JPH04332724A - Polyester copolymer composition - Google Patents

Abstract

PURPOSE:To provide a polyester copolymer having the nature of thermoplastic elastomer and excellent mechanical properties and moldability and especially excellent thermal stability and weather resistance. CONSTITUTION:The objective polyester copolymer composition is produced by compounding (A) a polyester copolymer containing at least one of a dihydroxy compound and a monohydroxy compound as constituent component with (B) an amine compound or an amide compound.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester copolymer which has properties as a thermoplastic elastomer and has excellent mechanical properties, moldability, particularly thermal stability and weather resistance.

0002

2. Description of the Related Art Thermoplastic elastomers exhibit rubber elasticity at room temperature and can be molded, so they are widely used in various industrial products. In particular, a polyester copolymer of an aromatic polyester and a lactone containing a dihydroxy or monohydroxy compound having a p-terphenyl or p-quarterphenyl skeleton is a thermoplastic elastomer with excellent mechanical properties.

0003

[Problem to be Solved by the Invention] In recent years, thermoplastic elastomers have been used in a wide variety of fields, including automobile parts, and have sufficient heat resistance and weather resistance, allowing them to be used in harsh environments. Thermoplastic elastomeric materials are becoming necessary.

However, when the above-mentioned polyester copolymers are used at high temperatures, they have the disadvantage that the molecular weight decreases due to decomposition, and the mechanical properties of the resulting molded articles decrease. Furthermore, the weather resistance was also unsatisfactory. In order to improve these drawbacks, it has been proposed to incorporate a stabilizer or treat with an oxazoline compound regarding thermal deterioration. Although heat resistance has been considerably improved by such methods, at present there has been little improvement in weather resistance, particularly in terms of resistance to ultraviolet light deterioration.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyester copolymer which has properties as a thermoplastic elastomer and has excellent heat resistance, weather resistance, and mechanical properties. The object of the present invention is to provide a combined composition.

[0006]

[Means for solving the problem] A polyester copolymer of an aromatic polyester and a lactone containing a dihydroxy or monohydroxy compound having a p-terphenyl or p-quarterphenyl skeleton has excellent mechanical properties. It is a thermoplastic elastomer. The present inventors have discovered that stability at high temperatures and weather resistance can be improved by blending a specific amine compound into the polyester copolymer, and have completed the present invention.

The polyester copolymer composition of the first invention comprises (A) an aromatic polyester comprising a diol component mainly containing ethylene glycol and/or butylene glycol and an acid component mainly containing terephthalic acid; ,
(B) A composition of a polyester copolymer obtained by reacting a lactone monomer and/or a polylactone, in which a dihydroxy compound whose general formula is represented by the following formula [I] is used as the diol component of the aromatic polyester. and a polyester copolymer containing at least one of the monohydroxy compounds represented by the following formula [II] as a constituent component, and in which the compound is contained in an amount of 0.1 mol% to 30 mol% of the diol component; A polyester copolymer composition containing an amine compound having a partial structure represented by formula [III], wherein the amine compound is 0.01% to 3.00% by weight based on the polyester copolymer. This achieves the above objective.

[0008] The polyester copolymer composition of the second invention also includes (A) an aromatic compound comprising a diol component mainly containing ethylene glycol and/or butylene glycol and an acid component mainly containing terephthalic acid. A composition of a polyester copolymer obtained by reacting a polyester with (B) a lactone monomer and/or a polylactone, the diol component of the aromatic polyester having a general formula represented by the following formula [I]. A polyester copolymer containing at least one of the dihydroxy compound represented by the formula [II] and the monohydroxy compound represented by the following formula [II], and in which the compound is contained in an amount of 0.1 mol% to 30 mol% of the diol component. and the molecular weight is 1000
or less, and contains an amide compound that generates a primary amino group and a carboxyl group by hydrolysis, and the amide compound is 0.01% by weight based on the polyester copolymer.
It is contained in a proportion of ~5.00% by weight, thereby achieving the above object.

[0009]

[C4]

(In the formula, R1 and R2 independently represent an alkylene group, p is 3 or 4, and q and r are independently 0.
Or indicates an integer greater than or equal to 1. )

[0011]

[C5]

(In the formula, R3 represents an alkylene group and l is 2
or 3, and m represents an integer of 0 or 1 or more. )

[0013]

[C6]

(wherein R4 represents hydrogen or an alkyl group).

The aromatic polyester used in the present invention is composed of a diol component mainly containing ethylene glycol and/or butylene glycol and an acid component mainly containing terephthalic acid.

As butylene glycol, either 1,4-butanediol or 1,3-butanediol can be used. As a diol component other than ethylene glycol and butylene glycol, at least one of the dihydroxy compound represented by the above formula [I] and the monohydroxy compound represented by the formula [II] is included.

The dihydroxy compound [I] is a low-molecular compound exhibiting liquid crystallinity, and has alkylene groups R1 and R2.
is preferably an ethylene group or a propylene group, and q and r are preferably 0 or 1. For example, 4,4''-dihydroxy-p-terphenyl, 4,4''-dihydroxy-p-quarterphenyl, 4,4''-di(2
-hydroxyethoxy)-p-quarterphenyl and the like are preferably used.

The transition temperature of the above-mentioned 4,4''-dihydroxy-p-terphenyl from the crystalline state to the liquid crystalline state is 260
that of 4,4'''-dihydroxy-p-quaterphenyl at 336°C and 4,4'''-di(
That of 2-hydroxyethoxy)-p-quarterphenyl is 403°C. In addition, 4,4'''-dihydroxy-p-quarterphenyl is, for example, Journal
of Chemical Society, 1379
-85 (1940). Furthermore, the liquid crystal state refers to a state in which molecules maintain their orientation even in a molten state.

Each of the above hydroxy compounds [I] may be used alone or in combination.

Liquid crystal molecules generally have high crystallinity, and the above-mentioned 4,4''-dihydroxy-p-terphenyl, 4,4
'''-dihydroxy-p-quarterphenyl and 4
, 4'''-di(2-hydroxyethoxy)-p-quaterphenyl, etc. have a high transition point from crystal to liquid crystal state, so when these dihydroxy compounds [I] are incorporated into the polymer chain, , the polymer exhibits unique properties. That is, since the dihydroxy compound [I] exhibits crystallinity and has a high transition point, a strong and highly heat-resistant physical crosslink is formed even when the amount of the dihydroxy compound [I] is small. As a result, it is presumed that a thermoplastic elastomer with high heat resistance can be obtained without impairing the flexibility derived from the soft segment.

The monohydroxy compounds represented by [II] above are rigid, low-molecular compounds having a paraphenylene skeleton, and reflecting their characteristic molecular structures, these compounds also have extremely high melting points. Furthermore, the paraphenylene skeleton is known to be effective as a mesogen for low-molecular crystalline compounds, and this is because the skeleton has strong cohesive force not only in the solid state but also in the high temperature state (molten state). This shows that. Therefore, when the above-mentioned monohydroxy compound [II] is incorporated at the end of the polymer, very strong and highly heat-resistant physical crosslinking is produced, and a thermoplastic elastomer with excellent heat resistance is produced.

In the monohydroxy compound represented by [II] above, R3 is preferably an ethylene group or a propylene group, and m is preferably 0 or 1. Examples of the above monohydroxy compounds include 4-hydroxy-p-quarterphenyl, 4-hydroxy-p-quarterphenyl, 4-(2-hydroxyethoxy)-p-quarterphenyl, 4-(2-hydroxyethoxy)-p-
Examples include quarter phenyl. The monohydroxy compounds [II] may be used alone or in combination.

[0023] An aromatic polyester consisting of at least one of ethylene glycol and butylene glycol, at least one of dihydroxy compound [I] and monohydroxy compound [II], and terephthalic acid is combined with a fat other than the above. group glycol, polyalkylene oxide, polysilicone having two hydroxyl groups,
Aromatic diol components other than formulas [I] and [II], aromatic dicarboxylic acids other than terephthalic acid, aromatic hydroxycarboxylic acids, and aliphatic dicarboxylic acids may be contained as constituent components; It is preferably 10 mol% or less of the total amount of acid components.

Examples of the above glycol include propylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-
Octanediol, 1,9-nonanediol, 1,10
-Decanediol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, etc. These may be used alone or in combination of two or more.

[0025] Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyhexamethylene dioxide, etc. These may be used alone or two or more types may be used in combination. Good too. The number average molecular weight of the polyalkylene oxide is preferably 20,000 or less, more preferably 5.
00 or less.

The above-mentioned polysilicone has two hydroxyl groups, preferably polysilicone with two hydroxyl groups at the ends of the molecule, such as dimethylpolysiloxane and diethyl polysiloxane, which have two hydroxyl groups at both ends of the molecule. Examples include polysiloxane and diphenylpolysiloxane. The number average molecular weight of the polysilicone is preferably 20,000 or less, more preferably 5,000 or less, since it becomes difficult to produce polyester if it becomes large.

Examples of the aromatic diol include hydroquinone, resorcinol, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4,4
'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,
4'-dihydroxydiphenylmethane, bisphenol A, 1,1-di(4-hydroxyphenyl)cyclohexane, 1,2-bis(4-hydroxyphenoxy)ethane, 1,4-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, etc. can give.

Examples of the aromatic dicarboxylic acids include isophthalic acid, metal salts of 5-sulfoisophthalic acid, and 4,4'-
Dicarboxybiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, 4,4'-dicarboxydiphenyl sulfone, 3,3'-dicarboxybenzophenone, 4,4'-dicarboxybenzophenone, 1,
2-bis(4-carboxyphenoxy)ethane, 1,4
-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, and the like.

The above-mentioned aromatic hydroxycarboxylic acids impart rigidity and liquid crystallinity to polyester, and include salicylic acid, metahydroxybenzoic acid, parahydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid,
Examples include 3-phenyl-4-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 4-hydroxy-4'-carboxybiphenyl, and preferred are parahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, and 4-hydroxy-4'-carboxybiphenyl. .

The aliphatic dicarboxylic acid is preferably a dicarboxylic acid having 10 or less carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, and sebacic acid.

The above dihydroxy compounds [I] and [I
I], at least one of ethylene glycol and butylene glycol, and an acid component mainly containing terephthalic acid. The dihydroxy compound [I] or monohydroxy compound [II] not only cannot obtain a sufficient increase in molecular weight but also has a high melting point and can no longer be used in the next melt transesterification step. The content of is preferably 0.1 to 30 mol% in all monomers constituting the aromatic polyester,
More preferably, it is 0.5 to 20 mol%, and still more preferably 1.0 to 10 mol%. In addition, when polyalkylenoxide or polysilicone is used as a non-aromatic diol, its constituent unit is counted as one monomer. That is, polyethylene oxide with a degree of polymerization of 10 is counted as 10 monomers. If the content of the hydroxy compound (combined dihydroxy compound [I] and monohydroxy compound [II]) decreases, heat resistance will decrease, and if it increases, a sufficient increase in molecular weight will not be obtained, so all monomers constituting the aromatic polyester It is preferable to set it as 0.1-30 mol% of the inside. At this time, the ratio of dihydroxy compound [I] and monohydroxy compound [II] is 0<[I
]/[I]+[II]<2/3 is preferably satisfied.

[0032] The aromatic polyester comprising the above-mentioned components can be produced using any of the generally known polycondensation methods listed below. For example, (2) a method of directly reacting a dicarboxylic acid with a diol component (including aliphatic diols, dihydroxy compounds, monohydroxy compounds, etc.);

(2) A method in which a lower ester of dicarboxylic acid and a diol component are reacted using transesterification.

(2) A method in which a dicarboxylic acid halide and a diol component are reacted in a suitable solvent such as pyridine.

(2) A method in which a metal alcoholate as a diol component is reacted with a dicarboxylic acid halide.

(2) A method of reacting an acetylated diol component with a dicarboxylic acid using transesterification.

[0037] In the polycondensation, catalysts generally used in producing polyester may be used.

Examples of the catalyst include lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, etc. metals, their organometallic compounds, organic acid salts, metal alkoxides,
Examples include metal oxides.

Particularly preferred catalysts are calcium acetate, diacyltinn, tetraacyltinn, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate,
These are tin dioctanoate, tin tetraacetate, triisobutylaluminum, tetrabutyl titanate, germanium dioxide, and antimony acid oxide. Two or more of these catalysts may be used in combination.

Furthermore, various additives such as antioxidants and stabilizers may be used to improve thermal stability during polymerization.

[0041] Furthermore, in order to efficiently distill off water, alcohol, glycol, etc. that are by-produced during polymerization and obtain a high molecular weight polymer, it is preferable to reduce the pressure of the reaction system to 1 mmHg or less in the late stage of polymerization. The reaction temperature is generally 150~
The temperature is 350°C.

The lactone monomer used in the present invention is
Those that open the ring and react with acids and hydroxyl groups to add an aliphatic chain, preferably those that have 4 or more carbon atoms in the ring, and more preferably 5- to 8-membered rings. be. Examples include ε-caprolactone, δ-valerolactone, γ-butyrolactone, enantolactone, and capryrolactone. Two or more types of lactone monomers may be used in combination. In addition, polylactone is a substance that is transesterified with the aromatic polyester to add an aliphatic chain, thereby imparting flexibility to the polyester donor polymer. Polylactones obtained by ring-opening polymerization of lactone monomers having 4 or more carbon atoms in the ring are preferred, and polylactones obtained from 5- to 8-membered ring lactone monomers are more preferred. Examples include polylactones polymerized from δ-valerolactone, enantlactone, caprylolactone, and the like. There is no problem even if two or more types of lactone monomers and polylactone are used together.

The composition ratio of the aromatic polyester and the lactone compound (lactone monomer and/or polylactone) is such that the weight ratio of the aromatic polyester/lactone compound is 30/70 from the viewpoint of the elastic properties of the resulting polyester copolymer. -80/20 is preferable, and the especially preferable range is 30/70 - 70/30.

The above catalysts may be used for the reaction with the aromatic polyester tractone monomer. The reaction temperature is
When the reaction is carried out in a solvent-free system, the temperature is usually set to a temperature at which the mixture of aromatic polyester and lactone monomer is uniformly melted and at least the melting point of the fresh block copolymer. When reacting the aromatic polyester and the lactone monomer in a solution system, the reaction temperature can be set appropriately. Generally, a temperature range of 180 to 300°C is preferred. 180
If the temperature is below 300°C, it is difficult for the aromatic polyester to dissolve easily and uniformly with the lactone monomer, and if the temperature exceeds 300°C, decomposition or other undesirable side reactions occur. Further, when the above reaction is carried out in a solution, the solvent must be a common solvent with the aromatic polyester and the lactone monomer. For example, α-methylnaphthalene can be used.

[0045] The transesterification reaction between aromatic polyester and polylactone proceeds without a catalyst, but the above-mentioned catalysts may also be used. Further, at this time, the above-mentioned stabilizer may be added. The reaction temperature is usually a temperature at which the mixture of aromatic polyester and polylactone is uniformly melted, and is higher than the melting point of the produced block copolymer. Generally 180℃
A range of 300°C to 300°C is preferred. If the temperature is lower than 180°C, it is difficult for the aromatic polyester to melt easily and uniformly with the polylactone, and if the temperature exceeds 300°C, decomposition and other undesirable side reactions occur.

[0046] For the transesterification reaction, a polymerization apparatus normally used for polymerizing polyester is suitably used. Also,
Transesterification between aromatic polyester and polylactone can also be carried out in an extruder or kneader.

Examples of the amine compound having the partial structure represented by [III] above include tetrakis(2,2
,6,6,-tetramethyl-4-piperidyl)1,2,
3,4-butanetetracarboxylate, tetrakis (
1,2,2,6,6-pentamethyl-4-piperidyl)
1,2,3,4-butanetetracarboxylate, bis(2,2,6,6,-tetramethyl-1-piperidyl)
Sebacate, bis(1,2,2,6,6,-bentamethyl-4-piperidinyl) n-butyl(3,5-di-t-
butyl-4-hydroxybenzyl) malonate, and the like. When the polyester copolymer composition contains this amine compound, the amount of the amine compound added is preferably 0.01 to 3.00% by weight based on the polyester copolymer. If the amount added is less than 0.01% by weight, no effect will be obtained, and if the amount added is more than 3.00% by weight, the physical properties will be adversely affected.

[0048] The amide compound used in the second invention is a compound having a molecular weight of 1000 or less and having at least one amide bond capable of producing a primary amino group and a carboxyl group upon hydrolysis. The primary amino group and carboxyl group generated here can be bonded to an aliphatic (including alicyclic) group, a substituted aliphatic (including alicyclic) group, an aromatic group, or a substituted aromatic group. . Further, a compound consisting only of a primary amino group or a carboxyl group, such as hydrazine or oxalic acid, may be produced.

Examples of the low-molecular amide compound include N,N'-dihexylaziboyldiamide, N,N'
-dihexyl sebacil diamide, 1,6-di(hexanoylamide)hexane, 1,6-di(hexanoylamide)octane, etc. are used, especially phthaldi(β-benzoyl)hydrazide and dodecadicarbonyl di(β- -o
-hydroxybenzoyl) hydrazide is preferably used.

The polyester copolymer composition according to the second invention can be obtained by blending the above-mentioned amide compound in an amount of 0.01 to 5.00% by weight with the above-mentioned polyester copolymer.

[0051] If the amount of the above-mentioned amide compound used is small, the molding stability and heat deterioration resistance will not clearly appear, and if the amount is too large, the mechanical properties of the polyester composition will be lost. , preferably 0.05-1
．． 0% by weight is added.

The polyester copolymer composition of the present invention can be obtained by a commonly known method. A method in which a polyester copolymer is added at the same time as a monomer when polymerizing it,
A method of charging in the late stage of polymerization, etc. can be adopted, and a method of uniformly mixing the polyester and the above compound after polymerization includes a melt-kneading method using a plastomill, extruder, kneader, Banbury mixer, etc.

Furthermore, an ultraviolet absorber may be added to improve weather resistance. Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-(2-hydroxy-5-methylphenyl)benzotriazole,
Examples include bis[(2-hydroxy-5-methylphenyl)benzotriazole]methane.

Further, the following additives may be added during or after the production of the polyester copolymer within a range that does not impair practicality. In other words, inorganic fibers such as glass fiber, carbon fiber, boron fiber, silicon carbide fiber, alumina fiber, amorphous fiber, silicon/titanium/carbon fiber, alumina fiber, amorphous fiber, silicon/titanium/carbon fiber, aramid fiber. organic fibers such as calcium carbonate, titanium oxide, mica, talc, etc., flame retardants such as hexabromocyclododecane, tris-(2,3-dichloropropyl) phosphate, pentabromophenyl allyl ether, N,N - Antistatic agents such as bis(hydroxyethyl)alkylamines, alkylarylsulfonates, and alkylsulfanates, inorganic substances such as barium sulfate, alumina, and silicon oxide; higher fatty acid salts such as sodium stearate, barium stearate, and sodium palmitate. Organic compounds such as benzyl alcohol and benzophenone; Crystallization promoters such as highly crystallized polyethylene terephthalate and polytrans-cyclohexanedimethanol terephthalate.

Furthermore, the polyester copolymer composition obtained by the production method of the present invention can be used with other thermoplastic resins such as polyolefin, modified polyolefin, polystyrene,
It may be used by mixing with polyamide, polycarbonate, polysulfone, polyester, etc., or by mixing with a rubber component to modify its properties.

The obtained polyester copolymer composition is as follows:
It can be used as a thermoplastic elastomer and made into a molded material by press molding, extrusion molding, injection molding, blow molding, etc. The physical properties of the molded product can be arbitrarily changed depending on its constituent components and their blending ratios. When polyester is prepared as a thermoplastic elastomer, the molded product is suitably used for flexible molded products such as automobile parts, hoses, belts, and packing, as well as paints, adhesives, and the like.

[0057]

EXAMPLES The present invention will be explained below based on examples.

Synthesis of polyester copolymer (A) 4,
Synthesis of 4'''-dihydroxy-p-quaterphenyl 100 g of methanol, 300 g of 10 wt% sodium hydroxide solution and 13 g of 5 wt% palladium/carbon were added to 60.0 g of 4'-hydroxy-4-bromophenyl, and the mixture was heated at 120°C and 5 atm. By reacting for 4 hours under these conditions, the disodium salt of 4,4'''-dihydroxy-p-quarterphenyl was obtained. This solid has N,
After adding N-dimethylformamide and separating the catalyst by heating and filtration, the filtrate was precipitated with dilute sulfuric acid and washed with methanol to obtain 4,4'''-dihydroxy- as a white crystalline powder.
p-quarterphenyl (hereinafter referred to as DHQ) was obtained. The liquid crystal transition temperature of DHQ was 336°C.

(B) Synthesis of aromatic polyester Into a glass flask with an internal volume of 1 liter equipped with a stirrer, a gas inlet and a distillation port, 194 g of dimethyl terephthalate (1.
0mol), ethylene glycol 138g (2.24m
ol), a small amount of calcium acetate and di-n-butyltin oxide were added as catalysts. After purging the inside of the flask with nitrogen, the inside of the flask was heated and reacted at 180° C. for 3 hours. Along with the reaction, methanol began to distill out from inside the flask, and bis(2-hydroxyethyl) terephthalate was obtained.

[0060] 50.7 g of the above DHQ was added to this flask, and the temperature of the flask was raised to 280°C.
Allowed time to react. Next, the distillation port was connected to a vacuum vessel, and the flask was reacted for 1 hour while the pressure inside the flask was reduced to 1 mmHg. During the reaction, ethylene glycol was distilled out, and an extremely viscous liquid was formed in the flask. After the flask was allowed to cool, the glass flask was broken and the product was taken out.

(C) Synthesis of polyester copolymer Internal volume: 1 liter, equipped with stirring blade, gas inlet, and distillation port
Into a glass flask, 200 g of the aromatic polyester obtained in section (B) above, 300 g of ε-caprolactone,
1.0 g of tetrabutyl titanate as a catalyst and 1.0 g of 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene as a heat stabilizer were charged. After purging the inside of the flask with nitrogen, it was heated to 250° C. in an oil bath while stirring. The reaction system became a homogeneous viscous liquid.

Subsequently, the reaction was carried out for 1 hour under a nitrogen stream, and then the gas inlet was connected to a vacuum pump, and the reaction was carried out for another 1 hour under the condition that the pressure inside the flask was reduced to 1 mmHg. The resulting polymer had a melting point of 220°C and a Shore D hardness of 40.
It had good rubber-like elasticity. In addition, the tensile strength at break is 350Kg/cm2, and the tensile elongation at break is 130Kg/cm2.
It was 0%.

(D) Heat deterioration resistance test (JIS K72
(Reference 12) The dumbbell piece obtained by the above method was left at 170° C. for the predetermined time shown in Table 1 in an open gear. After a predetermined period of time, the dumbbell piece was taken out and its elongation retention rate was measured. The elongation retention rate was determined by measuring the tensile elongation at break using Shimadzu Autograph AG-5000 in accordance with JIS K6301.
It was determined from the ratio before and after the heat resistance test.

(E) Evaluation of ultraviolet ray deterioration resistance test: Paint fading test (JIS
(Produced according to K5400 paint fading test method)
The specimens were exposed to ultraviolet light for a predetermined period of time, and the elongation retention rate was measured. The elongation retention rate was determined by measuring the tensile elongation at break using Shimadzu Autograph AG-5000 according to JIS K6301, and calculating the ratio before and after the light resistance test.

(Example 1) Tetrakis (2,2,
6,6-tetramethyl-4-piperidyl)1,2,3,
4-Butanetetracarboxylate (additive 1) in Table 1
, 2 and melt-kneaded using a Brabender Plastograph extruder at 220° C. for 10 minutes to obtain a resin composition. Next, injection molding (injection pressure 1
500 kgf/cm2, mold temperature 70°C, cylinder temperature 220°C) to obtain a No. 3 dumbbell. Further above (
Heat deterioration resistance and ultraviolet ray deterioration resistance tests were conducted using the methods shown in D) and (E). The results are shown in Tables 1 and 2.

(Example 2) A test was carried out in the same manner as in Example 1 except that the number of parts of Additive 1 added was changed. The results are shown in Tables 1 and 2.

(Example 3) Tetrakis (2
,2,6,6-tetramethyl-4-piperidyl)1,2
, 3,4-butanetetracarboxylate and the ultraviolet absorber bis[(2-hydroxy-5-octylphenyl)benzotriazole]methane (additive 2) were used, but the test was conducted in the same manner as in Example 1. The results are shown in Tables 1 and 2.

(Example 4) Tetrakis (2
,2,6,6-tetramethyl-4-piperidyl)1,2
, 3,4-butanetetracarboxylate and the antioxidant 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-
The test was conducted in the same manner as in Example 1 except that 1,1-dimethylethyl]2,4,8,10-tetraoxaspiro[5.5]undecane (additive 3) was used. Table 1 shows the results.
, 2.

(Comparative Example 1) Example 1 without adding additives
A similar test was conducted. The results are shown in Tables 1 and 2.

(Comparative Example 2) A test was conducted in the same manner as in Example 1, except that the number of additives 1 added was changed. The results are shown in Tables 1 and 2.

[0071]

[Table 1]

[0072]

[Table 2]

From Tables 1 and 2, it can be seen that by blending a specific amine compound into the polyester copolymer, the heat deterioration resistance and compatibility are improved.

(F) Evaluation of molding stability The intrinsic viscosity [η] of the obtained polyester composition was measured at 30° C. in orthochlorophenol. In addition, in order to evaluate the thermal stability during molding, the obtained polyester was
Dry at 00°C for 5 hours and use Shimadzu Flow Tester CFT5.
00 was used to measure the flow viscosity after 5 minutes and 30 minutes (test load 100 kg, die diameter 1 mm, die length 10 m).
m, flow temperature 240°C). In addition, the intrinsic viscosity of the strand sample obtained by flow viscosity measurement after 30 minutes was also measured.

(G) Evaluation of heat deterioration resistance The obtained resin was molded into a No. 3 dumbbell according to JIS K6301 by injection molding (injection pressure 1500 kgf/
cm2, cylinder temperature 240℃, mold temperature 70℃). J
A 150- and 300-hour heat deterioration test (gear open, 170° C.) was conducted on the dumbbells obtained based on IS K7212. The evaluation was performed by performing a tensile test on these dumbbells using Shimadzu Autograph AG-5000B based on JIS K6301, and determining the retention rate of elongation at break with respect to the sample before the thermal deterioration test.

(Example 5) Polyester copolymer 100
0.2 parts of phthaldi(β-benzoyl)hydrazide
The mixture was kneaded for 6 minutes at 220° C. using a plastomill, and the molding stability and heat deterioration resistance were evaluated using the methods shown in (F) and (G) above. The results are shown in Tables 3 and 4, respectively.

(Example 6) Polyester copolymer 100
0.0 parts of phthaldi(β-benzoyl)hydrazide
2 parts were added and kneaded for 6 minutes at 220° C. using a plastomill, and the molding stability and heat deterioration resistance were evaluated by the methods shown in (F) and (G) above. The results are shown in Tables 3 and 4, respectively.

(Example 7) Polyester copolymer 100
1.0 parts of phthaldi(β-benzoyl)hydrazide
The mixture was kneaded for 6 minutes at 220° C. using a plastomill, and the molding stability and heat deterioration resistance were evaluated using the methods shown in (F) and (G) above. The results are shown in Tables 3 and 4, respectively.

(Example 8) Polyester copolymer 100
The same procedure as in Example 5 was carried out except that 0.2 parts of decanedicarnyl di(β-o-hydroxybenzoyl)hydrazide was used. The results are shown in Tables 3 and 4, respectively.

(Example 9) Polyester copolymer 100
1.0 part of 1,6-di(hexanoylamide)hexane
The same procedure as in Example 5 was performed except that The results are shown in Tables 3 and 4, respectively.

(Comparative Example 3) As a control, the same procedure as in Example 5 was carried out without using a low-molecular amide compound. The results are shown in Tables 3 and 4, respectively.

(Comparative Example 4) Polyester copolymer 100
0.0 parts of phthaldi(β-benzoyl)hydrazide
5 parts were added and kneaded for 6 minutes at 220° C. using a plastomill, and the molding stability and heat deterioration resistance were evaluated by the methods shown in (F) and (G) above. The results are shown in Tables 3 and 4, respectively.

[0083]

[Table 3]

[0084]

[Table 4]

[0085]

Effects of the Invention By blending an amine compound or amide compound having a specific structure into a specific polyester copolymer, a polyester composition having excellent heat resistance, weather resistance, and mechanical properties can be obtained. The polyester composition thus obtained can be used as a thermoplastic elastomer for various members.

Claims (1)

[Claims] Claim 1: (A) an aromatic polyester comprising a diol component mainly containing ethylene glycol and/or butylene glycol and an acid component mainly containing terephthalic acid, and (B) a lactone monomer and/or polylactone. A polyester copolymer obtained by reacting a dihydroxy compound whose general formula is represented by the following formula [I] and a monohydroxy compound whose general formula is represented by the following formula [II] as the diol component of the aromatic polyester. A polyester copolymer in which at least one of the following is a constituent component and the compound is contained in 0.1 mol% to 30 mol% of the diol component, and an amine having a partial structure represented by the following formula [III] A polyester copolymer composition containing a compound, wherein the amine compound is contained in a proportion of 0.01% to 3.00% by weight based on the polyester copolymer. thing. [Formula 1] (wherein, R1 and R2 independently represent an alkylene group, and p
is 3 or 4, and q and r independently represent 0 or an integer of 1 or more. ) [Formula 2] (In the formula, R3 represents an alkylene group, l is 2 or 3, and m represents an integer of 0 or 1 or more.) [Formula 3] (In the formula, R4 represents hydrogen or an alkyl group. (Claim 2) (A) an aromatic polyester comprising a diol component mainly containing ethylene glycose and/or butylene glycol and an acid component mainly containing terephthalic acid; (B) a lactone monomer and/or or a polyester copolymer obtained by reacting a polylactone, wherein at least one of the dihydroxy compound according to claim 1 and the monohydroxy compound according to claim 1 is used as a diol component of the aromatic polyester. and the compound accounts for 0.1 mol% to 0.1 mol% of the diol component.
A polyester copolymer composition containing a polyester copolymer containing 30 mol% and an amide compound having a molecular weight of 1000 or less and generating a primary amino group and a carboxyl group by hydrolysis, The amide compound is 0.01% by weight based on the polyester copolymer.
A polyester copolymer composition containing ~5.00% by weight.