JP2003002961A - Thermoplastic polyester elastomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an extremely soft thermoplastic polyester elastomer having excellent low-temperature characteristics without mixing a plasticizer or an olefin elastomer. SOLUTION: A thermoplastic polyester elastomer composition comprises a thermoplastic polyester elastomer resin and at least one or more kinds of additives of an antioxidant, a light stabilizer or a lubricant. The thermoplastic polyester elastomer composition is composed of >=85 wt.% of the thermoplastic polyester elastomer resin and the surface hardness measured by JIS K6253 is smaller than 70A.

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 containing the following constituents A, B and C and satisfying the condition D. A. Aromatic dicarboxylic acid component B. Short chain glycol component C. A molecular weight of 2200 to 3 consisting of two or more different alkylene units having 2 to 10 carbon atoms and repeating at random.
800 Random Copolymeric Polyether Glycol Condition D: Less than 10 wt% of alkylene units with quaternary carbons in the total weight of all polyether glycol components of the thermoplastic polyester. Moreover, it is preferable that the thermoplastic polyester of the present invention further satisfies the condition E. Condition E: C is 70 in the thermoplastic polyester
Is about 90% by weight.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polyester elastomer of the present invention will be described in detail below. In the thermoplastic polyester elastomer of the present invention, the acid component is
Mainly 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. Aromatic dicarboxylic acid is 70% of the total acid component
It is at least mol%, preferably at least 80 mol%, more preferably at least 90 mol%.

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 of the present invention is a random copolymerized polyether glycol having a molecular weight of 2200 to 3800, which is composed of two or more different alkylene units having 2 to 10 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, measures such as adding a large amount of a lubricant and increasing the amount of soft segment of the thermoplastic polyester elastomer resin are usually adopted. Usually, when the thermoplastic polyester elastomer resin is contained in an amount of 85% or more to have high flexibility, 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 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. By using the random copolymerized polyether glycol having a specific molecular weight as in the present invention, it is possible to obtain a highly flexible thermoplastic polyester elastomer which solves these problems.

When the molecular weight of the random copolymerized polyether glycol is less than 2200, the polyester elastomer may not have sufficient flexibility and moldability. If 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 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, when the random copolymerized polyether glycol is used, an elastomer 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. Of the components used for the random copolymerized 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. E
If the O component exceeds 80 mol%, the water absorption becomes high, and it may not be preferable depending on the application.

It is desirable that both ends of the random copolymerized glycol are substantially all 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 of the present invention preferably contains the polyether glycol component of the above-mentioned random copolymerized polyether glycol, but the quaternary carbon is contained in the total weight of the total polyether glycol component of the thermoplastic polyester elastomer. It is preferable that it has less than 10% by weight of alkylene units, more preferably less than 5% by weight, still more preferably less than 3% by weight, and 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 of 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, poly (ethylene oxide) glycol having a molecular weight of 400 to 6000, poly (propylene oxide)
Polyalkylene ether glycols such as glycol and poly (tetramethylene oxide) glycol, mixtures thereof, and block or random copolymerized polyether glycols obtained by copolymerizing these polyether glycol constituents, and aliphatic groups having 2 to 12 carbon atoms. Polyesters produced from dicarboxylic acids and aliphatic glycols having 2 to 10 carbon atoms, such as polyethylene adipate, polytetramethylene adipate, polyethylene sebacate, polyneopentyl sebacate, polytetramethylene dodecaneate, polytetramethylene azelate, poly Examples include hexamethylene azelate and poly-ε-caprolactone. These glycols are used in an appropriate combination depending on the balance of various properties.

The random copolymerized 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. When the soft segment content is less than 70% by weight, low surface hardness may not be achieved, or the moisture permeability may be reduced. 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 thermoplastic polyester elastomer of the present invention may contain a trifunctional or higher 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 thermoplastic polyester elastomer of 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 thermoplastic polyester elastomer of 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 may be a known hindered phenol-based antioxidant, sulfur-based antioxidant, phosphorus-based antioxidant, hindered amine-based antioxidant, triazole-based antioxidant, etc.
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 to form a composition.

Examples of the hindered phenol type antioxidant include 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'-ethylidenebis (4 6-di-t-butylphenol), N, N'-bis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionyl]
Hydrazine, 2,2'-oxamide bis [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, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy- 2,6-dimethylbenzyl) isocyanurate,
3,5-di-t-butyl-4-hydroxyhydrocinnamic ahydr triester with-1,3,5-tris (2-hydroxyethyl) -S-triazine-2,4
6 (1H, 3H, 5H), N, N-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
Examples thereof include 8,10-tetraoxaspiro [5.5] undecane.

As the sulfur type antioxidant, dilauryl-
3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodiuroionic acid ester, distearyl-3,3'-thiodipropionic acid ester, laurylstearyl-3,3'-thiodipropionic acid ester,
Examples thereof include dilauryl thiodipropionate, dioctadecyl sulfide, pentaerythryl-tetra (β-lauryl-thiopropionate) ester and the like.

Examples of phosphorus antioxidants include 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 (2,2 4-di-t-butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,2
4-di-t-butylphenyl) -4,4'-biphenylenephosphanite, bis (2,6-di-t-butyl-
4-methylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenediphosphonite, triphenylphosphite, diphenyldecylphosphite,
Tridecyl phosphite, trioctyl phosphite,
Examples thereof include tridodecyl phosphite, trioctadecyl phosphite, trinonylphenyl phosphite, and tridodecyl trithiophosphite.

As the amine type antioxidant, N, N-diphenylethylenediamine, N, N-diphenylacetamidine, N, N-diphenylfluamidine, N-phenylpiperidine, dibenzylethylenediamine, triethanolamine, phenothiazine, N , N'-di-s
ec-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 and other amines and their derivatives and amines And the reaction product of an aldehyde and the reaction product of an amine and a ketone.

Examples of the hindered amine light stabilizers include polycondensates with dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate, poly [[6- (1,1,3,3-Tetrabutyl) imino-1,3,5-triazine-2,4-diyl] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imyl]], Bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester of 2-n-butylmalonic acid, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2, 3,4-butane tetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-
A polycondensation product of bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane, poly [(N, N'-bis (2,2,6,
6-Tetramethyl-4-piperidyl) hexamethylenediamine)-(4-monofolino-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-butane tetracarboxylate, 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-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- (1,2,2,2
6,6-Pentamethyl-4-piperidyl) amino] -6
-Chloro-1,3,5-triazine condensate and the like can be mentioned.

Examples of benzophenone-based, benzotriazole-based, triazole-based, nickel-based, and salicyl-based light stabilizers are 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and 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) benzo Triazole, 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 (3,3
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 10-15% mixture, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl)
Phenyl] -2H-benzotriazole, 2-ethoxy-2'-ethyloxazaric 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-
Examples thereof include light stabilizers such as octylphenyl) benzotriazole, 2-hydroxy-4-i-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, and phenyl salicylate. .

Examples of the lubricant include hydrocarbon type, fatty acid type, fatty acid amide type, ester type, alcohol type, metal soap type, natural wax type, silicone type and fluorine type compounds. Specifically, liquid paraffin, synthetic paraffin,
Synthetic hard paraffin, synthetic isoparaffin petroleum hydrocarbon, chlorinated paraffin, paraffin wax, microwax, low-polymer polyethylene, fluorocarboxylic oil,
Fatty acid compounds having 12 or more carbon atoms such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, hexylamide, octylamide, stearylamide, palmitylamide, oleylamide, erucylamide, ethylenebisstearylamide, Saturated or unsaturated aliphatic amides having 3 to 30 carbon atoms such as laurylamide, behenylamide, methylenebisstearylamide, and ricinolamide, and their derivatives, lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, and polyglycol esters of fatty acids. Butyl stearate, a fatty alcohol ester of fatty acids, hydrogenated castor oil,
Lubricants such as ethylene glycol monostearate and the like, cetyl alcohol, stearyl alcohol, ethylene glycol, polyethylene glycol having a molecular weight of 200 to 10,000 or more, polyglycerol, carnauba wax, candelilla wax, montan wax, dimethyl silicone, silicon gum, tetrafluoroethylene and the like can be mentioned. . Also,
A metal salt composed of a compound having a straight chain saturated fatty acid, a side chain acid, and a cinoleic acid, where the metal is (Li, Mg, Ca, Sr, B
Mention may also be made of metal soaps selected from a, Zn, Cd, Al, Sn, Pb). The content of the lubricant is 14% by weight in the thermoplastic polyester elastomer composition.
It is preferably below, more preferably 10% by weight
It is preferably 7% by weight or less, more preferably 5% by weight or less, and most preferably 3% by weight or less. The lubricant may not be contained.

As the filler, 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, oxides such as pumice balloon or manesium hydroxide, aluminum hydroxide, basic substances such as basic magnesium carbonate or hydroxide or magnesium carbonate, calcium carbonate, Carbonate such as barium carbonate, ammonium carbonate, calcium sulfite, dolomite, dawsonite, or (sulfite) salt such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, basic magnesium sulfate or sodium silicate,
Magnesium silicate, aluminum silicate, potassium silicate,
Silicates such as calcium silicate, talc, clay, mica, asbestos, glass fiber, montmorillonite, glass balloons, glass beads, pentonite, or kaolin (ceramic), perlite, iron powder, copper powder, lead powder, aluminum powder, tungsten Examples thereof include powder, molybdenum sulfide, carbon black, boron fiber, silicon carbide fiber, brass fiber, potassium titanate, lead zirconate titanate, zinc borate, aluminum borate, barium metaborate, calcium borate, and sodium borate.

Examples of the compound having an epoxy group include polyepoxy compounds such as sorbiol-polyglycidyl-ether, polyglycerol-polyglycidyl-ether, triglycidyl-tris (2-hydroxyethyl) isocyanurate, diethylene glycol diglycidyl ether and 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, bisphenol A
And epichlorohydrin condensates, bisphenol F and epichlorohydrin condensates, bisphenol F and epichlorohydrin condensates, diepoxy compounds, higher alcohol glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, stearyl glycidyl ether, methyl glycidyl ether, phenyl glycidyl ether And monoepoxy compounds such as glycidyl methacrylate and pt-butylphenyl glycidyl ether.

As a compound having a halogen-substituted phenyl group, tetrabromobisphenol A (TB
A), tetrabromobisphenol S (TBS), bis (dibromopropyl) tetrabromobisphenol A ether, TBA epoxy, TBA ethyl ether oligomer, TBA bis (2,3-dibromopropyl ether), TBA (allyl ether), TBA 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, brominated phenoxy, ethylene bis (tetrabromophthal) imide,
Examples thereof include brominated diphenyl oxide and brominated polystyrene.

Examples of the flame retardant aid include antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium pyroantimonate, tin dioxide, zinc metaborate, aluminum hydroxide, magnesium hydroxide, zirconium oxide, molybdenum oxide, red phosphorus. Examples thereof include system compounds, ammonium polyphosphate salts, melamine cyanurate, and tetrafluoroethylene.

Examples of the compound having a triazine group and / or its derivative include melamine, melamine cyanurate, and
Examples thereof include melamine phosphate and guanidine sulfamate.

Examples of the inorganic phosphorus compounds of phosphorus compounds include red phosphorus compounds and ammonium polyphosphate.
As the red phosphorus compound, red phosphorus coated with resin,
Examples thereof include 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 phosphate 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) phosphenyloxy of aromatic condensed phosphoric acid ester ] Benzene, 1,4- [bis (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.

In summary, the excellent characteristics of the thermoplastic polyester elastomer of the present invention will be described below. The thermoplastic polyester elastomer of the present invention can be used according to JIS even in a composition containing less plasticizer such that the thermoplastic polyester elastomer resin is 85% by weight or more.
The surface hardness measured based on K6253 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 composition using the thermoplastic polyester elastomer of the present invention, the thermoplastic polyester elastomer is preferably 87% by weight or more, more preferably 88% by weight or more, particularly preferably 89% by weight or more, and most preferably 90% by weight.
Even if it is constructed from the above, it shows high flexibility. In addition,
The upper limit of the content of the thermoplastic polyester elastomer resin is preferably 99.99% by weight, more preferably 99.9% by weight, further preferably 99.7% by weight.
Is. When the content of the thermoplastic polyester elastomer resin exceeds 99.99% by weight, the stabilizers may not work sufficiently and the light resistance and heat resistance may be poor.

The thermoplastic polyester elastomer of the present invention and the composition containing 85% by weight or more of the thermoplastic polyester elastomer are very flexible and have a small content of additives such as a plasticizer and stain the mold during molding. Rarely. Therefore, the mold deposit is unlikely to occur, and the mold cleaning does not take time even during the continuous molding.

Further, the thermoplastic polyester elastomer of the present invention and the composition containing 85% by weight or more of the thermoplastic polyester elastomer show little change in properties at low temperatures. For example, ASTM
Relative ratio of 50% elongation stress measured according to D638 α
(50% elongation stress at −30 ° C./5 at 23 ° C.
0% elongation stress) becomes 1 <α ≦ 4.0. The upper limit of α is preferably 3.5, more preferably 3.0, particularly preferably 2.7, and most preferably 2.5. As the lower limit of α, the closer it is to 1, the more preferable, but in reality, it is preferably about 1.1, and more preferably about 1.2.

The thermoplastic polyester elastomer of the present invention and the composition using 85% by weight or more of the same have the flexibility characteristics which change at low temperature and room temperature below 0 ° C., and are conventionally found in highly flexible polyester having many soft segments. Further, it is possible to solve the problem that it is inferior in flexibility at an extremely low temperature of -10 to -30 and is difficult to be used for use which requires flexibility in an extremely low temperature environment.

Further, the thermoplastic polyester elastomer of the present invention and the composition containing 85% by weight or more of the same can have low water absorption. For example, when immersed in water at 23 ° C for 24 hours, the water content is 25% by weight.
The following is preferable. 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 of the present invention and a composition using 85% by weight or more of the same are 40 ° C. 9% by the calcium chloride method of JIS Z0209.
The moisture permeability when measuring a film having a thickness of 10 μm under the condition of 0% RH is preferably 3000 g / m ² · day or more.

The water vapor transmission rate of the film measured with a thickness of 10 μm is more preferably 4000 g / m ² ·
day, more preferably 4500 g / m ² · day,
Particularly preferred is 4800 g / m ² · day, and most preferred is 5000 g / m ² · day. The higher the upper limit of the water vapor transmission rate, the more preferable, but in reality, 100,000 g / m
It is preferably ² · day.

Even when a film having a thickness of 20 μm was measured, the water vapor permeability of the film was 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 of the present invention can be used as a molding material for boots, emblems, belts, tubes, packings, sheets, etc. by taking advantage of its high flexibility, small change in characteristics at low temperatures and low water absorption. It can be processed into a sheet or film and used as a moisture permeable membrane. 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. Further, even when it is made into a composition, high flexibility can be obtained without adding a large amount of a plasticizer, and blooming and the mold are less contaminated.

[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

Example 1 Polyester Synthesis Example 1 Dimethyl terephthalate (DMT) 224.55 g,
1,4-butanediol (BD) 127.02 g, TH
F-EO random copolymer DC-3000 (manufactured by NOF CORPORATION), molecular weight 3000, THF / EO = 50/50
(Mol ratio)) 974.0 g, Irganox-133
0 (manufactured by Nippon Ciba Geigy) and 2.30 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 raised to 245 ° C. for 1 to 40 minutes.
The initial condensation reaction was performed at rr 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.

Comparative Example 1 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.

Comparative Example 2 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.

Comparative Example 3 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.

Example 2 Polyester Synthesis Example 5 Dimethyl terephthalate (DMT) 198.0 g,
1,4-butanediol (BD) 128.2 g, THF
And EO Random Copolymer DC-3000 802.1
g, Irganox-1330 2.30 g, and tetrabutyl titanate 1.2 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 50 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.

Comparative Example 4 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.

Formulation a and Evaluation (Examples 1 and 2, Comparative Examples 1 and 2) The polymer A obtained in Example 1, the polymer B obtained in Comparative Example 1, the polymer C obtained in Comparative Example 2, For each 100 parts by weight of polymer E obtained in Example 2, pentaerythritol tetrakis [3- (3,5-di-ter).
t-butyl-4-hydroxyphenyl) propionate], 0.3 part by weight of dilaurylthiopropionate, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5- 0.5 parts by weight of chlorobenzotriazole was blended, and the mixture was taken out into pellets using an extruder.

Formulation b and Evaluation (Example 1) Pentaerythritol tetrakis [3- (3,5-di-) was added to 100 parts by weight of the polymer A obtained in Example 1.
tert-Butyl-4-hydroxyphenyl) propionate], 0.3 part by weight of dilaurylthiopropionate, 2- (3,5-di-t-butyl-2)
-Hydroxyphenyl) -5-chlorobenzotriazole (0.5 parts by weight) and trimellitic acid trialkyl ester (3.0 parts by weight) were mixed, and the mixture was taken out into pellets using an extruder.

Formulation c and Evaluation (Comparative Example 2) Pentaerythritol tetrakis [3- (3,5-di-) was added to 100 parts by weight of Polymer D obtained in Comparative Example 3.
tert-Butyl-4-hydroxyphenyl) propionate], 0.3 part by weight of dilaurylthiopropionate, 2- (3,5-di-t-butyl-2)
0.5 parts by weight of -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 above-mentioned predetermined test results. Both the formulations a and b of Example 1 and the formulation a of Example 2 are very flexible and exhibit stable characteristics against temperature changes at low temperatures.
Furthermore, a polyester elastomer composition having low water absorption is obtained, and it is preferably used as various molding materials, sheets and films. Comparative Example 2 is excellent in flexibility at low temperatures, but 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 3, the flexibility was insufficient, and the flexibility increased at low temperatures, and it was difficult to use in applications requiring flexibility.

[0066]

[Table 1]

[0067]

The thermoplastic polyester elastomer 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 maintains flexibility as at room temperature even at low temperatures,
It is a great contribution to the industrial world.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J029 AA03 AB01 AC03 AD01 AD06                       AD10 AE01 AE18 BA01 BA03                       BA05 BA08 BA09 BA10 BB11A                       BB12A BB13A BF09 BF16                       BF17 BF19 BF27 BF28 CA02                       CA04 CA05 CA06 CB04 CD03                       JB193 JC053 JC233 JC283                       JC323 JC583 JE182 JF321                       JF361 JF381 JF471

Claims (2)

[Claims] 1. A thermoplastic polyester containing the following constituents A, B and C and satisfying the condition D. A. Aromatic dicarboxylic acid component B. Short chain glycol component C. A molecular weight of 2200 to 3 consisting of two or more different alkylene units having 2 to 10 carbon atoms and repeating at random.
800 Random Copolymeric Polyether Glycol Condition D: Less than 10 wt% of alkylene units with quaternary carbons in the total weight of all polyether glycol components of the thermoplastic polyester. 2. The thermoplastic polyester according to claim 1, which further satisfies the condition E. Condition E: C is 70 in the thermoplastic polyester
Is about 90% by weight.