JPH0717821B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention provides a thermoplastic resin having excellent solvent resistance, melt stability, and weather resistance, and having a good balance of heat resistance, mechanical strength, and flexibility. The present invention relates to a composition, particularly to a thermoplastic resin composition suitable as a molded article and an adhesive.

(Prior Art) Thermoplastic polyester elastomer has heat resistance,
Due to its strong mechanical properties and excellent oil resistance and chemical resistance, application development has progressed not only in the fields of automobiles, electricity, and industrial goods, but also in sports goods and household goods.
It is a material that has been drawing attention in recent years. However, the conventional thermoplastic polyester elastomer has a drawback that it is difficult to balance heat resistance, mechanical strength and flexibility as a drawback of the thermoplastic resin. That is, when heat resistance and mechanical strength are increased, it lacks flexibility. On the other hand, when flexibility is increased, not only heat resistance and mechanical strength but also heat resistance and moisture resistance are deteriorated. However, there is a problem in that it is difficult to use and its applications are limited.

In order to solve the above problems, the present inventors have found that a specific thermoplastic copolyester elastomer containing an aliphatic long-chain glycol having an average molecular weight of about 350 to 6000 as one component,
We first filed a composition consisting of a rubber component and a vulcanizing agent suitable for molding applications and adhesive applications (Japanese Patent Application No. 61-62579). Since this composition has a performance that is relatively balanced in mechanical strength, flexibility, hot water resistance, weather resistance, etc., it can solve the conventional problems. Therefore, there is a problem that solvent resistance, melt stability, etc. are likely to be deteriorated, and weather resistance cannot be sufficiently dealt with in fields where demanding characteristics such as special exterior fields of automobiles and special construction materials fields are severe.

(Problems to be Solved by the Invention) The present invention is intended to solve the above problems, and an object thereof is to have excellent solvent resistance, melt stability and weather resistance, and further to have heat resistance. Another object of the present invention is to provide a thermoplastic resin composition having a good balance of mechanical strength and flexibility.

(Means for Solving Problems) As a result of intensive studies for solving such problems, the present inventors have found that a specific thermoplastic copolymer resin composition has the above-mentioned characteristics, and The invention has been reached.

That is, the present invention provides (a) 40 to 10 aromatic dicarboxylic acids.
0 mol%, aliphatic dicarboxylic acid having a molecular weight of about 250 or less and /
Or an acid component composed of 0 to 60 mol% of alicyclic dicarboxylic acid,
(B) a glycol component consisting of a low molecular weight glycol having a molecular weight of about 250 or less and (c) an aliphatic long-chain dicarboxylic acid having an average molecular weight of about 300 to 6000 and / or a total glycol component of 1 to 30 mol% based on the total acid component. On the other hand, it comprises a thermoplastic copolymerized polyester (A) having an intrinsic viscosity of at least 0.3 consisting of an aliphatic long-chain glycol having an average molecular weight of about 300 to 6000 of 1 to 30 mol% and a vulcanizing agent (B). The ratio of the polymerized polyester (A) and the vulcanizing agent (B) is such that the vulcanizing agent (B) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic copolyester (A). The gist is a thermoplastic resin composition.

However, the intrinsic viscosity is phenol: tetrachloroethane =
It is measured at 20 ° C. in a mixed solvent of 1: 1 (weight ratio).

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition of the present invention comprises a specific thermoplastic copolyester as a resin component and a vulcanizing agent mixed therein. First, the thermoplastic copolyester is
It contains an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid and / or an alicyclic dicarboxylic acid as the acid component (a).

Examples of aromatic dicarboxylic acids include terephthalic acid,
Examples include isophthalic acid and naphthanedicarboxylic acid.
These aromatic dicarboxylic acids may be used alone or in combination of two or more. Particularly, terephthalic acid or a mixture of terephthalic acid and isophthalic acid is preferably used. Such an aromatic dicarboxylic acid component contributes to increasing the softening point of the thermoplastic copolyester, imparting heat resistance and mechanical strength, but the composition ratio in the acid component (a) is 40% or less. ˜100 mol%, preferably 60-95 mol%.

If the proportion of the aromatic dicarboxylic acid component is less than 40 mol%, the mechanical strength and heat resistance of the thermoplastic copolyester as the resin component will be low, and the mechanical strength and heat resistance of the molded product will tend to be low.

Examples of the aliphatic dicarboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and / or saturated aliphatic dicarboxylic acid. Examples of such branched isomers include cyclohexanedicarboxylic acid as an alicyclic dicarboxylic acid. The aliphatic dicarboxylic acid and alicyclic dicarboxylic acid components are appropriately selected and used for the purpose of adjusting the melting point and flexibility of the thermoplastic copolyester. In addition, the acid component (a)
The proportion thereof is 0 to 60 mol%.

Next, as the glycol component (b), a low molecular weight glycol having a molecular weight of about 250 or less is used. Examples of such low molecular weight glycols include fats such as ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol and 1,9-nonanediol. Examples thereof include group polyols and / or their branched isomers, oxyalkylene glycols such as diethylene glycol and triethylene glycol, and alicyclic glycols such as cyclohexanedimethanol, and these are used alone or as a mixture of two or more thereof. The molecular weight of the above low-molecular-weight glycol is preferably about 250 or less, and above that, the softening point of the obtained copolyester becomes low, the polyester becomes too soft, the resilience is lost, and the heat resistance also decreases. It will be easier.

Furthermore, in the thermoplastic copolyester of the present invention, in addition to the above acid component (a) and glycol component (b), an aliphatic long-chain dicarboxylic acid having an average molecular weight of about 300 to 6000 and / or an average molecular weight of 300 to 6000 is used. It is necessary to contain an aliphatic long chain glycol.

Examples of the aliphatic long-chain dicarboxylic acid having an average molecular weight of about 300 to 6000 include saturated aliphatic dicarboxylic acids such as eicosane diacid and docosandioic acid, and / or their branched isomers, and unsaturated compounds having 10 or more carbon atoms. One kind or two or more kinds selected from a dimer acid composed of a dimer of fatty acid is used. Preferred specific examples of the dimer acid include Versadim 288 (manufactured by Henkel), which is a dimer of linoleic acid, and Em.
Examples include pol104 (Emery). Furthermore, hydrogenated dimer acid obtained by hydrogenating the double bond in the dimer acid is
It is also excellent in heat stability and can be used preferably. Further, 1,2-polybutadiene dicarboxylic acid, 1,4-polybutadiene dicarboxylic acid, copolymers or mixtures thereof, and hydrogenated products thereof are used.

Examples of the aliphatic long-chain glycol having an average molecular weight of 300 to 6000 include 1,2-polybutadiene glycol, copolymers or mixtures thereof, hydrogenated products thereof, polyisoprene glycol and hydrogenated products thereof, polyolefin glycol, etc. Is preferably used.

Aliphatic long-chain dicarboxylic acids or aliphatic long-chain glycols with an average molecular weight of about 300 to 6000 play an important role in the formation of crosslinks by vulcanization. That is, when the thermoplastic copolyester is vulcanized in a state of being melt-kneaded with a vulcanizing agent, crosslinking occurs in that state, so that the mechanical strength and vulcanizate of the vulcanized product of the resin composition are maintained without losing thermoplasticity. Heat resistance etc. improves.

The amount of the aliphatic long-chain dicarboxylic acid or the aliphatic long-chain glycol having an average molecular weight of about 300 to 6000 is 1 to 30 mol% based on the total acid component, or 1 to the total glycol component.
~ 30 mol%. Therefore, the acid component (a) is in the range of 99 to 70 mol% with respect to the total acid component, and the glycol component (b) is in the range of 99 to 70 mol% with respect to the total glycol component. If the amount of the aliphatic long-chain dicarboxylic acid or the aliphatic long-chain glycol having an average molecular weight of about 300 to 6000 exceeds 30 mol%, the mechanical strength and heat resistance of the thermoplastic resin composition tend to decrease. On the other hand, if it is less than 1 mol%, the self-crosslinking ability of the thermoplastic copolyester becomes poor, and the mechanical strength and heat resistance of the vulcanizate of the thermoplastic resin composition are insufficiently improved. When either one of the aliphatic long-chain dicarboxylic acid and the aliphatic long-chain glycol is used, the ratio is preferably 3 mol% or more, although it depends on the average molecular weight. When both the aliphatic long-chain dicarboxylic acid and the aliphatic long-chain glycol are used, the total amount is preferably 3-40 mol%.

The average molecular weight of the aliphatic long-chain dicarboxylic acid or the aliphatic long-chain glycol needs to be in the range of about 300 to 6000, but 500 to 4500 is particularly preferable.
If the molecular weight is too high, the compatibility with other components deteriorates, making it difficult to polymerize the thermoplastic copolyester.
On the other hand, when it is less than 300, the flexibility of the thermoplastic copolyester obtained is lowered and the vulcanization tends to be difficult.

The intrinsic viscosity of the thermoplastic copolyester of the present invention is, as described above, between that of phenol and tetrachloroethane.
It is dissolved in a mixed solvent of 1: 1 (weight ratio) and measured at 20 ° C., but the thermoplastic copolyester of the present invention needs to have an intrinsic viscosity of at least 0.3. Practically, the range of 0.5 to 1.6 is preferable. If the intrinsic viscosity is less than 0.3, the strength of the resin becomes low and brittle due to the low molecular weight, which causes a problem in the strength of the composition even after vulcanization. Therefore, the thermoplastic resin composition of the present invention, the molding application and the adhesive application Is difficult to use as. When the thermoplastic resin composition of the present invention is used for molding, the higher the intrinsic viscosity of the thermoplastic copolyester resin is, the more preferable.

The method for producing the thermoplastic copolyester used in the present invention is not particularly limited, and a known method can be adopted. For example, the above-mentioned aromatic dicarboxylic acid component and, in some cases, an aliphatic dicarboxylic acid component are combined with a low molecular weight glycol component having a molecular weight of 250 or less and an aliphatic long chain dicarboxylic acid and / or an aliphatic long chain glycol having an average molecular weight of about 300 to 6000. It is possible to employ a method in which the components are directly esterified simultaneously or stepwise, or a method of transesterifying and then polymerizing is adopted. Also, a high or low molecular weight copolymer polyester and, in some cases, an average molecular weight of about 300 to 600
Aliphatic long-chain dicarboxylic acid of 0 and average molecular weight of about 300-6000
Transesterify the aliphatic long-chain glycol component of
Depending on the case, a method of carrying out the polymerization after that can also be adopted.

Further, for the dicarboxylic acid component, an ordinary ester such as an alkyl ester or an aryl ester can be used as an ester-forming derivative.

The vulcanizing agent used in the present invention is, for example, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, p-cymene hydroperoxide, diisopropylbenzene hydroperoxide. Peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cyclohexanone peroxide, methylcyclohexanone peroxide,
Peroxides such as 3,3,5-trimethylhexanone peroxide, dialkyl (aryl) peroxides such as di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, diacetylperoxide, dipropionyl peroxide, diisobutyryl Peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, bis- (3,
5,5-Trimethylhexanoyl) peroxide, benzoyl peroxide, m-toluyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxides such as peroxysuccinic acid, 2,2-di-t-butylperoxy Butane, 1,1-di-
t-butyl peroxycyclohexane, 1,1-di- (t-
Butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) ) Hexane-3,1,3-di- (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-
Dibenzoylperoxyhexane, 2,5-dimethyl-2,5
Peroxyketals such as -di- (peroxybensoyl) hexyne-3, n-butyl-4,4-bis- (t-butylperoxy) valerate, t-butylperoxyacetate, t-butylperoxyisobutyrate, t -Butyl peroxypivalate, t-butyl peroxy neodecanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy-2-ethyl hexanoate, (1,1,3, 3-tetramethylbutylperoxy)-
2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di- (t-butylperoxy) adipate, 2,5-dimethyl-2,5-di- (peroxy-2-ethylhexanoyl) ) Hexane,
Peroxyesters such as di- (t-butylperoxy) isophthalate, t-butylperoxymaleate, acetylcyclohexylsulphonyl peroxide, t-butylperoxyisopropyl carbonate, di-n-propylperoxydicarbonate, di- sec-Butyloxydicarbonate, di- (isopropylperoxy)
Dicarbonate, di- (2-ethylhexylperoxy) dicarbonate, di- (2-ethoxyethylperoxy) dicarbonate, di- (methoxyisopropylperoxy) dicarbonate, di- (3-methoxybutylperoxy) dicarbonate, di- (cyclohexylperoxy) dicarbonate , Peroxycarbonates such as bis- (4-t-butylcyclohexylperoxy) dicarbonate, organic peroxides such as acetylacetone peroxide, methyl ethyl ketone peroxide, ketone peroxides such as methyl isobutyl ketone peroxide, diazoaminobenzene, tetramethylene bis-
(Azidoformate), azo compounds, hexamethylenetetramine, acetaldehyde ammonia, aldehydes and ammonias such as n-butyraldehyde aniline, guanidines such as diphenylguanidine, di-o-tolylguanidine, 2-mercaptobenzothiazole, Dibenzothiazyl disulfide, thiazoles such as zinc salt of 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothiazyl sulfenamide, N-2-butyl-2-benzothiazyl sulfenamide, N- Oxydiethylene-2
-Sulfenamides such as benzothiazyl sulfenamide, thiurams such as tetramethylthiuram disulfide and tetraethyl thiuram disulfide, dithiocarbamates such as zinc dimethyldithiocarbamate and sodium diethyldithiocarbamate, zinc isopropylxanthogenate, butyl Zanthates such as zinc xanthate, thioureas such as ethylenethiourea, N, N'-diphenylthiourea, P-quinone dioxime, oximes such as P, P'-dibenzoylquinone dioxime, sulfurs, sulfur chloride, selenium , Inorganic vulcanizing agents such as zinc peroxide, tellurium, 4,
Organic sulfur compounds such as 4'-dithiodimorpholine, N, N'-dithio-bis- (hexahydro-2H-azepinone-2) and the like can be mentioned. Further, two or more of these compounds may be mixed and used.

The amount of the vulcanizing agent used is 0.1 to 10 depending on the type of the vulcanizing agent, based on 100 parts by weight of the thermoplastic copolyester.
It is appropriately selected within the range of parts by weight.

The thermoplastic resin composition of the present invention can be obtained by blending the above-mentioned thermoplastic copolyester and a vulcanizing agent. For example, a kneader, a kneader-ruder, a Banbury mixer or the like usually used for kneading can be used. It is also possible to use a simple melt extruder, in which the thermoplastic copolyester and the vulcanizing agent are put, and they are mixed and kneaded and melt-extruded. The resin composition of the present invention can be obtained by a simple operation using the above-mentioned simple device without using a special device. Also,
Suitable kneading and extrusion conditions are selected within a range that does not lose the thermoplasticity.

When the thermoplastic resin composition of the present invention is used for molding applications such as injection molding, extrusion molding, compression molding, etc., a method of molding the thermoplastic resin composition of the present invention and then vulcanizing by heating, or The thermoplastic resin composition of the present invention may be previously vulcanized to such an extent that the thermoplasticity is not lost, and a method such as molding may be employed. According to the latter method, not only the molding cycle and molding time can be shortened, but also the heating operation of the molded product, which is essential to the former method, can be omitted in some cases. On the other hand, in the former method, the performance can be further improved by vulcanization after molding.

The thermoplastic resin composition of the present invention as described above is preferably applied as a molded article such as automobile exterior parts, civil engineering, building materials, or an adhesive agent for metals, plastics, fibers, etc., which cannot be applied to conventional elastomers. You can When used as an adhesive, it can be used as a hot melt adhesive, a solvent type adhesive, or the like.

(Examples) Hereinafter, the present invention will be described more specifically with reference to Examples.
In the examples, “part” means “part by weight”.

The characteristic values in the examples are measured by the following methods.

(1) Melting point (° C) Using a DSC2C type manufactured by Perkin Elmer, the temperature was raised at 20 ° C / min and the melting peak temperature was measured.

(2) Tensile strength (kg / cm ² ) and elongation (%) Measured by JIS-K-6301 method.

(3) Weather resistance The sample was irradiated for 500 hours using a Sunshear In Weather Meter (Super Long Life manufactured by Suga Test Instruments Co., Ltd.),
The retention rate of the tensile strength or the adhesive strength of the sample after irradiation with respect to the sample before irradiation was evaluated.

(4) Vicat softening point (° C) Measured by the ASTM-D-1525 method.

Example 1 85 mol of dimethyl terephthalate, 15 mol of dimer acid having 36 carbon atoms (Emery Co., USA; Empor 1010), 140 mol of 1,4-butanediol, hydrogenated liquid polybutadiene glycol having an average molecular weight of about 1300 (Nippon Soda ( Co., Ltd .; GI-1
000) 5 mol and tetra-n-butynyl titanate 0.01 mol were added, and methanol produced by heating to 200 ° C. was distilled out of the system to carry out a transesterification reaction.

After the methanol was almost completely distilled off, the reaction product was transferred to a weight machine equipped with a stirrer, and the temperature was increased to a high vacuum of 0.1 to 0.3 mmHg while gradually increasing the degree of vacuum at 240 ° C for 30 minutes, followed by polycondensation for 4 hours. The reaction was carried out.

The obtained thermoplastic copolyester resin has an intrinsic viscosity
It had a melting point of 0.78, a melting point of 185 ° C, and a tensile strength of 325 kg / cm ² . This thermoplastic copolyester resin is referred to as resin (1).

100 parts of the above resin (1) and 2 parts of dicumyl peroxide (Kayakumil D manufactured by Nippon Kayaku Co., Ltd.) were placed in a kneader heated to 200 ° C. and kneaded for 5 minutes.

The vulcanized product was taken out from the kneader into a sheet and further cut into chips. The vulcanized product was molded into a dumbbell-shaped sample (according to JIS-K-6301) with an injection molding machine (J-100S manufactured by Japan Steel Works, Ltd.) and subjected to physical property measurement. The results are shown in Table 1.

Example 2 92 mol of dimethyl terephthalate, 8 mol of decamethylene dicarboxylic acid, 140 mol of 1,4-butanediol, and an average molecular weight of about 1
300 mol of hydrogenated liquid polybutadiene glycol (manufactured by Nippon Soda Co., Ltd .; GI-1000) (4 mol) and tetra-n-butyl titanate (0.01 mol) were added, and a thermoplastic copolyester resin was prepared in the same manner as in Example 1 below. Manufactured. The resulting thermoplastic copolyester resin has an intrinsic viscosity of 0.80,
The melting point was 197 ° C and the tensile strength was 383 kg / cm ² . This thermoplastic copolyester is referred to as resin (II).

100 parts of the above resin (II) and 0.3 part of benzoquinone dioxime (VULNOC GM manufactured by Ouchi Shinko Chemical Co., Ltd.) were kneaded in a melt extruder heated to 230 ° C., and dispensed into chips. Thereafter, a dumbbell-shaped sample was molded in the same manner as in Example 1 and subjected to physical property measurement. The results are shown in Table 1.

Comparative Example 1 The resin (I) obtained in Example 1 was molded into the same dumbbell-shaped sample as in Example 1 by the same injection molding machine as in Example 1, and the physical properties were measured. The results are shown in Table 1.

Comparative Example 2 The resin (II) obtained in Example 2 was formed into the same dumbbell-shaped sample as in Example 1 by the same injection molding machine as in Example 1 and subjected to physical property measurement. The results are shown in Table 1.

Comparative Example 3 80 mol of dimethyl terephthalate, 20 mol of decamethylene dicarboxylic acid, 140 mol of 1,4-butanediol and tetra-n-
A thermoplastic copolyester resin was produced in the same manner as in Example 1 from 0.01 mol of butyl titanate. The thermoplastic polymerized polyester resin obtained has an intrinsic viscosity of 0.82 and a melting point of 1
The tensile strength was 80 ° C and the tensile strength was 311 kg / cm ² . This thermoplastic copolyester is referred to as resin (III).

20 parts of 100 parts of this resin (III) and 2 parts of dicumyl peroxide
The mixture was placed in a kneader heated to 0 ° C and kneaded for 5 minutes. Then, the vulcanized product was taken out from the kneader into a sheet shape and further cut into chips. Thereafter, a dumbbell-shaped sample was molded in the same manner as in Example 1 and subjected to physical property measurement. The results are shown in Table 1.

Comparative Example 4 Dimethyl terephthalate 100 mol, 1,4-butanediol 140
A thermoplastic copolyester resin was produced in the same manner as in Example 1 using 20 mol of polyoxytetramethylene glycol having an average molecular weight of 1000 and 0.01 mol of tetra-n-butyl titanate. The thermoplastic copolyester resin obtained has an intrinsic viscosity of 0.80, a melting point of 190 ° C and a tensile strength of 420 kg /
It was cm ² . This thermoplastic copolyester resin is referred to as resin (IV).

2 parts of 100 parts of this resin (IV) and 2 parts of benzoquinone dioxime
The mixture was placed in a kneader heated to 00 ° C and kneaded for 5 minutes. The vulcanized product was taken out from the kneader into a sheet and further cut into chips. Thereafter, a dumbbell-shaped sample was molded in the same manner as in Example 1 and subjected to physical property measurement. The results are shown in Table 1.

As shown in Table 1, the thermoplastic resin composition comprising the thermoplastic copolyester resin of the present invention and the vulcanizing agent has excellent heat resistance and mechanical strength only by heating, and also has weather resistance and flexibility. It can be seen that it exhibits highly elastomeric properties.

On the other hand, only thermoplastic copolyester resin (Comparative Example 1,
In 2), it can be seen that the mechanical strength and heat resistance are lower than those obtained by vulcanizing the thermoplastic resin composition of the present invention. Also,
A composition comprising a thermoplastic copolymerized polyester resin containing neither an aliphatic long-chain dicarboxylic acid having an average molecular weight of about 350 to 6000 or an aliphatic long-chain glycol having an average molecular weight of about 350 to 6000 and a vulcanizing agent (Comparative Example 3, In 4), it can be seen that the self-crosslinking of the thermoplastic copolyester resin does not occur and the mechanical strength and heat resistance are not improved.

[Note] DKP means dicumyl peroxide, and BQO means benzoquinone dioxime.

Example 3 5 mol of dimethyl terephthalate, 15 mol of isophthalic acid, 5 mol of hydrogenated liquid polybutadiene dicarboxylic acid having an average molecular weight of about 1300 (CI-1000 manufactured by Nippon Soda Co., Ltd.) and 140 mol of 1,4-butanediol tetra-. n-Butyl titanate 0.0
1 mol was added and the methanol produced by heating to 200 ° C was distilled out of the system to carry out a transesterification reaction. After the methanol was almost completely distilled off, the reaction product was transferred to a polymerization vessel equipped with a stirrer, and the vacuum was gradually raised at a temperature of 240 ° C for 30 minutes to create a high vacuum of 0.1 to 0.3 mmHg, and then for 4 hours. A polycondensation reaction was performed.

The obtained thermoplastic copolyester resin has an intrinsic viscosity
It had a melting point of 0.75, a melting point of 188 ° C, and a tensile strength of 360 kg / cm ² . This thermoplastic copolyester resin is referred to as resin (V).

This resin (V) was molded into a dumbbell-shaped sample in the same manner as in Example 1, and the strength, elongation, weather resistance and Bicatus softening point were measured. The results were 360 kg / cm ² , 425%, 84% and 135%, respectively.
It was ℃.

100 parts of the above resin (V) and 1 part of dicumyl peroxide (Kayakumil D manufactured by Nippon Kayaku Co., Ltd.) were dispensed into chips with a melt extrusion device heated to 200 ° C. Thereafter, a dumbbell-shaped sample was formed in the same manner as in Example 1 and the strength, elongation, weather resistance and Bicatus softening point were measured.

As a result, the strength was 495 kg / cm ² , the elongation was 400%, the weather resistance was 88%, and the Vicat softening point was 174 ° C. The vulcanized product of the thermoplastic copolyester resin (V) of the present invention was compared to the unvulcanized product. It had excellent heat resistance, mechanical strength, and weather resistance.

(Effect of the invention) The resin composition of the present invention has an average molecular weight of about 300 as described above.
~ 6000 aliphatic long-chain dicarboxylic acids and average molecular weight about 300
Since it consists of a specific thermoplastic copolyester resin containing at least one of aliphatic long-chain glycols up to 6000 as a component and a vulcanizing agent, it has excellent solvent resistance, melt stability and weather resistance, and also has high heat resistance and heat resistance. Good balance between mechanical strength and flexibility.

Claims (1)

[Claims] 1. An acid component comprising (a) 40 to 100 mol% of aromatic dicarboxylic acid and 0 to 60 mol% of aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid having a molecular weight of about 250 or less,
(B) a glycol component consisting of a low molecular weight glycol having a molecular weight of about 250 or less and (c) an aliphatic long-chain dicarboxylic acid having an average molecular weight of about 300 to 6000 and / or a total glycol component of 1 to 30 mol% based on the total acid component. On the other hand, it comprises a thermoplastic copolymerized polyester (A) having an intrinsic viscosity of at least 0.3 consisting of an aliphatic long-chain glycol having an average molecular weight of about 300 to 6000 of 1 to 30 mol% and a vulcanizing agent (B). The ratio of the polymerized polyester (A) and the vulcanizing agent (B) is such that the vulcanizing agent (B) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic copolyester (A). Thermoplastic resin composition. However, the intrinsic viscosity is phenol: tetrachloroethane =
Measured at 20 ° C in a 1: 1 (weight ratio) mixed solvent.