JP5370112B2 - Polyester elastomer resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enhance flexural fatigue resistance of a thermoplastic polyester elastomer resin without detriment to properties at a low temperature. <P>SOLUTION: The polyester elastomer resin is obtained by chain-extending a thermoplastic polyester elastomer [A], constituted of an aromatic dicarboxylic acid (a1), a low-molecular weight glycol (a2) and a poly(oxytetramethylene)glycol (a3), and a thermoplastic polyester elastomer [B], constituted of an aromatic dicarboxylic acid (b1), a low-molecular weight glycol (b2) and a poly(oxytetramethylene)glycol (b3), with a compound [C] bearing at least two functional groups reactive with terminal functional groups of [A] and [B], where the number-average molecular weight of (a3) and that of (b3) are different and the glass transition temperature (Tg(A)) of [A] is different from the glass transition temperature (Tg(B)) of [B]. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a polyester elastomer resin used for molding such as injection molding. In particular, the present invention relates to a polyester elastomer resin that is used in electric parts, home appliances, automobile parts, and industrial members and has excellent bending fatigue resistance.

  Thermoplastic elastomers are used as an alternative to conventional rubber because of their superiority in environmental aspects of recyclability, performance of bending fatigue resistance, and cost of productivity. The application is wide, and the performance required for the resin is variously combined with flexibility, high heat resistance, and high bending fatigue resistance.

  In order to improve the bending fatigue resistance, the molecular weight of the entire polyester elastomer is improved, the weight ratio of the polyether glycol, which is a soft segment constituting the polyester elastomer, is increased, and the molecular weight of the polyether glycol contained in the polyester elastomer is increased. There is a way to make it bigger. Among these, the means for increasing the molecular weight of the polyether glycol contained in the polyester elastomer is particularly effective as a means for improving the bending fatigue resistance. However, the method of increasing the molecular weight of the entire polyester elastomer results in poor fluidity, and the method of increasing the weight ratio of polyether glycol decreases the surface hardness and crystal melting point, increasing the molecular weight of the polyether glycol contained in the polyester elastomer. The technique raises the melting point and increases the hardness at low temperatures. As described above, there are physical properties that decrease in each method. Particularly, in the method of increasing the molecular weight of the polyether glycol contained in the polyester elastomer, the change in hardness becomes remarkable due to the solidification of the polyether glycol at a low temperature. For this reason, it has been difficult to achieve both bending fatigue resistance and suppression of hardness change at low temperatures, particularly by increasing the molecular weight of the polyether glycol contained in the polyester elastomer.

  As a means for improving the molecular weight of the whole polyester elastomer and improving the bending fatigue resistance, there is chain extension by reaction with epoxy. As a means for chain extension by reaction with an epoxy, for example, Patent Document 1 proposes a method of reacting with a polyepoxide to prevent melt degradation. However, this is intended to maintain the molecular weight by reacting the melt-degraded part with epoxy, and the bending fatigue resistance is not sufficiently satisfactory. Patent Document 2 proposes a flexible boot made of a resin that is excellent in bending fatigue resistance, which is obtained by blending a glycidyl ester compound having two or more functionalities with a polyester block elastomer, but there is no description regarding hardness at low temperatures, and bending resistance. The expression of fatigue and the ability to suppress changes in hardness at low temperatures is also limited.

  In addition, there is a method of blending another copolymer having good low temperature characteristics in order to control the change in hardness at low temperature. For example, in Patent Document 3, a change in hardness at low temperatures is suppressed by blending a styrene diene type block copolymer having good low temperature characteristics, but the bending fatigue resistance is not fully satisfactory.

JP-A 48-1000049 Japanese Patent No. 4038742 Japanese Patent Laid-Open No. 50-82162

  It is an object of the present invention to achieve improvement in the bending fatigue resistance of a polyester elastomer resin without impairing other physical properties that could not be solved by conventional techniques. In particular, the purpose is to increase the molecular weight of polyether glycol contained in the polyester elastomer in order to improve the bending fatigue resistance, thereby suppressing the change in hardness at low temperatures.

  In order to solve the above-mentioned problems, the present inventors have intensively studied and studied, and finally completed the present invention. That is, the present invention relates to a thermoplastic polyester elastomer [A] comprising aromatic dicarboxylic acid (a1), low molecular weight glycol (a2), and poly (oxytetramethylene) glycol (a3) as constituent components, and aromatic dicarboxylic acid. The thermoplastic polyester elastomer [B] having (b1), low molecular weight glycol (b2), and poly (oxytetramethylene) glycol (b3) as structural components is reacted with terminal functional groups of [A] and [B]. A polyester elastomer resin chain-extended with a compound [C] having two or more functional groups, the number average molecular weight of (a3) is different from the number average molecular weight of (b3), and the glass transition temperature (Tg) of [A] (A)) and [B] have different glass transition temperatures (Tg (B)).

In this case, the Tg (A) is −65 to −40 ° C., the Tg (B) is higher than Tg (A) and −50 to −30 ° C., and [ When the mass part of A] is W (A), the mass part of [B] is W (B), and the mass part of [C] is W (C), the following (Formula 1) and (Formula 2) Is preferably satisfied.
(Formula 1) 0.4 <W (A) / W (B) <2.4
(Formula 2) 100 <(W (A) + W (B)) / W (C) <300

  In this case, the number average molecular weight of (a3) is preferably 500 to 1500, and the number average molecular weight of (b3) is preferably 1500 to 3000.

In this case, (a1) and (b1) are at least one selected from terephthalic acid and naphthalenedicarboxylic acid, and (a2) and (b2) are ethylene glycol and 1,4-butanediol. , 1,4-cyclohexanedimethanol, and dimer glycol are preferable.
(Here, (a1) and (b1) may be the same or different, and (a2) and (b2) may be the same or different.)

  In this case, it is preferable that the [C] is a compound having two or more epoxy groups.

According to the present invention, it is possible to achieve an improvement in bending fatigue resistance of a thermoplastic polyester elastomer resin without impairing physical properties at low temperatures.
Bending fatigue resistance proportional to the ratio of [A] and [B] by chain-extending the thermoplastic polyester elastomer [A] and the thermoplastic polyester elastomer [B] with the compound [C] and uniformly dispersing them. In spite of showing the performance, in the hardness change at a low temperature, the contribution at a low temperature of [B] having a high Tg (the number average molecular weight of the constituent poly (oxytetramethylene) glycol is large) is low ( The contribution of [A] (which has a small number average molecular weight of poly (oxytetramethylene) glycol as a constituent component) is absorbed, and there is an advantage that a change in hardness is suppressed.

Hereinafter, the present invention will be described in detail.
(Thermoplastic polyester elastomer [A])
The thermoplastic polyester elastomer [A] according to the present invention comprises an aromatic dicarboxylic acid (a1), a low molecular weight glycol (a2), and a poly (oxytetramethylene) glycol (a3) as constituent components.
In the thermoplastic polyester elastomer [A] according to the present invention, the aromatic dicarboxylic acid constituting the hard segment polyester is widely used as an ordinary aromatic dicarboxylic acid, and is not particularly limited, but the main aromatic dicarboxylic acid is terephthalic acid. Alternatively, naphthalenedicarboxylic acid is desirable. Other acid components include diphenyl dicarboxylic acid, isophthalic acid, aromatic dicarboxylic acid such as 5-sodium sulfoisophthalic acid, cycloaliphatic dicarboxylic acid, alicyclic dicarboxylic acid such as tetrahydrophthalic anhydride, succinic acid, glutaric acid, adipine Examples thereof include aliphatic dicarboxylic acids such as acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, and hydrogenated dimer acid. These are used within a range that does not significantly lower the melting point of the resin, and the amount thereof is less than 30 mol%, preferably less than 20 mol% of the total acid component.

  In the thermoplastic polyester elastomer [A] according to the present invention, the low molecular weight glycol constituting the hard segment polyester is not limited to a general aliphatic or alicyclic diol. 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, dimer glycol and the like. Ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol and dimer glyco are preferred, and 1,4-butanediol is particularly preferred.

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

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

  The soft segment in the thermoplastic polyester elastomer [A] used in the present invention is composed of poly (oxytetramethylene) glycol (a3). The number average molecular weight of the poly (oxytetramethylene) glycol (a3) is preferably 500 to 1500 for the following reasons. A preferred lower limit is 600, more preferably 800. A preferred upper limit is 1300, more preferably 1200. Other poly (oxyalkylene) glycols, aliphatic polyester glycols, and the like may be used as part of the soft segment as long as the characteristics of the present invention are not impaired.

  The thermoplastic polyester elastomer [A] according to the present invention is obtained by reacting a hard segment and a soft segment. The weight ratio of the soft segment is preferably 5 to 80% by weight, and more preferably 40 to 60% by weight, which can exhibit the elastomer performance. 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 glass transition temperature Tg (A) of the thermoplastic polyester elastomer [A] according to the present invention is preferably −65 to −40 ° C. In order to make Tg within this range, the poly (oxytetramethylene) glycol (a3) constituting the soft segment preferably has a number average molecular weight of 500 to 1500. The lower limit of Tg (A) is more preferably −63 ° C., further preferably −60 ° C. The upper limit is more preferably −45 ° C., further preferably −50 ° C., and particularly preferably −55 ° C.

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

Next, as a method for obtaining the thermoplastic polyester elastomer [A] according to the present invention, any known method can be employed. For example, any of a melt polymerization method, a solution polymerization method, a solid phase polymerization method and the like can be used as appropriate. In the case of a melt polymerization method, a transesterification method or a direct polymerization method may be used. In order to improve the viscosity of the resin, it is of course desirable to perform solid phase polymerization after melt polymerization.
As the catalyst used for the reaction, an antimony catalyst, a germanium catalyst, and a titanium catalyst are preferable. In particular, the titanium catalyst is preferably a tetraalkyl titanate such as tetrabutyl titanate or tetramethyl titanate, or an oxalic acid metal salt such as titanium potassium oxalate. The other catalyst is not particularly limited as long as it is a known catalyst, and examples thereof include tin compounds such as dibutyltin oxide and dibutyltin dilaurate, and lead compounds such as lead acetate.

(Thermoplastic polyester elastomer [B])
The thermoplastic polyester elastomer [B] according to the present invention comprises an aromatic dicarboxylic acid (b1), a low molecular weight glycol (b2), and a poly (oxytetramethylene) glycol (b3) as constituent components.
In the thermoplastic polyester elastomer [B] according to the present invention, a normal aromatic dicarboxylic acid is widely used as the aromatic dicarboxylic acid constituting the hard segment polyester, and the main aromatic dicarboxylic acid is terephthalic acid. Alternatively, naphthalenedicarboxylic acid is desirable. Other acid components include diphenyl dicarboxylic acid, isophthalic acid, aromatic dicarboxylic acid such as 5-sodium sulfoisophthalic acid, cycloaliphatic dicarboxylic acid, alicyclic dicarboxylic acid such as tetrahydrophthalic anhydride, succinic acid, glutaric acid, adipine Examples thereof include aliphatic dicarboxylic acids such as acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, and hydrogenated dimer acid. These are used within a range that does not significantly lower the melting point of the resin, and the amount thereof is less than 30 mol%, preferably less than 20 mol% of the total acid component.

  Further, in the thermoplastic polyester elastomer [B] according to the present invention, the low molecular weight glycol constituting the hard segment polyester is not limited to a general aliphatic or alicyclic diol. 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, dimer glycol and the like. Ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol and dimer glyco are preferred, and 1,4-butanediol is particularly preferred.

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

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

  The soft segment in the thermoplastic polyester elastomer [B] used in the present invention is composed of poly (oxytetramethylene) glycol (b3). The number average molecular weight of the poly (oxytetramethylene) glycol (b3) is preferably 1500 to 3000 for the following reasons. A preferred lower limit is 1600, more preferably 1800. A preferable upper limit is 2500, and more preferably 2200. Other poly (oxyalkylene) glycols, aliphatic polyester glycols, and the like may be used as part of the soft segment as long as the characteristics of the present invention are not impaired.

  The thermoplastic polyester elastomer [B] according to the present invention is obtained by reacting a hard segment and a soft segment. The weight ratio of the soft segment is preferably 5 to 80% by weight, and more preferably 40 to 60% by weight, which can exhibit the elastomer performance. 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 glass transition temperature Tg (B) of the thermoplastic polyester elastomer [B] according to the present invention is preferably higher than the Tg (A) and -50 to -30 ° C. In order to make Tg within this range, the number average molecular weight of poly (oxytetramethylene) glycol (b3) constituting the soft segment is preferably 1500 to 3000. The lower limit of Tg (B) is more preferably -48 ° C, and further preferably -45 ° C. The upper limit is more preferably −33 ° C., further preferably −35 ° C., and particularly preferably −40 ° C.
Tg (B) is preferably higher by 5 ° C. or higher than Tg (A), and more preferably higher by 10 ° C. or higher.

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

Next, as a method for obtaining the thermoplastic polyester elastomer [B] according to the present invention, any known method can be employed. For example, any of a melt polymerization method, a solution polymerization method, a solid phase polymerization method and the like can be used as appropriate. In the case of a melt polymerization method, a transesterification method or a direct polymerization method may be used. In order to improve the viscosity of the resin, it is of course desirable to perform solid phase polymerization after melt polymerization.
As the catalyst used for the reaction, an antimony catalyst, a germanium catalyst, and a titanium catalyst are preferable. In particular, the titanium catalyst is preferably a tetraalkyl titanate such as tetrabutyl titanate or tetramethyl titanate, or an oxalic acid metal salt such as titanium potassium oxalate. The other catalyst is not particularly limited as long as it is a known catalyst, and examples thereof include tin compounds such as dibutyltin oxide and dibutyltin dilaurate, and lead compounds such as lead acetate.

(Compound [C])
In the present invention, the compound [C] is a compound having two or more functional groups capable of reacting with the terminal functional group of the thermoplastic polyester elastomer. The terminal functional group of the thermoplastic polyester elastomer is a carboxyl group and / or a hydroxyl group. Examples of the functional group capable of reacting with the terminal functional group of the thermoplastic polyester elastomer include an isocyanate group, an epoxy group, a carboxyl group (an acid anhydride group), a hydroxyl group, a carbodiimide group, and an oxazoline group. Among these, the functional group of [C] is preferably an epoxy group, from the viewpoint of reaction control with the melt viscosity change during the melt residence and the thermoplastic polyester elastomer terminal functional group, and [C] has two or more epoxy groups. It is preferable that it is a compound which has.
As a specific example of the compound [C], the compound having an isocyanate group is an aliphatic polyisocyanate such as hexamethylene disocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate or lysine diisocyanate; a burette type adduct of these polyisocyanates. Cyclized product of isocyanurate;
Isophorone diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or-2,6-) diisocyanate, 1,3- (or 1,4-) di (isocyanatomethyl) cyclohexane, 1 Alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate and 1,3-cyclohexane diisocyanate; burette-type adducts and isocyanurate cycloadducts of these diisocyanates;
Xylylene diisocyanate, meta-xylene diisocyanate, tetramethylxylene diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-naphthalene diisocyanate, 4,4′-diphenyl ether isocyanate, (m or p) Aromatic diisocyanate compounds such as phenylene diisocyanate, 4,4′-biphenylene diisocyanate, 3,3′-dimethyl-4,4 ′ biphenine diisocyanate, bis (4-isocyanatophenyl) sulfone; a view of these diisocyanate compounds Let type adduct, isocyanurate ring adduct;
Triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 4,4′-dimethyldiphenylmethane-2,2 ′ Polyisocyanates having three or more isocyanate groups in one molecule such as, 5,5'-tetraisocyanate; burette type adducts, isocyanurate ring adducts of these diisocyanate compounds;
Urethane adducts obtained by reacting a polyisocyanate compound in an excess ratio of isocyanate groups with hydroxyl groups of polyols such as ethylene glycol, propylene glycol, 1,4-butylene glycols, etc .; Burette type addition of these diisocyanate compounds Products, isocyanurate cycloadducts and the like.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, and glycerin diglyceride. Aliphatic epoxy compounds such as glycidyl ether, trimethylolpropane triglycidyl ether, diglycerin tetraglycidyl ether;
Alicyclics such as dicyclopentadiene dioxide, epoxycyclohexenecarboxylic acid ethylene glycol diester, 3,4-epoxycyclohexenylmethyl-3′-4′-epoxycyclohexenecarboxylate, 1,2,: 8,9 diepoxy limonene Epoxy compounds;
Aromatic or heterocyclic epoxy compounds such as epoxy compounds obtained by the reaction of polyphenol compounds and epichlorohydrin and their hydrogenated compounds, diglycidyl phthalate, triglycidyl isocyanurate;
Examples thereof include a compound having an epoxy group at the terminal of the silicone oil and a compound having an alkoxysilane and an epoxy group.

  Examples of other compounds include pyromellitic anhydride, phthalic anhydride, polycarbodiimide, bisoxazoline compounds, and the like.

  As a commercial item of the compound having an isocyanate group of the compound [C], Asahi Kasei Duranate 50M, D-101, D-201, 24A-100, TPA 100, THA 100, Mitsui Chemicals Cosmonate T 80, M 100, NBDI, ND, Takenate 500, 600, 700, Sumidur T-08, 44S, N3200, N3300 from Sumika Bayer Urethane, Death Module H, W, I, Coronate T 08, Millionate from Nippon Polyurethane Industry MT, MR, HDI, Kyowa Hakko LTI, Shin-Etsu Silicone KBE-9007, and the like.

  Commercially available compounds having an epoxy group include Epicoat 806, 807, 1256, 152, 154, YX400, YL6400, SR-NPG, SR-16H, SR-16L, SR-manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. TMP, SR-HHPA, SR-HBA, SR-4GL, SR-SEP, Tepic-p, Tepic-s, Tepic-g manufactured by Nissan Chemical Industries, Denacol EX-201, EX-211 manufactured by Nagase ChemteX Corporation, EX-212, EX-252, EX-313, EX-314, EX-321, EX-411, EX-212L, Rikaresin HBE-100, DME-100, BPO-20E made by Shin Nippon Chemical Co., Ltd. DBG-DEP, Epogosay HD (M), 2EH, 2021P, 2000 made by Daicel Chemical Industries, Porid GT401, EHPE3150, YH-300, YH-301, YH-315, YH-324, YH-325, YD-127, YD-128, YD-134 made by Tohto Kasei, X-22-163 made by Shin-Etsu Silicone , KF-105, X-22-163A, X-22-163B, X-22-169AS, X-22-169B, X-22-9002, and the like.

(Polyester elastomer resin)
In the present invention, the polyester elastomer resin is obtained by chain-extending the thermoplastic polyester elastomer [A] and [B] with the compound [C].
In the present invention, it is desirable that [A] mass part · W (A) and [B] mass part · W (B) satisfy the following (formula 1).
(Formula 1) 0.4 <W (A) / W (B) <2.4
[A] parts by mass / W (A), [B] parts by mass / W (B), and [C] parts by mass / W (C) desirably satisfy the following (formula 2).
(Formula 2) 100 <(W (A) + W (B)) / W (C) <300
If each is in this range, it is possible to suppress changes in hardness at low temperatures while satisfying the bending fatigue resistance. Regarding the range of (W (A) + W (B)) / W (C) in (Formula 2), if (W (A) + W (B)) / W (C) ≧ 300, the bending fatigue resistance is sufficiently satisfied. When (W (A) + W (B)) / W (C) ≦ 100, the excessive reaction of the compound [C] causes the resistance to bending fatigue due to the foreign matter due to the compound [C] itself. .
However, if 0.25 ≦ W (A) / W (B) ≦ 4 and 50 ≦ (W (A) + W (B)) / W (C) ≦ 350 are satisfied, bending fatigue resistance and low temperature Although the hardness change is not at a sufficiently satisfactory level, it can be achieved at the same time.

  In addition, when the thermoplastic polyester elastomers [A] and [B] are reacted with the compound [C], a known catalyst may be used to promote the reaction.

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

  Examples of hindered phenolic antioxidants that can be incorporated into the thermoplastic polyester elastomer or polyester elastomer resin used 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-hydride) Xylphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-butylanilino) -1,3,5-triazine, 3,9-bis [1,1-dimethyl-2- {β- (3-t-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) pro Onate], 1,1,3-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6 (1H, 3H, 5H) -trione, , 3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di-t-butyl-4-hydroxyhydrocinnamic atide triester with-1 , 3,5-tris (2-hydroxyethyl) -S-triazine-2,4,6 (1H, 3H, 5H), N, N-hexamethylenebis (3,5-di-t-butyl-4- Hydroxy-hydrocinnamide), 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 8,10-tetraoxas Or the like can be mentioned Russia [5.5] undecane.

  Examples of the sulfur-based antioxidant that can be added to the thermoplastic polyester elastomer or polyester elastomer resin used in the present invention include dilauryl-3,3′-thiodipropionic acid ester and dimyristyl-3,3′-thiodiuropionic acid. Ester, distearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, dilaurylthiodipropionate, dioctadecyl sulfide, pentaerythritol-tetra (β- Lauryl-thiopropionate) ester and the like.

  Examples of the phosphorus-based antioxidant that can be blended in the thermoplastic polyester elastomer or polyester elastomer resin used 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-t-butylphenyl) butane, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phos Phyto, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenephosphanite, bi (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylenediphosphonite, tri Examples thereof include phenyl phosphite, diphenyl decyl phosphite, tridecyl phosphite, trioctyl phosphite, tridodecyl phosphite, trioctadecyl phosphite, trinonylphenyl phosphite, tridodecyl trithiophosphite and the like.

  Examples of amine-based antioxidants that can be incorporated into the thermoplastic polyester elastomer or polyester elastomer resin used in the present invention include N, N-diphenylethylenediamine, N, N-diphenylacetamidine, and N, N-diphenylfluamidine. N-phenylpiperidine, dibenzylethylenediamine, triethanolamine, 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, 4,4′-bis (4-α, α-dimethyl-) Benzyl) diphenylamine Examples thereof include amines and derivatives thereof, reaction products of amines and aldehydes, and reaction products of amines and ketones.

  As the benzophenone-based, benzotriazole-based, triazole-based, nickel-based, and salicyl-based light stabilizers that can be blended in the thermoplastic polyester elastomer or polyester elastomer resin used in the present invention, 2,2′-dihydroxy-4- Methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 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-dimethylbenzylphenyl) benzotriazole 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzazotriazole, 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) Monoethyl phosphate) nickel salt, 85-90% 2-ethoxy-5-t-butyl-2'-ethyl oxalic acid-bis-anilide and 2-ethoxy-5-t-butyl-2'-ethyl-4 '-T-Butyl oxalic acid-bis-anilide 10-15% mixture, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, Toxi-2′-ethyloxazalic acid bisanilide, 2- [2′-hydroxy-5′-methyl-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimide-methyl ) Phenyl] benzotriazole, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2-hydroxy-4-i- Examples of the light stabilizer include octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, and phenyl salicylate.

  Fillers that can be blended in the thermoplastic polyester elastomer or polyester elastomer resin used 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, diatomaceous earth, alumina fiber, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, and other oxides, manesium hydroxide, aluminum hydroxide, basic magnesium carbonate Basic substances or hydroxides such as magnesium carbonate, calcium carbonate, barium carbonate, ammonium carbonate, calcium sulfite, calcium sulfite, dolomite, dawsonite, or calcium sulfate, barium sulfate, ammonium sulfate (Sulfur) sulfate such as calcium, calcium sulfite, basic magnesium sulfate, or sodium silicate, magnesium silicate, aluminum silicate, potassium silicate, calcium silicate, talc, clay, mica, asbestos, glass fiber, montmorillonite, glass balloon, glass Silicates such as beads and 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, titanic acid Examples include potassium, lead zirconate titanate, zinc borate, aluminum borate, barium metaborate, calcium borate, and sodium borate.

  Flame retardant aids that can be incorporated into the thermoplastic polyester elastomer or polyester elastomer resin used in the present invention include antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium pyroantimonate, tin dioxide, zinc metaborate. , Aluminum hydroxide, magnesium hydroxide, zirconium oxide, molybdenum oxide, red phosphorus compound, ammonium polyphosphate, melamine cyanurate, ethylene tetrafluoride and the like.

  Examples of the thermoplastic polyester elastomer or the compound having a triazine group and / or a derivative thereof that can be incorporated into the polyester elastomer resin used in the present invention include melamine, melamine cyanurate, melamate phosphate, and guanidine sulfamate.

  Examples of the inorganic phosphorus compound of the phosphorus compound that can be blended with the thermoplastic polyester elastomer or the polyester elastomer resin used 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.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited thereto.
(Measurement method)
Bending fatigue resistance test:
According to JIS K 6260. The test was conducted at a test environment temperature of 100 ° C. using a Dematcher bending crack tester BE-102 (manufactured by Tester Sangyo Co., Ltd.). Evaluation was performed by the number of times until the test piece broke.
Regarding the evaluation of the bending fatigue resistance, ◎ is particularly excellent when the number of bendings until breakage is 12 million times or more, ◯, when it is excellent when the number of bending times until breakage is less than 12 million times or more than 8 million times, ○, the number of bending times until breakage is 800 In the case of less than 10,000 times and 7 million times or more, Δ, and in the case of less than 7 million times of bending until breakage and insufficient, ×.
Hardness change at low temperature:
Tensilon UTM-1-5000 (manufactured by Toyo Baldwin) was used to measure the stress at 50% elongation from room temperature (25 ° C.) to −30 ° C., (50% elongation stress at −30 ° C.) / (At room temperature The stress at 50% elongation) was evaluated as the hardness change at low temperature.
For evaluation of hardness change at low temperature, (2) (50% elongation stress at −30 ° C.) / (50% elongation stress at room temperature) <2, ○ ≦ 2 ≦ (50% elongation at −30 ° C.) (Stress) / (50% elongation stress at room temperature) <2.2, Δ (50% elongation stress at −30 ° C.) / (50% elongation stress at room temperature) ≧ 2.2 ×× did.
Glass transition temperature (Tg):
A dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.) is used, and a measurement sample is pressed with a hot plate heated to 240 ° C. using an NF type single-acting compression molding machine (manufactured by Shindo Metal Industry Co., Ltd.). Thus, a sheet having a thickness of 0.4 mm was prepared. The measurement was performed at a measurement frequency of 11 Hz, and the temperature rising rate was 2 ° C./min. The peak position was Tg at −150 ° C. to 150 ° C.

(Thermoplastic polyester elastomer [A1])
320 g of dimethyl terephthalate (DMT), 260 g of 1,4-butanediol (BD), 420 g of polytetramethylene glycol (PTMG, molecular weight 1000), 1.8 g of Irganox-1330 (manufactured by Ciba Japan), tetrabutyl titanate (TBT) 1.0 g was charged into a 4 L autoclave, and the temperature was increased from room temperature to 220 ° C. over 3 hours to conduct a transesterification reaction. Next, the inside of the can was gradually depressurized and further heated, and an initial condensation reaction was performed at 250 ° C. and 1 torr or less over 45 minutes. Further, a polymerization reaction was performed for 2 hours at 250 ° C. and 1 torr or less, and the polymer was taken out in a pellet form. The collected thermoplastic polyester elastomer [A1] had a Tg of −60 ° C.
(Thermoplastic polyester elastomer [A2])
320 g of dimethyl terephthalate (DMT), 260 g of 1,4-butanediol (BD), 420 g of polytetramethylene glycol (PTMG, molecular weight 1200), 1.8 g of Irganox-1330 (manufactured by Ciba Japan), tetrabutyl titanate (TBT) 1.0 g was charged into a 4 L autoclave, and the temperature was increased from room temperature to 220 ° C. over 3 hours to conduct a transesterification reaction. Next, the inside of the can was gradually depressurized and further heated, and an initial condensation reaction was performed at 250 ° C. and 1 torr or less over 45 minutes. Further, a polymerization reaction was performed for 2 hours at 250 ° C. and 1 torr or less, and the polymer was taken out in a pellet form. The collected thermoplastic polyester elastomer [A2] had Tg = −57 ° C.

(Thermoplastic polyester elastomer [B1])
320 g of dimethyl terephthalate (DMT), 260 g of 1,4-butanediol (BD), 420 g of polytetramethylene glycol (PTMG, molecular weight 2000), 1.8 g of Irganox-1330 (manufactured by Ciba Japan), tetrabutyl titanate (TBT) 1.0 g was charged into a 4 L autoclave, and the temperature was increased from room temperature to 220 ° C. over 3 hours to conduct a transesterification reaction. Next, the inside of the can was gradually depressurized and further heated, and an initial condensation reaction was performed at 250 ° C. and 1 torr or less over 45 minutes. Further, a polymerization reaction was performed for 2 hours at 250 ° C. and 1 torr or less, and the polymer was taken out in a pellet form. The collected thermoplastic polyester elastomer [B1] had Tg = −40 ° C.
(Thermoplastic polyester elastomer [B2])
320 g of dimethyl terephthalate (DMT), 260 g of 1,4-butanediol (BD), 420 g of polytetramethylene glycol (PTMG, molecular weight 1800), 1.8 g of Irganox-1330 (manufactured by Ciba Japan), tetrabutyl titanate (TBT) 1.0 g was charged into a 4 L autoclave, and the temperature was increased from room temperature to 220 ° C. over 3 hours to conduct a transesterification reaction. Next, the inside of the can was gradually depressurized and further heated, and an initial condensation reaction was performed at 250 ° C. and 1 torr or less over 45 minutes. Further, a polymerization reaction was performed for 2 hours at 250 ° C. and 1 torr or less, and the polymer was taken out in a pellet form. The collected thermoplastic polyester elastomer [B2] had Tg = −43 ° C.

[Example 1]
For compounds having two or more functional groups capable of reacting with the terminal functional group of the thermoplastic polyester elastomer [A1] and the thermoplastic polyester elastomer [B1], YD-128 (manufactured by Tohto Kasei: Bisphenol A and epichlorohydrin are overlapped). Polymer obtained by condensation) [C1], (W (A) + W (B)) / W (C) = 200, W (A) / W (B) = 1, After melting and kneading, it was passed through cold water to obtain a polyester elastomer resin with a cooling strand.

[Example 2]
Using the thermoplastic elastomers [A1], [B1], and [C], YH-300 (manufactured by Tohto Kasei: epoxy resin based on aliphatic polyglycidyl ether) [C2] as Example 1 A polyester elastomer resin was obtained by the same method.

[Example 3]
By using Denacol EX-313 (manufactured by Nagase Chemtex Co., Ltd .: glycerol polyglycidyl ether) [C3] as the thermoplastic elastomer [A1], [B1] and [C], a polyester is produced in the same manner as in Example 1. An elastomer resin was obtained.

[Example 4]
Example 1 using Tepic-p (manufactured by Nissan Chemical Industries, Ltd .: a trivalent epoxy compound having a triazine nucleus in the skeleton) [C4] as the thermoplastic elastomer [A1], [B1] and [C]. A polyester elastomer resin was obtained by the same method.

[Example 5]
As the thermoplastic elastomer [A1], [B1] and [C], Millionate MR-200 (manufactured by Nippon Polyurethane Industry Co., Ltd .: Monomeric MDI and a mixture of its polynuclear bodies) [C5] was used. A polyester elastomer resin was obtained by the same method.

[Example 6]
Polyester elastomer resin by the same method as Example 1 using carbodilite HMV-8CA (Nisshinbo Co., Ltd .: multivalent carbodiimide) [C6] as the thermoplastic elastomer [A1], [B1] and [C]. Got.

[Example 7]
As said thermoplastic elastomer [A1], [B1] and [C], using YD-128 (manufactured by Tohto Kasei) [C1], (W (A) + W (B)) / W (C) = 290, A polyester elastomer resin was obtained by the same method as in Example 1 with W (A) / W (B) = 1.

[Example 8]
As the thermoplastic elastomer [A1], [B1] and [C], using YD-128 (manufactured by Tohto Kasei) [C1], (W (A) + W (B)) / W (C) = 110, A polyester elastomer resin was obtained by the same method as in Example 1 with W (A) / W (B) = 1.

[Example 9]
As the thermoplastic elastomer [A1], [B1] and [C], using YD-128 (manufactured by Tohto Kasei) [C1], (W (A) + W (B)) / W (C) = 200, A polyester elastomer resin was obtained in the same manner as in Example 1 with W (A) / W (B) = 0.43.

[Example 10]
As the thermoplastic elastomer [A1], [B1] and [C], using YD-128 (manufactured by Tohto Kasei) [C1], (W (A) + W (B)) / W (C) = 200, A polyester elastomer resin was obtained by the same method as in Example 1 with W (A) / W (B) = 2.3.

[Example 11]
As the thermoplastic elastomer [A2], [B2] and [C], using YD-128 (manufactured by Tohto Kasei) [C1], (W (A) + W (B)) / W (C) = 200, A polyester elastomer resin was obtained by the same method as in Example 1 with W (A) / W (B) = 1.

[Comparative Example 1]
(Thermoplastic polyester elastomer [D])
320 g of dimethyl terephthalate (DMT), 260 g of 1,4-butanediol (BD), 420 g of polytetramethylene glycol (PTMG, molecular weight 1500), 1.8 g of Irganox-1330 (manufactured by Ciba Japan), tetrabutyl titanate (TBT) 1.0 g was charged into a 4 L autoclave, and the temperature was increased from room temperature to 220 ° C. over 3 hours to conduct a transesterification reaction. Next, the inside of the can was gradually depressurized and further heated, and an initial condensation reaction was performed at 250 ° C. and 1 torr or less over 45 minutes. Further, a polymerization reaction was performed for 2 hours at 250 ° C. and 1 torr or less, and the polymer was taken out in a pellet form.

  Using YD-128 (manufactured by Tohto Kasei) [C1] as the compound [C] having two or more functional groups capable of reacting with the terminal functional group of the thermoplastic polyester elastomer [D], (W (D)) / W (C) = 200. After melting and kneading with a twin-screw extruder, the mixture was passed through cold water to obtain a polyester elastomer resin with a cooling strand.

[Comparative Example 2]
Using YD-128 (manufactured by Tohto Kasei) [C1] as the thermoplastic elastomer [A1] and [C], W (A) / W (C) = 200, and melting and kneading with a twin screw extruder Then, it passed through cold water and obtained the polyester elastomer resin with the cooling strand.

[Comparative Example 3]
Using YD-128 (manufactured by Tohto Kasei) [C1] as the thermoplastic elastomer [B1] and [C], W (B) / W (C) = 200, and melting and kneading with a twin screw extruder Then, it passed through cold water and obtained the polyester elastomer resin with the cooling strand.

[ Reference Example 1 ]
As the thermoplastic elastomer [A1], [B1] and [C], using YD-128 (manufactured by Tohto Kasei) [C1], (W (A) + W (B)) / W (C) = 50, A polyester elastomer resin was obtained by the same method as in Example 1 with W (A) / W (B) = 1.

[ Reference Example 2 ]
As the thermoplastic elastomer [A1], [B1] and [C], using YD-128 (manufactured by Tohto Kasei) [C1], (W (A) + W (B)) / W (C) = 350, A polyester elastomer resin was obtained by the same method as in Example 1 with W (A) / W (B) = 1.

[ Reference Example 3 ]
As the thermoplastic elastomer [A1], [B1] and [C], using YD-128 (manufactured by Tohto Kasei) [C1], (W (A) + W (B)) / W (C) = 200, A polyester elastomer resin was obtained by the same method as in Example 1 with W (A) / W (B) = 0.25.

[ Reference Example 4 ]
As the thermoplastic elastomer [A1], [B1] and [C], using YD-128 (manufactured by Tohto Kasei) [C1], (W (A) + W (B)) / W (C) = 200, A polyester elastomer resin was obtained by the same method as in Example 1 with W (A) / W (B) = 4.

The composition ratios of the polyester elastomer resins produced in the above Examples, Comparative Examples and Reference Examples are shown in Table 1, and the physical properties of the obtained polyester elastomer resins are shown in Table 2.

  According to the present invention, it is possible to improve the bending fatigue resistance of the polyester elastomer resin, and at the same time, it is possible to suppress a change in hardness at low temperatures, which greatly contributes to the industry.

Claims (3)

Thermoplastic polyester elastomer [A] comprising aromatic dicarboxylic acid (a1), low molecular weight glycol (a2), and poly (oxytetramethylene) glycol (a3) as constituent components, aromatic dicarboxylic acid (b1), low molecular weight Two functional groups capable of reacting the terminal functional groups of [A] and [B] with the thermoplastic polyester elastomer [B] comprising glycol (b2) and poly (oxytetramethylene) glycol (b3) as constituent components A polyester elastomer resin chain-extended with the compound [C] having the above , wherein the number average molecular weight of (a3) is different from the number average molecular weight of (b3), and the number average molecular weight of (a3) is 500-1500, The number average molecular weight of (b3) is 1500 to 3000, and the glass transition temperature (Tg (A)) of [A] and [B] Glass transition temperature (Tg (B)) is varies, the Tg (A) is a -65 to-40 ° C., the Tg (B) is higher than the Tg (A), and -50-30 When the mass part of [A] in the polyester elastomer resin is W (A), the mass part of [B] is W (B), and the mass part of [C] is W (C) in the polyester elastomer resin, (equation 1) and polyester elastomer resin characterized that you satisfy (equation 2).
(Formula 1) 0.4 <W (A) / W (B) <2.4
(Formula 2) 100 <(W (A) + W (B)) / W (C) <300 (A1) and (b1) are at least one selected from terephthalic acid and naphthalenedicarboxylic acid, and (a2) and (b2) are ethylene glycol, 1,4-butanediol, 1,4 The polyester elastomer resin according to claim 1, which is at least one selected from cyclohexanedimethanol and dimer glycol.
(Here, (a1) and (b1) may be the same or different, and (a2) and (b2) may be the same or different.) Wherein [C] is a polyester elastomer resin according to claim 1 or 2 which is a compound having two or more epoxy groups.