JP2000281766A - Thermoplastic polyester elastomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic polyester elastomer excellent in weathering resistance, heat resistance, elastic performances, especially, thermal aging resistance, and water resistance, which elastomer has a specified bending modulus, a specified elongation at break (as measured on a sample subjected to a thermal aging resistance test), and a specified elongation at break (as measured on a sample subjected to a water aging resistance test). SOLUTION: This elastomer has a bending modulus <10,000 kg/cm2 (ASTM D790) and an elongation >150% (as measured on each of samples subjected to the above aging resistance tests). The thermal aging test consists of treating a sample at 170 deg.C for one week in a gear-type hot-air drier, and the water aging resistance test consists of treating a sample in boiling water at 100 deg.C for one two weeks. The elastomer desirably comprises units formula I, of formulae II, and of formula III and having a reduced viscosity of 0.5-4.0. In the formulae, D is a hydrogenated dimer diol residue; R is a 2-10C alkylene; a+b=1-25; R1 is a 6-18C aromatic group; R2 is a 2-4C alkylene or 1,4-cyclohexanedimethylene; R3 is a 1-25C alkylene; (c) is the amount (wt.% based on all types of repeating units of the polymer) of the related repeating units and is 30-95 wt.%; and (d) is the amount (mol% based on all types of repeating units of the polymer) of the related repeating units and is 0-20 mol%.

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, and more particularly to a thermoplastic polyester elastomer excellent in weather resistance, heat resistance and elasticity, especially heat aging resistance and water resistance, especially fibers, films and sheets. Thermoplastic polyester elastomers that can be used for various molding materials, and more particularly, suitable for molding materials such as elastic yarns and boots, gears, tubes, packings, and applications requiring heat resistance such as automobiles and home electric appliances, For example, the present invention relates to a thermoplastic polyester elastomer useful for joint boots, wire covering materials, and the like.

[0002]

2. Description of the Related Art As a thermoplastic polyester elastomer, polybutylene terephthalate (PBT) has been used.
Polyetherester elastomer having a hard segment as a unit and polytetramethylene glycol (PTMG) as a soft segment (Japanese Patent Publication No. 49-48195,49-31558), a hard segment as a PBT unit, and a soft segment as a polycaprolactone (PCL) unit Polyester ester elastomer (Japanese Patent Publication No. 48-4116,
No. 59-12926, JP-A-59-15117) and the like are known and have been put to practical use. However, when PTMG which is a polyether having low thermal stability is used for the soft segment,
It is known that the obtained elastomer is inferior in heat aging resistance and rapidly deteriorates in a high temperature atmosphere, and is inferior in water resistance when PCL which is an aliphatic polyester is used for the soft segment.

A polyester elastomer using only a hydrogenated dimer diol containing neither an ether bond nor an ester bond as a soft segment is excellent in heat aging resistance and water resistance, but has a small molecular weight of the hydrogenated dimer diol. Sufficient elastic performance cannot be obtained.

[0004]

An object of the present invention is to provide a thermoplastic polyester elastomer which solves the above-mentioned drawbacks of the prior art and is excellent in weather resistance, heat resistance and elasticity, especially heat aging resistance and water resistance. It is an issue.

The heat aging resistance and the water resistance will be described. It is practically desirable for the elastomer to have a sufficient elongation at break, for example, at least 200%, and even after the heat aging test or the water aging test, the elastomer has at least 150% elongation at break. It is desirable to have. Therefore, an elastomer having at least 150% elongation at break after the heat aging test was evaluated as an elastomer having excellent heat aging resistance, and an elastomer having at least 150% elongation at break after the water aging test was evaluated as water resistant. One of the objects of the present invention is to obtain an elastomer excellent in both heat aging resistance and water resistance.

[0006]

Means for Solving the Problems The present inventors have found that the above problems can be solved by using a specific soft segment, and have completed the present invention. That is, the present invention provides a thermoplastic polyester elastomer characterized by flexural modulus <10000 kg / cm ² , elongation at break after heat aging test> 150%, and elongation at break after water aging test> 150%. It is an object to provide (Where the flexural modulus is ASTM D7
90, and the elongation at break is AST
This is a value measured based on MD638. The heat aging test is 170 ° C using a gear-type hot air dryer.
Equivalent to one week of heat treatment, water aging test is 100 ℃
Of boiling water for 2 weeks. A preferred embodiment is mainly composed of a derivative of a hydrogenated dimer diol represented by the following general formula (1) and a repeating unit represented by the following general formulas (2) to (3), and has a reduced viscosity of 0.1. It is a thermoplastic polyester elastomer of 5 to 4.0.

[0007]

Embedded image

[0008]

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[0009]

Embedded image (Where D is a hydrogenated dimer diol residue, and R is C2-C2)
And 10 represents an alkylene group, and the sum of a and b is 1 to 25. Note that R may be two or more types. Moreover R ¹ is an aromatic group having 6 to 18 carbon atoms, R ² is glycol residue one selected from the group consisting of an alkylene group and a 1,4-cyclohexane dimethylene group 4 from 2 carbon atoms, R ³ is It represents an alkylene group having 1 to 25 carbon atoms. Also, c represents the weight% of the repeating unit in the whole polymer, d represents the mole% in the whole polymer, c is 30 to 95% by weight, and d is 0 to 2%.
0 mol%. )

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the thermoplastic polyester elastomer of the present invention, the hydrogenated dimer diol derivative used as the soft segment is a diol compound derived from the hydrogenated dimer diol as shown in the general formula (1).

The amount of the oxyalkylene component added to the hydrogenated dimer diol derivative, that is, the sum of a and b is 1 to
It is 25, and particularly preferably 6 to 10 from the viewpoint of heat aging resistance and elastic performance. The addition of the oxyalkylene component may be at both ends or only one end of the hydrogenated dimer diol. Further, the oxyalkylene component to be added may be one kind or a combination of two or more kinds. Specific examples thereof include an ethylene oxide adduct, a propylene oxide adduct, and an ethylene oxide / tetrahydrofuran random adduct of a hydrogenated dimer diol.

The hydrogenated dimer diol is, of course, not limited in its production method. For example, the following general formula obtained by hydrogenating dimer acid which is a dimer of unsaturated fatty acids (15 to 21 carbon atoms) A compound containing the compound represented by formula (4) as a main component (50% by weight or more), or a mixture of a compound represented by the following formula (4) and a compound represented by the following formula (5).

[0013]

Embedded image (In the above formula, R ⁴ , R ⁵ , R ⁶ , and R ⁷ are substantially free from unsaturated groups and are substantially linear, and among them, R ⁴ , R ⁵
Alkyl group, R ^6, R ⁷ is an alkylene group, R ⁴ ~
The total number of carbon atoms of R ⁷ is 22 to 34. The preferred range of the weight% of the hydrogenated dimer diol derivative in the whole polymer is 10 to 60%, and the particularly preferred range is 15 to 50%.

[0014]

Embedded image (In the above formula, R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are substantially free from unsaturated groups and are substantially linear, and among them, R ⁸ , R ⁹
Alkyl group, R ^10, R ¹¹ is an alkylene group, R ⁸
Total number of carbon atoms to R ¹¹ is 25 to 37. )

The acidic component constituting the repeating unit represented by the general formulas (2) and (3) is mainly composed of an aromatic dicarboxylic acid, and specifically includes terephthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and isophthalic acid. It is preferable to use one or a combination of two or more selected from 5-sodium sulfoisophthalic acid, and the aromatic dicarboxylic acid accounts for 70% by mole or more, preferably 80% by mole or more of the total acid component. As other acid components, alicyclic dicarboxylic acids and aliphatic dicarboxylic acids are used, and as the alicyclic dicarboxylic acids, cyclohexanedicarboxylic acid,
And tetrahydrophthalic anhydride. Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecandioic acid, dimer acid, and hydrogenated dimer acid. 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% of the total acid component.

The glycol component constituting the repeating unit represented by the general formula (2) (hereinafter referred to as the ester unit (2)) is mainly ethylene glycol, 1,4-butanediol or 1,4-cyclohexanedimethanol. is there. Although 1,4-cyclohexanedimethanol has two types of isomers, a cis form and a trans form, it is preferable that the ratio of the trans form is large. The amount of the ester unit (2) is desirably 30 to 95% by weight, preferably 40 to 90% by weight, and particularly preferably 50 to 85% by weight in the whole polymer.
If it exceeds 95% by weight, it is inferior in flexibility and it is difficult to obtain an elastomer having elasticity. If it is less than 30% by weight, the melting point and the crystallinity are lowered, and the heat resistance is inferior.

As the glycol component constituting the repeating unit represented by the general formula (3) (hereinafter referred to as ester unit (3)), an alkylene glycol having 1 to 25 carbon atoms can be used. For example, diethylene glycol, propylene glycol, 1,3-butanediol, 1,5-
Pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, dimethylol heptane, dimethylol pentane, tricyclodecane dimethanol, ethylene oxide derivatives of bisphenol X (X is A, S, F) And so on. These glycols are used in an appropriate combination depending on the balance of various properties. However, since it is premised that the crystallinity of the ester unit (2) is not hindered, the copolymerization amount of these glycols is 20 mol% of the total glycol component. It is desirable that:

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, 3 mol% or less of trimellitic anhydride, benzophenonetetracarboxylic acid, trimethylolpropane, glycerin, pyromellitic anhydride and the like can be used.

The thermoplastic polyester elastomer of the present invention may contain a small amount of a bifunctional polyether component. For example, PTMG, ethylene oxide modified PTMG, etc. can be used in an amount of 10% by weight or less.

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. In particular, titanium catalysts, more specifically, tetraalkyl titanates such as tetrabutyl titanate and tetramethyl titanate, and metal oxalates such as titanium potassium oxalate are preferable. 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 reduced viscosity of the obtained thermoplastic polyester elastomer of the present invention is 0.5 to 4.0, preferably
It is desirable to be 0.5-3.0, especially 0.8-2.0. If the reduced viscosity is less than 0.5, the mechanical properties are poor.
If it exceeds 0, it is not preferable because moldability is poor.

Further, the thermoplastic polyester elastomer of the present invention can be blended with various additives according to the purpose to obtain a composition. Examples of additives include known hindered phenol, sulfur, phosphorus, and amine antioxidants, hindered amine, triazole, benzophenone, benzoate, nickel, and salicyl light stabilizers, and antistatic agents. Agents, lubricants, molecular regulators such as peroxides, compounds having reactive groups such as epoxy compounds, isocyanate compounds, carbodiimide compounds, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, Acid agents, antibacterial agents, optical brighteners, fillers, flame retardants, flame retardant aids, organic and inorganic pigments, and the like can be added.

The hindered phenolic antioxidants which can be incorporated in the present invention include 3,5-di-t-butyl-4-hydroxy-toluene, n-octadecyl-β-
(4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, tetrakis [methylene-3-
(3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6′-tris (3,5-di-tert-butyl-
4-hydroxybenzyl) benzene, calcium (3,
5-di-t-butyl-4-hydroxy-benzyl-monoethyl-phosphate), triethylene glycol-
Bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-tert-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-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2'-oxamidobis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] , 1,1,3-tris (3 ′, 5′-di-tert-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 acid triester wizz-
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] Undecane and the like.

The sulfur-based antioxidants that can be incorporated in the present invention include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodiuropionate, distearyl-3,3'-thiodithioate. Propionate, lauryl stearyl-3,3'-thiodipropionate, dilauryl thiodipropionate, dioctadecyl sulfide, pentaerythryl-tetra (β-lauryl-thiopropionate) ester and the like. Can be.

The phosphorus-based antioxidants that can be added in the present invention include tris (mixed, mono- and dinolylphenyl) phosphite, tris (2,3-di-t-butylphenyl) phosphite, 4,4 ′ -Butylidene-
Bis (3-methyl-6-t-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, Tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butyl)
Butylphenyl) pentaerythritol-diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenephosphanite, bis (2,6-di-t-butyl-4-methyl) Phenyl) pentaeristol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylenediphosphonite, triphenylphosphite,
Examples thereof include diphenyldecyl phosphite, tridecyl phosphite, trioctyl phosphite, tridodecyl phosphite, trioctadecyl phosphite, trinonyl phenyl phosphite, and tridodecyl trithiophosphite.

The amine-based antioxidants that can be added to the present invention include N, N-diphenylethylenediamine, N, N
-Diphenylacetamidine, N, N-diphenylfluamidine, N-phenylpiperidine, dibenzylethylenediamine, triethanolamine, phenothiazine, N, N'-di-sec-butyl-p-phenylenediamine, 4,4'-tetra Methyl-diaminodiphenylmethane, P, P′-dioctyl-diphenylamine,
N, N'-bis (1,4-dimethyl-pentyl) -p-
Phenylenediamine, phenyl-α-naphthylamine,
Phenyl-β-naphthylamine, 4,4′-bis (4-
Examples thereof include amines such as (α, α-dimethyl-benzyl) diphenylamine and derivatives thereof, reaction products of amine and aldehyde, and reaction products of amine and ketone.

The hindered amine light stabilizer which can be blended in the present invention includes dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-succinate.
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,
Polycondensate 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-1,2,2
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-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 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 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, 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′-t-butyl-5′-methylphenyl) -5-chlorobenazotriazole, 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'-ethyl oxalic acid-85-90% of bis-anilide and 2-ethoxy-5-t-butyl-2'-ethyl-4'-t-butyl oxalic acid- Bis-anilide 10-15% mixture, 2- [2-hydroxy-3,5-bis (α, α
-Dimethylbenzyl) phenyl] -2H-benzotriazole, 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- Light stabilizers such as 4-i-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone and phenyl salicylate can be mentioned.

The lubricants that can be blended in the present invention include hydrocarbons, fatty acids, fatty acid amides, esters, alcohols, metal soaps, natural waxes, silicones and fluorine compounds. Specifically, liquid paraffin, synthetic paraffin, synthetic hard paraffin, synthetic isoparaffin petroleum hydrocarbon, chlorinated paraffin, paraffin wax, microwax, low-polymerized polyethylene, fluorocarboxylic oil, lauric acid having 12 or more carbon atoms, myristic acid, Fatty acid compounds such as palmitic acid, stearic acid, arachidic acid, and behenic acid, hexylamide, octylamide, stearylamide, palmitylamide, oleylamide, erucylamide, ethylenebisstearylamide, laurylamide, behenylamide,
C3-30 saturated or unsaturated aliphatic amides 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, silicone gum, and ethylene tetrafluoride. Also, linear saturated fatty acids, side chain acids,
A metal salt comprising a compound having cinoleic acid, wherein the metal is (L
i, Mg, Ca, Sr, Ba, Zn, Cd, Al, S
n, Pb) can also be mentioned.

The fillers that can be added in the present invention include magnesium oxide, aluminum oxide, silicon oxide,
Calcium oxide, titanium oxide (rutile type, anatase type), chromium oxide (trivalent), iron oxide, zinc oxide, silica, diatomaceous earth, alumina fiber, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, etc. Oxides or magnesium hydroxide, aluminum hydroxide, basic substances such as magnesium carbonate or hydroxides, or magnesium carbonate, calcium carbonate, barium carbonate, ammonium carbonate, calcium sulfite, dolomite, carbonates such as dawsonite or (Sulfite) such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, 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 or kaolin (porcelain), 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, and sodium borate.

Examples of the compound having an epoxy group which can be blended in the present invention include polyepoxy compounds such as sorbitol-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, diglycidyl hexahydrophthalate, A condensate of bisphenol A and epichlorohydrin,
Condensates of bisphenol F and epichlorohydrin, diepoxy compounds such as 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- Monoepoxy compounds such as t-butylphenyl glycidyl ether and the like can be mentioned.

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,
Brominated phenoxy, ethylene bis (tetrabromophthal) imide, brominated diphenyl oxide, brominated polystyrene and the like can be mentioned.

Examples of the flame retardant aid 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, Molybdenum oxide, red phosphorus compounds, ammonium polyphosphate, melamine cyanurate, ethylene tetrafluoride and the like can be mentioned.

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

Examples of the inorganic phosphorus compound of the phosphorus compound which can be blended in the present invention include a red phosphorus compound and an ammonium polyphosphate. Examples of the red phosphorus compound include red phosphorus coated with a resin, a composite compound with aluminum, and the like. Examples of the organic phosphorus compound include a phosphoric ester and a melamine phosphate. Phosphates include phosphates, phosphonates, phosphinates such as trimethyl phosphate, 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 phosphate
Phosphenyloxy] benzene, 1,4- [bis (2,
6-dimethylphenoxy) phosphenyloxy] benzene and the like are preferable from the viewpoint of hydrolysis resistance, heat stability, and flame retardancy.

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.

[0037]

The present invention will be specifically described below with reference to examples. In these examples, each measurement item followed the following method. The weight% of polycyclohexane dimethylene terephthalate, dimer acid derivative and the like in the obtained polymer is a value measured by proton NMR. Reduced viscosity: 0.05 g of polymer in 25 ml of a mixed solvent (phenol / tetrachloroethane = 60/40 (wt / w)
t)) and measured at 30 ° C. using an Ostwald viscometer. Melting point: The melting point was measured by DSC at a rate of 20 ° C./min from room temperature. Flexural modulus: Measured based on ASTM D790. Elongation after heat aging test: ASTM indicates elongation at break after heat treatment at 170 ° C for 1 week using a gear hot air dryer.
It measured based on D638. Elongation after water aging test: The test piece was immersed in boiling water at 100 ° C. for 2 weeks, and then the elongation at break was measured according to ASTM D63.
8 was measured.

Example 1 500 parts by weight of dimethyl terephthalate, 515 parts by weight of 1,4-cyclohexanedimethanol, hydrogenated dimer diol ethylene oxide adduct (HP8, manufactured by Toagosei Co., Ltd.)
00E) 235 parts by weight, 2 parts by weight of Irganox 1330 (manufactured by Nippon Ciba Geigy) and 1.8 parts by weight of tetrabutyl titanate were charged, and the temperature was raised from room temperature to 230 ° C. over 1.5 hours, and then further raised to 260 ° C. for 1 hour. And the transesterification reaction was performed. Then, the pressure inside the can was gradually reduced and the temperature was raised.
The pressure was reduced as follows to perform an initial condensation reaction. Further 280
The polymerization reaction was carried out at a temperature of 1 ° C. or lower at 3 ° C. for 3 hours, and the polymer was taken out in the form of pellets. The removed pellet was then subjected to solid-state polymerization. The reduced viscosity of the obtained polymer was 1.21, and the weight percentages of the polycyclohexane dimethylene terephthalate component and the hydrogenated dimer diol ethylene oxide adduct component in the polymer were 75% each.
% And 25%. The properties of the obtained polymer were measured, and the results are shown in Table 1.

Example 2 In Example 1, 437 parts by weight of 1,4-butanediol was used in place of 1,4-cyclohexanedimethanol so that the polybutylene terephthalate component in the polymer was 25% by weight. A thermoplastic elastomer was polymerized in the same manner as in Example 1, except that the reaction temperature was appropriately adjusted. Table 1 shows the results.

Example 3 In Example 1, 628 parts by weight of 2,6-dimethylnaphthalate was used instead of dimethyl terephthalate,
The reaction temperature was the same as in Example 1 except that 437 parts by weight of 1,4-butanediol was used instead of cyclohexanedimethanol to make the polybutylene naphthalate component in the polymer 25% by weight. Was appropriately adjusted to polymerize the thermoplastic elastomer. Table 1 shows the results.

Comparative Example 1 In Example 1, hydrogenated dimer diol and polytetramethylene glycol were used in place of the hydrogenated dimer diol ethylene oxide adduct. A thermoplastic elastomer was polymerized in the same manner as in Example 1 except that the content of the methylene glycol component was adjusted to 15% by weight. The results are shown in Table 1. As is clear from Table 1, the obtained elastomer has an elongation of less than 150% after the heat aging test.

COMPARATIVE EXAMPLE 2 In Example 1, hydrogenated dimer diol was used in place of the ethylene oxide adduct component, except that the hydrogenated dimer diol component in the polymer was 25% by weight. In the same manner as in Example 1,
The thermoplastic elastomer was polymerized. The results are shown in Table 1. As is clear from Table 1, the obtained elastomer has an elongation of less than 150% after the heat aging test.

Comparative Example 3 In Example 1, 75% by weight of a polybutylene terephthalate component was used instead of the polycyclohexane dimethylene terephthalate component, and a polytetramethylene glycol component was used instead of the hydrogenated dimer diol ethylene oxide adduct component. A thermoplastic elastomer was polymerized in the same manner as in Example 1 except that the amount was adjusted to 25% by weight, and the reaction temperature was appropriately adjusted. The results are shown in Table 1. As is clear from Table 1, the obtained elastomer was completely deteriorated after the heat aging test, and the elongation could not be measured.

Comparative Example 4 In Example 1, 75% by weight of a polybutylene naphthalate component was used instead of the polycyclohexane dimethylene terephthalate component, and a polytetramethylene glycol component was used instead of the hydrogenated dimer diol ethylene oxide adduct component. Was adjusted to 25% by weight in the same manner as in Example 1, and the reaction temperature was appropriately adjusted to polymerize the thermoplastic elastomer. The results are shown in Table 1. As is clear from Table 1, the obtained elastomer also shows that the elongation after the heat aging test is less than 150%.

Comparative Example 5 PBT for the hard segment and PCL for the soft segment
Table 1 shows the measurement results of the physical properties of the polyester elastomer Perprene S2000 manufactured by Toyobo Co., Ltd., which is composed of the following elastomers. It deteriorated completely after the aging test, and the elongation could not be measured.

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[Table 1]

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As is clear from Table 1, the thermoplastic polyester elastomer of the present invention having the above-mentioned structure has a higher heat aging test and water aging resistance than the polyester elastomer comprising PTMG or PCL as a soft segment. It is clear that both elongations after the test are excellent. Therefore, it is understood that the thermoplastic polyester elastomer of the present invention is excellent in weather resistance and elastic performance, particularly, heat aging resistance and water resistance. That is, the present invention is excellent in weather resistance and elastic performance, particularly excellent in heat aging resistance and water resistance, and therefore can be used for various molding materials including fibers, films and sheets. It is also suitable for molding materials such as elastic yarns and boots, gears, tubes, packings and the like.For example, applications requiring heat resistance and heat aging resistance of automobiles and home electric parts, specifically, joint boots and electric wires It is useful for coating materials and the like, 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 Institute 4J029 AA03 AB01 AC03 AE01 AE02 BA02 BA03 BA08 BA09 BA10 BD02 BD05A BF26 CA02 CA04 CA06 CA09 CB05A CB06A CB10A CC06A CH02 DB01 HA01 HB01

Claims (4)

[Claims] 1. A thermoplastic polyester elastomer having a flexural modulus of elasticity <10000 kg / cm ² , elongation at break after heat aging test> 150%, and elongation at break after water aging test> 150%. . (Here, the flexural modulus is a value measured based on ASTM D790,
The elongation at break is a value measured based on ASTM D638. The heat aging test corresponds to a heat treatment at 170 ° C. for one week using a gear hot air dryer, and the water aging test corresponds to a treatment in boiling water at 100 ° C. for two weeks. ) 2. The thermoplastic polyester elastomer according to claim 1, wherein the soft segment in the thermoplastic polyester elastomer comprises a derivative of a hydrogenated dimer diol represented by the following general formula (1). 3. The thermoplastic polyester elastomer according to claim 1, wherein the hard segment in the thermoplastic polyester elastomer comprises a repeating unit represented by the following general formula (2). 4. A derivative of a hydrogenated dimer diol represented by the following general formula (1):
And a repeating unit represented by (3), wherein the reduced polyester has a reduced viscosity of 0.5 to 4.0. Embedded image Embedded image Embedded image (Where D is a hydrogenated dimer diol residue, and R is C2-C2)
And 10 represents an alkylene group, and the sum of a and b is 1 to 25. Note that R may be two or more types. Further, R ¹ is an aromatic group having 6 to 18 carbon atoms, R ² is a kind of glycol residue selected from the group consisting of an alkylene group having 2 to 4 carbon atoms and a 1,4-cyclohexane dimethylene group, and R ³ is It represents an alkylene group having 1 to 25 carbon atoms. Also, c represents the weight% of the repeating unit in the whole polymer, d represents the mole% in the whole polymer, c is 30 to 95% by weight, and d is 0 to 20%.
Mol%. )