JP2008189713A - Thermoplastic polyester elastomer resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic polyester elastomer resin composition having excellent heat resistance, wear resistance and sliding properties as various resin members and further reducing a sliding sound, a contact sound, a collision sound etc. <P>SOLUTION: The thermoplastic polyester elastomer resin composition is a resin composition comprising (a) 100 pts.mass of a thermoplastic polyester elastomer, (b) 1-30 pts.mass of potassium titanate whiskers and (c) 0.01-20 pts.mass of substituted amides having a structure of R<SB>1</SB>-CONH-R<SB>2</SB>and having 1-10 melt flow rate at 230&deg;C (JIS K 6760). A molded product of the resin composition has 500-1,500 MPa flexural modulus, &le;10 mg wear loss and &lt;0.1 coefficient of dynamic friction according to the sliding wear test (JIS K 7218 type A). The thermoplastic polyester elastomer has 15-100 MPa tensile strength at break. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a thermoplastic polyester elastomer resin composition, and more particularly to a resin composition capable of obtaining an extruded product or an injection molded product having excellent heat resistance, wear resistance, and slidability. .

In order to improve the abrasion resistance and slidability of the resin material, it is known to blend potassium titanate whiskers (for example, Patent Documents 1 and 2). However, the effect is effectively exhibited in the case of a high-rigidity thermoplastic resin or a thermosetting resin, and the effect on a low-rigidity thermoplastic resin, particularly a thermoplastic polyester elastomer, is small. As a method for improving the wear resistance and slidability of thermoplastic polyester elastomer, one or more compounds selected from thermoplastic polyester elastomer, solid lubricant, higher alcohol higher fatty acid, derivatives thereof and long-chain hydrocarbon compounds are used. A method of blending (Patent Document 3) and a method of blending a specific substituted amide compound (Patent Document 4) are known.
In recent years, there has been a demand not only for slidability, but also for reducing noise generated during operation of the sliding member and for reducing noise such as contact noise and collision noise of various resin members. .
JP-A-10-36679 JP-A-11-217509 JP 52-65552 A Japanese Patent No. 3164173

  It can provide low-rigidity molded products that have heat resistance, wear resistance, slidability, and product design freedom, and when used as sliding members, not only has good slidability. Let's provide a thermoplastic polyester elastomer resin composition that can reduce sliding noise generated during the operation of sliding members and reduce contact noise and collision noise as various resin members, and can be used especially in heat-resistant applications. It is what.

The thermoplastic polyester elastomer composition according to the present invention that has solved the above-described problems employs the following configuration. That is,
1. (A) 1 to 30 parts by mass of (b) potassium titanate whisker and (c) substituted amides having a structure of R ₁ —CONH—R ₂ (R ₁ and R) with respect to 100 parts by mass of the thermoplastic polyester elastomer ₂ is 0.01 to 20 parts by mass of an alicyclic group having 6 or more carbon atoms, an aromatic group, a saturated aliphatic hydrocarbon group, or an unsaturated aliphatic hydrocarbon group. A resin composition having a melt flow rate (JIS K 6760) at 230 ° C. of 1 to 10, a flexural modulus of the resin composition molded article is 500 to 1500 MPa, and a sliding wear test (JIS K 7218 A method) ) Is a thermoplastic polyester elastomer resin composition characterized by having a wear amount of 10 mg or less and a coefficient of dynamic friction of less than 0.1,
2. The thermoplastic polyester elastomer resin composition according to the first invention, wherein the coefficient of dynamic friction is 0.07 or less.
Further, the thermoplastic polyester elastomer of the present invention for achieving the above object has a hard segment composed of a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol and a soft segment composed mainly of an aliphatic polycarbonate. A bonded polyester elastomer, which is heated from room temperature to 300 ° C. at a rate of temperature increase of 20 ° C./min using a differential scanning calorimeter of the thermoplastic polyester elastomer, held at 300 ° C. for 3 minutes, and then cooled down Melting point difference (Tm1−Tm3) between the melting point (Tm1) obtained by the first measurement and the melting point (Tm3) obtained by the third measurement when the cycle of lowering the temperature to room temperature at a rate of 100 ° C./min is repeated three times. Is 0 to 50 ° C., and the tensile strength at the time of cutting is 15 to 100 MPa. It is a polyester elastomer.
In this case, it is preferable that the hard segment is composed of a polybutylene terephthalate unit, and the melting point of the obtained elastomer is 200 to 225 ° C.
Moreover, in this case, it is preferable that the hard segment is composed of a polybutylene naphthalate unit, and the melting point of the obtained elastomer is 215 to 240 ° C.
In this case, when the average chain length (x) of the hard segment and the average chain length (y) of the soft segment calculated using the nuclear magnetic resonance method (NMR method) are used, the average chain length of the hard segment (x ) Is 5 to 20, and the block property (B) calculated by the following formula (1) is preferably 0.11 to 0.45.
B = 1 / x + 1 / y (1)
Further, in this case, it is preferable that the polyester is made by reacting a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol with an aliphatic polycarbonate diol having a molecular weight of 5000 to 80000 in a molten state.

The thermoplastic polyester elastomer resin composition of the present invention is a combination of a potassium titanate whisker and a substituted amide, so that the slidability and wear resistance are synergistically improved. Can also achieve the purpose. In addition, since the dispersibility of the potassium titanate whisker in the resin composition is good, there is little variation in wear and sliding properties, and a molded product having excellent extrusion moldability and stable performance can be obtained.
Furthermore, not only the slidability and wear resistance of molded products with low rigidity are improved, but also the sliding noise generated during operation as a sliding member is reduced. Etc. can be reduced. In particular, by using a thermoplastic polyester elastomer excellent in heat resistance, it can be used for heat resistance applications that could not be used in the prior art.

Hereinafter, the present invention will be described in detail.
In the thermoplastic polyester elastomer used in the present invention, a normal aromatic dicarboxylic acid is widely used as the aromatic dicarboxylic acid constituting the hard segment polyester, and the main aromatic dicarboxylic acid is terephthalic acid or naphthalene dicarboxylic acid. An acid is desirable. Other acid components include diphenyl dicarboxylic acid, isophthalic acid, aromatic dicarboxylic acid such as 5-sodium sulfoisophthalic acid, cycloaliphatic dicarboxylic acid, alicyclic dicarboxylic acid such as tetrahydrophthalic anhydride, succinic acid, glutaric acid, adipine Examples thereof include aliphatic dicarboxylic acids such as acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, and hydrogenated dimer acid. These are used within a range that does not significantly lower the melting point of the resin, and the amount thereof is less than 30 mol%, preferably less than 20 mol% of the total acid component.

  Further, in the thermoplastic polyester elastomer used in the present invention, the aliphatic or alicyclic diol constituting the hard segment polyester is widely used as a general aliphatic or alicyclic diol, and is not particularly limited. 2 to 8 alkylene glycols are desirable. Specific examples include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and the like. Most preferred are 1,4-butanediol and 1,4-cyclohexanedimethanol.

  The component constituting the hard segment polyester is preferably a butylene terephthalate unit or a butylene naphthalate unit from the viewpoint of physical properties, moldability, and cost performance.

  Moreover, the aromatic polyester suitable as polyester which comprises the hard segment in the thermoplastic polyester elastomer used for this invention can be easily obtained according to the manufacturing method of normal polyester. Moreover, what has the number average molecular weight 10000-40000 is desirable for this polyester.

  Moreover, it is preferable that the aliphatic polycarbonate which comprises the soft segment in the thermoplastic polyester elastomer used for this invention mainly consists of a C2-C12 aliphatic diol residue. Examples of these aliphatic diols include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2, 2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8- Examples include octanediol. In particular, aliphatic diols having 5 to 12 carbon atoms are preferable from the viewpoint of flexibility and low temperature characteristics of the obtained thermoplastic polyester elastomer. These components may be used alone or in combination of two or more as required, based on the case described below.

  As the aliphatic polycarbonate diol having a low temperature characteristic and constituting the soft segment of the thermoplastic polyester elastomer used in the present invention, those having a low melting point (for example, 70 ° C. or lower) and a low glass transition temperature are preferable. In general, an aliphatic polycarbonate diol composed of 1,6-hexanediol used to form a soft segment of a thermoplastic polyester elastomer has a low glass transition temperature of around -60 ° C and a melting point of around 50 ° C. Good low temperature characteristics. In addition, an aliphatic polycarbonate diol obtained by copolymerizing an appropriate amount of, for example, 3-methyl-1,5-pentanediol with the above aliphatic polycarbonate diol has a glass transition point with respect to the original aliphatic polycarbonate diol. Although the melting point is slightly increased, the melting point is lowered or becomes amorphous, so that it corresponds to an aliphatic polycarbonate diol having good low-temperature characteristics. Moreover, for example, an aliphatic polycarbonate diol composed of 1,9-nonanediol and 2-methyl-1,8-octanediol has a melting point of about 30 ° C. and a glass transition temperature of about −70 ° C., which is sufficiently low. Corresponds to aliphatic polycarbonate diol with good low-temperature properties.

  The above-mentioned aliphatic polycarbonate diol is not necessarily composed of only the polycarbonate component, and may be obtained by copolymerizing a small amount of other glycol, dicarboxylic acid, ester compound or ether compound. Examples of copolymer components include, for example, dimer diols, hydrogenated dimer diols and glycols such as modified products thereof, dicarboxylic acids such as dimer acid and hydrogenated dimer acid, aliphatic, aromatic, and alicyclic dicarboxylic acids Examples thereof include polyesters or oligoesters composed of glycol, polyesters or oligoesters composed of ε-caprolactone, polyalkylene glycol such as polytetramethylene glycol, polyoxyethylene glycol, or oligoalkylene glycol.

  The copolymer component can be used to such an extent that the effect of the aliphatic polycarbonate segment is not substantially lost. Specifically, it is 40 parts by mass or less, preferably 30 parts by mass or less, more preferably 20 parts by mass or less with respect to 100 parts by mass of the aliphatic polycarbonate segment. When the amount of copolymerization is too large, the resulting thermoplastic polyester elastomer has poor heat aging resistance and water resistance.

  As long as the thermoplastic polyester elastomer used in the present invention does not lose the effect of the invention, as a soft segment, for example, polyalkylene glycol such as polyethylene glycol and polyoxytetramethylene glycol, polyester such as polycaprolactone and polybutylene adipate, etc. A copolymer component may be introduced. The content of the copolymer component is usually 40 parts by mass or less, preferably 30 parts by mass or less, and more preferably 20 parts by mass or less with respect to 100 parts by mass of the soft segment.

  In the thermoplastic polyester elastomer used in the present invention, the mass part ratio of the polyester constituting the hard segment and the aliphatic polycarbonate and copolymer component constituting the soft segment is generally hard segment: soft segment = 30: 70 to 95. : 5, preferably 40:60 to 90:10, more preferably 45:55 to 87:13, and most preferably 50:50 to 85:15.

The thermoplastic polyester elastomer of the present invention is a polyester comprising a hard segment composed of a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol as described above and a soft segment composed mainly of an aliphatic polycarbonate. It is an elastomer. Here, the term “bonded” means that the hard segment and the soft segment are not bonded by a chain extender such as an isocyanate compound, but the units constituting the hard segment and the soft segment are directly bonded by an ester bond or a carbonate bond. The state is preferable.
For example, it is preferable to obtain the polyester constituting the hard segment, the polycarbonate constituting the soft segment, and if necessary, various copolymerization components while melting and repeating the transesterification reaction and depolymerization reaction for a certain period of time (hereinafter referred to as blocking reaction). Sometimes called).

  The blocking reaction is preferably performed at a temperature within the range of the melting point of the polyester constituting the hard segment to the melting point + 30 ° C. In this reaction, the concentration of the active catalyst in the system is arbitrarily set according to the temperature at which the reaction is carried out. That is, since the transesterification and depolymerization proceed rapidly at higher reaction temperatures, it is desirable that the active catalyst concentration in the system be low, and that there is some concentration of active catalyst at lower reaction temperatures. It is desirable that

  The catalyst may be an ordinary catalyst such as titanium compounds such as titanium tetrabutoxide and potassium oxalate titanate, or one or more tin compounds such as dibutyltin oxide and monohydroxybutyltin oxide. The catalyst may be pre-existing in the polyester or polycarbonate, in which case it need not be added anew. Furthermore, the catalyst in the polyester or polycarbonate may be partially or substantially completely deactivated in advance by any method. For example, when titanium tetrabutoxide is used as a catalyst, for example, phosphorous acid, phosphoric acid, triphenyl phosphate, tristriethylene glycol phosphate, orthophosphoric acid, carbethoxydimethyl diethyl phosphonate, triphenyl phosphite, trimethyl phosphate, trimethyl phosphite, etc. The deactivation is performed by adding a phosphorus compound or the like, but is not limited thereto.

  The above reaction can be carried out by arbitrarily determining a combination of reaction temperature, catalyst concentration, and reaction time. That is, the appropriate values of the reaction conditions vary depending on various factors such as the types and amount ratios of the hard segments and soft segments to be used, the shape of the apparatus to be used, and the stirring conditions.

  The optimum value of the reaction conditions is, for example, when the melting point of the obtained chain extension polymer and the melting point of the polyester used as the hard segment are compared, and the difference is 2 ° C to 60 ° C. When the melting point difference is less than 2 ° C., both segments are not mixed or / and reacted, and the resulting polymer exhibits poor elastic performance. On the other hand, when the difference between the melting points exceeds 60 ° C., the progress of the transesterification reaction is remarkable, so that the block property of the obtained polymer is lowered, and crystallinity, elastic performance and the like are lowered.

  It is desirable that the remaining catalyst in the molten mixture obtained by the above reaction is deactivated as completely as possible by any method. When the catalyst remains more than necessary, it is considered that the transesterification further proceeds during compounding or molding, and the physical properties of the obtained polymer fluctuate.

    This deactivation reaction can be performed, for example, in the manner described above, i.e., phosphorous acid, phosphoric acid, triphenyl phosphate, tristriethylene glycol phosphate, orthophosphoric acid, carbethoxydimethyl phosphonate, triphenyl phosphite, trimethyl phosphate, trimethyl phosphite, Although it is carried out by adding a phosphorus compound or the like, it is not limited to this.

  The thermoplastic polyester elastomer used in the present invention may contain a tri- or higher functional polycarboxylic acid or polyol only in a small amount. For example, trimellitic anhydride, benzophenone tetracarboxylic acid, trimethylolpropane, glycerin and the like can be used.

  Furthermore, the thermoplastic polyester elastomer used in the present invention can be blended with various additives depending on the purpose to obtain a composition. Additives include known hindered phenol-based, sulfur-based, phosphorus-based, amine-based antioxidants, hindered amine-based, triazole-based, benzophenone-based, benzoate-based, nickel-based, salicyl-based light stabilizers, antistatic agents, etc. Agents, lubricants, molecular modifiers such as peroxides, epoxy compounds, isocyanate compounds, compounds having reactive groups such as carbodiimide compounds, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, control agents Acid agents, antibacterial agents, fluorescent brighteners, fillers, flame retardants, flame retardant aids, organic and inorganic pigments, and the like can be added.

  Examples of the hindered phenolic antioxidant that can be blended in the present invention include 3,5-di-t-butyl-4-hydroxy-toluene, n-octadecyl-β- (4′-hydroxy-3 ′, 5 '-Di-t-butylphenyl) propionate, tetrakis [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2, 4,6′-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, calcium (3,5-di-t-butyl-4-hydroxy-benzyl-monoethyl-phosphate), triethylene glycol -Bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di- -Butylanilino) -1,3,5-triazine, 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis [3,3-bis (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, triphenol, 2,2 '-Ethylidenebis (4,6-di-t-butylphenol), N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2'- Oxamidobis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl -S- Liazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di -T-butyl-4-hydroxyhydrocinnamic ahydr triester with-1,3,5-tris (2-hydroxyethyl) -S-triazine-2,4,6 (1H, 3H, 5H), N, N-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methyl) Phenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane.

  Examples of the sulfur-based antioxidant that can be blended in the present invention include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodiuropionate, distearyl-3,3′-thiodi. Propionate, lauryl stearyl-3,3′-thiodipropionate, dilauryl thiodipropionate, dioctadecyl sulfide, pentaerythritol tetra (β-lauryl-thiopropionate) ester, etc. Can do.

  Examples of the phosphorus-based antioxidant that can be blended in the present invention include tris (mixed, mono and dinolylphenyl) phosphite, tris (2,3-di-t-butylphenyl) phosphite, 4,4 ′. -Butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecyl phosphite-5-tert-butylphenyl) ) Butane, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-) Butylphenyl) -4,4′-biphenylenephosphanite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-fo Phyto, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylene diphosphonite, triphenyl phosphite, diphenyl decyl phosphite, tridecyl phosphite, trioctyl phosphite, tridodecyl phosphite , Trioctadecyl phosphite, trinonyl phenyl phosphite, tridodecyl trithiophosphite and the like.

  Examples of amine antioxidants that can be blended in the present invention include N, N-diphenylethylenediamine, N, N-diphenylacetamidine, N, N-diphenylfluamidine, N-phenylpiperidine, dibenzylethylenediamine, and triethanol. Amine, phenothiazine, N, N′-di-sec-butyl-p-phenylenediamine, 4,4′-tetramethyl-diaminodiphenylmethane, P, P′-dioctyl-diphenylamine, N, N′-bis (1,4 -Dimethyl-pentyl) -p-phenylenediamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, amines such as 4,4′-bis (4-α, α-dimethyl-benzyl) diphenylamine and their derivatives and amines Product of aldehyde with aldehyde, reaction of amine and ketone Mention may be made from adult material.

As the hindered amine light stabilizer that can be blended in the present invention, a polycondensate with dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine oxalate, Poly [[6- (1,1,3,3-tetrabutyl) imino-1,3,5-triazine-2,4-diyl] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl ) Imyl]], bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester of 2-n-butylmalonic acid, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis (2,2,6,6-tetramethyl) -4-piperi Poly ((N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine)-(4), a polycondensate of (zyl) hexamethylenediamine and 1,2-dibromoethane. -Monoholino-1,3,5-triazine-2,6-diyl) -bis (3,3,5,5-tetramitylpiperazinone)], tris (2,2,6,6-tetramethyl-4 -Piperidyl) -dodecyl-1,2,3,4-butanetetracarboxylate, tris (1,2,2,6,6-pentamethyl-4-piperidyl) -dodecyl-1,2,3,4-butanetetra Carboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,6,11-tris [{4,6-bis (N-butyl-N- (1,2,2 , 6,6-Pentamethylpiperidine -4-yl) amino-1,3,5-triazin-2-yl) amino} undecane, 1- [2- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2, 2,6,6-tetromethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, 4, -Benzoyloxy-2,2,6,6-tetramethylpiperidine, N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6 , 6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate.

  The benzophenone, benzotriazole, triazole, nickel, and salicyl light stabilizers that can be blended in the present invention include 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octate. Xylbenzophenone, pt-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (2′-hydroxy-5′-methylphenyl) ) Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amyl-phenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethyl) Benzylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzazotri Azole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzothiazole, 2,5-bis- [5′-t-butylbenzoxazolyl- ( 2)]-thiophene, bis (3,5-di-t-butyl-4-hydroxybenzyl phosphoric acid monoethyl ester) nickel salt, 2-ethoxy-5-t-butyl-2'-ethyl oxalic acid-bis- A mixture of 85-90% anilide and 10-15% 2-ethoxy-5-t-butyl-2'-ethyl-4'-t-butyloxalic acid-bis-anilide, 2- [2-hydroxy-3, 5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-ethoxy-2′-ethyloxazalic acid bisanilide, 2- [2′-hydroxy-5′-methyl-3′- ( '', 4 '', 5 '', 6 ''-tetrahydrophthalimido-methyl) phenyl] benzotriazole, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2- (2'-hydroxy- 5'-t-octylphenyl) benzotriazole, 2-hydroxy-4-i-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, phenyl salicylate, etc. Can be mentioned.

  Examples of lubricants that can be blended in the present invention include hydrocarbon, fatty acid, fatty acid amide, ester, alcohol, metal soap, natural wax, silicone, and fluorine compounds. Specifically, liquid paraffin, synthetic paraffin, synthetic hard paraffin, synthetic isoparaffin petroleum hydrocarbon, chlorinated paraffin, paraffin wax, micro wax, low-polymerized polyethylene, fluorocarboxylic oil, lauric acid having 12 or more carbon atoms, myristic acid, Fatty acid compounds such as palmitic acid, stearic acid, arachidic acid, behenic acid, hexylamide, octylamide, stearylamide, palmitylamide, oleylamide, erucylamide, ethylenebisstearylamide, laurylamide, behenylamide, methylenebisstearylamide, C3-C30 saturated or unsaturated aliphatic amides and derivatives thereof such as ricinolamide, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters, fatty acid polyglycols Steal, butyl stearate, fatty alcohol ester of fatty acid, hydrogenated castor oil, ethylene glycol monostearate, etc., cetyl alcohol, stearyl alcohol, ethylene glycol, polyethylene glycol having a molecular weight of 200 to 10,000 or more, polyglycerol, carnauba wax, candelilla wax, montan wax And lubricants such as dimethyl silicone, silicon gum, and ethylene tetrafluoride. Also, a metal salt composed of a compound having a linear saturated fatty acid, a side chain acid, and cinnolic acid, wherein the metal is selected from (Li, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb) Can also be mentioned.

  Fillers that can be blended in the present invention include magnesium oxide, aluminum oxide, silicon oxide, calcium oxide, titanium oxide (rutile type, anatase type), chromium oxide (trivalent), iron oxide, zinc oxide, silica, Oxide such as diatomaceous earth, alumina fiber, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, basic substances or hydroxides such as manesium hydroxide, aluminum hydroxide, basic magnesium carbonate, or carbonic acid Carbonate such as magnesium, calcium carbonate, barium carbonate, ammonium carbonate, calcium sulfite, dolomite, and dawsonite, or (sulfur) sulfate such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, basic magnesium sulfate, or silicic acid Silicates such as thorium, magnesium silicate, aluminum silicate, potassium silicate, calcium silicate, talc, clay, mica, asbestos, glass fiber, montmorillonite, glass balloon, glass beads, pentonite, or kaolin (ceramic clay), perlite, iron powder , Copper powder, lead powder, aluminum powder, tungsten powder, molybdenum sulfide, carbon black, boron fiber, silicon carbide fiber, brass fiber, potassium titanate, lead zirconate titanate, zinc borate, aluminum borate, barium metaborate, boric acid Calcium, sodium borate and the like can be mentioned.

  Flame retardant aids that can be blended in the present invention include antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium pyroantimonate, tin dioxide, zinc metaborate, aluminum hydroxide, magnesium hydroxide, zirconium oxide, Examples include molybdenum oxide, red phosphorus compound, ammonium polyphosphate, melamine cyanurate, and ethylene tetrafluoride.

Examples of the compound having a triazine group and / or a derivative thereof that can be blended in the present invention include melamine, melamine cyanurate, melamine phosphate, and guanidine sulfamate.

  Examples of the inorganic phosphorus compound that can be blended in the present invention include red phosphorus compounds and ammonium polyphosphate. Examples of red phosphorus compounds include red phosphorus coated with a resin, and composite compounds with aluminum. Examples of organic phosphorus compounds include phosphate esters and melamine phosphate. Phosphate esters include phosphates, phosphonates, trimethyl phosphates of phosphinates, triethyl phosphate, tributyl phosphate, trioctyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl phosphate, tricresyl phosphate, Cresyl diphenyl phosphate, triphenyl phosphate, trixylenyl phosphate, tris-isopropylphenyl phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, bis (1,3-phenylenediphenyl) Phosphate, aromatic condensed phosphate ester 1,3- [bis (2,6-dimethylphenoxy) phosphenyloxy] benzene, 1,4- [bis 2,6-dimethyl-phenoxy) such as phosphorylase phenyloxy] benzene hydrolysis and heat stability, preferably a flame retardant.

  As a method for blending these additives, they can be blended using a kneader such as a heating roll, an extruder, or a Banbury mixer. Moreover, it can add and mix in the oligomer before the transesterification reaction or polycondensation reaction at the time of manufacturing a thermoplastic polyester elastomer resin composition.

  The thermoplastic polyester elastomer used in the present invention was heated from room temperature to 300 ° C. at a temperature rising rate of 20 ° C./min using a differential scanning calorimeter of the thermoplastic polyester elastomer, held at 300 ° C. for 3 minutes, and then cooled down. Melting point difference (Tm1−Tm3) between the melting point (Tm1) obtained by the first measurement and the melting point (Tm3) obtained by the third measurement when the cycle of lowering the temperature to room temperature at a rate of 100 ° C./min is repeated three times. Is important to be 0-50 ° C. The melting point difference is more preferably 0 to 40 ° C, further preferably 0 to 30 ° C. The melting point difference is a measure of the blockability retention of the thermoplastic polyester elastomer. The smaller the temperature difference, the better the blockability retention. When the difference in melting point exceeds 50 ° C., the blockability retention is deteriorated, the quality fluctuation at the time of molding is increased, and the uniformity of the quality of the molded product is deteriorated and the recyclability is deteriorated.

  By satisfy | filling the said characteristic, the outstanding block effect which the thermoplastic polyester elastomer used for the below-mentioned this invention has can be utilized effectively.

  In this invention, it is preferable that a hard segment consists of a polybutylene terephthalate unit, and melting | fusing point of the thermoplastic polyester elastomer obtained is 200-225 degreeC. 205-225 degreeC is more preferable.

  Moreover, in this invention, it is preferable that a hard segment consists of a polybutylene naphthalate unit and melting | fusing point of the thermoplastic polyester elastomer obtained is 215-240 degreeC. 220-240 degreeC is more preferable.

  When the hard segment is a polybutylene terephthalate unit or a polybutylene naphthalate unit, a commercially available polyester such as polybutylene terephthalate or polybutylene naphthalate can be used, which is advantageous in terms of economy.

  Moreover, when the melting point of the thermoplastic polyester elastomer used in the above is less than the lower limit, the block property is lowered, and the heat resistance and mechanical properties of the thermoplastic polyester elastomer are deteriorated. On the other hand, when the above upper limit is exceeded, the compatibility between the hard segment and the soft segment is lowered, and the mechanical properties of the thermoplastic polyester elastomer are deteriorated, which is not preferable.

  The thermoplastic polyester elastomer used in the present invention has a polyester unit as a hard segment and an aliphatic polycarbonate unit as a ft segment. The average chain length is the average number of repeating units constituting one homopolymer structural unit. In the present specification, unless otherwise indicated, values calculated using a nuclear magnetic resonance method (NMR method) are shown.

When the average chain length (x) of the hard segment and the average chain length (y) of the soft segment calculated using the nuclear magnetic resonance method (NMR method) are used, the average chain length (x) of the hard segment is 5 to 20 It is preferable that the block property (B) calculated by the following formula (1) is 0.11 to 0.45.
B = 1 / x + 1 / y (1)

  As for the thermoplastic polyester elastomer used for this invention, the average chain length of the polyester unit which is a hard segment structural component has preferable 5-20. More preferably, it is 7-18, More preferably, it is the range of 9-16.

  In the thermoplastic polyester elastomer used in the present invention, the average chain length (x) of the polyester unit of the hard segment is an important factor that determines the block property of the thermoplastic polyester elastomer, and greatly affects the melting point of the thermoplastic polyester elastomer. affect. Generally, as the average chain length (x) of the polyester units increases, the melting point of the thermoplastic polyester elastomer also increases. Further, the average chain length (x) of the polyester units of the hard segment is a factor that affects the mechanical properties of the thermoplastic polyester elastomer. When the average chain length (x) of the polyester unit of the hard segment is less than 5, it means that randomization has progressed, and the mechanical properties such as the decrease in heat resistance due to the decrease in melting point, hardness, tensile strength, elastic modulus, etc. Degradation of properties is large. When the average chain length (x) of the polyester unit of the hard segment is large, the compatibility with the aliphatic carbonate diol constituting the soft segment is lowered, causing phase separation, greatly affecting the mechanical properties, and its strength. , Reduce the elongation.

Moreover, it is preferable that block property (B) is 0.11-0.45. 0.13-0.40 is more preferable and 0.15-0.35 is still more preferable. As the value increases, the block property decreases. When the block property exceeds 0.4, the polymer properties such as the melting point of the thermoplastic polyester elastomer being lowered due to the block property decline are not preferable. On the other hand, if it is less than 0.10, the compatibility between the hard segment and the soft segment is lowered, causing deterioration of mechanical properties such as strong elongation and bending resistance of the thermoplastic polyester elastomer and an increase in fluctuation of the properties. Therefore, it is not preferable.
Here, the block property is calculated by the following equation (1).
B = 1 / x + 1 / y (1)

From the above relationship, the average chain length (y) of the soft segment is preferably 4-15.
Only when the above block property is satisfied, it is possible to achieve both high heat resistance and mechanical properties.

In the present invention, the method for bringing the above-mentioned blockability retention and blockability into the above ranges is not limited, but it is preferable to optimize the molecular weight of the polycarbonate diol as a raw material.
That is, it is preferably produced by reacting the polyester constituting the hard segment in the above-described thermoplastic polyester elastomer of the present invention with an aliphatic polycarbonate diol having a molecular weight of 5000 to 80000 in a molten state. The larger the molecular weight of the aliphatic polycarbonate diol, the higher the block property retention and the block property. The polycarbonate diol has a number average molecular weight of preferably 5000 or more, more preferably 7000 or more, and still more preferably 10,000 or more. The upper limit of the molecular weight of the polycarbonate diol is preferably 80000 or less, more preferably 70000 or less, and even more preferably 60000 or less, from the viewpoint of compatibility between the hard segment and the soft segment. If the molecular weight of the polycarbonate diol is too large, the compatibility is lowered, phase separation occurs, the mechanical properties are greatly affected, and the strength and elongation are lowered.
The tensile strength at the time of cutting of the thermoplastic polyester elastomer used in the present invention is 15 to 100 MPa, preferably 20 to 60 MPa.

  The thermoplastic polyester elastomer used in the present invention preferably has a flexural modulus of 1000 MPa or less. The flexural modulus is more preferably 800 MPa or less, and even more preferably 600 MPa or less. When the flexural modulus exceeds 1000 MPa, the flexibility of the thermoplastic polyester elastomer is insufficient, which is not preferable. The lower limit is preferably 50 MPa or more, more preferably 80 MPa or more, and further preferably 100 MPa or more. If the pressure is less than 50 MPa, the thermoplastic polyester elastomer is too soft to ensure the strength of the product.

  In addition, the thermoplastic polyester elastomer used in the present invention has an elongation retention at break of 70% or more after the heat aging test and after the water aging test of the thermoplastic polyester elastomer composition evaluated by the method described in the measurement method section. It is preferable that

  In addition, what has the number average molecular weight 10000-40000 is desirable for the aromatic polyester suitable as polyester which comprises the hard segment in the thermoplastic polyester elastomer used for this invention.

  The method for optimizing the molecular weight of the polycarbonate diol is not limited. An optimal molecular weight may be purchased or prepared, or a molecular weight adjusted by increasing the molecular weight in advance with a low molecular weight polycarbonate diol and a chain extender such as diphenyl carbonate or diisocyanate may be used. .

  For example, as a method for producing the above high molecular weight aliphatic polycarbonate diol, the above-mentioned aliphatic diol and the following carbonates, that is, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dimethyl carbonate, diphenyl carbonate It can obtain by making it react.

  Another method for producing a high molecular weight aliphatic polycarbonate diol is to react a low molecular weight aliphatic polycarbonate diol with dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dimethyl carbonate, diphenyl carbonate, etc. This is also possible.

  The thermoplastic polyester elastomer used in the present invention may contain a tri- or higher functional polycarboxylic acid or polyol only in a small amount. For example, trimellitic anhydride, benzophenone tetracarboxylic acid, trimethylolpropane, glycerin and the like can be used.

  Furthermore, the thermoplastic polyester elastomer used in the present invention can be blended with various additives depending on the purpose to obtain a composition. Additives include known hindered phenol-based, sulfur-based, phosphorus-based, amine-based antioxidants, hindered amine-based, triazole-based, benzophenone-based, benzoate-based, nickel-based, salicyl-based light stabilizers, antistatic agents, etc. Agents, lubricants, molecular modifiers such as peroxides, epoxy compounds, isocyanate compounds, compounds having reactive groups such as carbodiimide compounds, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, control agents Acid agents, antibacterial agents, fluorescent brighteners, fillers, flame retardants, flame retardant aids, organic and inorganic pigments, and the like can be added.

  Examples of the hindered phenolic antioxidant that can be blended in the present invention include 3,5-di-t-butyl-4-hydroxy-toluene, n-octadecyl-β- (4′-hydroxy-3 ′, 5 '-Di-t-butylphenyl) propionate, tetrakis [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2, 4,6′-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, calcium (3,5-di-t-butyl-4-hydroxy-benzyl-monoethyl-phosphate), triethylene glycol -Bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di- -Butylanilino) -1,3,5-triazine, 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis [3,3-bis (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, triphenol, 2,2 '-Ethylidenebis (4,6-di-t-butylphenol), N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2'- Oxamidobis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl -S- Liazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di -T-butyl-4-hydroxyhydrocinnamic ahydr triester with-1,3,5-tris (2-hydroxyethyl) -S-triazine-2,4,6 (1H, 3H, 5H), N, N-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methyl) Phenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane.

  Examples of the sulfur-based antioxidant that can be blended in the present invention include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodiuropionate, distearyl-3,3′-thiodi. Propionate, lauryl stearyl-3,3′-thiodipropionate, dilauryl thiodipropionate, dioctadecyl sulfide, pentaerythritol tetra (β-lauryl-thiopropionate) ester, etc. Can do.

  Examples of the phosphorus-based antioxidant that can be blended in the present invention include tris (mixed, mono and dinolylphenyl) phosphite, tris (2,3-di-t-butylphenyl) phosphite, 4,4 ′. -Butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecyl phosphite-5-tert-butylphenyl) ) Butane, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-) Butylphenyl) -4,4′-biphenylenephosphanite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-fo Phyto, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylene diphosphonite, triphenyl phosphite, diphenyl decyl phosphite, tridecyl phosphite, trioctyl phosphite, tridodecyl phosphite , Trioctadecyl phosphite, trinonyl phenyl phosphite, tridodecyl trithiophosphite and the like.

  Examples of amine antioxidants that can be blended in the present invention include N, N-diphenylethylenediamine, N, N-diphenylacetamidine, N, N-diphenylfluamidine, N-phenylpiperidine, dibenzylethylenediamine, and triethanol. Amine, phenothiazine, N, N′-di-sec-butyl-p-phenylenediamine, 4,4′-tetramethyl-diaminodiphenylmethane, P, P′-dioctyl-diphenylamine, N, N′-bis (1,4 -Dimethyl-pentyl) -p-phenylenediamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, amines such as 4,4′-bis (4-α, α-dimethyl-benzyl) diphenylamine and their derivatives and amines Product of aldehyde with aldehyde, reaction of amine and ketone Mention may be made from adult material.

As the hindered amine light stabilizer that can be blended in the present invention, a polycondensate with dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine oxalate, Poly [[6- (1,1,3,3-tetrabutyl) imino-1,3,5-triazine-2,4-diyl] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl ) Imyl]], bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester of 2-n-butylmalonic acid, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis (2,2,6,6-tetramethyl) -4-piperi Poly ((N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine)-(4), a polycondensate of (zyl) hexamethylenediamine and 1,2-dibromoethane. -Monoholino-1,3,5-triazine-2,6-diyl) -bis (3,3,5,5-tetramitylpiperazinone)], tris (2,2,6,6-tetramethyl-4 -Piperidyl) -dodecyl-1,2,3,4-butanetetracarboxylate, tris (1,2,2,6,6-pentamethyl-4-piperidyl) -dodecyl-1,2,3,4-butanetetra Carboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,6,11-tris [{4,6-bis (N-butyl-N- (1,2,2 , 6,6-Pentamethylpiperidine -4-yl) amino-1,3,5-triazin-2-yl) amino} undecane, 1- [2- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2, 2,6,6-tetromethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, 4, -Benzoyloxy-2,2,6,6-tetramethylpiperidine, N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6 , 6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate.

  The benzophenone, benzotriazole, triazole, nickel, and salicyl light stabilizers that can be blended in the present invention include 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octate. Xylbenzophenone, pt-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (2′-hydroxy-5′-methylphenyl) ) Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amyl-phenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethyl) Benzylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzazotri Azole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzothiazole, 2,5-bis- [5′-t-butylbenzoxazolyl- ( 2)]-thiophene, bis (3,5-di-t-butyl-4-hydroxybenzyl phosphoric acid monoethyl ester) nickel salt, 2-ethoxy-5-t-butyl-2'-ethyl oxalic acid-bis- A mixture of 85-90% anilide and 10-15% 2-ethoxy-5-t-butyl-2'-ethyl-4'-t-butyloxalic acid-bis-anilide, 2- [2-hydroxy-3, 5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-ethoxy-2′-ethyloxazalic acid bisanilide, 2- [2′-hydroxy-5′-methyl-3′- ( '', 4 '', 5 '', 6 ''-tetrahydrophthalimido-methyl) phenyl] benzotriazole, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2- (2'-hydroxy- 5'-t-octylphenyl) benzotriazole, 2-hydroxy-4-i-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, phenyl salicylate, etc. Can be mentioned.

  Examples of lubricants that can be blended in the present invention include hydrocarbon, fatty acid, fatty acid amide, ester, alcohol, metal soap, natural wax, silicone, and fluorine compounds. Specifically, liquid paraffin, synthetic paraffin, synthetic hard paraffin, synthetic isoparaffin petroleum hydrocarbon, chlorinated paraffin, paraffin wax, micro wax, low-polymerized polyethylene, fluorocarboxylic oil, lauric acid having 12 or more carbon atoms, myristic acid, Fatty acid compounds such as palmitic acid, stearic acid, arachidic acid, behenic acid, hexylamide, octylamide, stearylamide, palmitylamide, oleylamide, erucylamide, ethylenebisstearylamide, laurylamide, behenylamide, methylenebisstearylamide, C3-C30 saturated or unsaturated aliphatic amides and derivatives thereof such as ricinolamide, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters, fatty acid polyglycols Steal, butyl stearate, fatty alcohol ester of fatty acid, hydrogenated castor oil, ethylene glycol monostearate, etc., cetyl alcohol, stearyl alcohol, ethylene glycol, polyethylene glycol having a molecular weight of 200 to 10,000 or more, polyglycerol, carnauba wax, candelilla wax, montan wax And lubricants such as dimethyl silicone, silicon gum, and ethylene tetrafluoride. Also, a metal salt composed of a compound having a linear saturated fatty acid, a side chain acid, and cinnolic acid, wherein the metal is selected from (Li, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb) Can also be mentioned.

  Fillers that can be blended in the present invention include magnesium oxide, aluminum oxide, silicon oxide, calcium oxide, titanium oxide (rutile type, anatase type), chromium oxide (trivalent), iron oxide, zinc oxide, silica, Oxide such as diatomaceous earth, alumina fiber, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, basic substances or hydroxides such as manesium hydroxide, aluminum hydroxide, basic magnesium carbonate, or carbonic acid Carbonate such as magnesium, calcium carbonate, barium carbonate, ammonium carbonate, calcium sulfite, dolomite, and dawsonite, or (sulfur) sulfate such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, basic magnesium sulfate, or silicic acid Silicates such as thorium, magnesium silicate, aluminum silicate, potassium silicate, calcium silicate, talc, clay, mica, asbestos, glass fiber, montmorillonite, glass balloon, glass beads, pentonite, or kaolin (ceramic clay), perlite, iron powder , Copper powder, lead powder, aluminum powder, tungsten powder, molybdenum sulfide, carbon black, boron fiber, silicon carbide fiber, brass fiber, potassium titanate, lead zirconate titanate, zinc borate, aluminum borate, barium metaborate, boric acid Calcium, sodium borate and the like can be mentioned.

  Flame retardant aids that can be blended in the present invention include antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium pyroantimonate, tin dioxide, zinc metaborate, aluminum hydroxide, magnesium hydroxide, zirconium oxide, Examples include molybdenum oxide, red phosphorus compound, ammonium polyphosphate, melamine cyanurate, and ethylene tetrafluoride.

Examples of the compound having a triazine group and / or a derivative thereof that can be blended in the present invention include melamine, melamine cyanurate, melamine phosphate, and guanidine sulfamate.

  Examples of the inorganic phosphorus compound that can be blended in the present invention include red phosphorus compounds and ammonium polyphosphate. Examples of red phosphorus compounds include red phosphorus coated with a resin, and composite compounds with aluminum. Examples of organic phosphorus compounds include phosphate esters and melamine phosphate. Phosphate esters include phosphates, phosphonates, trimethyl phosphates of phosphinates, triethyl phosphate, tributyl phosphate, trioctyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl phosphate, tricresyl phosphate, Cresyl diphenyl phosphate, triphenyl phosphate, trixylenyl phosphate, tris-isopropylphenyl phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, bis (1,3-phenylenediphenyl) Phosphate, aromatic condensed phosphate ester 1,3- [bis (2,6-dimethylphenoxy) phosphenyloxy] benzene, 1,4- [bis 2,6-dimethyl-phenoxy) such as phosphorylase phenyloxy] benzene hydrolysis and heat stability, preferably a flame retardant.

  As a method for blending these additives, they can be blended using a kneader such as a heating roll, an extruder, or a Banbury mixer. Moreover, it can add and mix in the oligomer before the transesterification reaction or polycondensation reaction at the time of manufacturing a thermoplastic polyester elastomer resin composition.

  The thermoplastic polyester elastomer used in the present invention was heated from room temperature to 300 ° C. at a temperature rising rate of 20 ° C./min using a differential scanning calorimeter of the thermoplastic polyester elastomer, held at 300 ° C. for 3 minutes, and then cooled down. Melting point difference (Tm1−Tm3) between the melting point (Tm1) obtained by the first measurement and the melting point (Tm3) obtained by the third measurement when the cycle of lowering the temperature to room temperature at a rate of 100 ° C./min is repeated three times. Is important to be 0-50 ° C. The melting point difference is more preferably 0 to 40 ° C, further preferably 0 to 30 ° C. The melting point difference is a measure of the blockability retention of the thermoplastic polyester elastomer. The smaller the temperature difference, the better the blockability retention. When the difference in melting point exceeds 50 ° C., the blockability retention is deteriorated, the quality fluctuation at the time of molding is increased, and the uniformity of the quality of the molded product is deteriorated and the recyclability is deteriorated.

  By satisfy | filling the said characteristic, the outstanding block effect which the thermoplastic polyester elastomer used for the below-mentioned this invention has can be utilized effectively.

  In the thermoplastic polyester elastomer used in the present invention, it is preferable that the hard segment comprises a polybutylene terephthalate unit, and the thermoplastic polyester elastomer obtained has a melting point of 200 to 225 ° C. 205-225 degreeC is more preferable.

  Moreover, in the thermoplastic polyester elastomer used for this invention, it is preferable that a hard segment consists of a polybutylene naphthalate unit and melting | fusing point of the obtained thermoplastic polyester elastomer is 215-240 degreeC. 220-240 degreeC is more preferable.

  When the hard segment is a polybutylene terephthalate unit or a polybutylene naphthalate unit, a commercially available polyester such as polybutylene terephthalate or polybutylene naphthalate can be used, which is advantageous in terms of economy.

  Moreover, when the melting point of the thermoplastic polyester elastomer is less than the lower limit, the block property is lowered, and the heat resistance and mechanical properties of the thermoplastic polyester elastomer are deteriorated, which is not preferable. On the other hand, when the above upper limit is exceeded, the compatibility between the hard segment and the soft segment is lowered, and the mechanical properties of the thermoplastic polyester elastomer are deteriorated, which is not preferable.

  The thermoplastic polyester elastomer used in the present invention has a polyester unit as a hard segment and an aliphatic polycarbonate unit as a ft segment. The average chain length is the average number of repeating units constituting one homopolymer structural unit. In the present specification, unless otherwise indicated, values calculated using a nuclear magnetic resonance method (NMR method) are shown.

When the average chain length (x) of the hard segment and the average chain length (y) of the soft segment calculated using the nuclear magnetic resonance method (NMR method) are used, the average chain length (x) of the hard segment is 5 to 20 It is preferable that the block property (B) calculated by the following formula (1) is 0.11 to 0.45.
B = 1 / x + 1 / y (1)

  As for the thermoplastic polyester elastomer used for this invention, the average chain length of the polyester unit which is a hard segment structural component has preferable 5-20. More preferably, it is 7-18, More preferably, it is the range of 9-16.

  In the thermoplastic polyester elastomer used in the present invention, the average chain length (x) of the polyester unit of the hard segment is an important factor that determines the block property of the thermoplastic polyester elastomer, and greatly affects the melting point of the thermoplastic polyester elastomer. affect. Generally, as the average chain length (x) of the polyester units increases, the melting point of the thermoplastic polyester elastomer also increases. Further, the average chain length (x) of the polyester units of the hard segment is a factor that affects the mechanical properties of the thermoplastic polyester elastomer. When the average chain length (x) of the polyester unit of the hard segment is less than 5, it means that randomization has progressed, and the mechanical properties such as the decrease in heat resistance due to the decrease in melting point, hardness, tensile strength, elastic modulus, etc. Degradation of properties is large. When the average chain length (x) of the polyester unit of the hard segment is large, the compatibility with the aliphatic carbonate diol constituting the soft segment is lowered, causing phase separation, greatly affecting the mechanical properties, and its strength. , Reduce the elongation.

Moreover, it is preferable that block property (B) is 0.11-0.45. 0.13-0.40 is more preferable and 0.15-0.35 is still more preferable. As the value increases, the block property decreases. When the block property exceeds 0.4, the polymer properties such as the melting point of the thermoplastic polyester elastomer being lowered due to the block property decline are not preferable. On the other hand, if it is less than 0.10, the compatibility between the hard segment and the soft segment is lowered, causing deterioration of mechanical properties such as strong elongation and bending resistance of the thermoplastic polyester elastomer and an increase in fluctuation of the properties. Therefore, it is not preferable.
Here, the block property is calculated by the following equation (1).
B = 1 / x + 1 / y (1)

From the above relationship, the average chain length (y) of the soft segment is preferably 4-15.
Only when the above block property is satisfied, it is possible to achieve both high heat resistance and mechanical properties.

In the thermoplastic polyester elastomer used in the present invention, the method for bringing the above-mentioned blockability retention and blockability into the above ranges is not limited, but it is preferable to optimize the molecular weight of the polycarbonate diol as a raw material.
That is, it is preferably produced by reacting the polyester constituting the hard segment in the above-described thermoplastic polyester elastomer of the present invention with an aliphatic polycarbonate diol having a molecular weight of 5000 to 80000 in a molten state. The larger the molecular weight of the aliphatic polycarbonate diol, the higher the block property retention and the block property. The polycarbonate diol has a number average molecular weight of preferably 5000 or more, more preferably 7000 or more, and still more preferably 10,000 or more. The upper limit of the molecular weight of the polycarbonate diol is preferably 80000 or less, more preferably 70000 or less, and even more preferably 60000 or less, from the viewpoint of compatibility between the hard segment and the soft segment. If the molecular weight of the polycarbonate diol is too large, the compatibility is lowered, phase separation occurs, the mechanical properties are greatly affected, and the strength and elongation are lowered.
The tensile strength at the time of cutting of the thermoplastic polyester elastomer of the present invention is 15 to 100 MPa, preferably 20 to 60 MPa.

  In addition, the composition of the present invention is characterized in that the molded article has a flexural modulus of 500 to 1500 MPa, low rigidity, high flexibility and high elasticity, and preferably 500 to 1000 MPa. When the flexural modulus exceeds 1500 MPa, the effect of reducing the contact sound and collision sound generated from the molded product tends to be small. When the flexural modulus is less than 500 MPa, the wear resistance and slidability tend to decrease.

  In addition, the thermoplastic polyester elastomer used in the present invention has an elongation retention at break of 70% or more after the heat aging test and after the water aging test of the thermoplastic polyester elastomer composition evaluated by the method described in the measurement method section. It is preferable that

  In addition, what has the number average molecular weight 10000-40000 is desirable for the aromatic polyester suitable as polyester which comprises the hard segment in the thermoplastic polyester elastomer used for this invention.

  The method for optimizing the molecular weight of the polycarbonate diol is not limited. An optimal molecular weight may be purchased or prepared, or a molecular weight adjusted by increasing the molecular weight in advance with a low molecular weight polycarbonate diol and a chain extender such as diphenyl carbonate or diisocyanate may be used. .

  For example, as a method for producing the above high molecular weight aliphatic polycarbonate diol, the above-mentioned aliphatic diol and the following carbonates, that is, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dimethyl carbonate, diphenyl carbonate It can obtain by making it react.

  Another method for producing a high molecular weight aliphatic polycarbonate diol is to react a low molecular weight aliphatic polycarbonate diol with dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dimethyl carbonate, diphenyl carbonate, etc. This is also possible.

The potassium titanate whisker used in the present invention is a potassium titanate whisker represented by K ₂ O · nTiO ₂ (wherein n represents 6 or 8), and has a general formula K ₂ O · nTiO ₂ (formula N represents 6 or 8). Specific examples of the potassium titanate whisker include potassium 6 titanate whisker and 8 potassium titanate whisker. Among these, 8 potassium titanate fibers are preferable. In the present invention, a commercially available potassium titanate whisker can also be used. Specific examples thereof include, for example, trade name: Tismo N (6 potassium titanate fiber, manufactured by Otsuka Chemical), trade name: Tismo D (8 potassium titanate fiber, Otsuka Chemical Co., Ltd.). The potassium titanate whisker may be subjected to surface treatment with a silane coupling agent, a titanium coupling agent, or the like, if necessary. A potassium titanate whisker can be used individually by 1 type, or can use 2 or more types together.

The filling amount of the potassium titanate whisker is 1 to 30% by mass, preferably 3 to 20% by mass with respect to the total amount of the thermoplastic polyester elastomer and the potassium titanate whisker. If it is less than 1% by mass, the mechanical properties, particularly the slidability and wear resistance, may be insufficiently improved. Moreover, even if it fills exceeding 30 mass%, the improvement of a mechanical physical property cannot be expected, but there exists a possibility of causing the fall of mechanical characteristics on the contrary. Moreover, it is not preferable also economically.
An average whisker diameter of 0.05 to 4 μm (preferably 0.1 to 3 μm), an average whisker length of 5 to 500 μm (preferably 7 to 300 μm), and an aspect ratio of 7 or more (preferably 10 or more) It is. As long as the average whisker diameter, average whisker length and aspect ratio are provided, conventionally known whiskers can be widely used.

The substituted amides used in the present invention have a structure of R ₁ -CONH-R ₂ , and R ₁ and R ₂ are alicyclic groups, aromatic groups, saturated aliphatic hydrocarbons having 6 or more carbon atoms. A group or an unsaturated aliphatic hydrocarbon group, and preferably at least _one of R ₁ and R ₂ has one or more double bonds. For example, saturated aliphatic hydrocarbon groups include capryl group, lauryl group, palmityl group, stearyl group, isostearyl group, and behelyl group, and unsaturated aliphatic hydrocarbon groups include oleyl group, ercaryl group, and alicyclic group. Examples of the cyclohexyl group and the aromatic group include a phenylmethane group, a toluyl group, and a xylyl group. Of these, oleyl oleic acid amide, stefryl oleic acid amide, and oleyl stearic acid amide exhibit particularly good performance as a sliding agent.

  Here, when the compounding ratio of the substituted amide is 0.01 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic polyester elastomer, good performance is exhibited. If the mass is exceeded, poor compatibility will occur. Preferably it is 0.1-5 mass parts, More preferably, it is 0.2-3 mass parts.

  In the present invention, as described above, the potassium titanate whisker and the substituted amide are used in combination with the thermoplastic polyester elastomer so that the potassium titanate whisker and the substituted amide are synergistically slidable and wear-resistant. Therefore, even if the total amount of the potassium titanate whisker and the substituted amide is a small amount of 10% by mass or less in the composition, the object can be achieved. Moreover, since the dispersibility in the composition of the potassium titanate whisker is good, there is little variation in wear resistance and sliding property, and stable performance can be exhibited.

  Further, the composition of the present invention can produce a molded product having a wear amount of 10 mg or less and a dynamic friction coefficient of less than 0.1 by a sliding wear test (JIS K 7218 A method). The amount of wear is preferably 1 mg or less, more preferably 0.7 mg or less. The dynamic friction coefficient is preferably 0.07, more preferably 0.05 or less. As the amount of wear and the value of the dynamic friction coefficient are smaller, the contact sound and the collision sound of the molded product tend to be smaller.

  It does not specifically limit as a manufacturing method of the composition of this invention, It can carry out by arbitrary methods. For example, after mixing a thermoplastic polyester elastomer and each compound with a tumbler, etc., it is kneaded in a temperature range of 150 to 260 ° C. using a twin-screw extruder, discharged into a strand, cooled with water, and then converted into chips. is there. If necessary, an underwater cutter, a hot cutter, or a mist cutter may be used. In addition to the extruder, it can be heated and kneaded by a roll mill, a Banbury mixer or the like.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but is not limited thereto. In addition, in this specification, each measurement regarding the polymer characteristic evaluation of a thermoplastic polyester elastomer was performed according to the following method.
(1) Reduced viscosity of thermoplastic polyester elastomer 0.05 g of thermoplastic polyester elastomer was dissolved in 25 mL of a mixed solvent (phenol / tetrachloroethane = 60/40) and measured at 30 ° C. using an Ostwald viscometer.

(2) Melting point (Tm) of thermoplastic polyester elastomer
Thermoplastic polyester elastomer dried under reduced pressure at 50 ° C. for 15 hours was measured by using a differential scanning calorimeter DSC-50 (manufactured by Shimadzu Corporation) at a rate of 20 ° C./min from the room temperature. did.
In addition, 10 mg of a measurement sample was weighed in an aluminum pan (TA Instruments, product number 900793.901), sealed with an aluminum lid (TA Instruments, product number 900794.901), and measured in an argon atmosphere. .

(3) Tensile strength and elongation during cutting of the thermoplastic polyester elastomer The tensile strength and elongation during cutting of the thermoplastic polyester elastomer were measured according to ASTM D638. The test piece was injection-molded into a 100 mm × 100 mm × 2 mm flat plate at a cylinder temperature (Tm + 20 ° C.) and a mold temperature of 30 ° C. using an injection molding machine (model-SAV, manufactured by Yamashiro Seiki Co., Ltd.), and then a dumbbell shape. A No. 3 test piece was punched from a flat plate.

(4) Flexural modulus Measured according to ASTM D790.

(5) Heat aging resistance (Elongation retention at cutting after heat aging test)
<Preparation of test piece>
A polyfunctional epoxy compound (0.35 parts by mass), a catalyst (0.2 parts by mass) and a stabilizer (1.2 parts by mass) are placed in a drum tumbler at 100 parts by mass of a thermoplastic polyester elastomer pellet dried at 100 ° C. for 8 hours under reduced pressure. For 30 minutes. The mixture was melt-kneaded at a temperature of (Tm + 20 ° C.) using a 40 mmφ same-direction twin screw extruder with a vent hole and extruded into a strand shape, and the strand was cut into chips by cooling with water. The chip was dried under reduced pressure at 100 ° C. to obtain a chip of a thermoplastic polyester elastomer composition.
The thermoplastic polyester elastomer was injection molded into a 100 mm × 100 mm × 2 mm flat plate at a cylinder temperature (Tm + 20 ° C.) and a mold temperature of 30 ° C. using an injection molding machine (model-SAV manufactured by Yamashiro Seiki Co., Ltd.) A dumbbell-shaped No. 3 test piece was punched from the flat plate.
<Evaluation of elongation retention during dry heat treatment and cutting>
The test piece obtained by the above method was treated at 180 ° C. for 1000 hours in a gear-type hot air dryer, and then the elongation at break was measured according to ASTM D638. For the test pieces not subjected to the dry heat treatment, the elongation at break was measured by the same method, and the retention rate of the elongation at break after the dry heat treatment was calculated.

(6) Water aging resistance (Elongation retention at cutting after water aging test)
<Preparation of test piece>
It was produced by the same method as described in the above heat aging resistance measurement method.
<Evaluation of boiling water treatment, elongation retention during cutting>
After the test piece was treated in boiling water at 100 ° C. for 2 weeks, elongation at break was measured according to ASTM D638. For the test pieces not treated in boiling water, the elongation at break was measured in the same manner, and the retention of elongation at break after the boiling water treatment was calculated.

(7) Average chain length and block property of hard segment and soft segment (when the glycol component of the polyester is butanediol and the glycol in the aliphatic polycarbonate diol is an aliphatic diol having 5 to 12 carbon atoms)
[NMR measurement]
Apparatus: Fourier transform nuclear magnetic resonance apparatus (AVANCE500 manufactured by BRUKER)
Measuring solvent: Deuterated chloroform Sample solution concentration: 3-5 vol%
1H resonance frequency: 500.13 MHz
Detection pulse flip angle: 45 °
Data acquisition time: 4 seconds Delay time: 1 second Integration count: 50-200 times Measurement temperature: Room temperature

〔Method of calculation〕
The H-NMR integrated value (in arbitrary units) of the methylene peak adjacent to oxygen in the aromatic dicarboxylic acid-butanediol-butanediol of the aromatic dicarboxylic acid chain is defined as A.
The H-NMR integrated value (unit is arbitrary) of the peak of the methylene adjacent to oxygen closer to carbonic acid of butanediol of the aromatic dicarboxylic acid-butanediol-carbonic acid chain is defined as C.
H-NMR integrated value (unit is arbitrary) of the peak of methylene adjacent to oxygen closer to the aromatic dicarboxylic acid of aromatic dicarboxylic acid-C5-C12 aliphatic diol-carbonic acid chain hexanediol And
The H-NMR integrated value (unit is arbitrary) of the methylene peak adjacent to oxygen of the carbonic acid-aliphatic diol having 5 to 12 carbon atoms-aliphatic diol having 5 to 12 carbon atoms in the carbonic acid chain is defined as D.
Hard segment average chain length (x) is
x = ((((A / 4) + (C / 2)) / ((B / 2) + (C / 2)))) × 2.
Soft segment average chain length (y) is
y = (((D / 4) + (B / 2)) / ((B / 2) + (C / 2)))) × 2.
The block property (B) was calculated by the following equation (1) from the values of x and y obtained by the above method. The smaller the value of B, the higher the block property.
B = 1 / x + 1 / y (1)

(8) Blockability retention 10 mg of the thermoplastic polyester elastomer dried under reduced pressure at 50 ° C. for 15 hours is weighed in an aluminum pan (TA Instruments, product number 900793.901), and an aluminum lid (TA Instruments, product number). After preparing the measurement sample in a sealed state in 90079.901), a differential scanning calorimeter DSC-50 (manufactured by Shimadzu Corporation) was used, and the temperature was increased from room temperature to 300 ° C. at a temperature rising rate of 20 ° C./min under a nitrogen atmosphere. The sample was taken out of the sample pan, held at 300 ° C. for 3 minutes, and immersed in liquid nitrogen to be rapidly cooled. Thereafter, the sample was taken out from the liquid nitrogen and left at room temperature for 30 minutes. The measurement sample pan is set on a differential scanning calorimeter and allowed to stand at room temperature for 30 minutes, and then the temperature is raised again from room temperature to 300 ° C. at a temperature rising rate of 20 ° C./min. The melting point difference (Tm1−Tm3) between the melting point (Tm1) obtained by the first measurement when this cycle is repeated three times and the melting point (Tm3) obtained by the third measurement is obtained, and the melting point difference is determined as a block property. Retainability. The smaller the temperature difference, the better the blockability retention.
Based on the melting point difference evaluated by the above method, the blockability retention was determined and displayed according to the following criteria.
A: Melting point difference 0 to 30 ° C.
○: Melting point difference 30-40 ° C
Δ: Melting point difference 40-50 ° C
X: Melting point difference 50 ° C. or more

(9) Molecular weight of aliphatic polycarbonate diol A terminal group was calculated by dissolving an aliphatic polycarbonate diol sample in deuterated chloroform (CDCl3) and measuring H-NMR in the same manner as described in (7) above. And obtained by the following formula.
Molecular weight = 1000000 / ((Terminal group weight (equivalent / ton)) / 2)
(10) Number average molecular weight (Mn) of aromatic polyester
The value was calculated according to the following formula using the value of reduced viscosity (ηsp / c) determined by the same method as that for measuring the reduced viscosity of the thermoplastic polyester elastomer.
ηsp / c = 1.919 × 10 −4 × Mn 0.8929−0.0167

[Method for producing aliphatic polycarbonate diol]
Method for producing aliphatic polycarbonate diol (molecular weight 10,000):
Aliphatic polycarbonate diol (Ube Industries, Ltd. carbonate diol UH-CARB200, molecular weight 2000, 1,6-hexanediol type) 100 parts by mass and diphenyl carbonate 8.6 parts by mass were respectively charged and reacted at a temperature of 205 ° C. and 130 Pa. It was. After 2 hours, the contents were cooled and the polymer was removed. The molecular weight was 10,000.

Method for producing aliphatic polycarbonate diol (molecular weight 20000):
Aliphatic polycarbonate diol (Ube Industries, Ltd. carbonate diol UH-CARB200, molecular weight 2000, 1,6-hexanediol type) 100 parts by mass and diphenyl carbonate 9.6 parts by mass were respectively charged and reacted at a temperature of 205 ° C. and 130 Pa. It was. After 2 hours, the contents were cooled and the polymer was removed. The molecular weight was 20000.

Method for producing aliphatic copolymer polycarbonate diol (molecular weight 10,000):
Aliphatic copolymer polycarbonate diol (Asahi Kasei Chemicals carbonate diol T5652, molecular weight 2000, copolymer of 1,6-hexanediol and 1,5-pentanediol, amorphous) 100 parts by mass and diphenyl carbonate 8.6 Each mass part was charged and reacted at a temperature of 205 ° C. and 130 Pa. After 2 hours, the contents were cooled and the polymer was removed. The molecular weight was 10,000.

Production method of aliphatic polycarbonate diol (molecular weight 85000) Aliphatic polycarbonate diol (Ube Industries, Ltd. carbonate diol UH-CARB200, molecular weight 2000, 1,6-hexanediol type) and diphenyl carbonate were each 100 parts by mass and 10.7. Polymerization was advanced at a temperature of 205 ° C. and 130 Pa by charging a mass part. After 2 hours and 45 minutes, the contents were cooled and the polymer was removed. The molecular weight was 85000.

100 parts by mass of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 43 parts by mass of a polycarbonate diol having a number average molecular weight of 10000 prepared by the above method were stirred at 230 ° C. to 245 ° C. under 130 Pa for 1 hour, After confirming that it became transparent, the contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured, and the result is shown in Table 1. The polymer (thermoplastic polyester elastomer) obtained in this example had good properties and high quality.
100 parts by mass of the obtained polymer, 5.3 parts by mass of Tismo N (6-potassium titanate fiber, manufactured by Otsuka Chemical Co., Ltd.) as potassium titanate whisker, 0.5 parts by mass of oleyl stearamide as substituted amides, After mixing 0.5 parts by mass of polyethylene glycol-diglycidyl ether, 0.2 parts by mass of triphenylphosphine and 0.5 parts by mass of antioxidant Irganox 1010 as thickeners, the mixture was mixed in the same direction of 40 mmφ. It knead | mixed at 230 degreeC using the biaxial extruder, and it cut | disconnected with the strand cutter, discharging in strand form in the water tank, and cooling, and obtained the chip | tip of the composition.

100 parts by weight of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 43 parts by weight of a polycarbonate diol having a number average molecular weight of 20000 prepared by the above method were stirred at 230 ° C. to 245 ° C. under 130 Pa for 1.5 hours, After confirming that the resin became transparent, the contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured, and the result is shown in Table 1. The polymer (thermoplastic polyester elastomer) obtained in this example had the same quality as the thermoplastic polyester elastomer obtained in Example 1 and was of high quality.
The obtained polymer was used in the same manner as in Example 1 to obtain a chip of the composition.

100 parts by mass of polybutylene terephthalate (PBT) having a number average molecular weight of 30,000 and 43 parts by mass of an aliphatic copolymer polycarbonate diol having a number average molecular weight of 10,000 prepared by the above method are stirred at 230 ° C. to 245 ° C. under 130 Pa for 1 hour. After confirming that the resin became transparent, the contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured, and the result is shown in Table 1.
The polymer (thermoplastic polyester elastomer) obtained in this example had the same quality as the thermoplastic polyester elastomer obtained in Example 1 and was of high quality. Moreover, compared with the case where the polycarbonate diol which consists of 1, 6- hexanediol is used as a soft segment, it is excellent in the low temperature characteristic.
The obtained polymer was used in the same manner as in Example 1 to obtain a chip of the composition.

100 parts by weight of polybutylene naphthalate (PBN) having a number average molecular weight of 30,000 and 43 parts by weight of a polycarbonate diol having a number average molecular weight of 10,000 prepared by the above method are stirred at 245 ° C. to 260 ° C. under 130 Pa for 1 hour, and resin Was confirmed to be transparent, and the contents were taken out and cooled to obtain a polymer. The physical properties of the obtained polymer were measured, and the results are shown in Table 1. The polymer (thermoplastic polyester elastomer) obtained in this example was a block equivalent to the thermoplastic polyester elastomer obtained in Example 1. The thermoplastic polyester elastomer obtained in Example 1 had a higher melting point and higher quality than the thermoplastic polyester elastomer obtained in Example 1.
The obtained polymer was used in the same manner as in Example 1 to obtain a chip of the composition.

100 parts by mass of polybutylene terephthalate (PBT) having a number average molecular weight of 38000 and 43 parts by mass of a polycarbonate diol having a number average molecular weight of 12000 prepared by the above method are stirred at 230 to 245 ° C. and 130 Pa for 1 hour, and the resin is transparent. The contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured, and the result is shown in Table 1.
The polymer (thermoplastic polyester elastomer) obtained in this example had good properties and high quality.

[Comparative Example 1]
100 parts by mass of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 43 parts by mass of polycarbonate diol C (carbonate diol UH-CARB200, molecular weight 2000) manufactured by Ube Industries, Ltd. are stirred at 230 ° C. to 245 ° C. and 130 Pa for 10 minutes. After confirming that the resin became transparent, the contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured, and the result is shown in Table 1. The polymer (thermoplastic polyester elastomer) obtained in this comparative example was inferior in block property and block property retention. Furthermore, the reduced viscosity was low, the heat aging resistance was inferior, and the quality was low. Moreover, since the molecular weight was low, the flexural modulus could not be measured.
The obtained polymer was used in the same manner as in Example 1 to obtain a chip of the composition.

[Comparative Example 2]
100 parts by weight of polybutylene terephthalate (PBT) having a number average molecular weight of 30000 and 43 parts by weight of a polycarbonate diol having a number average molecular weight of 85000 prepared by the above method were stirred at 230 ° C. to 245 ° C. under 130 Pa for 5 hours. Remained cloudy. The contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured, and the results are shown in Table 1. The polymer (thermoplastic polyester elastomer) obtained in this comparative example has excellent blockability and blockability retention, but the compatibility between the hard segment and the soft segment is poor, so mechanical properties such as tensile strength are inferior. The characteristic variation was large and the quality was low.
The obtained polymer was used in the same manner as in Example 1 to obtain a chip of the composition.

[Comparative Example 3]
100 parts by weight of polybutylene terephthalate (PBT) having a number average molecular weight of 2000 and an aliphatic copolymer polycarbonate diol (carbonate diol T manufactured by Asahi Kasei Chemicals Corporation)
5652, molecular weight 2000, copolymer of 1,6-hexanediol and 1,5-pentanediol, amorphous) 43 parts by mass at 230 ° C. to 245 ° C. under 130 Pa for 10 minutes, the resin is transparent The contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured, and the result is shown in Table 2. The polymer (thermoplastic polyester elastomer) obtained in this comparative example was inferior in blockability and blockability retention and was of lower quality than the thermoplastic polyester elastomer obtained in Example 4. Moreover, since the molecular weight was low, the flexural modulus could not be measured.
The obtained polymer was used in the same manner as in Example 1 to obtain a chip of the composition.

[Comparative Example 4]
Regarding the thermoplastic polyester elastomer (polybutylene terephthalate unit / polyoxytetramethylene glycol unit = 63.5 / 36.5 (mass ratio)) composed of polybutylene terephthalate and polyoxytetramethylene glycol, the physical properties were measured and the results As shown in Table 1, it is clear that the heat aging resistance is inferior.
The obtained polymer was used in the same manner as in Example 1 to obtain a chip of the composition.

[Comparative Example 5]
Various properties of the thermoplastic polyester elastomer (polybutylene terephthalate unit / polycaprolactone unit = 70/30 (mass ratio)) composed of polybutylene terephthalate and polycaprolactone were measured and the results are shown in Table 2, but the water resistance is poor. It is clear. Further, a slight odor was felt when remelted.
The obtained polymer was used in the same manner as in Example 1 to obtain a chip of the composition.

[Comparative Example 6]
In Example 1, the modification which does not mix | blend an oleyl stearamide as a resin composition for molded articles was performed, and the chip | tip of the composition was obtained.

[Comparative Example 7]
In Example 1, the modification which does not mix | blend potassium titanate whisker as a resin composition for molded articles was performed, and the chip | tip of the composition was obtained.

Next, the chips of each composition obtained in Examples 1 to 5 and Comparative Examples 1 to 7 were dried at 100 ° C. for 2 hours with a shelf dryer, and then test test pieces were produced and molded with an injection molding machine. The product was evaluated and the results are shown in Tables 1 and 2. The heat aging resistance was evaluated by the same method as the polymer evaluation. After treatment at 180 ° C. for 1000 hours in a gear type hot air dryer, the elongation at break was measured according to ASTM D638, and dry heat treatment was performed. The retention of elongation at break after dry heat treatment was calculated in comparison with no test piece.
[Sliding wear test]
The amount of wear (mg) and the dynamic friction coefficient were measured in accordance with JIS K 7218 Method A. The mating material is S45C, the test speed is 30 cm / sec, the load is 98 N (10 kg), and the sliding distance is 500 m (50 min).

[Evaluation of collision sound]
The molded products having a size of 100 mm × 100 mm and a thickness of 2 mm were hit against each other, and ranked in four levels according to the height of the hitting sound generated at that time.
X: High impact noise is remarkable. Δ: High-pitched impact sound is slightly reduced. ○: Almost no high impact noise. A: Only a dull and low impact sound is generated.

  From Table 2, the polyester elastomer composition of the present invention has a stable extrudability moldability, can provide a molded product excellent in wear resistance and slidability, and the generated sound when the molded products collide with each other is remarkable. It can be seen that when it is used as a sliding member, the sound generated during operation can be reduced.

The polyester elastomer composition of the present invention has heat resistance, and not only improves the slidability and wear resistance of a low-rigidity molded product, but also prevents sliding noise generated during operation as a sliding member. In addition, various resin components can reduce contact noise and impact noise, and because they have excellent design flexibility, they can be used for a wide range of molded products that have never been used before. Is possible.

Claims (7)

(A) 1 to 30 parts by mass of (b) potassium titanate whisker and (c) substituted amides having a structure of R ₁ —CONH—R ₂ (R ₁ and R) with respect to 100 parts by mass of the thermoplastic polyester elastomer ₂ is 0.01 to 20 parts by mass of an alicyclic group having 6 or more carbon atoms, an aromatic group, a saturated aliphatic hydrocarbon group, or an unsaturated aliphatic hydrocarbon group. A resin composition having a melt flow rate (JIS K 6760) at 230 ° C. of 1 to 10, a flexural modulus of the resin composition molded article is 500 to 1500 MPa, and a sliding wear test (JIS K 7218 A method) A thermoplastic polyester elastomer resin composition having a wear amount of 10 mg or less and a dynamic friction coefficient of less than 0.1. 2. The thermoplastic polyester elastomer resin composition according to claim 1, wherein the coefficient of dynamic friction is 0.07 or less.   A thermoplastic polyester elastomer is a polyester elastomer in which a hard segment composed of a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol and a soft segment composed mainly of an aliphatic polycarbonate are bonded, and the thermoplastic elastomer Using a differential scanning calorimeter of polyester elastomer, the temperature was increased from room temperature to 300 ° C. at a temperature increase rate of 20 ° C./min, held at 300 ° C. for 3 minutes, and then cooled to room temperature at a temperature decrease rate of 100 ° C./min. The melting point difference (Tm1−Tm3) between the melting point (Tm1) obtained by the first measurement and the melting point (Tm3) obtained by the third measurement is 0 to 50 ° C., and the tensile strength at the time of cutting The thermoplastic polyester elastomer according to claim 1, wherein the strength is 15 to 100 MPa. Chromatography resin composition.   The thermoplastic polyester elastomer resin composition according to claim 1, wherein the thermoplastic polyester elastomer comprises a hard segment of polybutylene terephthalate units, and the thermoplastic polyester elastomer obtained has a melting point of 200 to 225 ° C.   The thermoplastic polyester elastomer resin composition according to claim 1, wherein the thermoplastic polyester elastomer comprises a hard segment of polybutylene naphthalate units, and the thermoplastic polyester elastomer obtained has a melting point of 215 to 240 ° C. . When the average chain length (x) of the hard segment and the average chain length (y) of the soft segment calculated by the nuclear magnetic resonance method (NMR method) of the thermoplastic polyester elastomer are used, the average chain length (x) of the hard segment The thermoplastic polyester elastomer resin composition according to claim 1, wherein the block property (B) calculated by the following formula (1) is 0.11 to 0.45. .
B = 1 / x + 1 / y (1) The thermoplastic polyester elastomer is produced by reacting a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol with an aliphatic polycarbonate diol having a molecular weight of 5000 to 80000 in a molten state. The thermoplastic polyester elastomer resin composition according to claim 1.