JP2007191664A - Manufacturing method of thermoplastic polyester elastomer and thermoplastic polyester elastomer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic polyester elastomer that is excellent in heat resistance, heat-ageing resistance, water resistance, light resistance, low-temperature properties and the like and exhibits excellent retention of a block property, and an economical manufacturing method thereof. <P>SOLUTION: The manufacturing method of the thermoplastic polyester elastomer, comprising a hard segment comprised of a polyester constituted of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol and, bonded thereto, a soft segment comprised mainly of an aliphatic polycarbonate, comprises causing a polyester having a specified hydroxy terminal group concentration to react with an aliphatic polycarbonate diol having a molecular weight range suitable for the hydroxy terminal group concentration in a melted state. The thermoplastic polyester elastomer exhibiting specific properties is obtained by the method. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a method for producing a thermoplastic polyester elastomer and a thermoplastic polyester elastomer, and more specifically, a thermoplastic polyester elastomer excellent in heat resistance, light resistance, heat aging resistance, water resistance, and low temperature characteristics, particularly fibers, films and sheets. Thermoplastic polyester elastomer that can be used for various molding materials such as, more specifically, it is suitable for molding materials such as elastic yarn and boots, gears, tubes, packing, etc., for example, heat aging resistance, water resistance of automobiles, home appliance parts, etc. The present invention relates to a method for producing a thermoplastic polyester elastomer useful for applications requiring low-temperature characteristics and heat resistance, for example, joint boots, wire coating materials, and the like, and a thermoplastic polyester elastomer.

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 this background, development of a polyester polycarbonate type elastomer having high block property and excellent block property retention has been strongly desired.

  On the other hand, in the above-mentioned patent documents 7 and 8, the polyester polymer component forming a hard segment and the polycarbonate diol component forming a soft segment are reacted in a molten state to form a block polymer, and then a production method for increasing the molecular weight with a chain extender Is disclosed. The production method is an effective method for increasing the molecular weight of the block polymer. However, the block property and block property retention are largely influenced by the reaction in the process of forming the block polymer. It is difficult to improve the block property and the block property retention by the method of increasing the molecular weight with a chain extender after forming the block polymer. Therefore, in the prior art, a thermoplastic polyester elastomer having the above-mentioned preferable characteristics has not been obtained. Therefore, establishment of a method for producing a polyester polycarbonate type elastomer for economically producing a thermoplastic polyester elastomer having the above-mentioned preferable characteristics is strongly desired.

  In view of the problems of the above-mentioned conventional thermoplastic polyester elastomers, the present invention has excellent heat resistance, heat aging resistance, water resistance, light resistance, low temperature characteristics, etc., and has excellent blockability retention. An object of the present invention is to provide an economical method for producing an elastomer and a thermoplastic polyester elastomer obtained thereby.

As a result of intensive studies on a method for producing a thermoplastic polyester elastomer for achieving the above object, it is possible to produce an aliphatic polycarbonate diol having a molecular weight suitable for the hydroxyl end group concentration of polyester as a hard segment by reacting in a molten state. We found it important and completed the present invention. That is, in the method for producing a thermoplastic polyester elastomer of the present invention, 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 combined. And a polyester composed of an aromatic dicarboxylic acid having a hydroxyl end group concentration of 55 to 100 eq / ton and an aliphatic or alicyclic diol, and an aliphatic polycarbonate diol having the following molecular weight range: It is a method for producing a thermoplastic polyester elastomer characterized in that it is produced by reacting in a molten state.
[Molecular weight range of aliphatic polycarbonate]
The lower limit of the molecular weight of the aliphatic polycarbonate diol is 5000 when the hydroxyl terminal group concentration of the polyester composed of the aromatic dicarboxylic acid and the aliphatic or alicyclic diol is 55 eq / ton, the aromatic dicarboxylic acid and the aliphatic or The point where the hydroxyl terminal group concentration of the polyester composed of the alicyclic diol is 40000 when the concentration is 100 eq / ton is not less than the molecular weight on a straight line, and the upper limit of the molecular weight is aromatic dicarboxylic acid and aliphatic Or the hydroxyl terminal group concentration of the polyester composed of alicyclic diol is 70,000 when the concentration of hydroxyl end group is 55 eq / ton, and the hydroxyl terminal group concentration of the polyester composed of aromatic dicarboxylic acid and aliphatic or alicyclic diol is On a straight line connecting the points at 80000 at 100 eq / ton When less molecular weight, the molecular weight in the range sandwiched by two straight lines.
In this case, it is preferable to adjust the molecular weight by previously increasing the molecular weight of the aliphatic polycarbonate diol with a chain extender.
The present invention also relates to a thermoplastic polyester elastomer obtained by the above production method, wherein the temperature of the thermoplastic polyester elastomer is increased from room temperature to 300 ° C. at a temperature increase rate of 20 ° C./min using a differential scanning calorimeter. The melting point (Tm1) obtained by the first measurement and the melting point (Tm3) obtained by the third measurement when the cycle of lowering to room temperature at a temperature lowering rate of 100 ° C / min after being held at 3 ° C for 3 minutes and repeated three times And a melting point difference (Tm1-Tm3) of 0 to 50 ° C.
In this case, it is preferable that the hard segment is composed of a polybutylene terephthalate unit, and the melting point of the obtained thermoplastic polyester 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 thermoplastic polyester elastomer obtained has a melting point of 215 to 240 ° C.
In this case, the average chain length (x) of the hard segment, where x is the average chain length of the hard segment calculated using the nuclear magnetic resonance method (NMR method) and y is the average chain length of the soft segment 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)

The method for producing the thermoplastic polyester elastomer of the present invention is a simple method in which an aliphatic polycarbonate diol having a molecular weight suitable for the hydroxyl end group concentration of the raw material polyester forming the hard segment is selected and reacted in the molten state, and the following characteristics are obtained. It has the advantage that the high-quality thermoplastic polyester elastomer can be produced economically and stably.
In addition, while maintaining the characteristics of the polyester polycarbonate type elastomer that the heat resistance obtained by the above production method is good and the heat aging resistance, water resistance and low temperature characteristics are excellent, the block property and the block property are maintained. Sex has been 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. In addition, the improvement of the block property retainability suppresses the fluctuation of the block property during the molding process, 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. 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, as the aliphatic or alicyclic diol constituting the hard segment polyester, general aliphatic or alicyclic diols are widely used and are not particularly limited. It is desirable that the alkylene glycol is ˜8. 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. In the case of naphthalate units, 2,6 are preferable.

  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.

  Moreover, it is preferable that the aliphatic polycarbonate chain which comprises the soft segment in the thermoplastic polyester elastomer of 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 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. In addition, 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, which is sufficiently low. Corresponds to aliphatic polycarbonate diol with good 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 or alicyclic dicarboxylic acids Examples thereof include poly or oligoesters composed of glycol, polyesters or oligoesters composed of ε-caprolactone, polyalkylene glycols such as polytetramethylene glycol and polyoxyethylene glycol, or oligoalkylene glycols.

  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.

  The thermoplastic polyester elastomer of the present invention is a soft segment such as a polyalkylene glycol such as polyethylene glycol 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. The content of the copolymer component is usually 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 soft segment.

  In the thermoplastic polyester elastomer of the present invention, the mass 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, it is in the range of 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 that is. 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 block copolymer polyester 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 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, 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, sulfur, phosphorus and amine antioxidants, hindered amine, triazole, benzophenone, benzoate, nickel, salicyl and other light stabilizers, antistatic 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, 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 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.

  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 differential scanning calorimeter of the thermoplastic polyester elastomer, and held at 300 ° C. for 3 minutes, and then the temperature falling rate 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 to room temperature at 100 ° C./min is repeated three times. It is important that the temperature is 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 during 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 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 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 of the present invention has a polyester unit as a hard segment and an aliphatic polycarbonate unit as a soft segment, and an average value of the number of repeating units constituting one homopolymer structural unit is an 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 of the hard segment calculated using the nuclear magnetic resonance method (NMR method) is x and the average chain length of the soft segment is y, 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, elastic modulus, etc. The deterioration of properties is large. When the average chain length (x) of the polyester unit of the hard segment is larger than 20, the compatibility with the aliphatic carbonate diol constituting the soft segment is lowered, causing phase separation, greatly affecting the mechanical properties, Its strength and elongation are reduced.

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 0.45, the polymer properties such as the melting point of the thermoplastic polyester elastomer being lowered due to the block property deterioration are not preferable. On the other hand, if it is less than 0.11, the compatibility between the hard segment and the soft segment is lowered, causing deterioration of mechanical properties such as high 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.

  Moreover, the tensile strength at the time of the cutting | disconnection of the thermoplastic polyester elastomer of this invention is 15-100 Mpa, Preferably it is 20-60 Mpa.

  Moreover, the tensile strength at the time of cutting | disconnection of the thermoplastic polyester elastomer of this invention is 15-100 Mpa, Preferably it is 20-60 Mpa.

  The thermoplastic polyester elastomer of the present invention preferably has a flexural modulus of 1000 MPa or less. The flexural modulus is more preferably 800 MPa or less, and further 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 more preferably 100 MPa. 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 of the present invention has an elongation retention ratio at break of 70% or more after the heat aging test and the water aging test of the thermoplastic polyester elastomer composition evaluated by the method described in the measurement method section. Preferably there is.

  In the present invention, the thermoplastic polyester elastomer has a molecular weight suitable for the hydroxyl end group concentration of a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol (hereinafter sometimes simply referred to as polyester). It is important to produce an aliphatic polycarbonate diol by reacting in a molten state. That is, it is preferable to produce an aromatic polyester that is a hard segment having a hydroxyl end group concentration of 55 to 100 eq / ton and an aliphatic polycarbonate diol having the following molecular weight range in a molten state.

  The molecular weight of the aliphatic polycarbonate in the above production method preferably satisfies the following range. That is, the lower limit of the molecular weight of the aliphatic polycarbonate diol is a straight line connecting the points where the hydroxyl end group concentration of the polyester is 5000 when the hydroxyl end group concentration is 55 eq / ton and 40000 when the hydroxyl end group concentration of the polyester is 100 eq / ton. The upper limit of the molecular weight is 70000 when the hydroxyl end group concentration of the polyester is 55 eq / ton, and the line having a straight line connecting the points when the hydroxyl end group concentration of the polyester is 100 eq / ton is 80000. When the molecular weight is less than or equal to the molecular weight, it is preferable that the molecular weight be in the range between two straight lines. The lower limit is more preferably the molecular weight above the line connecting the points where the polyester hydroxyl end group concentration is 55 eq / ton at 7000 and the polyester hydroxyl end group concentration is 100 eq / ton at 42,000. On the other hand, the upper limit is more preferably not more than the molecular weight on the line connecting the points where the hydroxyl end group concentration of the polyester is 70000 when the hydroxyl end group concentration is 55 eq / ton and 80000 when the hydroxyl end group concentration of the polyester is 100 eq / ton. The limitation that the upper limit of the molecular weight is 80,000 includes that it is difficult to produce a molecular weight higher than this.

  When the above upper limit is exceeded, the compatibility between the hard segment and the soft segment is decreased, the mechanical properties such as the strength and elongation of the resulting thermoplastic polyester elastomer are decreased, and fluctuations in the properties are preferably increased. Absent. The limitation that the upper limit of the molecular weight is 80000 includes that it is difficult to produce a molecular weight higher than this. On the contrary, in the range below the lower limit, the block property and the block property retention are deteriorated, which is not preferable.

  FIG. 1 shows the relationship between the hydroxyl end group concentration of the polyester and the preferred molecular weight of the aliphatic polycarbonate diol.

  If the said polyester has the composition and molecular weight which were mentioned above, and the hydroxyl terminal group density | concentration is 55-100 eq / ton, the composition and manufacturing method will not be limited. Also, the method for adjusting the hydroxyl end group concentration is not limited. For example, it is preferable to carry out by optimizing the production conditions of the polyester. Moreover, the method of performing by the decomposition | disassembly methods, such as a hydrolysis and thermal decomposition of polyester obtained by the usual method, the terminal group modification | denaturation method by an acid anhydride, cyclic ether, etc. are mentioned. Further, it may be carried out by the addition of glycol or dicarboxylic acid.

  The method for adjusting the molecular weight of the aliphatic polycarbonate diol in the present invention is not limited. For example, the molecular weight of a commercially available aliphatic polycarbonate diol is lower than the preferred molecular weight range of the present invention. A method in which the molecular weight is adjusted by increasing the molecular weight of a molecular weight aliphatic polycarbonate diol in advance with a chain extender is preferred. That is, it is preferable to carry out the reaction by increasing the molecular weight in advance with a chain extender and adjusting the molecular weight of the aliphatic polycarbonate diol so as to be within the above optimized range, and then supplying it to the blocking reaction.

  The above method using a commercially available low molecular weight product can easily produce an aliphatic polycarbonate diol having an arbitrary molecular weight, and the production can be carried out using an implant using the thermoplastic polyester elastomer production apparatus of the present invention. The economic effect is great because it can be done. Further, the above method is a simple method of changing the charging ratio of the chain extender and the aliphatic polycarbonate diol, and has an advantage that it can cope with any desired molecular weight using a commercially available low molecular weight aliphatic polycarbonate diol. Have.

The chain extender is not limited as long as it is a polyfunctional active compound containing two or more functional groups reactive with the terminal hydroxyl group of the aliphatic polycarbonate diol in one molecule.
Although it will not be limited if the number of functional groups is two or more, a bifunctional thing is preferable. Examples thereof include diphenyl carbonate, diisocyanate, and acid anhydrides of dicarboxylic acid.
A trifunctional or higher polyfunctional compound may be used in a small amount. Instead of diphenyl carbonate, carbonate compounds such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, and dimethyl carbonate may be used. Further, it may be a cyclic carbonate such as ethylene carbonate or a dithiocarbonate compound. Further, a carbonyl compound of a nitrogen-containing compound residue such as imidazole or lactam may be used instead of the phenoxy group of diphenyl carbonate.

  The low molecular weight aliphatic polycarbonate diol before the high molecular weight in the above method is preferably a commercially available product, but is not limited. For example, when a special copolymer is required as the aliphatic polycarbonate diol, a specially prepared product may be used.

  In the above method, the molecular weight of the resulting aliphatic polycarbonate diol can be adjusted by changing the molecular weight of the starting aliphatic polycarbonate diol and the charge ratio of the aliphatic polycarbonate diol to the chain extender. It can also be adjusted by the reaction time. The molecular weight of the resulting aliphatic polycarbonate diol increases as the molecular weight of the starting material increases and as the charge ratio of the chain extender decreases. What is necessary is just to set suitably according to the target molecular weight.

  The reaction method in the case of carrying out by the above method is that reaction conditions such as reaction temperature, reaction time, stirring conditions, etc., if an aliphatic polycarbonate diol having a molecular weight lower than the final molecular weight and a chain extender are mixed in the reactor. Although there is no limitation, for example, a method in which the molecular weight adjustment is divided into two or more stages is recommended. That is, after reacting for a predetermined time with a predetermined amount of charging ratio, the molecular weight of the obtained aliphatic polycarbonate diol is measured, and when the molecular weight is lower than the target molecular weight, an additional chain extender is added. When the molecular weight is too high, it is preferable to adjust the molecular weight by further adding the starting aliphatic polycarbonate diol and further continuing the reaction. By repeating this method, the adjustment accuracy of the molecular weight can be increased.

  In the present invention, it is preferable to produce a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol and the aliphatic polycarbonate diol obtained by increasing the molecular weight in a molten state. If the requirements are satisfied, the production conditions and the like are not limited, but for example, the following method is preferable.

  For example, as a polyester composed of an aromatic dicarboxylic acid and an aliphatic or alicyclic diol, a polybutylene terephthalate and a poly (polybutylene terephthalate) and a polycarbonate diol composed of high molecular weight 1,6-hexanediol are used. A predetermined amount is charged all at once into the reaction vessel, oxygen is removed from the reaction vessel with an inert gas, and then the pressure in the reaction vessel is reduced. The pressure in the reaction vessel is preferably 400 Pa or less. 270 Pa or less is more preferable, and 140 Pa or less is more preferable. The reaction is allowed to proceed at a temperature 5 to 40 ° C. higher than the melting point of polybutylene terephthalate while dissolving the reaction product while stirring and gradually raising the temperature while maintaining the degree of vacuum. The temperature difference is more preferably 7 to 35 ° C higher, and more preferably 10 to 30 ° C higher. When the temperature difference is lower than 5 ° C., polybutylene terephthalate is solidified and cannot be uniformly mixed, so that the quality of the obtained thermoplastic polyester elastomer may vary. On the other hand, if the temperature is higher than 40 ° C., the reaction proceeds too quickly, and thus a randomized thermoplastic polyester elastomer having poor heat resistance is produced. The reaction time is preferably shorter than 360 minutes, more preferably shorter than 300 minutes, and even more preferably shorter than 240 minutes. If the reaction time is too long, the production cycle will be extended and the production cost will increase. When each raw material becomes uniform, the reaction is terminated, stirring is stopped, the molten thermoplastic polyester elastomer is taken out from the take-out port at the bottom of the reaction can, cooled and solidified, and heated with a chip cutter such as a strand cutter. A plastic polyester elastomer chip is obtained.

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 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%
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 (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
(Triangle | delta): Melting | fusing point difference 40-50 degreeC
X: Melting point difference 50 ° C. or more

(9) Molecular weight of aliphatic polycarbonate diol An aliphatic polycarbonate diol sample was dissolved in deuterated chloroform (CDCl ₃ ), and the end group was determined by 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)

(10) Hydroxyl end group concentration sample 15 mg of aromatic polyester was dissolved in 0.1 ml of deuterated hexafluoroisopropanol (HFIP-d2) + deuterated chloroform CDCl ₃ (1 + 1), and 0.0125 M of triethylamine (TEA) Diluted with 0.42 ml of CDCl ₃ , 30 μl of heavy pyridine was added, and H-NMR was measured in the same manner as described in (7) above.

(11) 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

Example 1
[Molecular weight adjustment of aliphatic polycarbonate diol]
100 parts by weight of aliphatic polycarbonate diol (Ube Industries, Ltd., carbonate diol UH-CARB200, molecular weight 2000, 1,6-hexanediol type) and 8.6 parts by weight of diphenyl carbonate were respectively charged into a reaction can and gradually heated. And heated to a temperature of 205 ° C. Thereafter, the pressure was gradually reduced and the reaction was carried out at 130 Pa. After 2 hours, the contents were cooled and the polymer was removed. The molecular weight was 10,000.
[Production of thermoplastic polyester elastomer]
A polybutylene terephthalate (PBT) having a number average molecular weight of 30,000 and a hydroxyl terminal group concentration of 60 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 225 ° 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.

Examples 2 and 3
In the method for adjusting the molecular weight of the aliphatic polycarbonate diol of Example 1, the amount of diphenyl carbonate charged was changed to 10.2 parts by mass and 10.5 parts by mass, and the number average molecular weight was 38000 by the same method as in Example 1. 68,000 aliphatic polycarbonate diols were obtained. The thermoplastic polyester elastomers of Examples 2 and 3 were obtained in the same manner as in Example 1 except that the aliphatic polycarbonate diol having the molecular weight was used. The results are 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.

Comparative Example 1
In the method for adjusting the molecular weight of the aliphatic polycarbonate diol of Example 1, the amount of diphenyl carbonate charged was changed to 10.7 parts by mass, and the number average molecular weight was adjusted to 80000 by the same method as in Example 1, and the aliphatic polycarbonate diol was adjusted. A thermoplastic polyester elastomer of Comparative Example 1 was obtained in the same manner as in Example 1 except that the change was made so that The results are shown in Table 2.
Since the thermoplastic polyester elastomer obtained in this comparative example had poor compatibility between the hard segment and the soft segment, the mechanical properties such as tensile strength were inferior, and the variation in the properties was large and the quality was low.

Comparative Example 2
In the method for adjusting the molecular weight of the aliphatic polycarbonate diol of Example 1, the amount of diphenyl carbonate was changed to 6.4 parts by mass, and the number average molecular weight was adjusted to 5000 by the same method as in Example 1 to adjust the molecular weight of the aliphatic polycarbonate diol. A thermoplastic polyester elastomer of Comparative Example 1 was obtained in the same manner as in Example 1 except that the change was made so that The results are shown in Table 3.
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.

Examples 4-8
The thermoplastic polyester elastomers of Examples 4 to 8 were obtained in the same manner as in Example 1 except that the hydroxyl terminal group concentration of PBT and the molecular weight of the aliphatic polycarbonate diol were those listed in Table 1 as raw materials. The results are shown in Table 1.
All of the thermoplastic polyester elastomers obtained in these examples had the same quality as the thermoplastic polyester elastomer obtained in Example 1, and were of high quality.

Comparative Examples 3 and 4
The thermoplastic polyester elastomers of Comparative Examples 3 and 4 were obtained in the same manner as in Example 1, except that the hydroxyl terminal group concentration of PBT and the molecular weight of the aliphatic polycarbonate diol were those described in Table 2. The results are shown in Table 2.
Both of the thermoplastic polyester elastomers obtained in these comparative examples were inferior in blockability and blockability retention like the thermoplastic polyester elastomer obtained in Comparative Example 2. 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 was small.

Comparative Example 5
In the method of Example 8, the thermoplastic polyester elastomer of Comparative Example 5 was obtained in the same manner as in Example 8 except that the number average molecular weight of the aliphatic polycarbonate diol was changed to 80000. The results are shown in Table 2.
Since the thermoplastic polyester elastomer obtained in this comparative example has poor compatibility between the hard segment and the soft segment, the mechanical properties such as tensile strength are poor and the quality is low.

  Adjustment of the hydroxyl terminal group concentration of PBT used in Examples 4 to 8 and Comparative Examples 3 to 5 was performed by changing the production conditions of the PBT. The molecular weight of the aliphatic polycarbonate diol was adjusted in the same manner as in Example 1 by optimizing the feed ratio of the raw aliphatic polycarbonate diol and the chain extender and the reaction conditions. In this case, the molecular weight was finely adjusted by dividing into two or more stages as required. That is, after reacting for a predetermined time with a predetermined amount of charging ratio, the molecular weight of the obtained aliphatic polycarbonate diol is measured, and when the molecular weight is lower than the target molecular weight, an additional chain extender is added. When the molecular weight was too high, an additional raw material aliphatic polycarbonate diol was added to continue the reaction.

Example 9
Polycarbonate phthalate having a number average molecular weight of 33,000 and a hydroxyl end group concentration of 60 eq / ton (PBN: 2,6 naphthalate parts) of 100 parts by weight and polycarbonate diol having a number average molecular weight of 380000 prepared by the above method The temperature was gradually raised to 265 ° C. while stirring. The inside of the can was maintained at 130 Pa, and after the internal temperature reached 265 ° C., it was confirmed that the resin became transparent in 1 hour, 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 3. The thermoplastic polyester elastomer obtained in this example had good properties and high quality.

Comparative Examples 6 and 7
In the method of Example 9, the thermoplastic polyester elastomers of Comparative Examples 6 and 7 were obtained in the same manner as in Example 9, except that the molecular weight of the aliphatic polycarbonate diol was changed to that of 50000 and 80000, respectively. The results are shown in Table 3.
The thermoplastic polyester elastomer obtained in Comparative Example 6 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. Since the thermoplastic polyester elastomer obtained in Comparative Example 7 had poor compatibility between the hard segment and the soft segment, the mechanical properties such as tensile strength were inferior, and the variation in the properties was large and the quality was low.

In all of the aliphatic polycarbonate diols used in the above Examples and Comparative Examples, 85 to 100% of the end groups were hydroxyl end groups, and the remaining 0 to 15% consisted of chain extender residues.

  The characteristics of the thermoplastic elastomers obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were plotted in the relationship diagram between the hydroxyl end group concentration of PBT and the molecular weight of the aliphatic polycarbonate diol, and displayed as FIG. As for the characteristics, those having poor compatibility between the hard segment and the soft segment are indicated by asterisks, those having inferior blockability and blockability retention are indicated by crosses, and those satisfying both characteristics are indicated by marks. In addition, the straight line in a figure has shown the preferable molecular weight range in this invention. It can be understood that the use of an aliphatic polycarbonate diol having a molecular weight range suitable for the concentration of hydroxyl end groups of PBT, which is a hard segment component, is a critical factor in satisfying both of the above characteristics.

  As mentioned above, although the 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 combined suitably. For example, the configuration can be changed as appropriate without departing from the spirit of the invention.

The method for producing the thermoplastic polyester elastomer of the present invention is a simple method in which an aliphatic polycarbonate diol having a molecular weight suitable for the hydroxyl end group concentration of the raw material polyester is selected and reacted in a molten state, and has a high quality having the following characteristics. There is an advantage that a thermoplastic polyester elastomer can be produced economically and stably.
In addition, while maintaining the characteristics of the polyester polycarbonate type elastomer that the heat resistance obtained by the above production method is good and the heat aging resistance, water resistance and low temperature characteristics are excellent, the block property and the block property are maintained. Sex has been 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. In addition, the improvement of the block property retainability suppresses the fluctuation of the block property during the molding process, 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. 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. Therefore, it is important to contribute to the industry.

It is the relationship between the hydroxyl end group concentration of the raw material polyester of the present invention and the molecular weight of an aliphatic polycarbonate diol suitable for the hydroxyl end group concentration. It is the figure which plotted the characteristic of the thermoplastic elastomer obtained in Examples 1-8 and Comparative Examples 1-5 in the relationship figure of the hydroxyl terminal group density | concentration of PBT, and the molecular weight of aliphatic polycarbonate diol.

Claims (6)

A process for producing a thermoplastic polyester elastomer comprising 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. It is produced by reacting a polyester composed of an aromatic dicarboxylic acid having a group concentration of 55 to 100 eq / ton and an aliphatic or alicyclic diol with an aliphatic polycarbonate diol having the following molecular weight range in a molten state. A method for producing a thermoplastic polyester elastomer.
[Molecular weight range of aliphatic polycarbonate]
The lower limit of the molecular weight of the aliphatic polycarbonate diol is 5000 when the hydroxyl terminal group concentration of the polyester composed of the aromatic dicarboxylic acid and the aliphatic or alicyclic diol is 55 eq / ton, the aromatic dicarboxylic acid and the aliphatic or The point where the hydroxyl terminal group concentration of the polyester composed of the alicyclic diol is 40000 when the concentration is 100 eq / ton is not less than the molecular weight on a straight line, and the upper limit of the molecular weight is aromatic dicarboxylic acid and aliphatic Or the hydroxyl terminal group concentration of the polyester composed of alicyclic diol is 70,000 when the concentration of hydroxyl end group is 55 eq / ton, and the hydroxyl terminal group concentration of the polyester composed of aromatic dicarboxylic acid and aliphatic or alicyclic diol is On a straight line connecting the points at 80000 at 100 eq / ton When less molecular weight, the molecular weight in the range sandwiched by two straight lines.   2. The method for producing a thermoplastic polyester elastomer according to claim 1, wherein the aliphatic polycarbonate diol is previously polymerized with a chain extender to adjust the molecular weight.   A thermoplastic polyester elastomer obtained by the production method according to claim 1 or 2, wherein the thermoplastic polyester elastomer is heated from room temperature to 300 ° C at a temperature rising rate of 20 ° C / min using a differential scanning calorimeter, and 300 The melting point (Tm1) obtained by the first measurement and the melting point (Tm3) obtained by the third measurement when the cycle of lowering to room temperature at a temperature lowering rate of 100 ° C / min after being held at 3 ° C for 3 minutes and repeated three times A thermoplastic polyester elastomer having a difference in melting point (Tm1-Tm3) from 0 to 50 ° C.   The thermoplastic polyester elastomer according to claim 3, wherein the hard segment comprises a polybutylene terephthalate unit, and the obtained thermoplastic polyester elastomer has a melting point of 200 to 225 ° C.   The thermoplastic polyester elastomer according to claim 3, wherein the hard segment comprises a polybutylene naphthalate unit, and the thermoplastic polyester elastomer obtained has a melting point of 215 to 240 ° C. The average chain length (x) of the hard segment is 5 to 20, where x is the average chain length of the hard segment calculated using the nuclear magnetic resonance method (NMR method) and y is the average chain length of the soft segment. And the block property (B) calculated by the following (1) formula is 0.11-0.45, The thermoplastic polyester elastomer in any one of Claims 3-5 characterized by the above-mentioned.
B = 1 / x + 1 / y (1)

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