JP6717624B2 - Thermoplastic polyurethane resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic polyurethane resin composition (hereinafter, also simply referred to as “resin composition”), and more particularly to a thermoplastic polyurethane resin composition having improved processability.

Thermoplastic polyurethane resin (TPU) adjusts various physical properties such as hardness, elastic modulus, abrasion resistance, mechanical strength, etc. by reacting with the type and blending ratio of polyisocyanate and polyol, and other monomers. can do. The thermoplastic polyurethane resin is used as a molding material in a molding processing method of a thermoplastic resin such as extrusion molding and injection molding, and for example, shoe soles and insoles, automobile interior/exterior parts, electric component parts, baseball, golf. It is widely used in various industrial fields such as a cover for covering the core of a ball such as a ball, a roll, a hose, a tube, a sheet, a fiber, and a medical article.

On the other hand, in general, in a thermoplastic resin, in order to improve the processability, for example, a large number of fine crystals are generated by blending and kneading a nucleating agent to improve the crystallinity of the thermoplastic resin, It is known to promote workability.

Examples of such a nucleating agent include sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate and disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate. Carboxylic acid metal salt, sodium bis(4-tert-butylphenyl)phosphate, sodium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate and lithium-2,2'-methylenebis(4,4). Phosphate ester metal salts such as 6-di-tert-butylphenyl)phosphate, dibenzylidene sorbitol, bis(methylbenzylidene)sorbitol, bis(3,4-dimethylbenzylidene)sorbitol, bis(p-ethylbenzylidene)sorbitol, and , Bis(dimethylbenzylidene) sorbitol and other polyhydric alcohol derivatives, N,N',N"-tris[2-methylcyclohexyl]-1,2,3-propanetricarboxamide, N,N',N"-tricyclohexyl Amide compounds such as -1,3,5-benzenetricarboxamide, N,N'-dicyclohexylnaphthalene dicarboxamide, and 1,3,5-tri(2,2-dimethylpropanamide)benzene are known.

However, a thermoplastic polyurethane resin is a crystalline hard segment composed of urethane groups and urea groups having strong cohesive force due to hydrogen bonds, and an amorphous soft segment composed of a polyol component having a low glass transition point. Since the polyol component itself does not have a crystal structure, the hard segment portion cannot be increased even if a nucleating agent is added. Therefore, even if the nucleating agent is added to the thermoplastic polyurethane resin, it is difficult to improve the processability thereof.

As a method for improving the processability of a thermoplastic polyurethane resin, for example, Patent Document 1 discloses a resin composition obtained by adding a polyamide-based thermoplastic elastomer (modifier) to a polyurethane resin. Further, Patent Document 2 discloses a resin composition obtained by blending a polyurethane resin with an α,β-unsaturated carboxylic acid alkyl ester monomer such as polymethylmethacrylate (PMMA), and Patent Document 3 discloses. , A polyurethane resin containing siloxy-polytetrahydrofuran is disclosed. Furthermore, in Patent Document 4, a flexible composition obtained by blending a flexible composition obtained from a thermoplastic polyurethane and a rubber-based copolymer with a polyolefin compound modified with an α,β-unsaturated dicarboxylic acid anhydride monomer. Patent Document 5 discloses a cold-resistant resin composition in which a polyurethane resin is blended with a vinyl chloride resin having a degree of polymerization of 1300 or more. Further, Patent Document 6 proposes a polyurethane film in which a terpolymer of methyl methacrylate/butadiene/styrene is blended with a thermoplastic polyurethane resin having a Shore A hardness of 90 or more.

Japanese Patent Laid-Open No. 5-1154 JP-A-5-32845 JP-A-5-156024 JP-A-6-136257 JP-A-7-82448 JP, 2011-21167, A

However, the techniques described in the above-mentioned patent documents are those in which a polymer different from the thermoplastic polyurethane resin is added, or the structure of the polyurethane polymer is modified, which may impair the original properties of the thermoplastic polyurethane resin. there were. Therefore, it has been required to realize a thermoplastic polyurethane resin composition having improved processability while using the thermoplastic polyurethane resin alone without modification.

Therefore, an object of the present invention is to provide a thermoplastic polyurethane resin composition having improved processability without adding a polymer different from the thermoplastic polyurethane resin or modifying the structure of the thermoplastic polyurethane resin itself. To provide.

As a result of repeated studies, the present inventors have found that the above problem can be solved by incorporating a phosphoric acid ester metal salt having a specific structure into a thermoplastic polyurethane resin, and complete the present invention. Came to.

（一般式（１）中、Ｒ^１〜Ｒ^４は各々独立に、水素原子または炭素原子数１〜９の直鎖若しくは分岐を有するアルキル基を表し、Ｒ^５は炭素原子数１〜４のアルキリデン基を表す。）

（一般式（２）中、Ｒ^１〜Ｒ^５は、一般式（１）と同じものを表す。）

（一般式（３）中、Ｒ^６は無置換またはヒドロキシ基で置換された炭素原子数１〜４０の脂肪族基を表し、Ｍ^１は金属原子を表し、ｎは１〜４の整数であって、Ｍ^１の金属原子の価数を表す。） That is, the thermoplastic polyurethane resin composition of the present invention is based on 100 parts by mass of the thermoplastic polyurethane resin (A), and the aromatic phosphoric acid ester metal salt (B) represented by the following general formula (1) or (2). In an amount of 0.001 to 10 parts by mass, and 10 parts by mass of the fatty acid metal salt (C) represented by the following general formula (3) with respect to 100 parts by mass of the aromatic phosphate metal salt (B). It is characterized by containing 80 parts by mass.

(In the general formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms, and R ⁵ is alkylidene having 1 to 4 carbon atoms. Represents a group.)

(In general formula (2), R< ¹ >-R< ⁵ > represents the same thing as general formula (1).).

(In general formula (3), R ⁶ represents an unsubstituted or hydroxy-substituted aliphatic group having 1 to 40 carbon atoms, M ¹ represents a metal atom, and n is an integer of 1 to 4. Represents the valence of the metal atom of M ^1. )

The resin composition of the present invention preferably further contains sodium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate (D).

Further, in the resin composition of the present invention, the thermoplastic polyurethane resin (A) is preferably an ester polyurethane resin. Furthermore, the molded article of the present invention is characterized by being obtained by molding the thermoplastic polyurethane resin composition.

According to the present invention, a thermoplastic polyurethane resin composition having improved processability is provided without adding a polymer different from the thermoplastic polyurethane resin or modifying the structure of the thermoplastic polyurethane resin itself. be able to.

Hereinafter, embodiments of the present invention will be described in detail.
First, the thermoplastic polyurethane resin (A) according to the present invention will be described.
As the thermoplastic polyurethane resin (A) used in the resin composition of the present invention, known polyurethanes such as ester-based, ether-based, ester-ether-based and carbonate-based thermoplastic polyurethane resins can be used. Of these, ester polyurethane resins are preferable because they are inexpensive and have excellent heat resistance. Examples of commercially available products of such a thermoplastic polyurethane resin include "Resamine" manufactured by Dainichiseika Kogyo Co., Ltd. and the like.

（一般式（１）中、Ｒ^１〜Ｒ^４は各々独立に、水素原子または炭素原子数１〜９の直鎖若しくは分岐を有するアルキル基を表し、Ｒ^５は炭素原子数１〜４のアルキリデン基を表す。）

（一般式（２）中、Ｒ^１〜Ｒ^５は、一般式（１）と同じものを表す。） Next, the aromatic phosphoric acid ester metal salt (B) will be described.
In the present invention, a compound selected from the aromatic phosphate metal salt (B) represented by the following general formula (1) or (2) is used as the nucleating agent component.

(In the general formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms, and R ⁵ is alkylidene having 1 to 4 carbon atoms. Represents a group.)

(In general formula (2), R< ¹ >-R< ⁵ > represents the same thing as general formula (1).).

Examples of the linear or branched alkyl group having 1 to 9 carbon atoms represented by R ^{1 to} R ⁴ in the general formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Group, sec-butyl group, tert-butyl group, isobutyl group, amyl group, tert-amyl group, hexyl group, heptyl group, octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, nonyl group, isononyl group Etc. Among them, a tert-butyl group is preferable as R ^{1 to} R ⁴ .

Examples of the alkylidene group having 1 to 4 carbon atoms represented by R ⁵ in the general formula (1) include a methylene group, an ethylidene group, a propylidene group, a butylidene group, and the like, but in the present invention, A methylene group is preferred.

As the method for producing the aromatic phosphoric acid ester metal salt (B) represented by the general formula (1) or (2), for example, cyclic phosphoric acid having a corresponding structure, a metal hydroxide, a metal oxide, Examples thereof include a method of reacting a metal compound such as a metal halide, a metal sulfate, a metal nitrate and a metal alkoxide compound with a reaction agent such as a basic compound used as necessary. In addition, an alkali metal salt of a cyclic phosphate having a corresponding structure and a metal compound such as a metal hydroxide, a metal oxide, a metal halide, a metal sulfate, a metal nitrate, or a metal alkoxide compound may be used, if necessary. There are also mentioned a method of carrying out a salt exchange reaction using the reactant used, and a method of producing cyclic phosphoric acid by hydrolysis using cyclic phosphorus oxychloride as a starting material and reacting it with a metal compound.

Specific examples of the compound represented by the general formula (1) include the following compounds. However, the present invention is not limited to these compounds.

Specific examples of the compound represented by the general formula (2) include the following compounds. However, the present invention is not limited to these compounds.

The compounding amount of the aromatic phosphate ester metal salt (B) represented by the general formula (1) or (2) is 0.001 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic polyurethane resin (A). And preferably 0.01 to 5 parts by mass. If the amount of the aromatic phosphate ester metal salt (B) is less than 0.001 part by mass, the effect of the present invention may not be obtained, and if it exceeds 10 parts by mass, the amount of the aromatic polyurethane ester metal salt in the thermoplastic polyurethane resin may be reduced. Dispersion becomes difficult, which may adversely affect the physical properties and appearance of the molded product.

（一般式（３）中、Ｒ^６は無置換またはヒドロキシ基で置換された炭素原子数１〜４０の脂肪族基を表し、Ｍ^１は金属原子を表し、ｎは１〜４の整数であって、Ｍ^１の金属原子の価数を表す。） In addition, the resin composition of the present invention further has the following general formula (3) with respect to 100 parts by mass of the aromatic phosphate metal salt (B) represented by the general formula (1) or (2). It is preferable to contain 10 to 80 parts by mass of the represented fatty acid metal salt (C).

(In the general formula (3), R ⁶ represents an unsubstituted or hydroxy-substituted aliphatic group having 1 to 40 carbon atoms, M ¹ represents a metal atom, and n is an integer of 1 to 4. Represents the valence of the metal atom of M ^1. )

In the general formula (3), the aliphatic group having 1 to 40 carbon atoms represented by R ⁶ is a hydrocarbon such as an alkyl group, an alkenyl group, or an alkyl group having two or more unsaturated bonds introduced therein. Groups, which may be substituted with hydroxyl groups and which may be branched.
Specifically, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethylhexanoic acid, undecylic acid, lauric acid, tridecyl acid, myristin Acids, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecyl acid, arachidic acid, heicosyl acid, behenic acid, tricosylic acid, lignoceric acid, cerotic acid, montanic acid, saturated fatty acids such as mericinic acid, 4-decenoic acid, 4-dodecenoic acid, palmitoleic acid, α-linolenic acid, linoleic acid, γ-linolenic acid, stearidonic acid, petroselinic acid, oleic acid, elaidic acid, vaccenic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, etc. Examples include chain unsaturated fatty acids and aromatic fatty acids such as trimesic acid.
In the present invention, an aliphatic group having 7 to 21 carbon atoms is preferable, and saturated fatty acids such as myristic acid, stearic acid and 12-hydroxystearic acid are particularly preferable.

In the general formula (3), the metal atom represented by M ¹ is an alkali metal, magnesium, aluminum, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, yttrium, barium or hafnium. Can be mentioned. Among these, alkali metals such as sodium, lithium and potassium are particularly preferably used.

In the present invention, as the fatty acid metal salt (C), lithium stearate, sodium stearate, magnesium stearate, zinc stearate, aluminum stearate, lithium myristate is used because of its good performance and relatively easy availability. , Magnesium behenate, lithium 12-hydroxystearate and the like are preferable, and lithium myristate, lithium stearate and lithium 12-hydroxystearate are more preferable.

The fatty acid metal salt (C) is a synthetic method in which a carboxylic acid compound is reacted with a metal hydroxide, followed by washing with water, dehydration and drying (double decomposition method), and a direct synthetic method without using water (direct method). Can be manufactured in.

The amount of the fatty acid metal salt (C) used is in the range of 10 to 80 parts by mass with respect to 100 parts by mass of the aromatic phosphate metal salt (B) represented by the general formula (1) or (2). It is preferable that If it is less than 10 parts by mass, the effect of the aromatic phosphate metal salt (B) as a dispersant may not be obtained in some cases, and if it is more than 80 parts by mass, the effect of the present invention may be impaired.

When the resin composition of the present invention is further blended with sodium-2,2′-methylenebis(4,6-di-tert-butylphenyl)phosphate (D), the above-mentioned general formula (1) or (2) is obtained. The effect of the present invention becomes remarkable due to the synergistic effect with the represented aromatic phosphate metal salt (B), which is preferable.

Aromatic phosphoric acid ester metal salt (B) represented by the general formula (1) or (2) and sodium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate (D) The preferable ratio of is in the range of (B):(D)=4:1 to 1:2 by mass ratio. If the amount exceeds the above range, the effect of adding the component (D) may not be sufficiently obtained.

Further, the resin composition of the present invention may optionally contain a known resin additive within a range that does not significantly impair the effects of the present invention. As such a resin additive, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, an ultraviolet absorber, a hindered amine compound, or the above general formula (1) or (2) is used. Examples thereof include nucleating agents, flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, antistatic agents, pigments and dyes, which are different from the aromatic phosphate metal salt (B).

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol and 2,2′-methylenebis(4 -Ethyl-6-tert-butylphenol), 2,2'-thiobis-(6-tert-butyl-4-methylphenol), 2,2'-thiodiethylenebis[3-(3,5-di-tert- Butyl-4-hydroxyphenyl)propionate], 2-methyl-4,6-bis(octylsulfanylmethyl)phenol, 2,2'-isobutylidene bis(4,6-dimethylphenol), isooctyl-3-(3 ,5-Di-tert-butyl-4-hydroxyphenyl)propionate, N,N′-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide, 2,2'-Oxamido-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-ethylhexyl-3-(3',5'-di-tert-butyl -4'-hydroxyphenyl)propionate, 2,2'-ethylenebis(4,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxy-benzenepropanoic acid and C13-15 alkyl Ester, 2,5-di-tert-amylhydroquinone, a polymer of hindered phenol (trade name AO.OH.98, manufactured by ADEKA Palmarol Co., Ltd.), 2,2′-methylenebis[6-(1-methylcyclohexyl) -P-cresol], 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5 -Di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 6-[3-(3-tert-butyl-4-hydroxy-5-methyl)propoxy]-2,4. 8,10-Tetra-tert-butylbenz[d,f][1,3,2]-dioxaphosphobin, hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate, bis[monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate] calcium salt, 5,7-bis(1,1-dimethylethyl)-3-hydroxy-2 Reaction product of (3H)-benzofuranone and o-xylene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol , DL-a-tocophenol (vitamin E), 2,6-bis(α-methylbenzyl)-4-methylphenol, bis[3,3-bis-(4′-hydroxy-3′-tert-butyl- (Phenyl)butanoic acid]glycol ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxy) Phenyl)propionate, distearyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, tridecyl-3,5-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis[(3,5- Di-tert-butyl-4-hydroxyphenyl)propionate], 4,4′-thiobis(6-tert-butyl-m-cresol), 2-octylthio-4,6-di(3,5-di-tert-). Butyl-4-hydroxyphenoxy)-s-triazine, 2,2′-methylenebis(4-methyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyl Ric acid]glycol ester, 4,4′-butylidene bis(2,6-di-tert-butylphenol), 4,4′-butylidene bis(6-tert-butyl-3-methylphenol), 2,2′-ethylidene bis (4,6-di-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6]. -(2-Hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, 1 ,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2 ,4,6-Trimethylbenzene, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis Su[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl) -5-methylbenzyl)phenol, 3,9-bis[2-(3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy)-1,1-dimethylethyl]-2,4,8, 10-tetraoxaspiro[5.5]undecane, triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], stearyl-3-(3,5-di-tert. -Butyl-4-hydroxyphenyl)propionic acid amide, palmityl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide, myristyl-3-(3,5-di-tert-butyl) 3-(3,5-dialkyl-4-hydroxyphenyl)propion such as -4-hydroxyphenyl)propionic amide and lauryl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic amide Examples thereof include acid derivatives.
When compounding a phenolic antioxidant, 0.001-5 mass parts is preferable with respect to 100 mass parts of thermoplastic polyurethane resin (A), and 0.03-3 mass parts is more preferable.

Examples of phosphorus antioxidants include triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenyl isooctyl phosphite, diisooctyl phenyl phosphite, diphenyl. Tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris(dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis (Tridecyl)phosphite, tris(isodecyl)phosphite, tris(tridecyl)phosphite, diphenyldecylphosphite, dinonylphenylbis(nonylphenyl)phosphite, poly(dipropyleneglycol)phenylphosphite, tetraphenyldipropyl Glycol diphosphite, trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,4-di-tert-butyl-5-methylphenyl)phosphite, tris[2 -Tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tri(decyl)phosphite, octyldiphenylphosphite, di(decyl)mono Phenyl phosphite, distearyl pentaerythritol diphosphite, mixture of distearyl pentaerythritol and calcium stearate, alkyl (C10) bisphenol A phosphite, di(tridecyl) pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol Diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,2 4,6-Tri-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tetraphenyl-tetra(tridecyl)pentaerythritol tetraphosphite, bis(2,2 4-di-tert-butyl-6-methylphenyl)ethylphosphite, tetra(tridecyl)isopropylidenediphenol Diphosphite, tetra(tridecyl)-4,4'-n-butylidene bis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-) 5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide , (1-Methyl-1-propenyl-3-ylidene)tris(1,1-dimethylethyl)-5-methyl-4,1-phenylene)hexatridecylphosphite, 2,2'-methylenebis(4,6) -Di-tert-butylphenyl)-2-ethylhexylphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-octadecylphosphite, 2,2'-ethylidenebis(4,6- Di-tert-butylphenyl)fluorophosphite, 4,4′-butylidenebis(3-methyl-6-tert-butylphenylditridecyl)phosphite, tris(2-[(2,4,8,10-tetrakis- tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, 3,9-bis(4-nonylphenoxy)-2,4,8, 10-Tetraoxa-3,9-diphosfespiro[5,5]undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4'-isopropylidenediphenol C12-15 alcohol phosphite and the like can be mentioned.
When the phosphorus antioxidant is blended, the blending amount is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 part by mass, relative to 100 parts by mass of the thermoplastic polyurethane resin (A). ..

Examples of thioether antioxidants include tetrakis[methylene-3-(laurylthio)propionate]methane, bis(methyl-4-[3-n-alkyl(C12/C14)thiopropionyloxy]5-tert-butylphenyl. ) Sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate Nate, lauryl/stearyl thiodipropionate, 4,4′-thiobis(6-tert-butyl-m-cresol), 2,2′-thiobis(6-tert-butyl-p-cresol), distearyl-di One example is sulfide.
When the thioether-based antioxidant is blended, the blending amount is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 part by mass, relative to 100 parts by mass of the thermoplastic polyurethane resin (A). ..

Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5′-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2-hydroxy-5-methylphenyl). ) Benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2 -Hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-) Octyl-6-benzotriazolylphenol), polyethylene glycol ester of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole, 2-[2-hydroxy-3-(2-acryloyloxy) Ethyl)-5-methylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]benzotriazole, 2-[2-hydroxy-3-(2- Methacryloyloxyethyl)-5-tert-octylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]-5-chlorobenzotriazole, 2-[2 -Hydroxy-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy -3-tert-amyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(3-methacryloyloxypropyl)phenyl]-5-chlorobenzo Triazole, 2-[2-hydroxy-4-(2-methacryloyloxymethyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropyl)phenyl]benzotriazole, 2- 2-(2-hydroxyphenyl)benzotriazoles such as [2-hydroxy-4-(3-methacryloyloxypropyl)phenyl]benzotriazole; Phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy)benzoate , Dodecyl (3,5-di-tert-butyl-4-hydroxy)benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy)benzoate, hexadecyl (3,5-di-tert-butyl-4) -Hydroxy)benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy)benzoate, behenyl (3,5-di-tert-butyl-4-hydroxy)benzoate and other benzoates; 2-ethyl-2 Substituted oxanilides such as'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3-methyl-3-( Cyanoacrylates such as p-methoxyphenyl)acrylate; various metal salts or metal chelates, particularly nickel or chromium salts, or chelates.
The amount of the ultraviolet absorber blended is preferably 0.001 to 10 parts by mass and more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the thermoplastic polyurethane resin (A).

Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6- Tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3 ,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6- Tetramethyl-4-piperidyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-di(tridecyl)- 1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4) -Hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinole/diethyl succinate polycondensate, 1,6-bis(2,2,6) ,6-Tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidyl Amino)hexane/2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2 ,6,6-Tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4- Bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8-12-tetraazadodecane, 1 , 6,11-Tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1 , 6,11-Tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, Bis{4-(1-octyloxy-2,2,6,6- Tetramethyl)piperidyl}decandionate, bis{4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidyl)carbonate, and TINUVIN NOR 371 manufactured by Ciba Specialty Chemicals.
When the hindered amine compound is blended, the blending amount is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 0.5 part by mass, relative to 100 parts by mass of the thermoplastic polyurethane resin (A).

Examples of the nucleating agent different from the aromatic phosphate metal salt represented by the general formula (1) or (2) include sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate and Carboxylic acid metal salts such as disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate, dibenzylidene sorbitol, bis(methylbenzylidene)sorbitol, bis(3,4-dimethylbenzylidene)sorbitol, bis( Polyhydric alcohol derivatives such as p-ethylbenzylidene)sorbitol and bis(dimethylbenzylidene)sorbitol, N,N',N"-tris[2-methylcyclohexyl]-1,2,3-propanetricarboxamide, N,N'. , N"-tricyclohexyl-1,3,5-benzenetricarboxamide, N,N'-dicyclohexylnaphthalene dicarboxamide, 1,3,5-tri(dimethylisopropoylamino)benzene and other amide compounds. You can
The blending amount of the nucleating agent is 100 parts by mass of the thermoplastic polyurethane resin (A), and the aromatic phosphate metal salt (B) represented by the general formula (1) or (2). The total amount including is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass.

Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis(diphenyl phosphate), (1-methylethylidene). -4,1-phenylene tetraphenyl diphosphate, 1,3-phenylene tetrakis (2,6-dimethylphenyl) phosphate, ADEKA Co., Ltd. trade name ADEKA STAB FP-500, ADEKA Co. Ltd. trade name ADEKA STAB FP-600, stock Adeka Stab FP-800 and other aromatic phosphates, phenylphosphonate divinyl, phenylphosphonate diallyl, phenylphosphonate (1-butenyl) and other phosphonates, phenyl diphenylphosphinate, methyl diphenylphosphinate , Phosphinic acid esters such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, phosphazene compounds such as bis(2-allylphenoxy)phosphazene, dicresylphosphazene, melamine phosphate, pyrophosphate Melamine, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compounds and phosphorus-based flame retardants such as red phosphorus, magnesium hydroxide, aluminum hydroxide, etc. Metal hydroxide, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis(pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4 -(1,2-Dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris(tribromophenoxy) -1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, and brominated flame retardants such as brominated styrene. Can be mentioned. These flame retardants are preferably used in combination with anti-dripping agents such as fluororesins and flame retardant aids such as polyhydric alcohols and hydrotalcite.
When blending the flame retardant, the blending amount is preferably 1 to 50 parts by mass, and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic polyurethane resin (A).

The lubricant is added for the purpose of imparting lubricity to the surface of the molded product and enhancing the scratch preventing effect. Examples of the lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide, butyl stearate, stearyl alcohol, stearic acid monoglyceride, sorbitan monopalmitate, Examples thereof include sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearic acid amide, oleic acid amide, and ethylenebisstearic acid amide. These may be used alone or in combination of two or more.
The blending amount of the lubricant is preferably 0.03 to 2 parts by mass, more preferably 0.01 to 0.5 part by mass, relative to 100 parts by mass of the thermoplastic polyurethane resin (A).

Examples of the filler include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, dolomite. , Silica, alumina, potassium titanate whiskers, wollastonite, fibrous magnesium oxysulfate, and the like, and the particle diameter (fiber diameter or fiber length and aspect ratio in the case of fibrous material) may be appropriately selected and used. it can. The filler may be surface-treated if necessary.
When compounding a filler, 0.01-80 mass parts is preferable with respect to 100 mass parts of thermoplastic polyurethane resin (A), and 1-50 mass parts is more preferable.

ここで、一般式（４）中、ｘ１およびｘ２はそれぞれ下記式、
０≦ｘ２／ｘ１＜１０，２≦ｘ１＋ｘ２≦２０
で表される条件を満たす数を表し、ｐは０または正の数を表す。

ここで、一般式（５）中、Ａ^q-は、ｑ価のアニオンを表し、ｐは０または正の数を表す。
また、ハイドロタルサイト類における炭酸アニオンは、一部を他のアニオンで置換したものでもよい。 Hydrotalcites are complex salt compounds consisting of magnesium, aluminum, a hydroxyl group, a carbonic acid group, and arbitrary crystal water, which are known as natural products or synthetic products, and a part of magnesium or aluminum is mixed with other metal such as alkali metal or zinc. Examples thereof include those substituted with a metal and those substituted with a hydroxyl group or a carbonate group with another anion group. Specifically, for example, the metal of hydrotalcite represented by the following general formula (4) is changed to an alkali metal. The substituted one can be mentioned. In addition, as the Al-Li-based hydrotalcites, compounds represented by the following general formula (5) can also be used.

Here, in the general formula (4), x1 and x2 are respectively the following formulas,
0≦x2/x1<10, 2≦x1+x2≦20
Represents a number satisfying the condition represented by, and p represents 0 or a positive number.

Here, in the general formula (5), A ^q− represents a q-valent anion, and p represents 0 or a positive number.
The carbonate anion in hydrotalcites may be partially replaced with another anion.

The hydrotalcites may be those obtained by dehydrating water of crystallization, higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal salts of oleic acid, organic sulfonic acid metal salts such as alkali metal salts of dodecylbenzene sulfonic acid. It may be coated with a salt, higher fatty acid amide, higher fatty acid ester, wax or the like.

Hydrotalcites may be natural products or synthetic products. Examples of the method for synthesizing the compound include Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, and Japanese Patent Publication No. 61-174270. Known methods are described in, for example, Kaihei 5-179052. Further, hydrotalcites can be used without being limited by their crystal structure, crystal particles and the like.
The blending amount of the hydrotalcites is preferably 0.001 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the thermoplastic polyurethane resin (A).

Examples of the antistatic agent include cationic antistatic agents such as fatty acid quaternary ammonium ion salt and polyamine quaternary salt; higher alcohol phosphate ester salt, higher alcohol EO adduct, polyethylene glycol fatty acid ester, anionic alkyl Anionic antistatic agents such as sulfonates, higher alcohol sulfuric acid ester salts, higher alcohol ethylene oxide adduct sulfuric acid ester salts, and higher alcohol ethylene oxide adduct phosphoric acid ester salts; polyhydric alcohol fatty acid esters, polyglycol phosphoric acid esters, polyoxy Nonionic antistatic agents such as ethylene alkyl allyl ether; amphoteric alkyl betaines such as alkyldimethylaminoacetic acid betaine; and amphoteric antistatic agents such as imidazoline type amphoteric active agents. Such antistatic agents may be used alone, or two or more kinds of antistatic agents may be used in combination.
When compounding the antistatic agent, the compounding amount is preferably 0.03 to 2 parts by mass, and more preferably 0.1 to 0.8 part by mass, relative to 100 parts by mass of the thermoplastic polyurethane resin (A).

As the pigment, a commercially available pigment may be used, and for example, Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112. , 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224. , 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114 , 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23; , 27, 29, 30, 32, 37, 40, 50 and the like.

Examples of the dye include azo dye, anthraquinone dye, indigoid dye, triarylmethane dye, xanthene dye, alizarin dye, acridine dye, stilbene dye, thiazole dye, naphthol dye, quinoline dye, nitro dye, indamine dye, oxazine dye, phthalocyanine dye. , Cyanine dyes and the like, and a plurality of these may be mixed and used.

When molding the thermoplastic polyurethane resin composition of the present invention, it can be molded using a known method for molding a thermoplastic resin composition. For example, a molded product can be obtained by using an injection molding method, an extrusion molding method, a blow molding method, a vacuum molding method, an inflation molding method, a calender molding method, a slush molding method, a dip molding method, a foam molding method, or the like.

Applications of the thermoplastic polyurethane resin composition of the present invention include automobile materials such as bumpers, dashboards, instrument panels, housing applications such as refrigerators, washing machines, and vacuum cleaners, tableware, buckets, household products such as bath products, toys, etc. General goods, storage such as tanks, molded articles such as storage containers, films, fibers and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples and the like.

(Pellet preparation conditions)
As the thermoplastic polyurethane resin (TPU) (A), a phenol-based antioxidant (tetrakis[methylene-3-((methylene-3-( 3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane) 0.1 part by mass, phosphorus-based antioxidant (tris(2,4-di-tert-butylphenyl)phosphite) 0. 1 part by mass and the additive composition shown in Table 1 below were blended, mixed for 30 minutes with a rocking mill, and then kneaded at 200° C. using a twin-screw extruder to obtain pellets. The following evaluation was performed on the obtained pellets.
However, for Comparative Example 1, the above procedure was carried out without blending the additive composition to obtain pellets.

(Crystallization temperature)
The crystallization temperature (Tc) of the pellet obtained by the above method was measured using a differential scanning calorimeter (manufactured by Diamond Perkin Elmer). A small amount of the obtained pellet was cut, heated from room temperature to 230° C. at a rate of 50° C./min, held for 10 minutes, and then cooled to 50° C. at a rate of −10° C./min. The temperature at which the reaction reached the peak top was defined as the crystallization temperature. The results are shown in Table 1 below.

化合物Ａ：リチウム−２，２’−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）ホスフェート（一般式（１）で表される芳香族リン酸エステル金属塩（Ｂ））
化合物Ｂ：アルミニウムヒドロキシビス［２，２’メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）ホスフェート］（一般式（２）で表される芳香族リン酸エステル金属塩（Ｂ））
化合物Ｃ：ソディウム−２，２’−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）ホスフェート（（Ｄ）成分）
化合物Ｄ：タルク；日本タルク株式会社製商品名「ナノエースＰ−４」
化合物Ｅ：１，３：２，４−ビス−ｏ−（３，４−ジメチルベンジリデン）−Ｄ−ソルビトール
ＬＩＭ：ミリスチン酸リチウム（（Ｃ）成分）

Compound A: Lithium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate (aromatic phosphate metal salt represented by general formula (1) (B))
Compound B: Aluminum hydroxybis[2,2′methylenebis(4,6-di-tert-butylphenyl)phosphate] (aromatic phosphoric acid ester metal salt (B) represented by general formula (2))
Compound C: Sodium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate ((D) component)
Compound D: talc; trade name "Nanoace P-4" manufactured by Nippon Talc Co., Ltd.
Compound E: 1,3:2,4-bis-o-(3,4-dimethylbenzylidene)-D-sorbitol LIM: lithium myristate ((C) component)

From Comparative Examples 1 to 4, when the aromatic phosphate metal salt (B) represented by the general formula (1) or (2) was not contained, the crystallization temperature was not improved so much.

On the other hand, from Example 1 and Example 2, the thermoplastic polyurethane resin composition containing the aromatic phosphate ester metal salt (B) represented by the general formula (1) or (2) had a high crystallization. The temperature was indicated.

Further, according to Comparative Examples 1 and 2, although sodium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate (D) was blended alone, the crystallization temperature was lowered. From Example 1 and Example 4, the synergistic effect is exhibited and the crystallization temperature is increased by using the aromatic phosphate metal salt (B) represented by the general formula (1) or (2) together. did.

From the above, it was confirmed that the thermoplastic polyurethane resin composition of the present invention can contribute to the improvement of the processability of the molded product due to the high crystallization temperature.

Claims (4)

With respect to 100 parts by mass of the thermoplastic polyurethane resin (A), 0.001 to 10 parts by mass of the aromatic phosphate metal salt (B) represented by the following general formula (1) or (2) is contained , 10 to 80 parts by mass of the fatty acid metal salt (C) represented by the following general formula (3) is contained in 100 parts by mass of the aromatic phosphate metal salt (B). Resin composition.

(In the general formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms, and R ⁵ is alkylidene having 1 to 4 carbon atoms. Represents a group.)

(In general formula (2), R< ¹ >-R< ⁵ > represents the same thing as general formula (1).).

(In the general formula (3), R ⁶ represents an unsubstituted or hydroxy-substituted aliphatic group having 1 to 40 carbon atoms, M ¹ represents a metal atom, and n is an integer of 1 to 4. Represents the valence of the metal atom of M ^1. ) Furthermore, Sodiumu 2,2'-methylenebis (4,6-di -tert- butylphenyl) thermoplastic polyurethane resin composition according to claim 1, containing phosphate (D). The thermoplastic polyurethane resin (A) is, according to claim 1 or 2 thermoplastic polyurethane resin composition wherein the ester polyurethane resin. A molded article obtained by molding the thermoplastic polyurethane resin composition according to any one of claims 1 to 3.