JPH0678478B2 - Thermoplastic resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition which is flexible and has excellent heat resistance, mechanical strength, weather resistance, water resistance and moisture resistance. .

(Prior Art) (Problems to be Solved by the Invention) In 1965, Shell Co. of the United States of America used styrene-butadiene block copolymers (SBS) and styrene-isoprene block copolymers as elastomers that did not require a vulcanization process. Polymers (SIS) were announced, but they have rubber elasticity at normal temperature and are easily plasticized at high temperature and can be molded, so they have been widely used due to their characteristics. . Next, in 1972, Uniroyal, Inc. of the United States announced a thermoplastic polyolefin elastomer. This thermoplastic polyolefin elastomer has excellent weather resistance, cold resistance, and low cost, so it is often used for automobile bumpers and the like. It has been.

However, since these SBS, SIS and thermoplastic polyolefin elastomers have low heat resistance and mechanical strength,
It has a drawback that it cannot be used in a field where the environment temperature is high and strength is required.

On the other hand, in the same year, DuPont USA announced a thermoplastic polyester elastomer. This thermoplastic polyester elastomer has brands with different heat resistance and mechanical strength, but brands with excellent heat resistance and mechanical strength lack flexibility, while brands with excellent flexibility have heat resistance, There is a problem that weather resistance and moisture resistance are poor, so that it is difficult to use for outdoor applications and the applications are limited.

On the other hand, it has been proposed to use partially vulcanized butyl rubber as a base polymer for heat-resistant hot melt adhesives or sealants, and attempts have been made to improve the adhesiveness at high temperatures by mixing various compounding agents (polyamide, polypropylene). It has been done. However, with this partially vulcanized butyl rubber, it was not possible to obtain both low temperature adhesiveness and high temperature adhesiveness at the same time.

It is known that increasing the aromatic dicarboxylic acid component is effective in increasing the mechanical strength of the thermoplastic copolyester elastomer, but on the other hand,
There is a drawback that the flexibility of the resin becomes poor. On the other hand, it is also known to copolymerize a long chain ester segment in order to give flexibility to a thermoplastic copolyester elastomer, but in this case, there is a problem that heat resistance and mechanical strength are lowered. .

In order to solve the above problems, the present inventors have made use of a specific thermoplastic copolyester elastomer containing an aliphatic long-chain glycol having an average molecular weight of about 350 to 6000 and a rubber component, and are used for molding and adhesives. A composition suitable for was previously filed.

Since this composition is excellent in mechanical strength, flexibility, weather resistance, hot water resistance, and moisture resistant adhesiveness, it can solve the conventional problems, but it has heat resistance and mechanical strength. Further improvements in various properties have been desired.

The present invention is intended to provide a composition having further excellent properties.

That is, the first object of the present invention is to provide a thermoplastic resin composition which can be easily vulcanized only by heating to form a vulcanized product having excellent heat resistance, mechanical strength, cold resistance, water resistance and moisture resistance. To provide things.

A second object of the present invention is to produce a vulcanized product which retains thermoplasticity even after vulcanization and is excellent in heat resistance, mechanical strength, cold resistance, water resistance and moisture resistance. It is to provide a thermoplastic resin composition.

(Means for Solving Problems) As a result of intensive studies for solving such problems, the present inventors have found that a thermoplastic resin composition comprising a specific thermoplastic copolyester resin, a rubber component and a vulcanizing agent. The inventors arrived at the present invention by finding that the objects have the above characteristics.

That is, the present invention provides (A) aromatic dicarboxylic acid 40 to 10
Aliphatic long-chain glycol 1 with 0 mol% and aliphatic dicarboxylic acid 0-60 mol% as an acid component, low molecular weight glycol 70-99 mol% with a molecular weight of 250 or less, and average molecular weight 350-6000
A thermoplastic copolyester resin having a glycol component of ˜30 mol% and an intrinsic viscosity [measured in a mixed solvent of phenol: tetrachloroethane = 1: 1 (weight ratio) at 20 ° C.] of at least 0.2, ( B) composed of a rubber component and (C) a vulcanizing agent, and the weight ratio of (A) and (B) is 30 to 95:70 to 5, and the weight ratio of (C) is (A). )
The gist is a thermoplastic resin composition which is 0.1 to 10 parts by weight with respect to 100 parts by weight as the total of (1) and (B).

Next, the present invention will be described in detail.

The thermoplastic copolyester resin used in the present invention comprises an aromatic dicarboxylic acid 40 to 100 mol% and an aliphatic dicarboxylic acid 0 to 60 mol% as an acid component, and a low molecular weight glycol having a molecular weight of about 250 or less 70 to 99 mol%, An aromatic long-chain glycol having an average molecular weight of about 350 to 6000 is used as a glycol component, and aromatic dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid. Although one or more of these can be used, terephthalic acid or a mixture of terephthalic acid and isophthalic acid is particularly preferably used.

The aromatic dicarboxylic acid component increases the softening point of the thermoplastic copolyester resin, contributes to heat resistance and contributes to increasing the mechanical strength, but the composition ratio in the acid component is 40 to 100. Mol%.

The range of the suitable composition ratio of the aromatic dicarboxylic acid component is somewhat different depending on the use of the thermoplastic resin composition of the present invention, and is 60 to 100 mol%, particularly 70 to 95 for molding use.
Mol% is preferred, 40-90 mol% for adhesive applications,
Particularly, the range of 50 to 80 mol% is preferable.

If the proportion of the aromatic dicarboxylic acid component is less than 40 mol%, the mechanical strength and heat resistance of the thermoplastic copolyester resin will be low. Therefore, a molded article using the thermoplastic resin composition of the present invention Mechanical strength and heat resistance are 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, brassylic acid, hexadecanedioic acid, eicosanedioic acid. One or more selected from saturated aliphatic dicarboxylic acids such as acids and docosandioic acid and / or their isomers having a branch, and dimer acids consisting of dimers of unsaturated fatty acids having 10 or more carbon atoms, Can be used. A preferred example of the dimer acid is Versadim 288 (manufactured by Henkel), which is a dimer of linoleic acid, and Empol 104.
(Made by Emery Co., Ltd.) and the like. Furthermore, the hydrogenated dimer acid obtained by hydrogenating the double bond in the dimer acid has excellent thermal stability and can be preferably used.

The aliphatic dicarboxylic acid component is appropriately selected and used for the purpose of adjusting the melting point and the melt viscosity of the thermoplastic copolyester resin and improving the compatibility of the thermoplastic copolyester resin and the rubber component. It The composition ratio of the acid component is 0 to 60 mol%.

Examples of the low molecular weight glycol having a molecular weight of about 250 or less include ethylene glycol, trimethylene glycol, 1,4
-Butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,9-nonanediol and other aliphatic polyols and / or their branched isomers, diethylene glycol, triethylene glycol, etc. Alicyclic glycols such as oxyalkylene glycol and cyclohexanedimethanol, which are used alone or as a mixture of two or more kinds. Its composition ratio in the glycol component is 7
It is 0 to 99 mol%. Further, the molecular weight of the low-molecular-weight glycol is preferably about 250 or less, and beyond that, the softening point of the obtained resin is lowered, the resin becomes flexible, the repulsion force is lost, and the heat resistance is deteriorated.

Examples of the aliphatic long-chain glycol having an average molecular weight of about 350 to 6000 include 1,2-polybutadiene glycol, 1,4-polybutadiene glycol, copolymers or mixtures thereof, hydrogenated products thereof, polyisoprene glycol and water thereof. Additives and polyolefin glycols are preferably used, but those capable of being crosslinked by vulcanization are particularly preferable.

The aliphatic long-chain glycol having an average molecular weight of about 350 to 6000 not only enhances the compatibility between the thermoplastic copolyester resin and the rubber component, but also plays an important role in forming a network structure by vulcanization. That is, when the thermoplastic copolymerized polyester resin and the rubber component are vulcanized in a compatible state, a network structure is generated in that state, so that the thermoplastic copolymerized polyester resin exists in a complicated state in the network structure. However, the mechanical strength and heat resistance of the vulcanizate of the thermoplastic resin composition are improved. On the other hand, when a thermoplastic copolymerized polyester resin that is incompatible with the rubber component is blended with the rubber component and vulcanized, only the rubber component is vulcanized, and therefore the rubber component having a network structure and the thermoplastic copolymer Since the polyester resins exist separately in a phase-separated state, the mechanical strength and heat resistance of the vulcanizate of the thermoplastic resin composition are not improved even if the rubber component has a network structure.

Further, when a vulcanizable component is used as the aliphatic long-chain glycol having an average molecular weight of about 350 to 6000, the cross-linked crosslink between the copolymerized polyester resin and the rubber component of the vulcanized thermoplastic resin composition is used. A mesh structure is generated.

Therefore, in such a case, mechanical strength and heat resistance of the vulcanized product of the thermoplastic resin composition are further improved, which is preferable.

The amount of the aliphatic long-chain glycol having an average molecular weight of about 350 to 6000 used is 1 to 30 mol% of the total glycol component. 30 mol%
If it exceeds, the mechanical strength and heat resistance of the thermoplastic resin composition deteriorate. On the other hand, if it is less than 1 mol%, the compatibility between the thermoplastic copolyester resin and the rubber component becomes poor, and the mechanical strength and heat resistance of the vulcanizate of the thermoplastic resin composition are not improved.

The average molecular weight of the aliphatic long-chain glycol is about 35
0 to 6000, particularly 500 to 4500 are preferred. If the molecular weight is too large, the compatibility becomes poor and it becomes difficult to polymerize the thermoplastic copolyester resin. On the contrary, when the molecular weight is less than 350, not only the flexibility of the obtained thermoplastic copolyester resin is deteriorated but also the compatibility with the rubber component is poor, so that a vulcanized product of the thermoplastic resin composition using the same is obtained. Neither mechanical strength nor heat resistance is improved.

The intrinsic viscosity of the thermoplastic copolyester resin used in the present invention is at least 0.2 when measured at 20 ° C. when dissolved in a 1: 1 (weight ratio) mixed solvent of phenol / tetrachloroethane. When the intrinsic viscosity is less than 0.2, the strength of the resin becomes low and brittle due to the low molecular weight, and a problem occurs in the strength of the composition vulcanized after blending with the rubber component. Therefore, the thermoplastic resin composition of the present invention is used for molding. It is difficult to use it for adhesives. 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. However, when it is used for adhesives, especially for hot melt adhesives, if one with an intrinsic viscosity of more than 1.6 is used,
Since the melt viscosity becomes too high and it becomes difficult to use, less than 1.6 is preferable.

The method for producing the thermoplastic copolyester resin used in the present invention is not particularly limited, and known ordinary methods can be adopted. For example, the aromatic dicarboxylic acid component and optionally the aliphatic dicarboxylic acid component may have a molecular weight of about 250
Following low molecular weight glycol component and average molecular weight about 350
It is possible to employ a method in which the aliphatic long-chain glycol component of up to 6000 is directly or stepwise directly esterified or subjected to an ester exchange reaction and then polymerized. Also, a method in which a high-molecular weight or low-molecular weight copolymer polyester, an aliphatic dicarboxylic acid in some cases, and an aliphatic long-chain glycol component having an average molecular weight of about 350 to 6000 are subjected to transesterification reaction, and then polymerization is performed in some cases. Can also be adopted. In the polymerization or transesterification reaction, various known catalysts, stabilizers, modifiers, additives, etc. may be used.

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

As the rubber component in the present invention, those conventionally used as molding materials or adhesive base polymers are used. Examples thereof include polyisoprene, polyisobutylene, butyl rubber, halogenated butyl rubber, polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene. Examples include ethylene / butylene / styrene block copolymer, ethylene / propylene / diene copolymer, chlorosulfonated polyethylene, chlorinated polyethylene, acrylic rubber, epichlorohydrin rubber, EVA, polyurethane rubber and natural rubber.

The blending ratio of the thermoplastic copolyester resin and the rubber component in the present invention is such that the thermoplastic copolyester resin 30
The rubber component is in the range of 70 to 5% by weight with respect to 95% by weight. When the blending ratio of the thermoplastic copolyester resin is less than 30% by weight, the mechanical strength and heat resistance of the vulcanizate of the thermoplastic resin composition are not improved, and when it exceeds 95% by weight, the thermoplastic resin composition is The vulcanizate has poor flexibility, low temperature properties, and adhesion.

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. Oxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cyclohexanone peroxide, methylcyclohexanone peroxide, 3,3,5
-Peroxides such as trimethylhexanone peroxide, dialkyl (allyl) peroxides such as di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, diacetyl peroxide,
Dipropionyl peroxide, diisobutyl 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-butylperoxybutane, 1 , 1-di-t
-Butylperoxycyclohexane, 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-di-
(Peroxybenzoyl) hexyne-3, n-butyl-4,4
-Bis- (t-butylperoxy) valerate and other peroxyketals, t-butylperoxyacetate, t
-Butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxy neodecanoate, t
-Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2-ethylhexanoate,
(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, di-
Peroxyesters such as (t-butylperoxy) isophthalate, t-butylperoxymaleate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyisopropyl carbonate, di-n-propylperoxydicarbonate, di-sec-butylperoxy Dicarbonate, di- (isopropyloxy) dicarbonate, di- (2-ethylhexylperoxy)
Dicarbonate, di- (2-ethoxyethylperoxy) dicarbonate, di- (methoxyisopropylperoxy) dicarbonate, di- (3-methoxybutylperoxy) dicarbonate, di- (cyclohexylperoxy) dicarbonate, bis- (4-t-butylcyclohexyl) Peroxy carbonates such as (peroxy) dicarbonate, organic peroxides such as ketone peroxides such as acetylacetone peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, azo compounds such as diazoaminobenzene, tetramethylene bis- (azidoformate), Aldehydes and ammonias such as hexamethylenetetramine, acetaldehyde ammonia, n-butyraldehyde aniline, diphenylguanine Emissions, guanidines such as di--o- tolyl guanidine, 2-mercaptobenzothiazole,
Dibenzothiazyl disulfide, thiazoles such as zinc salt of 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothiazylsulfenamide, N-Z-butyl-2-benzothiazylsulfenamide, N-oxydiethylene 2-Sulfenamides such as benzothiazylsulfenamide, thiurams such as tetramethylthiuram disulfide and tetraethylthiuram disulfide, dithiocarbamates such as zinc dimethyldithiocarbamate and sodium diethyldithiocarbamate,
Zandates such as zinc isopropylxanthate, zinc butylxanthate, ethylenethiourea, N, N'-
Thioureas such as diphenylthiourea, P-quinonedioximes, oximes such as P, P′-dibenzoylquinonedioximes, sulfurs, sulfur chloride, selenium, zinc peroxide,
Inorganic vulcanizing agents such as tellurium, organic sulfur compounds such as 4,4'-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.
At times, vulcanization accelerating aids and activators are also used in combination.

The amount of the vulcanizing agent used is appropriately selected in the range of 0.1 to 10 parts by weight, depending on the type of the vulcanizing agent, with respect to 100 parts by weight of the total amount of the thermoplastic copolyester resin and the rubber component.

The thermoplastic resin composition of the present invention can be produced by various production methods. For example, a kneader which is often used for kneading,
Rubber component, thermoplastic copolyester resin for kneader ruder, melt extruder, Banbury mixer, etc.
It is manufactured by adding a vulcanizing agent, mixing, kneading, and extruding. Suitable kneading melt extrusion conditions are selected within a range in which the thermoplastic resin composition is not vulcanized.

When the thermoplastic resin composition of the present invention is used for molding such as injection molding, extrusion molding and compression molding, a method of molding the thermoplastic resin composition of the present invention and then heating and vulcanizing it, or A method such as a method in which the thermoplastic resin composition of the present invention is vulcanized to such an extent that thermoplasticity is not lost and then this is molded can be employed.

The latter method has the advantage that 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, the former method can improve the performance by vulcanization after molding.

When the thermoplastic resin composition of the present invention is used for molding, an antioxidant to be mixed with a usual molding resin,
Heat stabilizer, flame retardant, flame retardant, UV absorber, pigment, plasticizer, glass fiber, other reinforcing agent, carbon black,
Various additives such as alumina, silica gel, clay and the like can be blended as necessary.

When the thermoplastic resin composition of the present invention is used for adhesion, a method of applying it to an adherend in a molten state by using a general hot melt applicator or a roll coater, powder, chip, tape , String,
After being formed into various forms such as film or wave, it is sandwiched between the adherends and then heated at a temperature above the softening point of the adhesive to fuse the adherends. Various methods such as a method used for improving the surface of a base material, a method of using as a hot melt adhesive which is melted in a solvent, applied to a base material and dried, and then adhered by reheat activation can be adopted.

In any of these cases, the thermoplastic resin composition of the present invention can be used for adhesion and then vulcanization by heating, or using a vulcanized product vulcanized to such an extent that the thermoplasticity is not lost, The above operation can also be performed.

When the adhesive is heated and vulcanized after bonding, the adhesive strength and heat resistance are improved. On the other hand, when using a vulcanized product that has been previously vulcanized,
It has the advantage that the vulcanization operation after bonding can be shortened or even omitted in some cases.

When the thermoplastic resin composition of the present invention is used for adhesion purposes, an adhesion promoter resin, a plasticizer, an antioxidant, a filler and the like, which are compounded in a usual rubber component, can be contained as necessary. .

In particular, since the thermoplastic copolyester resin used in the present invention has excellent compatibility with the tackifier resin, the thermoplastic resin composition comprising the thermoplastic copolyester resin also has a very good dispersion state and excellent adhesive strength. Is obtained.

(Examples) Hereinafter, the present invention will be described more specifically with reference to Examples.
In addition, "part" in an example means a "weight part."

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

(1) Intrinsic viscosity Measured at 20 ° C. in a mixed solvent of phenol: tetrachloroethane = 1: 1 (weight ratio).

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

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

(4) Hot water resistance The sample was immersed in boiling water and taken out at regular intervals to measure the tensile strength, and the number of days until the initial value reached 50% was investigated.

(5) Weather resistance A sunshine weather meter (Super Long Life manufactured by Suga Test Instruments Co., Ltd.) was used to evaluate the retention of tensile strength or adhesive strength of the sample after irradiation for 500 hours.

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

(7) Softening point (° C) Measured by the ring and ball method according to JIS JAI-7.

(8) Shear creep softening temperature (℃) A test piece (kraft paper / kraft paper) bonded with a bonding area of 2.5 cm × 2.5 cm is loaded with 300 g in the shear direction and heated at 2 ℃ / 5 minutes. Then, the temperature when the weight fell was measured.

(9) Melt viscosity (cps) Measured at a temperature of 200 ° C. using a Brookfield Thermosel System HBTD type (manufactured by Brookfield Engineering Laboratories, Inc., USA).

(10) Peel adhesion strength (kg / 25 mm) According to JIS K-6854, the peel adhesion strength at room temperature (20 ° C) was measured at a peel speed of 50 mm / min.

The adhesion conditions are as follows.

(A) Substrate: Aluminum plate (0.5 mm thickness) / Aluminum plate (0.5 mm thickness) (b) Bonding: Adhesive with hot melt applicator
It was heated and melted at 200 ° C, applied to an adherend with a width of 25 mm and a wrap length of 50 mm, and pressure-bonded.

Example 1 85 moles of dimethyl terephthalate, 15 moles of dimer acid having 36 carbon atoms (Emery Corporation, USA; Empol 1010), 140 moles of 1,4-butanediol, hydrogenated liquid polybutadiene glycol having an average molecular weight of about 1300 (Nippon Soda Co., Ltd.) Made; GI-100
0) 5 mol and tetra-n-butyl titanate 0.01 mol were added, and methanol generated 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 bring it to a high vacuum of 0.1 to 0.3 mmHg, and then for 4 hours. A polycondensation reaction was performed.

The thermoplastic copolyester resin (I) thus obtained had an intrinsic viscosity of 0.78, a melting point of 185 degrees and a tensile strength of 325 kg / cm ² .

70 parts of this thermoplastic copolyester resin (I), 30 parts of ethylene-propylene-diene copolymer (EPDM) (Nippon Synthetic Rubber Co., Ltd., EP-43) and dicumyl peroxide (Nippon Kayaku Co., Ltd.) , Kayak mill D) 0.5 part 140
The mixture was placed in a kneader heated to ℃ and kneaded for 8 minutes. The temperature of the contents reached 200 ° C for 2 minutes after the start of kneading. Simultaneously with the end of the kneading, 1 part of pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Ciba Geigy, Irganox 1010) was added as an antioxidant. Kneading was continued for 1 minute to obtain a vulcanized product.

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 (Nippon Soda Co., Ltd .; GI-1000) (4 mol) and tetra-n-butyl titanate (0.01 mol) were added, and a thermoplastic copolymer polyester resin (II) was prepared in the same manner as in Example 1. Manufactured. The resulting thermoplastic copolyester resin (II) has an intrinsic viscosity of 0.
The melting point was 80, the melting point was 197 ° C, and the tensile strength was 383 kg / cm ² .

80 parts of this thermoplastic copolyester resin (II), 20 parts of butyl rubber (Japan Synthetic Rubber Co., Ltd., Butyl065) and 0.8 parts of benzoquinone dioxime (Ouchi Shinko Chemical Co., Ltd., VULNOC GM) were heated to 140 ° C. It was placed in a kneader and kneaded for 8 minutes. The temperature of the contents is 2 minutes after the kneading starts
It reached 200 ° C. Simultaneously with the end of kneading 2,4 as an antioxidant
-Bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine (Ciba Geigy, Irganox 565) 1.6 parts was added, and Kneading was continued for 1 minute to obtain a vulcanized product.

The vulcanized product was taken out from the kneader into a sheet and further cut into chips. This vulcanizate was dumbbell-shaped sample (JIS K) with an injection molding machine (same as in Example 1).
(According to −6301) and subjected to physical property measurement. The results are shown in Table 1.

Comparative Example 1 70 parts of the thermoplastic copolymerized polyester resin (I) obtained in Example 1, 30 parts of a copolymer of ethylene-propylene-diene (Japan Synthetic Rubber Co., Ltd., EP-43) and an antioxidant Pentaerythrityl-tetrakis [3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate] (Ciba Geigy, Irganox 1010) 1
The parts were placed in a kneader preheated to 140 ° C and kneaded for 10 minutes.

The mixed composition was taken out from the kneader into a sheet shape and further cut into chips. This composition was dumbbell-shaped sample (JIS
(According to K-6301) and subjected to physical property measurement. The results are shown in Table 1.

Comparative Example 2 80 parts of the thermoplastic copolyester resin (II) obtained in Example 2 and butyl rubber (Nippon Synthetic Rubber Co., Ltd., But
yl 065) and 2,4-bis- (n as an antioxidant
-Octylthio) -6- (4-hydroxy-3,5-di-
1.6 parts of t-butylanilino) -1,3,5-triazine (Ciba Geiger, Irganox 565) were added, and kneading was continued for 1 minute.

The mixed composition was taken out from the kneader into a sheet shape and further cut into chips. This composition was dumbbell-shaped sample (JIS
(According to K-6301) and subjected to physical property measurement. The results are shown in Table 1.

Comparative Example 3 Dimethyl terephthalate 100 mol, 1,4-butanediol 140
A thermoplastic copolyester resin (IV) was produced in the same manner as in Example 1 using 20 mol of polyoxytetramethylene glycol having an average molecular weight of about 1000 and 0.01 mol of tetra-n-butyl titanate. The thermoplastic copolyester resin (IV) obtained had an intrinsic viscosity of 0.80, a melting point of 190 ° C,
The tensile strength was 420 kg / cm ² .

70 parts of this thermoplastic copolyester resin (IV), 30 parts of a copolymer of ethylene-propylene-diene (Nippon Synthetic Rubber Co., Ltd., EP-43) and dicumyl peroxide (Nippon Kayaku Co., Ltd., Kayacum Mill D) ) 0.5 part in Example 1
Kneading was carried out in the same manner as above to obtain a vulcanized product, which was molded by an injection molding machine and subjected to physical property measurement. The results are shown in Table 1.

Comparative Example 4 80 mol of dimethyl terephthalate, 20 dimethyl isophthalate
A thermoplastic copolyester resin (V) was produced in the same manner as in Example 1, using 20 mol of 1,6-hexanediol, 120 mol of 1,4-butanediol and 0.01 mol of tetra-n-butyl titanate. . The thermoplastic copolyester resin (V) thus obtained had an intrinsic viscosity of 0.75, a melting point of 186 ° C. and a tensile strength of 475 kg / cm ² .

80 parts of this thermoplastic copolyester resin (V), 20 parts of butyl rubber (Nippon Synthetic Rubber Co., Ltd., Butyl065) and 0.8 part of benzoquinone dioxime (Ouchi Shinko Chemical Co., Ltd., VULNOC GM) were used as in Example 2. And knead
A vulcanized product was obtained, molded with an injection molding machine, 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, the rubber component and the vulcanizing agent is excellent in heat resistance and mechanical strength only by heating, and further, in hot water resistance. , It is understood that it exhibits elastomeric properties with excellent weather resistance and flexibility.

On the other hand, it can be seen that the composition comprising the thermoplastic copolyester resin and the rubber component has lower mechanical strength, heat resistance and hot water resistance than those obtained by vulcanizing the thermoplastic resin composition of the present invention. Further, in a composition comprising a thermoplastic copolymer polyester resin having an average molecular weight of about 350 to 6000 and not containing an aliphatic long-chain glycol, a rubber component and a vulcanizing agent, the compatibility between the thermoplastic copolymer polyester resin and the rubber component is high. Since it was bad, only the rubber component was vulcanized even if it was vulcanized, and not only the strength and elongation of the vulcanized product, but also the heat resistance and hot water resistance were poor and the flexibility was not improved.

Example 3 70 mol of dimethyl terephthalate, 10 dimethyl isophthalate
Mol, decamethylenedicarboxylic acid 20 mol, 1,4-butanediol 140 mol, hydrogenated liquid polybutadiene glycol having an average molecular weight of about 1300 10 mol, and tetra-n-butyl titanate 0.01 mol were added, and the same procedure as in Example 1 was conducted. To produce a thermoplastic copolyester resin (III). The thermoplastic copolyester resin (III) thus obtained had an intrinsic viscosity of 0.65, a B & R softening point of 180 ° C. and a tensile strength of 168 kg / cm ² .

40 parts of this thermoplastic copolyester resin (III),
Styrene-isoprene-styrene block copolymer (Shell Chemical Co., TR-1107) 60 parts and t-butyl cumyl peroxide 0.3 parts, triallyl isocyanurate
0.3 part (vulcanization aid) was put into a kneader heated to 140 ° C., and kneaded for 8 minutes for vulcanization. The temperature of the contents reached 200 ° C for 2 minutes after the start of kneading. Simultaneously with the completion of kneading, 2,2-thio-diethylenebis- [3- (3,5-
1 part of (di-t-butyl-4-hydroxyphenyl) propionate] (Ciba Geigy, Irganox 1035) was added, and kneading was continued for 1 minute, and then the vulcanized product was taken out into a sheet.

To 100 parts of this vulcanized product, 75 parts of ester of hydrogenated rosin (Hercules, Foral 85) as a tackifier and alicyclic hydrocarbon resin (Arakawa Chemical Co., Ltd., Alcon P-
90) 75 parts were put into a kneader and heated and stirred to prepare a hot melt adhesive.

The mixed state of the obtained hot melt adhesive was good.

The B & R softening point, melt viscosity, shear creep softening temperature, and peel adhesion strength of an aluminum plate of this hot melt adhesive were measured. The results are shown in Table 2.

Example 4 40 parts of thermoplastic copolymerized polyester resin (III), 60 parts of styrene-isoprene-styrene block copolymer (Shell Chemical Co., Ltd., TR-1107), 0.5 part of t-butyl cumyl peroxide, triallyl isocyanate 0.3 part of nurate was kneaded at 140 ° C. for 1 minute to obtain a composition. Next, to 100 parts of this composition, 75 parts of ester of hydrogenated rosin (Hercules, Foral 85) and 75 parts of alicyclic hydrocarbon resin (Arakawa Chemical Industry Co., Ltd., Alcon P-90) were put in a kneader. Then, the mixture was heated and stirred to prepare an unvulcanized hot melt adhesive.

The B & R softening point, melt viscosity, and the adhesion to the adherend of the obtained hot melt adhesive were measured, and the shear creep softening temperature and the peel adhesion strength to an aluminum plate after vulcanization at 180 ° C. for 5 minutes under pressure were measured. The results are shown in Table 2.

Comparative Example 5 40 parts of thermoplastic copolyester resin (III), 60 parts of styrene-isoprene-styrene block copolymer (Shell Chemical Co., TR-1107) and 1 part of antioxidant (Irganox 1035) In the same manner as in Example 3, kneading was performed to obtain a composition. Next, to 100 parts of this composition, 75 parts of ester of hydrogenated rosin (Hercules, Foral 85) as a tackifier and alicyclic hydrocarbon resin (Arakawa Chemical Industry Co., Ltd., Alcon P-90) 75 Parts were added and heated and stirred to prepare a hot melt adhesive.

The B & R softening point, melt viscosity, shear creep softening temperature, and peel adhesion strength to an aluminum plate of the obtained hot melt adhesive were measured. The results are shown in Table 2.

As shown in Table 2, an adhesive composition obtained by blending a vulcanized product of the thermoplastic resin composition of the present invention with a tackifier (Example 3)
Is higher in softening point and higher in heat resistance (shear creep softening point) than the adhesive composition (Comparative Example 5) in which the same adhesion-imparting agent is simply added to the unvulcanized thermoplastic resin composition. Since it was remarkably improved and the melt viscosity was almost unchanged, favorable results were obtained as a hot-melt type adhesive.

It also has excellent adhesion to aluminum plates.

Furthermore, the unvulcanized adhesive composition (Example 4) has a low softening point in the unvulcanized state, but the vulcanization after adhesion increases the softening point, and the heat resistance is significantly improved. The adhesiveness to aluminum plate also shows excellent value.

(Effect of the invention) In the thermoplastic resin composition of the present invention, since the aliphatic long-chain glycol having an average molecular weight of 350 to 6000 is used as the glycol component of the thermoplastic copolyester resin constituting the thermoplastic resin composition, Good compatibility between the thermoplastic copolyester resin and the rubber component. Therefore, a vulcanizate having excellent heat resistance, mechanical strength, cold resistance, water resistance, and moisture resistance can be easily obtained only by heating the thermoplastic resin composition of the present invention.

Therefore, the resin composition of the present invention is preferably used for molded articles such as automobile exterior parts and civil engineering building materials, which cannot be applied to conventional elastomers, or for adhesion to metals, plastics, fibers and the like.

Claims (1)

[Claims] (A) An aromatic dicarboxylic acid of 40 to 100 mol% and an aliphatic dicarboxylic acid of 0 to 60 mol% as an acid component, and a low molecular weight glycol having a molecular weight of about 250 or less 70 to 99 mol% and an average molecular weight of about 350. To 6000 aliphatic long-chain glycol 1 to 30 mol% as a glycol component and intrinsic viscosity [phenol: tetrachloroethane = 1: 1 (weight ratio) in a mixed solvent,
[Measured at 20 ° C.] is at least 0.2 and comprises a thermoplastic copolymerized polyester resin, (B) a rubber component and (C) a vulcanizing agent, and the mixing ratio of (A) and (B) is 30 to 30 by weight.
The thermoplastic resin composition is 95:70 to 5 and the compounding ratio of (C) is 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of (A) and (B).