JP2003003050A - Thermoplastic polyester elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic polyester elastomer which is very flexible without being mixed with a plasticizer or an olefin elastomer and has excellent low-temperature properties. SOLUTION: In a thermoplastic polyester elastomer composition containing a thermoplastic polyester elastomer resin and at least one additive selected from an antioxidant, a light stabilizer and a lubricant, the content of the thermoplastic polyester elastomer resin is from 85% by weight or more. JIS K6
A thermoplastic polyester elastomer composition characterized by having a surface hardness of more than 70 A measured based on 253.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic polyester elastomer. More specifically, thermoplastic polyester elastomers that have both flexibility and heat resistance at low temperatures, especially automobile exterior parts (gears, boots, emblems,
The present invention relates to a novel thermoplastic polyester elastomer suitable as a molding material for belts, tubes, etc.) and industrial products (packings, sheets, etc.).

[0002]

2. Description of the Related Art Polybutylene terephthalate (PBT) has hitherto been used as a thermoplastic polyester elastomer.
A polyether ester elastomer whose unit is a hard segment and polytetramethylene glycol (PTMG) is a soft segment (JP-B-49-48195, 4).
9-31558), a polyester ester elastomer having a PBT unit as a hard segment and a polycaprolactone (PCL) unit as a soft segment (JP-B-48-4116, JP-A-59-12926, and JP-A-59-29). 15117), and a polyester ester elastomer having a PBT unit as a hard segment and a dimer fatty acid as a soft segment (JP-A-54).
No. 127,955) is known and put into practical use. Further, in order to obtain a flexible thermoplastic polyester elastomer having a surface hardness of 70 A or less, it is known to mix a plasticizer or another flexible olefin elastomer.

[0003]

However, the above-mentioned conventional elastomer has a problem that it cannot maintain the flexibility like that at room temperature because the rubber property is deteriorated in a low temperature region. In addition, when a plasticizer or an olefin elastomer is mixed, apparent flexibility is obtained but the elastic modulus is not stable. Particularly when a plasticizer is mixed, the plasticizer also contaminates the mold during molding. The present invention solves this drawback, expands the range of application by rubber elasticity, and provides a thermoplastic polyester elastomer having excellent low-temperature properties.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that by using a specific hard segment and a specific soft segment in a polyester elastomer, The inventors have found that the problems are solved and have reached the present invention.

That is, the present invention is a thermoplastic polyester elastomer satisfying the following conditions. 1. In the thermoplastic polyester elastomer composition containing a thermoplastic polyester elastomer resin and at least one additive selected from antioxidants, light stabilizers and lubricants, the thermoplastic polyester elastomer resin is 8
A thermoplastic polyester elastomer composition comprising 5% by weight or more and having a surface hardness, measured according to JIS K6253, of more than 70 A. 2. Relative ratio α of 50% elongation stress measured according to ASTM D638 (50% elongation stress at −30 ° C./2
50% elongation stress at 3 ° C.) is 1 <α ≦ 4.0, a thermoplastic polyester elastomer composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polyester elastomer composition of the present invention comprises 85% by weight or more of a thermoplastic polyester elastomer resin, and JIS K625 is used.
The thermoplastic polyester elastomer composition is characterized in that the surface hardness measured based on 3 is softer than 70 A (70 A or less).

The surface hardness is preferably 68 A or less, more preferably 67 A or less, particularly preferably 66 A or less, and most preferably 65 A or less. The lower limit of the surface hardness is not particularly defined, but as a practical property of the molding material or the like, 40 A or more, 50 A or more, and further 55 A or more.
More preferably, it is 58A or more. Also,
In the thermoplastic polyester elastomer composition, the thermoplastic polyester elastomer resin is preferably 87% by weight or more, more preferably 88% by weight or more, and particularly preferably 8% by weight or more.
It is composed of 9% by weight or more, most preferably 90% by weight or more. Further, the upper limit of the content of the thermoplastic polyester elastomer resin is preferably 99.99% by weight, more preferably 99.9% by weight, and further preferably 99.7% by weight. When the content of the thermoplastic polyester elastomer resin exceeds 99.99% by weight,
In some cases, stabilizers do not work sufficiently and are inferior in light resistance and heat resistance. In addition, the thermoplastic polyester elastomer resin represents only a polyester component (including a catalyst) to which various additives are not added.

[0008] The thermoplastic polyester elastomer composition of the present invention is very flexible, has a small content of additives such as a plasticizer, and does not stain the mold during molding. Therefore, the mold deposit is unlikely to occur, and the mold cleaning does not take time even during the continuous molding.

Furthermore, the thermoplastic polyester elastomer composition of the present invention has a relative ratio α (50 at -30 ° C.) of 50% elongation stress measured according to ASTM D638.
0% elongation stress / 50% elongation stress at 23 ° C) is 1 <
α ≦ 4.0. The upper limit of α is preferably 3.
5, more preferably 3.0, particularly preferably 2.7,
Most preferably it is 2.5. As the lower limit of α, the closer it is to 1, the better, but in reality, it is about 1.1.
Further, it is preferably about 1.2.

By setting the relative ratio α of 50% elongation stress within the above range, the flexibility characteristics are changed at a low temperature of 0 ° C. or below and at room temperature, and it has been found in the conventional polyester having a high flexibility that the number of soft segments is large. It is possible to solve the problem that the flexibility is inferior at -30 at an extremely low temperature, and it is difficult to use for use requiring flexibility in an extremely low temperature environment.

Further, the thermoplastic polyester elastomer composition of the present invention preferably has a water content of 25% by weight or less when immersed in water at 23 ° C. for 24 hours. The water content is more preferably 20% by weight or less, further preferably 15% by weight, particularly preferably 10% by weight, and most preferably 7% by weight or less. The smaller the water absorption is, the more preferable it is, but in reality, it is preferably 0.005% by weight or more. If the water content exceeds 25% by weight, the molded product may be deformed or expanded due to moisture absorption, and when laminated with other materials, the peeling strength may be lowered due to moisture absorption or water wetting.

In addition, the thermoplastic polyester elastomer composition of the present invention has a water vapor transmission rate of 3000 g / m ² · when a film having a thickness of 10 μm is measured by the calcium chloride method of JIS Z0209 at 40 ° C. and 90% RH. d
It is preferably ay or more.

When the resin composition of the present invention is used to measure a film having a thickness of 10 μm, the water vapor permeability of the film is more preferably 4000 g / m ² · day, further preferably 450
0g / m ² · day, particularly preferably 4800 g / m ² ·
day, most preferably 5000 g / m ² · day. The higher the upper limit of the water vapor transmission rate, the more preferable, but in reality, it is preferably 100,000 g / m ² · day.

Even when a film having a thickness of 20 μm is measured, the water vapor permeability of the film is 3000 g / m ²
・ Day or more is preferable, and more preferably 4
000 g / m ² · day, more preferably 4500 g
/ M ² · day, particularly preferably 4800g / m ² · da
y, most preferably 5000 g / m ² · day.

Further, even when a film having a thickness of 30 μm is measured, the water vapor transmission rate of the film is 3000 g /
It is preferably m ² · day or more, more preferably 4000 g / m ² · day, still more preferably 450.
0g / m ² · day, particularly preferably 4800 g / m ² ·
day, most preferably 5000 g / m ² · day.

By setting the moisture permeability to the above range, both high moisture permeability and flexibility can be achieved, and it can be suitably used as a flexible moisture permeable film.

The thermoplastic polyester elastomer composition that achieves the characteristics of the present invention will be described in detail below. In the thermoplastic polyester elastomer resin used in the present invention, the acid component is mainly composed of aromatic dicarboxylic acid. As the aromatic dicarboxylic acid, for example, it is preferable to use one kind or a combination of two or more kinds selected from terephthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, isophthalic acid, and 5-sodiumsulfoisophthalic acid, and among them, more preferable Are terephthalic acid and naphthalenedicarboxylic acid. The aromatic dicarboxylic acid accounts for 70 mol% or more, preferably 80 mol% or more, and more preferably 90 mol% or more of the total acid components.

Aliphatic dicarboxylic acids and aliphatic dicarboxylic acids are used as other acid components, and examples of the alicyclic dicarboxylic acids include cyclohexanedicarboxylic acid and tetrahydrophthalic anhydride. Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, hydrogenated dimer acid and the like. These are used in 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%, more preferably less than 10 mol% of the total acid components.

The soft segment in the thermoplastic polyester elastomer resin used in the present invention is a random copolymer polyether glycol having a molecular weight of 2200 to 3800, which is composed of two or more different alkylene units having 2 to 10 different carbon atoms which are randomly repeated. Is preferred.

Among them, the molecular weight is more preferably 24
00 or more, more preferably 2600 or more, particularly preferably 2700 or more, more preferably 3600 or less, further preferably 3400 or less, particularly preferably 3
It is 300 or less.

In order to increase the flexibility of the thermoplastic polyester elastomer composition, measures such as adding a large amount of a lubricant and increasing the soft segment amount of the thermoplastic polyester elastomer resin are usually adopted. When the thermoplastic polyester elastomer resin is contained in an amount of 85% or more to have high flexibility as in the present invention, the soft segment amount of the thermoplastic polyester elastomer resin is increased to increase the flexibility.

However, since the flexibility is increased,
If the soft segment amount is too large, the polyester elastomer resin may not be able to maintain crystallinity and may be inferior in moldability. That is, it is important to achieve both sufficient flexibility and moldability. It is possible to increase the molecular weight of the soft segment in order to increase the amount of the soft segment while maintaining the crystallinity.However, if the molecular weight of the soft segment is increased, phase separation occurs during polymerization and a thermoplastic resin with a satisfactory molecular weight is usually used. It is difficult to obtain a polyester elastomer resin. As an example, by using a random copolymerized polyether glycol having a specific molecular weight, it is possible to obtain a highly flexible thermoplastic polyester elastomer composition that solves these problems.

When the molecular weight of the random copolymerized polyether glycol is less than 2200, sufficient flexibility and moldability may not be obtained when the polyester elastomer resin is 90% by weight or more. When the molecular weight of the random copolymerized polyether glycol exceeds 3800, the polyether glycol and other raw materials may be phase-separated during the production, and a polyester elastomer resin having a satisfactory molecular weight may not be obtained. Further, by using the random copolymerized polyether glycol, an elastomer having a small change in flexibility and strength-elongation characteristics and a low temperature dependence in a wide range from a low temperature below zero to a room temperature and a high temperature range exceeding 80 ° C. Is obtained.

The components of the random copolymerized polyether glycol include -OCH ₂ CH _2- (hereinafter sometimes abbreviated as EO component), -OCH ₂ CH ₂ CH _2- , -OCH ₂ CH ₂ CH ₂ CH _2-. (Hereinafter THF
Sometimes abbreviated as _{component), - OCH 2 CH (CH} 3) - ( Sometimes abbreviated as follows PO _{component), - OCH 2 C (CH} 3) 2 CH 2 -, and the like.

Furthermore, by using a random copolymerized polyether glycol, an elastomer composition having a low water absorption rate can be obtained even if an EO component is used as a component of the random copolymerized polyether glycol. Among the components used in the random copolymer polyether glycol,
The EO component is preferably 80 mol% or less, more preferably 70 mol% or less, and particularly preferably 65 mol% or less. Further, the EO component may not be contained. If the EO component exceeds 80 mol%, the water absorption becomes high, and it may not be preferable depending on the application.

It is desirable that substantially all of both ends of the random copolymer glycol are hydroxyl groups derived from the EO component. As a random copolymer glycol satisfying this condition, for example, a random copolymer of THF and EO, DC-3000 (manufactured by NOF CORPORATION, molecular weight 300).
0, THF / EO = 50/50 (mol ratio)) and the like. When the terminal is a hydroxyl group derived from the THF component,
Poly (oxytetramethylene) consisting of THF component only
Needless to say, not only glycols but also random copolymerized glycols are not preferable in terms of generation of by-products and odor due to the formation of THF by the ring closure reaction at the terminals.

The thermoplastic polyester elastomer resin used in the present invention preferably contains the polyether glycol component of the above-mentioned random copolymerized polyether glycol, but the total amount of all the polyether glycol components of the thermoplastic polyester elastomer is 4 in the total weight. The alkylene unit having a primary carbon is preferably less than 10% by weight, more preferably less than 5% by weight, further preferably 3%.
Less than wt%, most preferably no quaternary carbon in the polyether glycol component. Polyester elastomers having quaternary carbon may deteriorate during use under severe conditions. The weight of the alkylene unit having a quaternary carbon in the weight of the polyether glycol component is calculated based on the alkylene oxide unit which is a raw material for producing the polyether glycol.

In the thermoplastic polyester elastomer resin used in the present invention, a soft segment component other than the random copolymerized polyether glycol may be copolymerized. As the soft segment component other than the copolymerized polyether glycol, polyalkylene ether glycols such as poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol having a molecular weight of 400 to 6000, and mixtures thereof A block or random copolymerized polyether glycol obtained by copolymerizing these polyether glycol constituents, or a polyester produced from an aliphatic dicarboxylic acid having 2 to 12 carbon atoms and an aliphatic glycol having 2 to 10 carbon atoms, such as polyethylene. Adipate, polytetramethylene adipate, polyethylene sebacate, polyneopentyl sebacate, polytetramethylene dodecaneate, polytetramethylene azelate, polyhexamethylene azelate Door, poly -ε- caprolactone, and the like. These glycols are used in an appropriate combination depending on the balance of various properties.

The random copolymer polyether glycol is preferably 50% by weight in all the soft segment components.
The above content is more preferably 60% by weight or more, further preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more. When it is less than 50% by weight, flexibility and moldability may not be balanced.

The content of the soft segment used in the thermoplastic polyester elastomer of the present invention is 70 to 95% by weight based on the total polymer, including the random copolymer polyether glycol and the soft segment components other than the random copolymer polyether glycol. Is preferred. A more preferred lower limit is 75% by weight, and an even more preferred lower limit is 78.
%, And a particularly preferred lower limit is 80% by weight. A more preferable upper limit is 90% by weight, a still more preferable upper limit is 87% by weight, and a particularly preferable upper limit is 85% by weight. If the soft segment content is less than 70% by weight, the surface hardness in the range of the present application may not be achieved, or the moisture permeability may decrease. On the other hand, if it exceeds 95% by weight, the block property of the obtained elastomer is lowered, and thus the melting point or softening point of the polymer may be lowered.

The short-chain glycol component in the polyester elastomer used in the present invention has a carbon number of 1 to 1.
Twenty-five glycols and their ester-forming derivatives can be used. A glycol having 1 to 25 carbon atoms means
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, dimethylolheptane, dimethylolpentane, tricyclodecanedimethanol, an ethylene oxide derivative of bisphenol X (X is A, S,
F) and their ester-forming derivatives.
Preferred examples include ethylene glycol, 1,4-butanediol and ester-forming derivatives thereof.
Particularly preferred is 1,4-butanediol.

The polyester elastomer used in the present invention may contain a tricarboxylic or higher functional polycarboxylic acid or polyol component only in a small amount. For example, trimellitic anhydride, benzophenonetetracarboxylic acid, trimethylolpropane, glycerin, pyromellitic dianhydride, etc. can be used in an amount of 3 mol% or less. The total amount of trifunctional or higher polycarboxylic acid and polyol components is 10 and the total of all polycarboxylic acid components and polyol components of the polyester is 10
When it is 0 mol%, it is 5 mol% or less, preferably 3 mol% or less.

The reduced viscosity of the polyester elastomer used in the present invention is preferably 1.0 to 4.0. If the reduced viscosity is 1.0 or less, the mechanical properties may be poor, and if it exceeds 4.0, the moldability may be poor due to poor fluidity, and the range of use as a molding material is limited. A more preferable lower limit of the reduced viscosity is 1.5, a further preferable lower limit is 2.0, a particularly preferable lower limit is 2.3, a particularly preferable lower limit is 2.5, and a more preferable upper limit of the reduced viscosity is 3.7, and further preferable. The upper limit is 3.4, the particularly preferred upper limit is 3.2, and the particularly preferred upper limit is 3.0.

Any known method can be applied to the production of the polyester elastomer used in the present invention. For example, a melt polymerization method, a solution polymerization method, a solid phase polymerization method, or the like can be appropriately used. In the case of the melt polymerization method, it may be a transesterification method or a direct polymerization method. In order to improve the viscosity of the resin, it is of course desirable to carry out solid state polymerization after melt polymerization. After the polyester is polymerized, the chain may be extended with an isocyanate compound or an epoxy compound.

As the catalyst used in the reaction, antimony catalyst, germanium catalyst and titanium catalyst are preferable. Particularly preferred are titanium catalysts, more specifically, tetraalkyl titanates such as tetrabutyl titanate and tetramethyl titanate, and metal oxalate salts such as potassium 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 dilaurylate, and lead compounds such as lead acetate.

Further, the obtained polyester elastomer includes known antioxidants such as hindered phenol type, sulfur type and phosphorus type, hindered amine type, triazole type,
Benzophenone-based, benzoate-based, nickel-based, salicyl-based light stabilizers, antistatic agents, lubricants, molecular regulators such as peroxides, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, control agents. Acidic agents, antibacterial agents, optical brighteners, glass fibers, carbon fibers, silica fibers, inorganic fiber materials such as alumina fibers, carbon black, silica, quartz powder,
Glass beads, glass powder, calcium silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, metal oxides such as iron oxide, titanium oxide, zinc oxide, alumina, calcium carbonate, barium carbonate Such as metal carbonates, powdered fillers such as other various metal powders, mica, glass flakes, plate-like fillers such as various metal powders, flame retardants, flame retardant aids, organic / inorganic pigments, etc. More than one kind can be added. The thermoplastic polyester elastomer composition of the present invention contains, as an essential component, at least one of antioxidants, light stabilizers and lubricants among these additives.

The hindered phenol-based antioxidant which can be blended in the present invention includes 3,5-di-t-butyl-4-hydroxy-toluene and 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-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) 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′-ethylidene bis (4,4)
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-triazine-2,4,6 (1H, 3
H, 5H) -trione, 1,3,5-tris (4-t-
Butyl-3-hydroxy-2,6-dimethylbenzyl)
Isocyanurate, 3,5-di-t-butyl-4-hydroxyhydrocinnamic ahydride triester with-
1,3,5-Tris (2-hydroxyethyl) -S-triazine-2,4,6 (1H, 3H, 5H), N, N-
Hexamethylene bis (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] Examples include undecane.

Sulfur-based antioxidants that can be blended in the present invention include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodiuropionate, distearyl-3,3'-thiodiester. Propionate ester, lauryl stearyl-3,3′-thiodipropionate ester, dilauryl thiodipropionate, dioctadecyl sulfide, pentaerythryl-tetra (β-lauryl-thiopropionate) ester, etc. You can

The phosphorus-based antioxidant that can be blended in the present invention includes tris (mixed, mono- and dinolylphenyl) phosphite, tris (2,3-di-t-butylphenyl) phosphite, 4,4 '. -Butylidene-
Bis (3-methyl-6-t-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-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-methyl) Phenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenediphosphonite, triphenylphosphite,
Examples thereof include diphenyldecylphosphite, tridecylphosphite, trioctylphosphite, tridodecylphosphite, trioctadecylphosphite, trinonylphenylphosphite, tridodecyltrithiophosphite, and the like.

As the amine-based antioxidant that can be blended in the present invention, N, N-diphenylethylenediamine,
N, N-diphenylacetamidine, 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)-
Amine such as p-phenylenediamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, 4,4′-bis (4-α, α-dimethyl-benzyl) diphenylamine and their derivatives, and reaction products of amine and aldehyde , The reaction products of amines and ketones.

Examples of the hindered amine light stabilizer that can be blended in the present invention include dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-.
Polycondensate with tetramethylpiperidine, 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 (1,2,2,2-n-butylmalonic acid
2,6,6-Pentamethyl-4-piperidyl) ester, 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 (2,2,2
Polycondensation product of 6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-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, 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-pentamethylpiperidin-4-yl) amino-1,3,5-triazine-
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 etc. can be mentioned.

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, p-t-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'-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-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-butyloxalic acid -Bis-anilide 10-15%
A mixture of 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 ''-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, salicylic acid Light stabilizers such as phenyl may be mentioned.

Examples of lubricants that can be blended in the present invention include hydrocarbon compounds, fatty acid compounds, fatty acid amide compounds, ester compounds, alcohol compounds, metal soap compounds, natural wax compounds, silicone compounds, and fluorine compounds. Specifically, liquid paraffin, synthetic paraffin, synthetic hard paraffin, synthetic isoparaffin petroleum hydrocarbon, chlorinated paraffin, paraffin wax, microwax, low-polymerization 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,
Saturated or unsaturated aliphatic amides having 3 to 30 carbon atoms such as methylenebisstearylamide and ricinolamide and derivatives thereof, lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids Butyl stearate, hydrogenated castor oil, ethylene glycol monostearate, etc., cetyl alcohol, stearyl alcohol, ethylene glycol, molecular weight 200 to 1000
0 or more polyethylene glycol, polyglycerol,
Lubricants such as carnauba wax, candelilla wax, montan wax, dimethyl silicone, silicon gum, and tetrafluoroethylene are mentioned. In addition, straight chain saturated fatty acid, side chain acid,
A metal salt composed of a compound having cinoleic acid, wherein the metal is (L
i, Mg, Ca, Sr, Ba, Zn, Cd, Al, S
Mention may also be made of metal soaps selected from n, Pb). The content of the lubricant in the thermoplastic polyester elastomer composition is preferably 14% by weight or less, more preferably 10% by weight or less, further preferably 7% by weight or less, particularly preferably 5% by weight or less, Most preferably, it is 3% by weight or less. The lubricant may not be contained.

As the filler which can be blended in the present invention, 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, etc. Or hydroxide of manesium hydroxide, aluminum hydroxide, basic magnesium carbonate or a basic substance or hydroxide, or carbonate such as magnesium carbonate, calcium carbonate, barium carbonate, ammonium carbonate, calcium sulfite, dolomite, dawsonite or , (Sulfites) such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, and basic magnesium sulfate, or sodium silicate, magnesium silicate, aluminum silicate, potassium silicate, calcium silicate, talc, clay, mica, a Best, glass fiber, montmorillonite, glass balloon, glass beads,
Silicates such as pentonite, kaolin (porcelain 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, Examples thereof include lead zirconate titanate, zinc borate, aluminum borate, barium metaborate, calcium borate, sodium borate and the like.

Examples of the compound having an epoxy group which can be blended in the present invention include polyepoxy compounds such as sorbiol-polyglycidyl-ether, polyglycerol-polyglycidyl-ether, triglycidyl-tris (2-hydroxyethyl) isocyanurate, and diethylene glycol. Diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydroophthalic acid diglycidyl ester, A condensate of bisphenol A and epichlorohydrin,
Diepoxy compounds such as condensates of bisphenol F and epichlorohydrin, condensates of bisphenol F and epichlorohydrin, higher alcohol glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, stearyl glycidyl ether, methyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, p- Examples include monoepoxy compounds such as t-butylphenyl glycidyl ether.

Compounds having a halogen-substituted phenyl group which can be blended in the present invention include tetrabromobisphenol A (TBA) and tetrabromobisphenol S.
(TBS), bis (dibromopropyl) tetrabromobisphenol A ether, TBA epoxy, TBA ethyl ether oligomer, TBA bis (2,3-dibromopropyl ether), TBA (allyl ether), TB
A bis (2-hydroxyethyl ether), TBA carbonate oligomer, TBS bis (2,3-dibromopropyl ether), hexabromobenzene, tetrabromophthalic anhydride, decabromodiphenine oxide, tris (tribromophenoxy) triazine, Bis (pentabromophenyl) ethane, bis (tribromophenoxy) ethane, bis (pentabromophenoxy) ethane,
Examples thereof include brominated phenoxy, ethylenebis (tetrabromophthal) imide, brominated diphenyl oxide, brominated polystyrene and the like.

The flame retardant aids which can be blended in the present invention include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate, tin dioxide, zinc metaborate, aluminum hydroxide, magnesium hydroxide, zirconium oxide, Examples thereof include molybdenum oxide, red phosphorus compounds, ammonium polyphosphate, melamine cyanurate, and tetrafluoroethylene.

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

Examples of the inorganic phosphorus compound which can be blended in the present invention include red phosphorus compounds and ammonium polyphosphate. Examples of the red phosphorus compound include red phosphorus coated with a resin and a composite compound with aluminum. Examples of the organic phosphorus compound include phosphoric acid ester and melamine phosphate. As the phosphoric acid ester, 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, 1,3- [bis (2,6-dimethylphenoxy) of aromatic condensed phosphoric acid ester
Phosphenyloxy] benzene, 1,4- [bis (2,2
6-Dimethylphenoxy) phosphenyloxy] benzene and the like are preferable from the viewpoint of hydrolysis resistance, thermal stability and flame retardancy.

As a method of compounding these additives, a kneading machine such as a heating roll, an extruder or a Banbury mixer can be used. Further, it can be added and mixed in the oligomer before the transesterification reaction or before the polycondensation reaction in producing the thermoplastic polyester elastomer resin composition. The thermoplastic polyester elastomer composition of the present invention utilizes its high flexibility, low blooming, low property change at low temperature, and low water absorption to make boots, emblems, belts, tubes, packings, sheets, etc. It can be used as a moisture permeable film after being processed into a sheet or film. Further, since it has a certain property from low temperature to room temperature, it can be suitably used as a core material or a cover material for play balls such as golf balls, soft balls and gate balls.

[0051]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. In addition, each measurement item in these Examples followed the following method.

(1) 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.

(2) Melting point The melting point was raised from room temperature at 20 ° C./min using a DSC (differential scanning calorimeter) manufactured by Seiko Denshi Kogyo Co., Ltd., and the peak temperature was used as a measured value. The sample was placed in an aluminum pan and sealed with a lid.

(3) Surface hardness It was measured according to JIS K6253.

(4) 50% elongation stress It was measured by ASTM D638 at -30 ° C and 23 ° C and expressed as a relative ratio α (50% elongation stress at -30 ° C / 50% elongation stress at 23 ° C). (5) A test piece having a water absorption of 100 × 100 × 2 mm was prepared, and the test piece was dried at 100 ° C. and 10 torr or less for 24 hours. This was immersed in water at 23 ° C. for 24 hours. Water absorption rate = (weight after immersion−weight before immersion) / weight before immersion × 100 (%) (6) Moisture vapor transmission A film having a thickness of about 30 μm was obtained by extrusion molding. Using this film, the moisture permeability was measured according to the calcium chloride method described in JIS Z0209. The measurement condition is 40
It was carried out at 90 ° C. and 90% RH. (7) Mold stain during continuous molding A test piece of 100 × 100 × 2 mm was continuously molded by injection molding. The mold stains at that time were visually observed. ○: No change △: Slightly dirty mold ×: Slightly dirty mold

Polyester Synthesis Example 1 Dimethyl terephthalate (DMT) 225.15 g,
127.48 g of 1,4-butanediol (BD), TH
F-EO random copolymer DC-3000 (manufactured by NOF CORPORATION), molecular weight 3000, THF / EO = 50/50
(Mol ratio)) 973.94 g, Irganox-13
2.40 g of 30 (manufactured by Nippon Ciba Geigy) and 1.20 g of tetrabutyl titanate (TBT) were charged into a 5 L autoclave, and the temperature was raised from room temperature to 200 ° C. over 3 hours to carry out a transesterification reaction. Next, the pressure in the can was gradually reduced and the temperature was further raised, and the temperature was increased to 245 ° C. and 1 t over 45 minutes.
The initial condensation reaction was performed at orrr or less. 245 more
Polymerization reaction was carried out for 2 hours at a temperature of 1 ° C. or less, and the polymer was taken out into pellets to obtain polymer A.

Polyester Synthesis Example 2 DMT 225.15 g, BD 127.48 g, PT
MG (molecular weight 3000) 973.94 g, Irganox-1330 2.40 g, TBT 1.20 g 5
It was charged in an L autoclave to polymerize the thermoplastic elastomer. The reaction temperature was appropriately optimized to obtain a polymer B.

Polyester Synthesis Example 3 DMT 225.13 g, BD 126.42 g, polyethylene glycol / polypropylene glycol / polyethylene glycol block copolymer (molecular weight 290
0, PEG / PPG = 60/40 wt%, Asahi Denka Co., Ltd.
Made) 975.00 g, Irganox-1330
2.40 g and 1.20 g of TBT were charged into a 5 L autoclave to polymerize the thermoplastic elastomer. The reaction temperature was appropriately adjusted to obtain polymer C.

Polyester Synthesis Example 4 DMT 334.00 g, BD 193.76 g, PT
MG (molecular weight 2000) 859.999g, Irganox-1330 2.40g, TBT 1.20g 5
It was charged in an L autoclave to polymerize the thermoplastic elastomer. The reaction temperature was appropriately optimized to obtain a polymer D.

Polyester Synthesis Example 5 Dimethyl terephthalate (DMT) 197.1 g,
1,4-butanediol (BD) 127.5 g, THF
And EO random copolymer DC-3000 800.4
g, Irganox-1330 2.20 g, and tetrabutyl titanate 1.1 g were charged into a 5 L autoclave, and the temperature was raised from room temperature to 200 ° C. over 3 hours to carry out a transesterification reaction. Then, the inside of the can was gradually decompressed and further heated, and the initial condensation reaction was performed at 245 ° C. and 1 torr or less over 45 minutes. Further 245 ° C, 1 torr
Polymerization reaction was carried out for 2 hours under the condition of r or less, and the polymer was taken out in the form of pellets to obtain polymer E.

Polyester Synthesis Example 6 DMT 334.00 g, BD 193.76 g, PT
MG (molecular weight 2000) 1000 g, Irganox-1330 2.40 g, and TBT 1.20 g were charged into a 5 L autoclave to polymerize the thermoplastic elastomer. The reaction temperature was appropriately adjusted to obtain a polymer F. The polymer F thus obtained did not crystallize and was hardly used as a molding material, and thus was not evaluated.

Examples 1, 3 and 4, Comparative Example 1 Polymer A obtained in Polyester Synthesis Example 1, Polymer B obtained in Polyester Synthesis Example 2, Polymer C obtained in Polyester Synthesis Example 3, polyester For each 100 parts by weight of Polymer E obtained in Synthesis Example 5, pentaerythritol tetrakis [3- (3,5-di-tert.
-Butyl-4-hydroxyphenyl) propionate]
0.3 parts by weight, and dilauryl thiopropionate to 0.
3 parts by weight of 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole was added to 0.3%.
5 parts by weight were compounded, and the mixture was taken out into pellets using an extruder.

Example 2 100 parts by weight of Polymer A obtained in Polyester Synthesis Example 1 was mixed with pentaerythritol tetrakis [3-
0.3 parts by weight of (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 0.3 parts by weight of dilaurylthiopropionate, 2- (3,5-di-
0.5 parts by weight of t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole and 3.0 parts by weight of trimellitic acid trialkyl ester were blended, and the mixture was taken out into pellets using an extruder.

Comparative Example 2 Pentaerythritol tetrakis [3-] was added to 100 parts by weight of Polymer D obtained in Polyester Synthesis Example 4.
0.3 parts by weight of (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 0.3 parts by weight of dilaurylthiopropionate, 2- (3,5-di-
0.5 parts by weight of t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole and 20.0 parts by weight of trimellitic acid trialkyl ester were blended, and the mixture was taken out into pellets using an extruder.

Table 1 shows the results of predetermined tests performed on Examples 1 to 4 and Comparative Examples 1 and 2. In each of Examples 1, 2 and 4, a polyester elastomer composition which is extremely flexible and has stable properties against temperature changes at low temperatures and has low water absorption is obtained, and various molding materials, sheets and films are obtained. Is preferably used as. Although Example 3 is excellent in flexibility at low temperature, it has high water absorption and is considered to be difficult to use in applications where water absorption is a problem. In Comparative Examples 1 and 2, the flexibility is insufficient, and the flexibility increases at lower temperatures,
It was difficult to use in applications requiring flexibility.

[0066]

[Table 1]

[0067]

The thermoplastic polyester elastomer composition of the present invention has a very low surface hardness and is flexible. In addition, it becomes possible to provide a thermoplastic polyester elastomer that retains flexibility at room temperature even at low temperatures, which is a great contribution to the industrial world.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 AE032 AE042 AE052 BB002                       BB032 BD152 CF031 CH012                       CH022 CP032 EC048 EC068                       EE037 EF058 EG018 EH038                       EH048 EH078 EJ026 EJ036                       EJ046 EJ067 EN036 EN067                       EN106 EP018 EP028 EQ026                       ER006 EU076 EU077 EU177                       EU186 EU187 EU196 EV046                       EV066 EV096 EV307 EV316                       EV327 EW046 EW047 EW066                       EW126 FD019 FD047 FD076                       FD139 FD172 FD178 GC00                       GM00 GM01

Claims (2)

[Claims] 1. A thermoplastic polyester elastomer resin containing 85% by weight or more of a thermoplastic polyester elastomer resin and a thermoplastic polyester elastomer composition containing at least one additive selected from an antioxidant, a light stabilizer and a lubricant. Comprised of JIS K6
A thermoplastic polyester elastomer composition having a surface hardness measured according to 253 of more than 70 A. 2. A relative ratio α of 50% elongation stress measured according to ASTM D638 (50% elongation stress at −30 ° C./50% elongation stress at 23 ° C.) is 1 <α ≦.
A thermoplastic polyester elastomer composition characterized in that it is 4.0.