JP5194577B2 - Thermoplastic polyester elastomer - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a thermoplastic polyester elastomer, and in particular, is used for various molding materials including a thermoplastic polyester elastomer excellent in heat resistance, light resistance, heat aging resistance, water resistance, low temperature characteristics, etc., particularly fibers, films and sheets. Suitable for molding materials such as elastic yarns and boots, gears, tubes, packings, etc., such as heat aging resistance, water resistance, low temperature characteristics and heat resistance of automobiles, home appliance parts, etc. The present invention relates to a thermoplastic polyester elastomer useful for required applications, for example, joint boots and wire coating materials.

As thermoplastic polyester elastomers, crystalline polyesters such as polybutylene terephthalate (PBT) and polybutylene naphthalate (PBN) are used as hard segments, and polyoxyalkylenes such as polytetramethylene glycol (PTMG) and / or Or what uses polyester, such as polycaprolactone (PCL) and polybutylene adipate (PBA), as a soft segment, is known and put into practical use. (For example, Patent Documents 1 and 2)
Japanese Patent Laid-Open No. 10-17657 JP 2003-192778 A

  However, polyester polyether type elastomers using polyoxyalkylenes in the soft segment are excellent in water resistance and low-temperature properties, but are inferior in heat aging resistance, and polyester polyester type elastomers using polyester in the soft segment are Although excellent in heat aging resistance, it is known to be inferior in water resistance and low temperature characteristics.

In order to solve the above drawbacks, polyester polycarbonate type elastomers using polycarbonate as a soft segment have been proposed (see, for example, Patent Documents 3 to 8).
Japanese Patent Publication No. 7-39480 JP-A-5-295049 JP-A-6-306202 Japanese Patent Laid-Open No. 10-182784 JP 2001-206939 A JP 2001-240663 A

  Although the above-mentioned problems are solved, the polyester polycarbonate type elastomer disclosed in these patent documents has a block property and the above-mentioned polyester polycarbonate type elastomer because the molecular weight of the polycarbonate diol used as a raw material is small. The polyester polycarbonate type elastomer has a problem that it is poor in blockability when held in a molten state (hereinafter sometimes simply referred to as blockability).

  For example, if the block property is low, the melting point of the polyester polycarbonate type elastomer will be low. For example, in the case of the above joint boot or wire coating material, it is used in a high temperature environment such as around the engine of an automobile. In such cases, lack of heat resistance may be a problem. Patent Documents 4, 7 and 8 disclose that a high melting point can be achieved by introducing a naphthalate skeleton as a polyester component. However, since introduction of a naphthalate skeleton is expensive, polyester having an inexpensive terephthalate skeleton is disclosed. It is desired to increase the melting point of the components. Further, regarding a polyester polycarbonate type elastomer composed of a polyester component having a naphthalate skeleton, there is a demand for further increasing the melting point to meet the cost increase.

  Further, in recent years, from the viewpoint of environmental load and cost reduction, it has been demanded to reuse unconventional products or recycle products. In order to satisfy this requirement, high block property retention is required. From these backgrounds, development of a polyester polycarbonate type elastomer having a high block property and an excellent block property retention is strongly desired.

  In view of the problems of the above-mentioned conventional thermoplastic polyester elastomer, the present invention combines excellent heat resistance, heat aging resistance, water resistance, light resistance, low temperature characteristics, etc., and has blockability retention, It is an object of the present invention to provide a thermoplastic polyester elastomer in which the melt viscosity of the thermoplastic polyester elastomer can be easily adjusted with a chain extender.

In order to achieve the above object, the thermoplastic polyester elastomer of the present invention comprises a hard segment composed of a polyester composed of an aromatic dicarboxylic acid and butanediol, and an aliphatic diol mainly having 5 or more carbon atoms as a diol component. A thermoplastic polyester elastomer formed by bonding a soft segment made of an aliphatic polycarbonate, the carboxyl end group concentration of the thermoplastic polyester elastomer being 30 to 70 eq / ton, and the nuclear magnetic resonance method of the thermoplastic polyester elastomer ( The block property (B) calculated by the following formula (1) from the average chain length (x) of the hard segment and the average chain length (y) of the soft segment calculated using the NMR method) is 0.10 to 0.50. Thermoplastic polyester characterized in that An elastomer.
B = 1 / x + 1 / y (1)

  In this case, the thermoplastic polyester elastomer was heated from room temperature to 300 ° C. at a temperature rising rate of 20 ° C./min using a scanning differential calorimeter, held at 300 ° C. for 3 minutes, and then cooled at a 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 when the cycle of lowering the temperature to room temperature is repeated three times is 0 to 50 ° C. Preferably there is.

  In this case, the aliphatic polycarbonate chain preferably has a repeating unit represented by the following formula (2), and the average chain length n is 4 to 15.

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.
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.

  The thermoplastic polyester elastomer of the present invention is excellent in block properties and heat resistance, and maintains the characteristics of the polyester polycarbonate type elastomer that is excellent in heat aging resistance, water resistance, low temperature characteristics, etc. Block property and block property retention are improved. Due to the high block property, a decrease in heat resistance due to a decrease in melting point is suppressed, and mechanical properties such as hardness, tensile strength and elastic modulus are improved. By improving the block property retention, fluctuations in the block property during molding can be suppressed, so that the uniformity of the quality of the molded product can be enhanced. In addition, recyclability is enhanced by the characteristics, which can lead to environmental load and cost reduction. Further, since the carboxyl end group concentration of the thermoplastic polyester elastomer of the present invention is appropriately controlled, for example, melt viscosity adjustment with a chain extender such as a polyfunctional epoxy compound (hereinafter sometimes referred to as thickening treatment). ) Is easy and a stable thickening treatment can be performed. Therefore, the thickening treatment for imparting melt viscosity characteristics suitable for the molding method is easy, and there is an advantage that it can be used in a wide range of molding methods. Therefore, since the thermoplastic polyester elastomer of the present invention has the above-described excellent characteristics and advantages, it can be used for various molding materials including fibers, films, and sheets. It is also suitable for molding materials such as elastic yarns and boots, gears, tubes, packings, etc., for example, applications such as automobiles and home appliance parts that require heat aging resistance, water resistance, low temperature characteristics, specifically, It is useful for applications such as joint boots and wire coating materials. In particular, it can be suitably used as a material for parts that require high heat resistance, such as joint boots used around automobile engines and wire coating materials.

Hereinafter, the thermoplastic polyester elastomer of the present invention will be described in detail.
In the thermoplastic polyester elastomer of the present invention, the aromatic dicarboxylic acid constituting the hard segment polyester is not particularly limited, and the main aromatic dicarboxylic acid is terephthalic acid or naphthalenedicarboxylic acid. It is desirable that 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.

  In the thermoplastic polyester elastomer of the present invention, the diol constituting the hard segment polyester is preferably 1,4-butanediol. If it is less than 10 mol%, other glycols may be used in combination.

  The polyester of the hard segment is preferably PBT and PBN 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 of this invention can be easily obtained according to the manufacturing method of a normal polyester. In addition, it is generally desirable that the polyester has a number average molecular weight of 10,000 to 40,000.

  The aliphatic polycarbonate constituting the soft segment in the thermoplastic polyester elastomer of the present invention is preferably mainly composed of an aliphatic diol residue having 5 or more carbon atoms. Examples of these aliphatic diols include 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1, Examples include 5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,9-nonanediol, and 2-methyl-1,8-octanediol. 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 good low-temperature characteristics constituting the soft polyester elastomer segment in the present invention, those having a low melting point (for example, 70 ° C. or less) 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 and glycols. And polyalkylene glycols such as ε-caprolactone, polyalkylene glycols such as polytetramethylene glycol and polyoxyethylene glycol, and oligoalkylene glycols.

  The thermoplastic polyester elastomer of the present invention is a soft segment such as a polyalkylene oxide such as polyethylene oxide and polyoxytetramethylene glycol, a polyester such as polycaprolactone and polybutylene adipate, etc. as long as the effects of the invention are not lost. A polymerization component may be introduced.

  In the thermoplastic polyester elastomer of 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 elastomer in which a hard segment composed of a polyester composed of the above aromatic dicarboxylic acid and butanediol and a soft segment composed mainly of an aliphatic polycarbonate are bonded. 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 difference in melting point is less than 2 ° C., both segments are not mixed or / and reacted, and the resulting polymer exhibits inferior elastic performance. On the other hand, when the difference in melting point exceeds 60 ° C., the block property of the obtained polymer is lowered due to the remarkable progress of the transesterification reaction, 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 is carried out in the above-described manner, for example, phosphorous acid, phosphoric acid, triphenyl phosphate, tristriethylene glycol phosphate, orthophosphoric acid, carboxydimethyl diethyl phosphonate, triphenyl phosphite, trimethyl phosphate, trimethyl phosphite, etc. Although it is carried out by adding a phosphorus compound or the like, it is not limited to this.

  The thermoplastic polyester elastomer of the present invention may contain a trifunctional or higher 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 of 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 the lubricant that can be blended in the present invention include hydrocarbon, fatty acid, fatty 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, lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycols of fatty acids Steal, butyl stearate, fatty alcohol ester of fatty acid, hydrogenated castor oil, ethylene glycol monostearate, 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 of the present invention has a polyester unit as a hard segment and an aliphatic polycarbonate unit as a ft segment, and the average value of the number of repeating units constituting one homopolymer structural unit is the average chain length. 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 of this invention, the average chain length of the polyester unit which is a hard segment structural component has 5-20 preferable. More preferably, it is 7-18, More preferably, it is the range of 9-16.

  In the thermoplastic polyester elastomer of 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. Effect. 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, and elastic modulus. 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 degree of stretch.

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 addition, the thermoplastic polyester elastomer of the present invention was heated from room temperature to 300 ° C. at a temperature rising rate of 20 ° C./min using a scanning differential calorimeter, and held at 300 ° C. for 3 minutes. 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 when the cycle of lowering the temperature to room temperature at a temperature lowering rate of 100 ° C./min is repeated three times. ) Is 0 to 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 below-mentioned thermoplastic polyester elastomer of this invention has can be utilized effectively.

  In the present invention, the method for bringing the block property and block property retention 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 aforementioned polyester with an aliphatic polycarbonate diol having a molecular weight of 5000 to 80000 in a molten state. Both properties improve as the molecular weight increases. 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.

  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 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 of the present invention preferably has the above characteristics and simultaneously satisfies that the carboxyl end group concentration of the thermoplastic polyester elastomer is 30 to 70 eq / ton. The carboxyl end group concentration is more preferably 40 to 65 eq / ton. If the carboxyl end group concentration is less than 30 eq / ton, it is not preferable because the ease of melt viscosity adjustment by the thickening treatment deteriorates. That is, when molding is performed using the thermoplastic polyester elastomer of the present invention, different melt viscosity characteristics are required in various molding methods. The melt index at 230 ° C. in the case of injection molding (hereinafter sometimes referred to as MI) is 5 to 20, 2 to 12 in the case of extrusion molding, and 0.1 to 2 in the case of blow molding. preferable. In order to cope with the wide range of MI, the thermoplastic polyester elastomer obtained in the present invention is subjected to a thickening treatment. Therefore, the thermoplastic polyester elastomer of the present invention is required to have excellent suitability for the thickening treatment. The MI of the thermoplastic polyester elastomer of the present invention varies depending on the molecular weight of the thermoplastic polyester elastomer at the end of the blocking reaction, but is generally 0.1-20. The thickening treatment is often performed using an epoxy compound. The reaction during the thickening treatment with the epoxy compound is carried out by the reaction between the carboxyl end group of the thermoplastic polyester elastomer and the thickener. Accordingly, the suitability for thickening treatment is affected by the carboxyl end group concentration of the thermoplastic polyester elastomer. The higher the carboxyl end group concentration, the higher the reactivity of the thickening treatment. When the carboxyl end group concentration of the thermoplastic polyester elastomer is less than 30 eq / ton, the reactivity of the thickening treatment is low. For example, in order to achieve 0.1 to 2, which is a preferred MI for blow molding, It is necessary to increase the proportion of trifunctional compounds used as epoxy compounds. Increasing the blending ratio of the trifunctional epoxy compound is not preferable because a gelation reaction may occur during the thickening treatment or in the subsequent molding step, and the quality of the molded product may be lowered. Hereinafter, this characteristic is referred to as thickening.

  On the other hand, when the carboxyl end group concentration exceeds 70 eq / ton, the carboxyl end group concentration after the thickening treatment may exceed 10 eq / ton. When the carboxyl end group concentration after the thickening treatment exceeds 10 eq / ton, stability such as hydrolysis stability of the thickened thermoplastic polyester elastomer is lowered, and a molded article using the thermoplastic polyester elastomer is reduced. Since durability may deteriorate, it is not preferable. Hereinafter, this property is referred to as end group blocking property.

  Therefore, by satisfying the above carboxyl end group concentration range, it is possible to satisfy both the properties of thickening and end group blocking properties at the same time, and it can be applied to a wide range of molding methods.

In the present invention, the method for satisfying the above-mentioned carboxyl end group concentration range is not limited. However, as the raw material polyester used for the blocking reaction in order to form the hard segment, the carboxyl end group concentration is 43 to 95 eq / ton. It is preferable to use polyester. More preferably, a polyester having a carboxyl end group concentration of 50 to 95 eq / ton is used.

  Also, a blocking reaction is performed using a polyester having a carboxyl end group concentration of less than 43 eq / ton as a raw material, and the resulting blocked product is reacted with an acid anhydride such as phthalic anhydride to adjust the carboxyl end group concentration. It's okay.

  The thermoplastic polyester elastomer of the present invention is formed from a melt by ordinary molding techniques such as injection molding, flat film extrusion, extrusion blow molding, and coextrusion.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but is not limited thereto. In this specification, each measurement 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 flat plate of 100 mm × 100 mm × 2 mm 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 a flat plate.

(4) Flexural modulus Measured according to ASTM D790.

(5) Heat aging resistance (Elongation retention at cutting after heat aging test)
<Production 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 Tm + 20 ° C. using a 40 mmφ co-axial twin screw extruder with a vent hole, extruded into a strand, 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 the polyester elastomer composition of the present invention.
The test piece was injection molded into a flat plate of 100 mm × 100 mm × 2 mm 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 a flat plate.
<Evaluation of elongation retention during dry heat treatment and cutting>
After the test piece was treated at 180 ° C. for 1000 hours in a gear-type hot air dryer, elongation at break was measured by the above method. The elongation at break was also measured for a test piece that was not subjected to dry heat treatment, and the retention of elongation at break after dry heat treatment was calculated.

(6) Water aging resistance (Elongation retention at cutting after water aging test)
<Production 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) were 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 using a 40 mmφ same-direction twin screw extruder with a vent hole (Tm + 20 ° C.) 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 the polyester elastomer composition of the present invention.
The test piece was injection molded into a flat plate of 100 mm × 100 mm × 2 mm 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 a flat plate.
<Evaluation of boiling water treatment, elongation retention during cutting>
After the test piece was treated in boiling water at 100 ° C. for 2 weeks, the elongation at break was measured by the above method. The elongation at break was also measured for a test piece not treated in boiling water, and the retention of elongation at break after 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 / wt%
¹ H 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 (unit is arbitrary) of the methylene peak adjacent to oxygen of the aromatic dicarboxylic acid-butanediol-butanediol of the aromatic dicarboxylic acid is A.
The H-NMR integrated value (in arbitrary units) of the peak of methylene adjacent to the oxygen near the carbonic acid of the aromatic dicarboxylic acid-butanediol-carbonic acid chain butanediol is C.
The H-NMR integrated value (unit is arbitrary) of the methylene peak adjacent to oxygen closer to the aromatic dicarboxylic acid of the aromatic dicarboxylic acid-aliphatic diol having 5 or more carbon atoms-carbonate chain diol is defined as B.
Carbon dioxide-aliphatic diol having 5 or more carbon atoms-H-NMR integrated value (unit is arbitrary) of a methylene peak adjacent to oxygen of an aliphatic diol having carbon number of carbon chain or more 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
(Triangle | delta): Melting | fusing point difference 40-50 degreeC
X: Melting point difference 50 ° C. or more

(9) MI Evaluation Method The pellets of the thermoplastic polyester elastomer composition obtained in Examples and Comparative Examples are based on the test method (Method A) described in JIS K7210 (ASTM D1238), and melt flow at 230 ° C. and 2160 g. The rate (MFR: g / 10 min) was measured. For the measurement, a composition having a moisture content of 0.1% by weight or less was used.

(10) Carboxyl end group concentration 0.5 g of thermoplastic polyester elastomer was dissolved in 100 ml of benzyl alcohol / chloroform (50/50 mass ratio) and titrated with an ethanol solution of KOH. Phenol red was used as the indicator. Expressed as equivalents (eq / ton) in 1 ton of resin.

(11) Evaluation of viscosity increase 100 parts by mass of a thermoplastic polyester elastomer, 0.5 to 1.5 parts by mass of polypropylene glycolidyl glycidyl ether as a chain extender, and 0.2 parts by mass of 2-methyl-4-ethylimidazole as a catalyst Place in tumbler and mix for 30 minutes at room temperature. 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 MI of the obtained chip was evaluated and judged according to the following criteria.
○: MI can be adjusted in the range of 0.1 to 20 by adjusting the blending amount of polypropylene glycolidyl glycidyl ether, which is a chain extender. ×: Adjusting the blending amount of polypropylene glycolidlyglycidyl ether, which is a chain extender, as described above. MI cannot be adjusted within the range of 0.1-20

(12) End group blocking property The carboxyl end group concentration of the thermoplastic polyester elastomer thickened by the same method as in the thickening evaluation of (11) was evaluated and judged according to the following criteria.
○: In adjusting the MI range, the carboxyl end group concentration does not exceed 10 eq / ton. X: In adjusting the MI range, the carboxyl end group concentration exceeds 10 eq / ton.

(13) Molecular weight of aliphatic polycarbonate diol A terminal group was determined by dissolving an aliphatic polycarbonate diol sample in deuterated chloroform (CDCl ₃ ) and measuring H-NMR in the same manner as described in (7) above. It calculated and calculated | required with the following formula.
Molecular weight = 1000000 / ((Terminal group weight (equivalent / ton)) / 2)

[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.

Method for producing aliphatic polycarbonate diol (molecular weight 85000):
Aliphatic polycarbonate diol (Ube Industries' carbonate diol UH-CARB200, molecular weight 2000, 1,6-hexanediol type) and diphenyl carbonate were charged in 100 parts by mass and 10.7 parts by mass, respectively, at a temperature of 205 ° C. and 130 Pa. The polymerization proceeded at. After 2 hours and 45 minutes, the contents were cooled and the polymer was removed. The molecular weight was 85000.

[Example 1]
A polybutylene terephthalate (PBT) having a number average molecular weight of 30,000 and a carboxyl end group concentration of 75 eq / ton and 100 parts by mass of a polycarbonate diol having a number average molecular weight of 10,000 prepared by the above method are 230 ° C. to 245 ° C. The mixture was stirred at 130 Pa for 1 hour to confirm that the resin became transparent, and 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 thermoplastic polyester elastomer obtained in this example had good properties and high quality.

[Example 2]
A thermoplastic polyester elastomer was obtained in the same manner as in Example 1 except that PBT having a number average molecular weight of 27000 and a carboxyl end group concentration of 85 eq / ton was used. The results are shown in Table 1. The thermoplastic polyester elastomer obtained in this example had the same properties as the thermoplastic polyester elastomer obtained in Example 1 and was of high quality.

[Comparative Example 1]
100 mass parts of PBT having a number average molecular weight of 30000 and a carboxyl end group concentration of 75 eq / ton and 43 mass parts of polycarbonate diol C (carbonate diol UH-CARB200, molecular weight 2000, manufactured by Ube Industries) under 230 Pa to 245 ° C. and 130 Pa. The mixture was stirred for 10 minutes to confirm that the resin became transparent, and 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 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.

[Comparative Example 2]
100 parts by mass of PBT having a number average molecular weight of 30000 and a carboxyl end group concentration of 75 eq / ton and 43 parts by mass of a polycarbonate diol having a number average molecular weight of 85000 prepared by the above method are stirred at 230 ° C. to 245 ° C. under 130 Pa for 5 hours. However, the resin remained cloudy. The contents were taken out and cooled to obtain a polymer. Each physical property of the obtained polymer was measured and shown in result 1. The 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 the mechanical properties such as tensile strength are inferior, and the properties The fluctuation was large and the quality was low.

[Comparative Example 3]
A thermoplastic polyester elastomer was obtained in the same manner as in Example 1 except that PBT having a number average molecular weight of 24,000 and a carboxyl end group concentration of 40 eq / ton and 43 parts by mass of a polycarbonate diol having a number average molecular weight of 20000 were used.
The results are shown in Table 2. The thermoplastic polyester elastomer obtained in this comparative example was inferior in thickening.

[Comparative Example 4]
A thermoplastic polyester elastomer was obtained in the same manner as in Example 1 except that PBT having a number average molecular weight of 20000 and a carboxyl end group concentration of 110 eq / ton was used. The results are shown in Table 2. The thermoplastic polyester elastomer obtained in this comparative example was inferior in end group blocking properties. The PBT was prepared by thermally degrading the PBT used in Example 1.

Example 3
100 parts by mass of PBT used in Example 1 and 43 parts by mass of 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, and the resin became transparent. After confirming this, 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 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.

Example 4
100 parts by mass of PBT used in Example 1 and 43 parts by mass of an aliphatic copolymerized polycarbonate diol having a number average molecular weight of 10,000 prepared by the above method were stirred at 230 ° C. to 245 ° C. and 130 Pa for 1 hour, and the resin became transparent. After confirming that the contents were obtained, 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 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.

[Comparative Example 5]
In the method of Example 4, as the aliphatic copolymer polycarbonate diol, carbonate diol T5652 (molecular weight 2000, 1,6-hexanediol and 1,5-pentane) manufactured by Asahi Kasei Chemicals Corporation without performing the molecular weight increasing reaction in the above-described method. A thermoplastic polyester elastomer was obtained in the same manner as in Example 4 except that a copolymer with diol (amorphous) was directly used. The obtained results are shown in Table 2. The 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.

Example 5
In the production of the thermoplastic polyester elastomer used in Comparative Example 3, 0.5 parts by mass of phthalic anhydride was added to 100 parts by mass of the thermoplastic polyester elastomer at the time when the blocking reaction was completed. A thermoplastic polyester elastomer was obtained by adjusting the carboxyl end group concentration of the elastomer to 50 eq / ton.
The results are shown in Table 1. The thermoplastic polyester elastomer obtained in this example had the same characteristics as the thermoplastic polyester elastomer obtained in Examples 1 and 2, and was of high quality.

Example 6
100 parts by mass of polybutylene naphthalate (PBN) having a number average molecular weight of 30,000 and a carboxyl end group concentration of 80 eq / ton and 43 parts by mass of a polycarbonate diol having a number average molecular weight of 10,000 prepared by the above method are 245 ° C. to 260 ° C. The mixture was stirred at 130 Pa for 1 hour to confirm that the resin became 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 thermoplastic polyester elastomer obtained in this example has the same block properties and block as the thermoplastic polyester elastomer obtained in Example 1. The melting point was higher than that of the thermoplastic polyester elastomer obtained in Example 1, and the quality was higher.

Example 7
A number average molecular weight of 30000, a carboxyl end group concentration of 40 eq / ton polybutylene terephthalate (PBT) 100 parts by mass and a polycarbonate diol 43 parts by mass having a number average molecular weight of 33000 prepared by the above method at 230 to 245 ° C. under 130 Pa. Stir for 1 hour, confirm that the resin became transparent, add 0.3 parts by mass of Ricacid TMEG-200 (manufactured by Nippon Nippon Chemical Co., Ltd.), stir for 15 minutes, take out the contents, cool, and polymer (Thermoplastic polyester elastomer) was obtained. Each physical property was measured, and the result is shown in Table 1. The polymer obtained in this example had good properties and high quality.

[Comparative Example 6]
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.

[Comparative Example 7]
Various properties of a 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 1, but the water resistance is poor. It is clear. Further, a slight odor was felt when remelted.

  As mentioned above, although the thermoplastic thermoplastic polyester elastomer of this invention was demonstrated based on several Example, this invention is not limited to the structure described in the said Example, The structure described in each Example is shown. The configuration can be changed as appropriate within a range not departing from the spirit of the invention, such as appropriate combination.

The thermoplastic polyester elastomer of the present invention is excellent in block properties and heat resistance, and maintains the characteristics of the polyester polycarbonate type elastomer that is excellent in heat aging resistance, water resistance, low temperature characteristics, etc. Block property and block property retention are improved. Due to the high block property, a decrease in heat resistance due to a decrease in melting point is suppressed, and mechanical properties such as hardness, tensile strength and elastic modulus are improved. By improving the block property retention, fluctuations in the block property during molding can be suppressed, so that the uniformity of the quality of the molded product can be enhanced. In addition, recyclability is enhanced by the characteristics, which can lead to environmental load and cost reduction. In addition, since the carboxyl end group concentration of the thermoplastic polyester elastomer of the present invention is appropriately controlled, for example, it is easy to adjust the melt viscosity with a chain extender such as a polyfunctional epoxy compound, and a stable thickening treatment is possible. it can. Therefore, the thickening treatment for imparting melt viscosity characteristics suitable for the molding method is easy, and there is an advantage that it can be applied to a wide range of molding methods. Therefore, since the thermoplastic polyester elastomer of the present invention has the above-described excellent characteristics and advantages, it can be used for various molding materials including fibers, films, and sheets. It is also suitable for molding materials such as elastic yarns and boots, gears, tubes, packings, etc., for example, applications such as automobiles and home appliance parts that require heat aging resistance, water resistance, low temperature characteristics, specifically, It is useful for applications such as joint boots and wire coating materials. In particular, it can be suitably used as a material for parts that require high heat resistance such as joint boots used around automobile engines and wire coating materials, which greatly contributes to the industry.

Claims (5)

Thermoplastic polyester elastomer comprising a hard segment comprising a polyester composed of an aromatic dicarboxylic acid and butanediol and a soft segment comprising an aliphatic polycarbonate mainly comprising an aliphatic diol having 5 or more carbon atoms as a diol component Because
When the raw polyester forming the hard segment and the aliphatic polycarbonate diol having a molecular weight of 5000 to 80000 forming the soft segment are reacted in the molten state, the raw material polyester having a carboxyl end group concentration of 43 to 95 eq / ton is used as the raw polyester. Or a polyester polyester elastomer obtained by reacting a raw material polyester having a carboxyl end group concentration of less than 43 eq / ton and reacting the resulting reaction product with an acid anhydride. ,
The thermoplastic polyester elastomer has a carboxyl end group concentration of 30 to 70 eq / ton, and the average chain length (x) of the hard segment and the soft segment calculated using the nuclear magnetic resonance method (NMR method) of the thermoplastic polyester elastomer A thermoplastic polyester elastomer having a block property (B) calculated from the average chain length (y) of the following formula (1) of 0.10 to 0.50.
B = 1 / x + 1 / y (1) The thermoplastic polyester elastomer is heated from room temperature to 300 ° C. at a heating rate of 20 ° C./min using a scanning differential calorimeter, held at 300 ° C. for 3 minutes, and then cooled to room temperature at a cooling rate of 100 ° C./min. The melting point difference (Tm1−Tm3) between the melting point (Tm1) obtained by the first measurement when the cycle is repeated three times and the melting point (Tm3) obtained by the third measurement is 0 to 50 ° C. The thermoplastic polyester elastomer according to claim 1. The thermoplastic polyester elastomer according to claim 1 or 2, wherein the aliphatic polycarbonate chain has a repeating unit represented by the following formula (2) and has an average chain length n of 4 to 15.
The thermoplastic polyester elastomer according to any one of claims 1 to 3, wherein the hard segment comprises a polybutylene terephthalate unit, and the obtained elastomer has a melting point of 200 to 225 ° C. The thermoplastic polyester elastomer according to any one of claims 1 to 3, wherein the hard segment comprises a polybutylene naphthalate unit, and the obtained elastomer has a melting point of 215 to 240 ° C.