JP2000159988A - Thermoplastic polyester elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition with markedly improved light resistance, heat deterioration resistance and residence stability of the high- melting elastomer, useful as e.g. a molding material for boots and the like by specifying the relationship among hard segment constituent wt.%, crystal melting point and Vicat softening temperature. SOLUTION: This elastomer composition is obtained by compounding (A) 100 pts.wt. of a thermoplastic polyester elastomer with (B) 0.05-5 pts.wt. of a light stabilizer, and pref. furthermore (C) a hindered phenol-based antioxidant. This composition thus obtained has a crystal melting point shown by the relationship: y>=200+0.5x (x is substantial hard segment constituent wt.% based on the component A; y is crystal melting point ( deg.C) determined by raising temperature from room temperature at a rate of 20 deg.C/min using DSC), Vicat softening temperature shown by the relationship: z>=50+1.5x (z is Vicat softening temperature( deg.C) determined in accordance with the ASTM D1525), and elongation at break (determined in accordance with the JIS K6251) of >=100%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic polyester elastomer composition, and more particularly, to a high melting point thermoplastic polyester elastomer composition excellent in moldability, water resistance, heat resistance and light resistance, particularly fibers, films and sheets. Thermoplastic polyester elastomer composition that can be used for various molding materials including, more specifically, suitable for molding materials such as boots, gears, tubes, etc. ,
The present invention relates to a thermoplastic polyester elastomer composition useful for joint boots, wire covering materials, and the like.

[0002]

2. Description of the Related Art Thermoplastic polyester elastomer compositions have conventionally been known as polybutylene terephthalate (PB) as a constituent thermoplastic polyester elastomer.
T) Polyetherester elastomer having a hard segment as a unit and polytetramethylene glycol (PTMG) as a soft segment (JP-B-49-48195, 49-31558)
JP, JP-B-48-4116, JP-A-59-12926, JP-A-59-15117), polyester ester elastomers having a PBT unit as a hard segment and a polycaprolactone (PCL) unit as a soft segment. And PBT
Polyester ester elastomers whose units are hard segments and dimer fatty acids are soft segments (JP-A
No. 54-127955) is known and put to practical use. However, when using PBT for the hard segment,
Since the melting point of PBT is 230 ° C. or less, the melting point of the elastomer does not exceed 230 ° C. In order to improve these, an elastomer using a high melting point polyethylene naphthalate or polycyclohexane dimethylene terephthalate as a hard segment has been proposed (Japanese Patent Laid-Open Publication No.
However, since polytetramethylene glycol is mainly used as the soft segment, the proportion of the hard segment is limited to 60% by weight or less due to the problem of elastic performance, and the elastomer has a high melting point of 230 ° C. or more. Has not been obtained.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art and provides moldability, water resistance, heat resistance, light resistance,
An object of the present invention is to provide a high melting point thermoplastic polyester elastomer composition having excellent heat aging resistance and retention stability. The high melting point will be described. Generally, the melting point and softening point of an elastomer improve as the content of the hard segment increases and the elastic modulus increases. Therefore,
When the elastic modulus is increased, it is possible to increase the melting point and the softening point of the elastomer. However, an elastomer having a high modulus of elasticity has a high glass transition temperature due to an increase in the content of the hard segment, and cannot exhibit excellent elastic performance. In the present invention, while making the elastomer have a high melting point, it is considered that the elastic modulus and the glass transition temperature do not become unnecessarily high, that is, even if they have the same degree of elasticity, the melting point is sufficient. An object which becomes higher is defined as a high melting point elastomer, and an object of the present invention is to remarkably improve the light resistance, heat aging resistance and retention stability of the high melting point elastomer.

[0004]

Means for Solving the Problems The present inventors have a specific relationship between the thermoplastic polyester elastomer and the weight% constituting the hard segment, the crystal melting point and the Vicat softening temperature, and contain a light stabilizer. It has been found that the above-mentioned problems can be solved by using the composition described in the above, and the present invention has been completed. That is, the present invention relates to (A) 100 parts by weight of a thermoplastic polyester elastomer,
(B) A composition containing 0.05 to 5 parts by weight of a light stabilizer has a crystal melting point represented by the following formula (1) and a Vicat softening temperature represented by the following formula (2), and has an elongation at break. It is a thermoplastic polyester elastomer composition characterized by being 100% or more. Crystal melting point: y ≧ 200 + 0.5x (1) Vicat softening temperature: z ≧ 50 + 1.5x (2) (where x is a weight% substantially constituting a hard segment with respect to the thermoplastic polyester elastomer of the composition) And y is the crystal melting point (° C.) measured by increasing the temperature from room temperature by DSC at 20 ° C./min, and z is ASTM D1525.
Shows the Vicat softening temperature (° C.) measured based on The elongation at break is a value measured based on JIS K6251. In a preferred embodiment, x, which is a weight% substantially constituting the hard segment with respect to the base resin of the composition, is in the range of 30 to 95, and the hard segment in the thermoplastic polyester elastomer has the following general formula: It comprises the repeating unit represented by (1) and contains a hindered phenolic antioxidant (C).

Embedded image (In the formula, R represents an aromatic group having 6 to 18 carbon atoms.) Further, the relationship between the weight percentage of the hard segment and the crystal melting point is preferably y ≧ 200 + 0.55x, more preferably y ≧ 200 + 0.6x. The relationship between the weight% constituting the hard segment and the Vicat softening point is preferably z ≧ 50 + 1.7x, more preferably z ≧ 70 + 1.7x. If the above formulas (1) and (2) are not satisfied, the heat resistance is not sufficient, and it is difficult to use in applications requiring heat resistance such as automobiles and home electric parts. Vicat softening temperature is AS
It is basically measured by TM D1525,
Depending on the shape of the sample, the softening temperature of the resin conforming to the standard can be defined by the measured temperature. For example, the temperature at which the storage elastic modulus (E ') measured by a dynamic viscoelasticity measurement device starts to decrease, or JI
An extrapolated melting start temperature or the like defined by SK7121 can be used. In the present invention, the temperature at which the storage elastic modulus starts to decrease by dynamic viscoelasticity measurement is used as a substitute for the Vicat softening temperature. Dynamic viscoelasticity is
For example, Toyo Baldwin's Leo Vibron DDV
-II, and a thickness of 100 to 50
A 0 μm measurement material is heated at a rate of 2 ° C./min, and the softening temperature is determined from the storage elastic modulus obtained by measuring at a frequency of 110 Hz.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the thermoplastic polyester elastomer composition of the present invention, in order to satisfy the expressions (1) and (2),
The acid component constituting the repeating unit of the thermoplastic polyester elastomer is mainly composed of an aromatic dicarboxylic acid, specifically, a kind selected from terephthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, isophthalic acid, and 5-sodium sulfoisophthalic acid. Or it is preferable to use a combination of two or more, especially terephthalic acid,
It is preferable to use one or a combination of two selected from naphthalenedicarboxylic acids. The aromatic dicarboxylic acid is preferably at least 70 mol%, more preferably at least 80 mol% of the total acid components. As other acid components, alicyclic dicarboxylic acids and aliphatic dicarboxylic acids are used, and examples of the alicyclic dicarboxylic acids include cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride and the like.
As aliphatic dicarboxylic acids, succinic acid, glutaric acid,
Adipic acid, azelaic acid, sebacic acid, dodecane diacid, dimer acid, hydrogenated dimer acid and the like can be mentioned. These are used in a range that does not significantly lower the melting point of the resin, and the amount thereof is preferably less than 30 mol%, more preferably less than 20 mol% of the total acid components.

The glycol component used for the repeating unit substantially constituting the hard segment is not particularly limited, but an alkylene glycol having 1 to 25 carbon atoms can be used. For example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, dimethylol Heptane, dimethylolpentane, tricyclodecanedimethanol, methylpentanediol, 2,4-diethyl-
1,5-pentanediol, ethylene oxide derivatives of bisphenol X (X is A, S, F) and the like. One or two or more glycols selected from these glycols are used in an appropriate combination depending on the balance of various properties. In particular, cyclohexane dimethanol is preferably used, and the crystallinity of the hard segment comprising the dicarboxylic acid is preferably used. Therefore, the copolymerization amount of these glycols is desirably 20 mol% or less based on the total glycol. 1,4-
Cyclohexanedimethanol has two types of isomers, a cis-form and a trans-form, and it is preferable that the ratio of the trans-form is large. The hard segment is desirably composed of a repeating unit represented by the general formula (1). The repeating unit substantially constituting the hard segment is preferably 30 to 95% by weight, more preferably 40 to 80% by weight, and particularly preferably 50 to 75% by weight of the whole polymer.
Is desirable. If it exceeds 95% by weight, it is inferior in flexibility because it is difficult to obtain an elastomer having elasticity, and if it is less than 30% by weight, the melting point is lowered and the heat resistance is deteriorated. The repeating unit substantially constituting the hard segment comprises an acid component constituting the repeating unit of the thermoplastic polyester elastomer, and a glycol component substantially constituting the repeating unit constituting the hard segment.

[0007] The glycol component used in the repeating unit substantially constituting the soft segment of the thermoplastic polyester elastomer is not particularly limited. For example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or a derivative thereof may be used. Terminal ethylene oxyside adducts are desirable. The molecular weight of the polyalkylene glycol is 400 to 60
00 preferably 800 to 3000, especially 1000 to 20
00 is desirable. If the molecular weight is less than 400, the elasticity is insufficient, and the blockability of the obtained elastomer is reduced, so that the melting point and softening temperature of the polymer are reduced.
When the molecular weight exceeds 6000, phase separation becomes easy,
This is also not preferable since it also causes insufficient elasticity.

It is preferable to use hydrogenated dimer diol as another glycol component which substantially constitutes the soft segment of the thermoplastic polyester elastomer. The hydrogenated dimer diol is, of course, not limited to its production method, but may be, for example, an unsaturated fatty acid (having 15 to 2 carbon atoms).
A compound represented by the following general formula (2) obtained by hydrogenating dimer acid which is a dimer of 1) as a main component (50% by weight)
Or a mixture of a compound represented by the following general formula (2) and a compound represented by the following general formula (3).

[0009]

Embedded image (In the above formula, R ¹ , R ² , R ³ , and R ⁴ are substantially free from unsaturated groups and are substantially linear, and among them, R ¹ ,
R ² is an alkyl group, R ³ and R ⁴ are alkylene groups,
The total number of carbon atoms of R ^{1 to} R ⁴ is 22 to 34. )

[0010]

Embedded image (In the above formula, R ⁵ , R ⁶ , R ⁷ , and R ⁸ are substantially free from unsaturated groups and are substantially linear, and among them, R ⁵ ,
R ⁶ is an alkyl group, R ⁷ and R ⁸ are alkylene groups,
The total number of carbon atoms of R ⁵ to R ⁸ is 25 to 37. )

As another glycol component which substantially constitutes the soft segment of the thermoplastic polyester elastomer, a hydrogenated dimer diol derivative can be mentioned. The hydrogenated dimer diol derivative is a diol compound substantially derived from hydrogenated dimer diol,
Specific examples include an ethylene oxide and / or propylene oxide adduct of a hydrogenated dimer diol. The addition of the oxide compound may be at both ends or only one end of the hydrogenated dimer diol. The number of moles of the oxide compound to be added is preferably equimolar to 20 times the number of moles of the hydrogenated dimer diol.

The proportion of the diol compound derived from the polyalkylene glycol and the hydrogenated dimer diol which substantially constitutes the soft segment is not particularly limited because it is used in an appropriate combination depending on the balance of various properties. The ratio of the polyalkylene glycol to the sum is from 0.01 to 0.99, preferably from 0.05 to 0.99.
0.95, especially 0.1 to 0.9 is desirable. Less than 0.01 lacks elasticity as an elastomer,
If it is more than 0.99, the compatibility with the hard segment will be lacking, and the elastic performance of the elastomer will also be lacking.

The thermoplastic polyester elastomer of the present invention may contain a tri- or higher functional polycarboxylic acid or polyol component in a small amount. For example, trimellitic anhydride, benzophenonetetracarboxylic acid, trimethylpropane, glycerin, pyromellitic anhydride, etc.
Mol% or less can be used.

Next, as a method for obtaining the thermoplastic polyester elastomer of the present invention, any known method can be adopted. For example, any of a melt polymerization method, a solution polymerization method, and a solid phase polymerization method may be appropriately used. In the case of a melt polymerization method, a transesterification method or a direct polymerization method may be used. It is, of course, desirable to carry out solid phase polymerization after melt polymerization in order to improve the viscosity of the resin. As a catalyst used for the reaction, an antimony catalyst, a germanium catalyst, and a titanium catalyst are preferable. Particularly, the titanium catalyst is preferably a tetraalkyl titanate such as tetrabutyl titanate or tetramethyl titanate, or a metal oxalate 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.

The light stabilizers used in the present invention include hindered amine light stabilizers, benzophenone-based, benzoate-based, triazole-based, nickel-based and salicyl-based light stabilizers. Examples of the hindered amine light stabilizer include a polycondensate with dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate, poly [[6- (1, 1,3,3
3-tetrabutyl) imino-1,3,5-triazine-
2,4-diyl] hexamethylene [(2,2,6,6-
Tetramethyl-4-piperidyl) imyl]], 2-n-
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester of 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- Piperidyl) hexamethylenediamine and 1,
Polycondensate with 2-dibromoethane, poly [(N, N'-
Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine)-(4-monophorino-
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-butanetetracarboxylate, Screws (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 and the like.

The benzophenone-based, benzotriazole-based, triazole-based, nickel-based and salicyl-based light stabilizers which can be blended in the present invention include 2,2'-dihydroxy-4-methoxybenzophenone and 2-hydroxy-4- n-octoxybenzophenone, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-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′-tert-butyl-
5'-methylphenyl) -5-chlorobenazotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-
Butylphenyl) -5-chlorobenzotyriazole,
2,5-bis- [5′-t-butylbenzoxazolyl-
(2)]-thiophene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphoric acid monoethyl ester) nickel salt, 2-ethoxy-5-t-butyl-2′-ethyloxalic acid-bis -Anilide 85-90%
And 2-ethoxy-5-t-butyl-2'-ethyl-4 '
-T-butyl oxalic acid-bis-anilide 1
0-15% mixture, 2- [2-hydroxy-3,5-
Bis (α, α-dimethylbenzyl) phenyl] -2H-
Benzotriazole, 2-ethoxy-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)
Light stabilizers such as benzotriazole, 2-hydroxy-4-i-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone and phenyl salicylate can be mentioned.

A particularly preferred light stabilizer is 300 ° C.
Under the condition of heating at 10 ° C./min using a thermobalance, 10
It is preferred that the temperature at which the% weight loss occurs is 250 ° C or higher. If the temperature at which the heating loss is reduced by 10% is lower than 250 ° C., the light stabilizer is sublimated and the appearance is remarkably deteriorated, which is not preferable. In order to incorporate the light stabilizer described above into the resin composition, 0.01 to 20 parts by weight, preferably 0.05 to 1 part by weight of the light stabilizer is added to 100 parts by weight of the thermoplastic elastomer.
0 parts by weight, particularly preferably in the range of 0.1 to 5 parts by weight. When the amount of the light stabilizer exceeds 20 parts by weight, poor appearance due to bleeding occurs, which is not preferable. The light stabilizer is 0.01%.
If it is less than 1, the light resistance is poor, which is not preferable. These light stabilizers may be used alone, or two or more light stabilizers may be combined. Particularly, a combination of a hindered amine light stabilizer and a benzophenone light stabilizer and / or a benzotriazole light stabilizer is used. Is preferable because the light resistance is remarkably improved. The total amount of the light stabilizers in these combinations is 0.1 to 20 parts by weight, preferably 0.1 to 5 parts by weight. If the total amount of the light stabilizer exceeds 20 parts by weight, poor appearance due to bleeding occurs, which is not preferable. When the amount of the light stabilizer is less than 0.1, a remarkable effect of improving light resistance is not recognized.

The hindered phenolic antioxidants which can be incorporated in the resin composition of 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-tert-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-t-butyl- 5-methyl-4-hydroxyphenyl) 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) propionyloxydiethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis [3,3-bis (4′-hydroxy-3′-t-) Butylphenyl) butyric acid] glycol ester, triferol, 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-tert-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6 (1
H, 3H, 5H) -trione, 1,3,5-tris (4
-Tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di-tert-butyl-4
-Hydroxyhydrocinnamic acid 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-t-butyl-4-hydroxy-5
-Methylphenyl) propionyloxy {-1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane.

The hindered phenolic antioxidant contained in the thermoplastic polyester elastomer composition of the present invention is 0.05 to 5 parts by weight, preferably 0.1 to 5 parts by weight.
4 parts by weight are preferred. If the amount of the hindered phenolic antioxidant exceeds 5 parts by weight, the antioxidant bleeds, which is not preferable because the appearance of the product is impaired. If the amount of the antioxidant is less than 0.05 part by weight, heat deterioration such as foaming during extrusion or molding and heat aging resistance are extremely poor, which is not preferable. In the present invention, the hindered phenol-based antioxidant is not limited to one kind, and the combination of two or more hindered phenol-based antioxidants is not particularly limited. Furthermore, by combining a hindered phenol-based antioxidant with a known non-hindered phenol-based antioxidant, the heat aging resistance, the retention stability and the product appearance can be remarkably improved. Other antioxidants include sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants.

The method of compounding the resin composition of the present invention includes:
The compounding can be carried out using a kneader such as a heating roll, an extruder or a Banbury mixer. Further, it can be added and mixed into the oligomer before the transesterification reaction or before the polycondensation reaction when producing the thermoplastic polyester elastomer resin composition.

Further, the composition of the present invention may contain known additives such as sulfur-based, phosphorus-based, and amine-based antioxidants, antistatic agents, lubricants, molecular regulators such as peroxides, epoxy compounds, isocyanate compounds. Compounds, compounds having reactive groups such as carbodiimide compounds, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, antacids, antibacterial agents, fluorescent brighteners, fillers, flame retardants, and Flame retardant aids, organic and inorganic pigments and the like can be added. These additives can be compounded using a kneader such as a heating roll, an extruder, or a Banbury mixer. Further, it can be added and mixed into the oligomer before the transesterification reaction or before the polycondensation reaction when producing the thermoplastic polyester elastomer resin composition.

The reduced viscosity of the thermoplastic polyester elastomer used in the present invention is preferably 0.5 to 4.0,
More preferably, it is 0.5 to 3.0. The reduced viscosity is 0.
If it is less than 5, mechanical properties are inferior, and if it exceeds 4.0, moldability is inferior. The lower limit of the melting point of the thermoplastic polyester elastomer composition of the present invention is not particularly limited, but is generally preferably 150 ° C. or higher. 200 ° C. or higher is preferred for applications requiring heat resistance, but 230 ° C. or higher is particularly preferred for applications requiring heat resistance. By the way, Adv. Chem. . Ser. , 176, 12
9 (1979). According to this publication, it is described that in a polyester elastomer composed of only polycyclohexane dimethylene terephthalate and polytetramethylene glycol, when polycyclohexane dimethylene terephthalate is contained in an amount of 50% by weight or more, phase separation occurs and no elastic performance as an elastomer is exhibited. However, surprisingly, in the present invention, by changing the soft segment from polyalkylene glycol alone to a combined system of polyalkylene glycol and hydrogenated dimer diol and / or a derivative thereof, the amount of hard segment can be increased to 50% by weight or more. It has been found by the present inventor and others that sufficient elasticity is exhibited. Although the reason for this is not clear, the hydrogenated dimer diol having a cyclohexane skeleton and / or a derivative thereof acts as a compatibilizing agent for polycyclohexane dimethylene terephthalate and polyalkylene glycol, so that the compatibility between both is improved. It is estimated to be.

[0023]

The present invention will be specifically described below with reference to examples. In addition, in these Examples, each measurement item followed the following method. The weight% of polycyclohexane dimethylene terephthalate, polytetramethylene glycol and the like in the obtained polymer is a value measured by proton NMR. Reduced viscosity: 0.05 g of the polymer was dissolved in 25 ml of a mixed solvent (phenol / tetrachloroethane = 60/40) and measured at 30 ° C. using an Ostwald viscometer. Crystal melting point: The crystal melting point was measured by DSC at a rate of 20 ° C./min from room temperature. Surface hardness: measured according to ASTM D2240. Flexural modulus: measured according to ASTM D790. Tensile strength, elongation at break: Measured according to JIS K6251. Vicat softening temperature: measured according to ASTM D1525. Light fastness: Elongation retention at break after irradiation with a fade meter at 83 ° C. for 500 hours was measured according to JIS K6251.

Polyester Synthesis Example 1 460 parts by weight of dimethyl terephthalate, 460 parts by weight of cyclohexanedimethanol, 50 parts by weight of hydrogenated dimer diol (HP1000, manufactured by Toagosei Co., Ltd.), 300 parts by weight of polytetramethylene glycol (molecular weight 1000), antioxidant Agent A-7 (shown in Table 1) (2 parts by weight) and tetrabutyl titanate (0.9 parts by weight) were charged, and the temperature was raised from room temperature to 260 ° C. over 2 hours, followed by heating at 260 ° C. for 1 hour to perform a transesterification reaction. went. Then, the pressure inside the can was gradually reduced and the temperature was raised.
The initial polycondensation reaction was performed as follows. 275 ° C,
The polymerization reaction was carried out for 4 hours at a pressure of 1 torr or less, and the polymer was taken out in the form of pellets to obtain polymer A. The reduced viscosity of the obtained polymer was 1.04, and the weight percents of the polycyclohexane dimethylene terephthalate component, the polytetramethylene glycol component, and the hydrogenated dimer diol component in the polymer were 65%, 30%, and 5%, respectively. Was.

Polyester Synthesis Example 2 530 parts by weight of dimethyl terephthalate, 750 parts by weight of cyclohexanedimethanol, 50 parts by weight of hydrogenated dimer diol (HP1000, manufactured by Toagosei Co., Ltd.), 200 parts by weight of polytetramethylene glycol (molecular weight: 1000), antioxidant Agent A-7 (shown in Table 1) (2 parts by weight) and tetrabutyl titanate (0.9 parts by weight) were charged, and the temperature was raised from room temperature to 260 ° C. over 2 hours, followed by heating at 260 ° C. for 1 hour to perform a transesterification reaction. went. Then, the pressure inside the can was gradually reduced and the temperature was raised.
The initial polycondensation reaction was performed as follows. 275 ° C,
The polymerization reaction was carried out for 4 hours under the condition of 1 torr or less, and the polymer was taken out in the form of pellets to obtain polymer B. The reduced viscosity of the obtained polymer was 1.10, and the weight percents of the polycyclohexane dimethylene terephthalate component, the polytetramethylene glycol component, and the hydrogenated dimer diol component in the polymer were 75%, 20%, and 5%, respectively. Was.

Polyester Synthesis Example 3 570 parts by weight of dimethyl terephthalate, 580 parts by weight of 1,4-butanediol, 350 parts by weight of polytetramethylene glycol (molecular weight 1000), antioxidant A-7
2 parts by weight (shown in Table 1), tetrabutyl titanate 0.
9 parts by weight were charged, the temperature was raised from room temperature to 200 ° C. over 2 hours, and then the mixture was heated at 200 ° C. for 1 hour to carry out a transesterification reaction. Next, the pressure inside the can was gradually reduced and the temperature was raised, and the initial polycondensation reaction was performed at 245 ° C. and 1 torr or less over 45 minutes. Further, a polymerization reaction was carried out at 245 ° C. and 1 torr or less for 3 hours, and the polymer was taken out in the form of pellets to obtain polymer C. The reduced viscosity of the obtained polymer was 1.49, and the weight percents of the polybutylene terephthalate component and the polytetramethylene glycol component in the polymer were 65% and 35%, respectively.

Examples 1 to 8, Comparative Examples 1 to 3 Polymers A to C obtained in Polymer Synthesis Examples 1 to 3 and Table 1
Light stabilizers and antioxidants shown in Tables 2 and 3
The pellets were taken out using an extruder and dried with a hot air drier to a moisture content of 0.1% or less. Injection molding was performed under appropriate conditions, and each measurement was performed. The results are shown in Tables 4 and 5.

[0028]

[Table 1]

The composition tables in Tables 2 and 3 below are shown in parts by weight.

[Table 2]

[0030]

[Table 3]

X in Tables 4 and 5 is a weight percentage that substantially constitutes a hard segment of the polyester elastomer.

[Table 4]

[0032]

[Table 5]

[0033]

As described above, the thermoplastic polyester elastomer composition of the present invention has a melting point of about 60.degree. C. and a Vicat softening temperature of about 50.degree. C. higher than the conventional polyester elastomer composition having the same elastic modulus. Excellent heat resistance. In addition, it can be seen that the light resistance was significantly improved. In other words, due to the synergistic effect of the high melting point polyester elastomer and the light stabilizer, it has a high level of light resistance,
It can withstand unusual use in a high temperature range. That is, the present invention is excellent in heat resistance, light resistance, heat aging resistance, retention stability and mechanical properties and has a high melting point, so that it can be used for various molding materials such as fibers, films and sheets. It is also suitable as a molding material for boots, gears, tubes and the like. For example, timing belt,
It is useful for joint boots, wire covering materials, etc., and greatly contributes to the industrial world.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Seiji Nakayama 2-1-1 Katata, Otsu-shi, Shiga F-term in Toyobo Co., Ltd. Research Laboratory (reference) 4J002 CF041 EH127 EJ026 EJ067 EN007 EU157 FD047 FD076 4J029 AA03 AB07 AC01 AD06 AD10 AE01 BD03A CB05A CB06A CC05A HA01 HB01 HB02 JB193 JC023 JC033 JC053 JD06

Claims (4)

[Claims] A composition comprising (A) 100 parts by weight of a thermoplastic polyester elastomer and 0.05 to 5 parts by weight of a light stabilizer (B) is mixed with a crystalline melting point represented by the following formula (1): A thermoplastic polyester elastomer composition having a Vicat softening temperature represented by the following formula (2) and an elongation at break of 100% or more. Crystal melting point: y ≧ 200 + 0.5x (1) Vicat softening temperature: z ≧ 50 + 1.5x (2) (where x is a weight% substantially constituting a hard segment with respect to the thermoplastic polyester elastomer of the composition) And y is the crystal melting point (° C.) measured by increasing the temperature from room temperature by DSC at 20 ° C./min, and z is ASTM D1525.
Shows the Vicat softening temperature (° C.) measured based on The elongation at break is a value measured based on JIS K6251. ) 2. The thermoplastic polyester elastomer composition according to claim 1, wherein (A) a thermoplastic polyester elastomer and (B) a light stabilizer and (C) a hindered phenolic antioxidant are blended. 3. The thermoplastic polyester elastomer, wherein x is a weight% substantially constituting a hard segment.
3. The thermoplastic polyester elastomer composition according to claim 1, wherein the range is 30 to 95. 4. 4. The thermoplastic polyester elastomer composition according to claim 1, wherein the hard segment in the thermoplastic polyester elastomer comprises a repeating unit represented by the following general formula (1). Embedded image (In the formula, R represents an aromatic group having 6 to 18 carbon atoms.)