoms. ] The urethane resin particles (D) according to claim 7, wherein R ⁴ in the general formula (3) is an ethylene group. The urethane resin particle (D) according to any one of claims 4 to 8, wherein R ¹ is represented by the general formula (4) in the general formula (1) or (2).

[Wherein R ⁵ represents a monovalent hydrocarbon group having 1 to 28 carbon atoms. ] The urethane resin particle (D) according to claim 9, wherein R ⁵ in the general formula (4) is a phenyl group. In the urethane resin or urethane urea resin (U), the structural unit (x) represented by the general formula (1) is contained in an amount of 0.1 to 30% by weight based on the weight of (U). 10. The urethane resin particles (D) according to any one of 10 above. In general formula (1) and (2), a is 1 or 2, The urethane resin particle (D) of any one of Claims 4-11. A urethane resin or urethane urea resin (U1) having a structural unit (x1) in which a is 1 in the general formulas (1) and (2) at the molecular end, wherein the structural unit (x1) is the weight of (U1) The urethane resin particles (D) according to claim 12, which are contained in an amount of 0.1 to 5% by weight based on the weight. A urethane resin or urethane urea resin (U2) having a structural unit (x2) in which a is 3 or 4 in the general formulas (1) and (2), wherein the structural unit (x2) is based on the weight of (U2) The urethane resin particles (D) according to any one of claims 4 to 11, which are contained in an amount of 0.1 to 3% by weight. It is an object for slush molding, The urethane resin particle (D) of any one of Claims 1-14. The urethane resin particles (D) according to claim 15, and an additive (F) that is at least one selected from the group consisting of inorganic fillers, pigments, plasticizers, mold release agents, antiblocking agents, and stabilizers. A thermoplastic urethane resin particle composition (P) for slush molding.

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