JPH04304257A - Polyester composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic polyester composition excellent in heat resistance, color-fastness to light and mechanical properties by mixing a specified polyester with a specified amine compound. CONSTITUTION:100 pts.wt. polyester comprising an aliphatic dicarboxylic acid of formula I (wherein n is 0-10), an aliphatic diol (e.g. ethylene glycol) and a dihydroxy compound of formula II (wherein R<1> and R<2> are each alkylene; p is 3-4; q and r are each an integer of 0, 1 or greater) and/or a monohydroxy compound of formula III (wherein R<3> is R<1>; L is 2-3; and m is q) is mixed with 0.01-5 pts.wt. amine compound, e.g. tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4- butanetetracarboxylate.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester composition which has properties as a thermoplastic elastomer and is excellent in heat deterioration resistance, light resistance and mechanical strength.

0002

2. Description of the Related Art Generally, in order for a material to exhibit rubber elasticity, it is necessary that an amorphous polymer whose molecular chain rotates easily be partially crosslinked. For example, in elastic rubber, sulfur molecules are bridged by chemical bonds between molecular chains to form a network structure. In addition to rubber, materials that combine various polymer compounds and crosslinking agents have been proposed. Molding these materials requires a crosslinking step, and once chemically crosslinked, they do not exhibit thermoplastic properties, so crosslinked materials cannot be molded by injection molding or extrusion.

[0003] In recent years, thermoplastic elastomers that exhibit rubber elasticity at room temperature and become plasticized at high temperatures have been developed, and various types of thermoplastic elastomers are manufactured and commercially available. This thermoplastic elastomer does not require a long crosslinking process unlike conventional rubber, and can be molded by injection molding or extrusion molding. The molecular structure of thermoplastic elastomers is characterized by crosslinking that does not rely on strong chemical bonds, that is, a system that imposes some kind of inter-polymer restraint that is only effective at around room temperature. An aggregate is a typical structure of thermoplastic elastomers. Soft segments and hard segments have different chemical structures, and in a hybrid composition of the two, the homogeneous parts aggregate and the different parts form a micro-disequilibrium structure that is phase-separated from each other. The aggregation portion exhibits the constraining effect between the molecules.

[0004] As a thermoplastic elastomer, in particular, a polyester containing a dihydroxy or monohydroxy compound having a p-terphenyl or p-quarterphenyl skeleton can provide a thermoplastic elastomer with excellent mechanical properties. A related invention has already been filed (for example, Japanese Patent Application No. 1-2634
No. 76).

[0005]

As described above, thermoplastic elastomers exhibit rubber elasticity at room temperature and can be molded, so they are widely used in automobile parts and various industrial products. Particularly in recent years, the applications of thermoplastic elastomer materials have been expanded to a wide range of fields, and there is a need for thermoplastic elastomer materials that can be used satisfactorily in harsh environments. Specifically, a material is desired that has sufficient weather resistance, excellent heat deterioration resistance, and excellent mechanical strength. However, at present, there is no commercially available elastomer material that satisfies all of these conditions.

In order to obtain an elastomer with excellent heat resistance and weather resistance, for example, Japanese Patent Publication No. 1-27101 discloses a stabilized polyether ester copolymer containing a hindered amine type light stabilizer and a phenolic antioxidant. Kosho 6
2-31023 proposes a polyether ester copolymer composition containing a hindered amine type light stabilizer as a copolymerized segment, but although these have been recognized to have a stabilizing effect, they do not side)
Since it contains a glycol skeleton, it cannot be said that it maintains sufficient heat resistance and weather resistance.

[0007] Also, in JP-A-50-91652, stabilization by adding a specific stabilizer is proposed, but the effect is insufficient.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyester composition that has properties as a thermoplastic elastomer and has excellent heat resistance, light resistance, and mechanical properties. Our goal is to provide the following.

[0009]

[Means for Solving the Problems] An aliphatic polyester comprising a dihydroxy compound having a p-terphenyl p-quaterphenyl skeleton has a transition point (melting point) from a crystalline state to a liquid crystal state of this hydroxy compound. It is a thermoplastic elastomer with extremely strong and heat-resistant physical crosslinks, reflecting its characteristic molecular structure, and has excellent heat resistance and mechanical properties. By blending a stabilizer with a specific structure into an elastomer having such characteristics, an elastomer material with excellent heat resistance, weather resistance, and mechanical strength was obtained, and the present invention was completed.

That is, the polyester composition of the first invention comprises an aliphatic dicarboxylic acid represented by the general formula [I],
For 100 parts by weight of a polyester comprising an aliphatic diol and at least one of a dihydroxy compound whose general formula is represented by the following formula [II] and a monohydroxy compound represented by the following formula [III], The following formula [IV
] The above object can be achieved by blending 0.01 to 5 parts by weight of an amine compound having a structure represented by the following.

The polyester composition of the second invention also contains an aliphatic dicarboxylic acid and an aliphatic diol whose general formula is represented by the following formula [I], and a dihydroxy compound whose general formula is represented by the following formula [II]. and a monohydroxy compound represented by the following formula [III], and an amide compound having a molecular weight of 1000 or less, and the amide compound is the polyester 10.
It is contained in a proportion of 0.01 to 5.00 parts by weight to 0 parts by weight, thereby achieving the above object.

0012

[C5]

[0013]

[C6]

[0014]

[C7]

[0015]

[Chemical formula 8]

If a dicarboxylic acid having more than 10 carbon atoms is used among the above aliphatic dicarboxylic acids, the physical properties of the molded article obtained from the polyester will deteriorate. Examples of the dicarboxylic acids include oxalic acid, malonic acid, succinic acid,
Glutaric acid, adipic acid, suberic acid and sebacic acid are preferably used.

[0017] Examples of the aliphatic diols include glycols and polyalkylene oxides. Examples of the above glycol include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol. Diol, 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-
Examples include dimethanol, which may be used alone or in combination of two or more.

Examples of the above-mentioned polyalkylene oxide include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polyhexamethylene oxide, etc., and these may be used alone or in combination of two or more. good. The number average molecular weight of the polyalkylene oxide is 100 to 20,000, because if it becomes small, the ability to impart flexibility to the polyester produced will decrease, and if it becomes too large, the physical properties such as thermal stability of the polyester obtained will decrease. is preferable, and more preferably 500 to 5,000.

The dihydroxy compound represented by the above formula [II] is a low-molecular compound exhibiting liquid crystallinity, and the alkylene groups R1 and R2 are preferably ethylene or propylene groups, and q and r are preferably 0 or 1. 4,4''-dihydroxy-p-terphenyl represented by the following formula [A], 4,4''-dihydroxy- represented by the following formula [B]
p-quarterphenyl and 4 represented by the following formula [C],
4'''-di(2-hydroxyethoxy)-p-quarterphenyl and the like are preferably used.

[0020]

[Chemical formula 9]

The transition temperature of 4,4''-dihydroxy-p-terphenyl [A] from the crystalline state to the liquid crystalline state is 26
At 0°C, that of 4,4'''-dihydroxy-p-quaterphenyl [B] is 4,4'''-di(
2-hydroxyethoxy)-p-quarterphenyl [
C] is 403°C. Note that the crystalline state refers to a state in which the compound is in a molten state and the molecules maintain an oriented state. Each of the above dihydroxy compounds [II] may be used alone or in combination.

Liquid crystal molecules generally have high crystallinity, and as mentioned above, 4,4''-dihydroxy-p-terphenyl [A], 4,4''-dihydroxy-p-quarterphenyl [B] and 4,4'''-di(2-hydroxyethoxy)-p-quarterphenyl [C] have a high transition point from crystal to liquid crystal state, so these dihydroxy compounds [II] are incorporated into the polymer chain. When incorporated, the polymer exhibits unique properties. That is, since the dihydroxy compound [II] 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 [II] 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 [III] above are rigid, low-molecular compounds having a paraphenylene skeleton, and the melting points of these compounds are extremely high, reflecting their characteristic molecular structure. 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 [III] is incorporated at the polymer end, it results in a very strong and highly heat-resistant physical crosslink,
A thermoplastic elastomer with excellent heat resistance is produced.

In the monohydroxy compound represented by [III] above, R3 is preferably an ethylene group or a propylene group, and m is preferably 0 or 1. As the monohydroxy compound, for example, 4-hydroxy-p-
Examples include terphenyl, 4-hydroxy-p-quarterphenyl, 4-(2-hydroxyethoxy)-p-terphenyl, 4-(2-hydroxyethoxy)-p-quarterphenyl, and the like. Monohydroxy compound [II
I] may be used alone or in combination.

[0025] A polyester made of at least one of the above aliphatic dicarboxylic acid [I], an aliphatic diol, a dihydroxy compound [II], and a monohydroxy compound [III], and a polysilicone having two hydroxyl groups; Lactone or aromatic hydroxycarboxylic acid may be included as a constituent component.

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. As the number average molecular weight of polysilicone decreases, its ability to impart flexibility to the resulting polyester decreases.
If it gets too big, it becomes difficult to produce polyester, so 1
00 to 20,000 is preferable, more preferably 500
~5,000.

[0027] The above-mentioned lactone reacts with an acid and a hydroxyl group by ring-opening and adds an aliphatic chain, which gives flexibility to polyester, and which has four or more carbon atoms in the ring. It is preferable to have a ring, more preferably a 5- to 8-membered ring, and examples thereof include ε-caprolactone, δ-valerolactone, and γ-butyrolactone.

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, and 3-methyl- 4-Hydroxybenzoic acid, 3-phenyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3-promo-4-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 4-hydroxy-4 '-carboxybiphenyl, etc., preferably parahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 4-
Hydroxy-4'-carboxybiphenyl.

Furthermore, the polyester may contain an aromatic diol or an aromatic dicarboxylic acid other than the dihydroxy compound [II] as a constituent component in order to improve the mechanical properties of the polyester.

Examples of the aromatic diol include hydroquinone, resorcinol, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydronone, 4,4'
-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 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 be given. Examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 5-
Metal salt of sulfoisophthalic acid, 4,4'-dicarboxybiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, 4,4'-dicarboxydiphenyl sulfone, 3,3'-dicarboxybenzophenone, 4,
Examples include 4'-dicarboxybenzophenone, 4,4'-dicarboxybenzophenone, 1,2-bis(4-carboxyphenoxy)ethane, 1,4-dicarboxynaphthalene, or 2,6'-dicarboxynaphthalene. .

The aliphatic polyester made of the dihydroxy compound [II], an aliphatic diol, and an aliphatic dicarboxylic acid has a low heat resistance when the content of the dihydroxy compound [II] is low, and a high elastic modulus and flexibility when the content of the dihydroxy compound [II] is high. The content of the dihydroxy compound [II] is 0.1 to 30% of the total monomers constituting the polyester.
It is preferably mol%, more preferably 0.5 to 20 mol%, still more preferably 1.0 to 10 mol%. In addition, when using polyalkylenoxide or polysilicone as a diol other than aromatic, the constituent unit is 1
Count as monomer. That is, polyethylene oxide with a degree of polymerization of 10 is counted as 10 monomers. In addition, in the aliphatic polyester made of the monohydroxy compound [III], an aliphatic diol, and an aliphatic dicarboxylic acid, when the content of the monohydroxy compound [III] decreases, the heat resistance decreases, and when the content increases, the molecular weight of the aliphatic polyester decreases. It is preferable that the content be 0.01 to 20 mol% of the total monomers constituting the aliphatic polyester, since the amount of polyester will not increase sufficiently and the physical properties will be poor. Furthermore, a hydroxy compound [II] which is a combination of the above dihydroxy compound [II] and a monohydroxy compound [III] and a monohydroxy compound [
If the content of the hydroxy compound combined with III) decreases, the heat resistance will decrease, and if it increases, the flexibility will decrease and a sufficient increase in molecular weight will not be obtained. It is preferable to set it as 30 mol%. At this time, the ratio of dihydroxy compound [II] and monohydroxy compound is 0<[III]/[II]+[III]
A range satisfying <2/3 is preferable.

[0032] The polyester comprising the above-mentioned components can be produced using any of the generally known polycondensation methods listed below.

(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.

[0038] In the polycondensation, catalysts generally used in producing polyester may be used. This catalyst includes metals such as lithium, sodium, potassium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, etc. Examples thereof include organometallic compounds, organic acid salts, metal alkoxides, and 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 trioxide. Two or more of these catalysts may be used in combination. 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 to 350°C.

[0040] Also, during polymerization, dihydroxy compound [II]
It is also possible to control the structure of the resulting polyester by changing the order of addition. For example, if the dihydroxy compound [II] is charged together with the dicarboxylic acid and other diol components, a random copolymer will be easily obtained, and the dihydroxy compound [II] will be added in the late stage of polymerization.
II], it becomes easier to obtain a floc copolymer. It is also possible to knead the dihydroxy compound [II] or an acetyl compound of the dihydroxy compound into a pre-synthesized polyester under reduced pressure and heat, and introduce a segment based on the dihydroxy compound into the molecular chain by removing ethylene glycol or transesterifying the polyester. be.

The amine compound having the partial structure represented by [IV] above is a hindered amine light stabilizer,
This includes 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-tetramethol-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 composition contains this amine compound, the amount of the amine compound added is 0.01 parts by weight per 100 parts by weight of the polyester.
to 5 parts by weight (hereinafter referred to as parts). If the amount added is less than 0.01 part, no effect will be obtained, and if the amount added is more than 5 parts, the physical properties will be adversely affected.

The above amine compound may be blended at any stage. When added during polymerization, it can be added to the charging composition or during the reaction. When blending after polymerization, it is preferable to melt-knead using an extruder, plastograph, Banbury mixer, or the like. The melt-kneading temperature is desirably the lowest temperature at which mixing is possible in order to suppress decomposition of the resin.

The amide compound used in the present invention is a compound having a molecular weight of 1000 or less and having at least one amide bond that can produce 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.

[0044] Examples of the above amide compound include N,
Examples include N'-dihexylaziboyldiamide, N,N'-dihexylsebacyldiamide, 1,6-di(hexanoylamide)hexane, 1,6-di(hexanoylamide)octane, and especially phthaldi(β). -benzoyl) hydrazide and dodecadicarbonyl di(β-o-hydroxybenzoyl) hydrazide are preferably used.

The polyester product according to the present invention contains 0.01 parts of the above amide compound in 100 parts of the above polyester.
It is obtained by blending ~5.00 parts.

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. parts, preferably from 0.05 to
1.0 part is blended.

[0047] When the polyester composition of the present invention contains an amide compound, the polyester composition can be obtained by a commonly known method. When polymerizing polyester, it is possible to adopt the method of charging the above compound at the same time as the monomer, the method of charging it in the late stage of polymerization, etc. As a method of uniformly mixing the polyester and the above compound after polymerization, plastomill, extruder, kneader, etc. , a melt kneading method using a Banbury mixer or the like is performed.

[0048] Furthermore, the following additives may be added during or after the production of polyester to the extent that practicality is not impaired. That is, 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,
Organic fibers such as aramid fibers, inorganic fillers such as calcium carbonate, titanium oxide, mica, and talc, triphenyl phosphite, trilauryl phosphite, 2-tert-
Butyl-α-(3-tert-butyl-4-hydroxyphenyl)-p-cumenylbis(p-nonylphenyl)
Heat stabilizers such as phosphite, flame retardants such as hexapromocyclododecane, tris-(2,3-dichloropropyl) phosphate, pentapromophenyl allyl ether,
2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-(2
-hydroxy-5-methylphenyl)benzotriazole, bis[(2-hydroxy-5-octylphenyl)
UV absorbers such as benzotrizole] methane p-tert-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2-carboxybenzophenone, 2,4,5-trihydroxybutyrophenone, Triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3.5-dibutyl-4-hydroxyphenyl)] propionate], tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 3,9-bis[2-
[3-(3-t-Butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]2,4,8,10-tetraoxaspiro[5,5
] Antioxidants such as undecane, butylated hydroxyanisole, butylated hydroxytoluene, distealisthiodipropionate, dilaurylthiodipropionate, N
, N-bis(hydroxyethyl)alkylamines, alkylarylsulfonates, antistatic agents such as alkylsulfanates; inorganic substances such as barium sulfate, alumina, and silicon oxide; high-grade agents such as sodium stearate, barium stearate, and sodium palmitate. Fatty acid salts; Organic compounds such as benzyl alcohol and benzophenone; Highly crystallized polyethylene terephthalate, polytrans-
Examples include crystallization promoters such as cyclohexanedimethanol terephthalate. Furthermore, the polyester composition of the present invention can be mixed with other thermoplastic resins such as polyolefins, modified polyolefins, polystyrene, polyamides, polycarbonates, polysulfones, polyesters, etc., or mixed with rubber components to modify its properties. May be used.

The polyester composition of the present invention is made into a molded article by press molding, extrusion molding, injection molding, blow molding or the like. The physical properties of the molded product can be arbitrarily changed depending on its constituent components, their blending ratios, and the like. 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.

[0050]

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

Example 1 Synthesis of polyester (A) 292.5 g (2 mol) of adipic acid and 4,4'
”-dihydroxy-p-quarterphenyl (hereinafter referred to as D
To a monomer mixture of 67.7 g (0.02 mol) (referred to as HQ), 200 mg of germanium dioxide as a catalyst and 1.3.5-trimethyl-2,4,6- as a stabilizer.
400 mg of tris(3.5-di-t-butyl-4hydroxybenzyl)benzene and 400 mg of tris(2.4-di-t-butylphenyl)phosphite were added, and the reaction system was kept at 200°C for 2 hours under nitrogen. , an esterification reaction was performed. The reaction system was then heated to 320°C in 30 minutes, maintained at normal pressure for 20 minutes, and then heated to 300°C.
As a result of the polycondensation reaction being carried out for 2 hours under a reduced pressure of 1 mmHg or less, a pale yellow resin was obtained.

Intrinsic viscosity of the obtained polyester (A)
η] is the result of measurement at 30°C in orthochlorophenol [
η]=1.2.

Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1 was added to the polyester elastomer (A) obtained above as a hindered amine type stabilizer.
, 2,3,4-butanetetracarboxylate (Additive 1) were blended in the predetermined proportions shown in Tables 1 and 2, and melt-kneaded at 235°C for 10 minutes using a Brabender Plastograph extruder to form a resin composition. I got it. Next, a No. 3 dumbbell was obtained by injection molding (injection pressure 1500 kgf/cm2, mold temperature 70°C, cylinder temperature 230°C).

Furthermore, heat deterioration resistance and light resistance tests were conducted using the methods described below.

[0055] Heat deterioration resistance test (JIS K7212 reference) The dumbbell pieces obtained by the above method were 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. The results are shown in Table 1.

Light resistance test: Exposure to ultraviolet rays for a predetermined period of time using a paint fading tester (model FM-1) manufactured by Suga Test Instruments Co., Ltd. (manufactured in accordance with JIS K5400 paint fading test method) to maintain elongation. The 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. The results are shown in Table 2.

Example 2 As shown in Tables 1 and 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.

Example 3 Tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4, butanetetracarboxylate as additives and ultraviolet absorber bis[(2-hydroxy-5 -Octylphenyl)benzotriazole]methane (additive 2) was used in the amounts shown in Tables 1 and 2, 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 as additives and antioxidant 3,9-bis[2- [3-
(3-t-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]
The test was conducted in the same manner as in Example 1, except that 2,4,8,10-tetraoxaspiro[5,5]undecane (Additive 3) was used in the amounts shown in Tables 1 and 2. The results are shown in Tables 1 and 2.

Comparative Example 1 A test was conducted in the same manner as in Example 1 except that no additives were added. The results are shown in Tables 1 and 2.

Comparative Example 2 As shown in Tables 1 and 2, a test was conducted in the same manner as in Example 1 except that the number of additives 1 added was changed. Table 1 shows the results.
, 2.

Comparative Example 3 Injection molding (injection pressure 1500 kgf/cm2, mold temperature 7
0° C., cylinder temperature 220° C.), a No. 3 dumbbell was obtained, and the same test as in Example 1 was conducted. The results are shown in Tables 1 and 2.
Shown below.

[0063]

[Table 1]

[0064]

[Table 2]

Example 5 Synthesis of polyester (B) 348.4 g (2 mol) of dimethyl adipate, 298 g (2.4 mol) of ethylene glycol and 4,4'
''-dihydroxy-p-quarterphenyl (hereinafter referred to as
67.7 g (0.2 mol) of a monomer mixture (abbreviated as DHQ) was added with 200 mg of antimony trioxide as a catalyst.
and 440 mg of calcium acetate and 1 as a stabilizer.
3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene 40
0mg and 400mg of tris(2,4-di-t-butylphenyl)phosphite were added, and the reaction system was heated to 200ml under nitrogen.
The mixture was kept at ℃ for 2 hours to carry out the transesterification reaction. Next, this reaction system was heated to 320°C for 30 minutes, maintained at normal pressure for 20 minutes, and then lowered to 300°C to form a 1 mm
As a result of carrying out the polycondensation reaction for 1 hour under reduced pressure to below Hg, a light gray resin was obtained.

0.2 parts of phthaldi(β-benzoyl)hydrazide was added to 100 parts of polyester (B) and kneaded for 6 minutes at 23° C. using a plastomill, and the molding stability and heat deterioration resistance were evaluated. The results are shown in Tables 3 and 4, respectively.

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.

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℃). A 150- and 300-hour heat deterioration test (gear open, 170° C.) was conducted on the dumbbells obtained based on JIS 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 of fracture strength and fracture elongation for the sample before the thermal deterioration test.

Example 6 0.2 parts of phthaldi(β-benzoyl)hydrazide was added to 100 parts of polyester (B), and the mixture was kneaded for 6 minutes at 235°C using a plastomill, and the molding stability and heat deterioration resistance were evaluated. Ta. The results are shown in Tables 3 and 4, respectively.

Example 7 1.0 part of phthaldi(β-benzoyl)hydrazide was added to 100 parts of polyester (B) and kneaded for 6 minutes at 235°C using a plastomill, and the molding stability and heat deterioration resistance were evaluated. Ta. The results are shown in Tables 3 and 4, respectively.

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

Example 9 The same procedure as in Example 5 was carried out except that 1.0 part of 1,6-di(hexanoylamide)hexane was added to 100 parts of polyester (B). The results are shown in Tables 3 and 4, respectively.

Comparative Example 4 For comparison, the same procedure as in Example 1 was carried out without using the low molecular weight amide compound. The results are shown in Tables 3 and 4, respectively.

Comparative Example 5 0.005 part of phthaldi(β-benzoyl)hydrazide was added to 100 parts of polyester and kneaded for 6 minutes at 235°C in a plastomill, and the molding stability and heat deterioration resistance were evaluated. The results are shown in Tables 3 and 4, respectively.

[0075]

[Table 3]

[0076]

[Table 4]

Table 3 shows that the polyester composition of the present invention has excellent molding stability as the intrinsic viscosity decreases less than that of the comparative example, and Table 4 shows that the retention of breaking strength and elongation at break is lower than that of the comparative example. It can be seen that the larger the value, the better the heat deterioration resistance.

[0078]

According to the present invention, it is possible to provide a polyester composition in which deterioration due to long-term heating during processing and deterioration due to long-term use at high temperatures is reduced. The polyester obtained in this way has a segment based on a dihydroxy compound or monohydroxy compound with high crystallinity and a high melting point introduced into an aliphatic polyester mainly composed of a resinous dicarboxylic acid and an aliphatic diol. In addition, a hindered amine type light stabilizer or amide compound with a specific structure is blended with a specific polyester, so it can be used as a resin with excellent heat resistance, light resistance, and mechanical properties, especially as a thermoplastic elastomer for various parts. It can be used for.

Claims (2)

[Claims] Claim 1: An aliphatic dicarboxylic acid, an aliphatic diol whose general formula is represented by the following formula [I], and an aliphatic diol whose general formula is represented by the following formula [II]
For 100 parts by weight of a polyester containing at least one of the dihydroxy compound represented by the formula [III] and the monohydroxy compound represented by the following formula [III],
A polyester composition obtained by blending 0.01 to 5 parts by weight of an amine compound having a partial structure represented by the following formula [IV]. [Formula 1] [Formula 2] [Formula 3] [Formula 4] 2. An aliphatic carboxylic acid, an aliphatic diol whose general formula is represented by the above formula [I], and an aliphatic diol whose general formula is represented by the above formula [II].
] A polyester containing at least one of the dihydroxy compound represented by the formula [III] and the monohydroxy compound represented by the formula [III], and a polyester having a molecular weight of 10
00 or less and an amide compound capable of producing a primary amino group and a carboxyl group by hydrolysis, the amide compound containing 0.015 to 5.00 parts by weight based on 100 parts by weight of the polyester. 00 parts by weight of the polyester composition.