JPH10279732A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition, having oil and heat resistances equal to those of a polyester resin, excellent in mechanical strength and having flexibility and compression set equal to those of a rubber by using a copolyester as a polyester resin. SOLUTION: This composition is obtained by kneading (A) 1-90 pts.wt. copolyester resin, containing a copolymerization component in an amount of >=13 mol.% based on the sum total of the whole acid component and the whole glycol component and having <200 deg.C crystal melting point or softening point with (B) 10-90 pts.wt. rubber (preferably an acrylonitrile-butadiene copolymer rubber, etc.). Furthermore, (C) <=90 pts.wt. polyester resin having <13 mol.% copolymerization component and 110-250 deg.C crystal melting point is preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer composition comprising a polyester synthetic resin and rubber.

[0002]

2. Description of the Related Art A thermoplastic elastomer composition is produced by so-called dynamic vulcanization in which a crystalline polyester and an ethylene propylene non-conjugated diene copolymer rubber (EPDM) are kneaded at a high shear rate and vulcanized with a vulcanizing agent. This is known from Japanese Patent Publication No. 55-14099. However, the conventional polyester-based thermoplastic elastomer composition has a problem that the mechanical properties are insufficient, the flexibility such as rubber is poor, the compression set is large, and it is not practical.

[0003]

SUMMARY OF THE INVENTION According to the present invention, by using a copolymerized polyester resin as a polyester resin, oil resistance and heat resistance are almost the same as those of the polyester resin, the mechanical strength is excellent, and the rubber and rubber are used. It is intended to provide a thermoplastic elastomer composition having comparable flexibility and compression set.

[0004]

The thermoplastic elastomer composition of the present invention contains at least 13 mol% of a copolymer component based on the total of all acid components and all glycol components. And 1 to 90 parts by weight of a copolymerized polyester resin A having a crystal melting point or a softening point of less than 200 ° C. and 10 to 90 parts by weight of a rubber B.

[0005] The above-mentioned copolymerized polyester resin A is a substantially random copolymer and is composed of a main component and a copolymerized component. Mol% or more, and the crystalline melting point is 2 in the case of crystallinity, and the softening point is 2 in the case of amorphous.
Less than 00 ° C. When the content of the above copolymer component is 1
When the amount is less than 3 mol%, the polarity of the copolymerized polyester resin A is high, and the affinity for the rubber B is lowered, which is not preferable.

The main acid components include terephthalic acid, 2,6-naphthalenedicarboxylic acid and ester-forming derivatives thereof. Examples of the glycol component include 1,4-tetramethylene glycol and ethylene glycol.

Examples of the acid component of the copolymerization component include aromatic dicarboxylic acids such as isophthalic acid, orthophthalic acid, 4,4'-diphenyldicarboxylic acid and 5-sodium sulfoisophthalic acid, and fatty acids such as 1,4-cyclohexenedicarboxylic acid. Aliphatic dicarboxylic acids such as cyclic dicarboxylic acids, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, hydrogenated dimer acid, and maleic acid, hydroxybenzoic acid,
and oxycarboxylic acids such as ε-caprolactone. In addition, if it is less than 1 mol% with respect to all components, it is also possible to use a polycarboxylic acid having three or more functional groups such as trimellitic anhydride and pyromellitic anhydride. However, if it is 1 mol% or more, the polymer chain becomes three-dimensional and the thermoplasticity disappears, which is not preferable.

The glycol component of the copolymer component includes 1,4-tetramethylene glycol, ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, neopentyl pivalate, hexanediol, cyclohexanedimethanol,
C2-C18 aliphatic glycols such as tricyclodecane dimethanol, hydroquinone, resorcinol, 3,3
And bishydroxyethoxyphenylpropane and adducts of ethylene oxide of 2.0 mol or more.
In addition, as long as it is less than 1 mol% with respect to all components, a glycol having three or more functional groups such as glycerin, trimethylolpropane, and pentaerythritol can also be used. However, 1
If it is at least mol%, the polymer chains will be three-dimensional, and the thermoplasticity will disappear, which is not preferable. In addition, the molecular weight of 400 to 600
Polytetramethylene glycol, polyethylene glycol, poly-ε-caprolactone, polyadipate, etc. of 0 can be used in a range not exceeding 2 mol%. However, if it exceeds 2 mol%, the affinity for rubber B is undesirably reduced.

In the present invention, another polyester resin C can be added to the above-mentioned copolymerized polyester resin A. That is, as described in claim 2, the content of the copolymer component relative to the sum of all the acid components and all the glycol components is 1%.
90 parts by weight or less of a polyester resin having a crystal melting point of less than 3 mol% and a crystal melting point of 110 to 250 ° C. can be added. This polyester resin C is a segmented polyester resin composed of a hard segment and a soft segment,
This includes homopolyester resins. However, when the content of the above-mentioned copolymer component is 13 mol% or more, the crystal melting point of the polyester resin C becomes low, and the heat resistance becomes poor. On the other hand, when the crystal melting point is lower than 110 ° C., the heat resistance is insufficient. On the other hand, when the crystal melting point is higher than 250 ° C., molding at a high temperature is required, and thermal deterioration of the rubber B to be used occurs. Disappears.

As the homopolyester resin having a crystal melting point of 110 to 250 ° C., polytetramethylene terephthalate (PBT), polytetramethylene-2,6-naphthalate (PBN), polyethylene terephthalate (PE)
T), polyethylene-2,6-naphthalate (PEN)
Is mentioned.

In the segmented polyester resin having a crystalline melting point of 110 to 250 ° C., a crystalline aromatic polyester constitutes a hard segment and has a molecular weight of 400 to 600.
An aliphatic ether or aliphatic ester of 0 constitutes a soft segment. The composition ratio (weight ratio) of the hard segment and the soft segment is 10 / 90-
90/10.

The hard segment (crystalline aromatic polyester) is a polymer mainly composed of an ester bond, and has at least one kind of aromatic group in a repeating unit.
It is a crystalline aromatic polyester having a crystalline melting point of 150 ° C. or more. Specifically, polyethylene terephthalate, polytetramethylene terephthalate, polyethylene-2,6
Homopolyesters such as -naphthalate and poly-1,4-cyclohexylenedimethyl terephthalate; and copolyesters containing these polyester units in an amount of 60 mol% or more. However, when the content of the copolymer component exceeds 40 mol%, the crystal melting point becomes less than 150 ° C., which is not preferable. The copolymer components are the same as those of the above-mentioned copolymer polyester resin A.

The soft segment shows a substantially amorphous state at room temperature in the copolymer with the above-mentioned hard segment, and has a melting point or softening point of 80 ° C. or less as measured only by the soft segment. is there. Specific examples include polyether glycols such as polyethylene glycol and polytetramethylene glycol, and mixtures and copolymers thereof. Further, polyesters comprising an aliphatic or alicyclic dicarboxylic acid having 2 to 12 carbon atoms and an aliphatic or alicyclic glycol having 2 to 10 carbon atoms, for example, polyethylene adipate, polyethylene sebacate, poly-ε-caprolactone, etc. And polyesters and their mixtures and copolymers. Further, a mixture or a copolymer of an aliphatic polyester and an aliphatic polyether can also be used. Among them, polytetramethylene glycol and poly-ε-caprolactone are preferred.

The rubber B used in the present invention is optional. Natural rubber, polyisoprene rubber, styrene / butadiene random copolymer rubber, styrene / butadiene block copolymer rubber, polybutadiene rubber, acrylonitrile / butadiene copolymer rubber, and acrylate ester Non-halogen diene rubber such as butadiene copolymer rubber, hydrogenated polyisoprene rubber, hydrogenated styrene / butadiene random copolymer rubber, hydrogenated styrene / butadiene block copolymer rubber, hydrogenated polybutadiene rubber, hydrogenated acrylonitrile / butadiene copolymer Polymerized rubber, hydrogenated non-halogen diene rubber such as hydrogenated acrylate / butadiene copolymer rubber, (meth) acrylate rubber, (meth)
Acrylic rubber such as acrylate / ethylene copolymer rubber, (meth) acrylate / ethylene / (meth) acrylic acid copolymer rubber, (meth) acrylate / ethylene / glycidyl (meth) acrylate copolymer Olefin rubbers such as epichlorohydrin rubber composed of a homopolymer of epichlorohydrin and a copolymer with ethylene oxide, ethylene-propylene copolymer rubber and ethylene-propylene-diene terpolymer rubber, chloroprene rubber, chlorinated polyethylene rubber, chloro Examples thereof include halogenated rubbers such as sulfonated polyethylene rubber and chlorinated butyl rubber, and silicone rubbers such as dimethylpolysiloxane, methylvinylpolysiloxane and methylphenylvinylsiloxane. Butadiene copolymer rubber (N
(BR), hydrogenated acrylonitrile / butadiene copolymer rubber (hydrogenated NBR), ethylene / propylene / diene terpolymer rubber (EPDM), (meth) acrylate / ethylene / (meth) acrylate copolymer rubber, Meta)
Acrylic ester / ethylene / glycidyl (meth) acrylic acid astell copolymer rubber, in particular, NBR, hydrogenated NBR and EPDM are preferable, as described in claim 3, and flexibility and rubber elasticity are obtained by using these rubbers. improves.

Although the composition of the present invention does not necessarily require vulcanization with a vulcanizing agent, the vulcanization with sulfur, a sulfur-containing compound or an organic peroxide can further improve the strength. . Examples of the sulfur-containing compound include well-known vulcanization accelerators such as benzothiazyl disulfide, mercaptobenzothiazole, sulfenamide, thiuram monosulfide, thiuram disulfide, and thiuram tetrasulfide. Further, as the organic peroxide, known organic peroxides such as dialkyl peroxide, peroxyester, hydroperoxide and the like can be used. In addition, monomers such as trimethylolpropane tri (meth) acrylate, triallyl cyanurate, and a maleimide compound can be used as a co-crosslinking assistant. Then, additives such as a plasticizer and an antioxidant can be appropriately added.

The thermoplastic elastomer composition according to claim 1 is used in an amount of 1 to 90 parts by weight, preferably 1 to 70 parts by weight, particularly preferably 5 to 4 parts by weight of the copolymerized polyester resin A.
0 parts by weight and 10 to 90 parts by weight of rubber B, preferably 10 parts by weight.
To 80 parts by weight, particularly preferably 20 to 70 parts by weight. In this case, particularly by using the above-mentioned copolymerized polyester resin A and rubber B, not only the mechanical strength of the composition is improved, but also the flexibility is increased,
Bending fatigue resistance is improved. Then, by adding a crosslinking agent such as an organic oxide or sulfur at the time of kneading and performing dynamic crosslinking, strength and compression set are further improved. However, the mixing ratio of the copolymerized polyester resin A and the rubber B is 1/9.
If it is less than 0, the strength becomes insufficient, while if it exceeds 90/10, the flexibility becomes insufficient and the compression set becomes excessive.

On the other hand, the thermoplastic elastomer composition according to claim 2 is 1 to 90 parts by weight, preferably 1 to 70 parts by weight, particularly preferably 5 to 40 parts by weight of the copolymerized polyester resin A according to claim 1. Parts, 10 to 90 parts by weight of rubber B, preferably 10 to 80 parts by weight, particularly preferably 20 parts by weight.
The polyester resin C having a copolymer component content of less than 13 mol% and a crystal melting point of 110 to 250 ° C. is 90 parts by weight or less, preferably 80 parts by weight or less, particularly preferably 6 parts by weight to 70 parts by weight.
It is manufactured by kneading and adding 0 parts by weight or less, and by adding this polyester resin C, mechanical strength and bending fatigue resistance are improved. However, if the amount exceeds 90 parts by weight, flexibility and compression set become poor.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiment 1 In a usual kneader such as a twin-screw extruder, a Brabender or a Banbury mixer, a copolymer polyester resin A having a copolymer component content of 13 mol% or more and a crystal melting point or a softening point of less than 200 ° C is used. 5 to 40 parts by weight and 20 to 70 parts by weight of rubber B such as NBR, hydrogenated NBR and EPDM are charged. Next, 1 to 60 parts by weight of a plasticizer and 0.1 to 5 parts by weight of an antioxidant are added to 100 parts by weight of the total of the copolymerized polyester resin A and the rubber B,
The mixture is kneaded at a temperature of 100 to 220 ° C. for 0.1 to 10 minutes to obtain an uncrosslinked thermoplastic elastomer composition. The obtained composition is formed into an arbitrary shape, for example, a sheet, and is punched into a desired shape before use.

Embodiment 2 In the above embodiment 1, the copolymerized polyester resin A
After kneading the rubber B, 0.1 to 15 parts by weight of sulfur or an organic peroxide as a cross-linking agent is added per 100 parts by weight of the total of the above-mentioned copolymerized polyester resin A and rubber B, and at a temperature of 120 to 250 ° C. Kneading for 0.1 to 5 minutes to perform dynamic crosslinking, then adding a plasticizer and an antioxidant, etc., and kneading at a temperature of 150 to 250 ° C for 0.1 to 5 minutes to form a crosslinked thermoplastic elastomer composition Get. The obtained composition is formed into an arbitrary shape, for example, a sheet, and is punched into a desired shape before use.

Embodiment 3 5-4 of the copolymerized polyester resin A of the above-mentioned Embodiment 1
0 parts by weight and 20 to 70 parts by weight of rubber B, the content of the copolymer component is less than 13 mol%, and the crystal melting point is 110 to 2 parts.
An uncrosslinked thermoplastic elastomer composition is obtained in the same manner as in Embodiment 1, except that the polyester resin C at 50 ° C. is added in an amount of 60 parts by weight or less, for example, molded into a sheet, and further punched into a desired shape for use.

Embodiment 4 5-4 of the copolyester resin A of Embodiment 2 above
0 parts by weight and 20 to 70 parts by weight of rubber B, the content of the copolymer component is less than 13 mol%, and the crystal melting point is 110 to 2 parts.
A crosslinked thermoplastic elastomer composition is obtained in the same manner as in Embodiment 1 except that the polyester resin C at 50 ° C. is added in an amount of 60 parts by weight or less. For example, the crosslinked thermoplastic elastomer composition is formed into a sheet, and further punched into a desired shape for use.

Embodiment 5 The crosslinked thermoplastic elastomer 1 obtained in Embodiment 2
A crosslinked thermoplastic elastomer composition is obtained in the same manner as in Embodiment 1 except that 90 parts by weight or less of the polyester resin C having a crystal melting point of 110 to 250 ° C. is added to 00 parts by weight. It is punched into a desired shape and used.

[0023]

EXAMPLES The following polyester resin A1 was used as the copolymerized polyester resin A.
To A4 were used. A1 Total copolymer component: about 41 mol% (total of adipic acid and polytetramethylene glycol) Crystal melting point: 120 ° C., glass transition temperature: −18 ° C. A2 Total copolymer component: about 17 mol% (isophthalic acid and adipic acid) A3 Total copolymerization component: about 45 mol% (total of isophthalic acid and neopentyl glycol) Softening temperature: 171 ° C, Glass transition temperature: 65 ° C A4 Copolymerization component: about 30 mol% (total of sebacic acid and neopentyl glycol) Softening temperature: 133 ° C, glass transition temperature: 10 ° C

The following B1 to B5 were used as the rubber B. B1 Medium-high nitrile rubber (Nipol 1042, manufactured by Zeon Corporation) Nitrile concentration: 33% by weight B2 High nitrile rubber (Nipol DN101, manufactured by Zeon Corporation) Nitrile concentration: 42% by weight B3 Powdered high nitrile rubber (Japan "JSR PN20HA" manufactured by Synthetic Rubber Co., Ltd. B4 Hydrogenated nitrile rubber ("Zetpol 2020" manufactured by Nippon Zeon Co., Ltd.) Nitrile concentration: 36% by weight B5 ENB type EPDM ("Mitsui EPT4070" manufactured by Mitsui Petrochemical Industries, Ltd.)

As the polyester resin C, the following C1 to C
3 was used. C1 Hard segment: PBT Soft segment: polytetramethylene glycol having a molecular weight of about 1000 Total copolymerization component (soft segment) concentration: about 10 mol% Crystal melting point: 180 ° C. C2 Hard segment: PBT Soft segment: polytetramethylene having a molecular weight of about 1000 Glycol Total copolymer component (soft segment) concentration: about 3 mol% Crystal melting point: 215 ° C. C3 polytetramethylene terephthalate (PBT) Total copolymer component (soft segment) concentration: 0 mol% Crystal melting point: 225 ° C., glass transition temperature : 53 ° C

As the organic peroxide D, the following D1 and D
2 was used. D1 2,5-Dimethyl-2,5-di (t-butylperoxy) hexine "Perhexin 25B" manufactured by NOF Corporation D2 Dibenzothiazyl disulfide "Succinol DM" manufactured by Sumitomo Chemical Co., Ltd.

The following antiaging agents E were used. E tetrakis [methylene-3- (3 ', 5'-di-
[t-butyl-4'-hydroxyphenyl) propionate] methane "IRGANOX101" manufactured by Ciba-Geigy Japan
0 "

Various physical properties were measured as follows. Crystal melting point and glass transition temperature Using a differential scanning calorimeter, the melting peak temperature of a thermograph obtained at a heating rate of 20 ° C./min was defined as the crystal melting point.
The measurement was performed under the same conditions, and the rising point of the glass transition peak was defined as the glass transition temperature. Softening temperature was measured by a ring and ball method. Hardness (Hs) Measured according to JIS K6253. Breaking strength (TB) and breaking elongation (EB) Measured according to JIS K6251. Compression set (C-set) Measured at 120 ° C. for 72 hours in accordance with JIS K6262. Oil resistance Based on JIS K6258, using No. 3 oil, 120
The rate of volume change (%) was measured at 72 ° C. for 72 hours. Heat aging resistance The retention of elongation at break (EB) was measured at 125 ° C. for 168 hours in accordance with JIS K6257. Flexural fatigue resistance According to JIS K6260, 100 ° C, 300 times /
The presence or absence of cracks was tested under the conditions of minutes and 30 hours.

Example 1 and Comparative Examples 1 and 2 The thermoplastic resin of Example 1 was prepared by using the above-mentioned copolymerized polyester resin A2, rubber B1, organic peroxide D1 and antioxidant E in the composition shown in Table 1 below. An elastomer composition was produced. That is, 30 parts by weight of the copolymerized polyester resin A1 and 70 parts by weight of the rubber B1 were mixed with a Brabender-type kneader (“Laboplast Mill R-50” manufactured by Toyo Seiki Co., Ltd.).
0 ") and kneaded thoroughly at a temperature of 130 ° C., and 1 part by weight of an organic peroxide D1 is added as a crosslinking agent, and
kneading at 170 rpm for about 20 minutes to perform dynamic crosslinking,
Next, 0.5 parts by weight of the antioxidant E was added, and kneaded for 2 minutes under the same conditions. Thereafter, the thermoplastic elastomer composition (Example 1) was taken out, and its physical property values were measured. Also described in 1. Comparative Example 1 using polyester resin C2 instead of rubber B1 of Example 1 and Comparative Example 2 consisting only of the above-mentioned copolymerized polyester resin A1
Was measured and the results are also shown. Note that “parts by weight” is simply abbreviated as “parts”.

Table 1 Example 1 Comparative Example 1 Comparative Example 2 Formulation A2 (parts) 30 50 100 B1 (parts) 70--C2 (parts)-50-D1 (parts) 1--E (parts) 0.5 0.5 0.5 Physical properties Hs (degrees) 70 94 92 EB (%) 550 630 490 TB (kgf / cm ² ) 190 370 210 Cset (%) 45 75 80 Flexural fatigue resistance (cracks) None None Cutting

As shown in Table 1, Example 1 was excellent in all physical properties. On the other hand, Comparative Example 1 lacked the B component, so that the hardness Hs and the compression set Cset were excessive. In Comparative Example 2, since the B component and the C component were absent, the compression set Cset was excessive, and the sample was cut one hour after the start in the bending fatigue resistance test.

Example 2 20 parts of copolyester resin A2, 50 parts of rubber B
A thermoplastic elastomer composition was prepared in the same manner as in Example 1 using 1, 1 part of an organic peroxide D1 and 0.5 part of an antioxidant E, and then 30 parts of a polyester resin C1 were added. The mixture was introduced into a single screw extruder having a diameter of 40 mm and extruded at 210 ° C. to obtain a thermoplastic elastomer composition of Example 2. The physical properties were measured in the same manner as described above, and the results are shown in Table 2 together with the composition. In addition,
In Table 2, “Example” is simply “Real” and “Comparative Example”
Is simply abbreviated as “ratio”.

Examples 3 and 4 and Comparative Examples 3 and 4 20 parts of copolyester resin A1, 50 parts of rubber B
After dry-blending 3,30 parts of the polyester resin C1 and 1 part of the crosslinking agent D1 in advance, the mixture was introduced into a 35 mm-diameter twin-screw extruder, kneaded at 150 rpm and 210 ° C., and 0.5 part of the antioxidant E Example 3 by mixing and discharging
Was produced. Further, the thermoplastic elastomer compositions of Example 4 and Comparative Example 3 were produced in the same manner as described above except that the composition was changed to the description in Table 2. The physical properties of Examples 3 and 4 and Comparative Example 3 were measured, and the results are shown in Table 2. In addition, polyester resin C
The physical property values of Comparative Example 4 consisting of only 1 were measured and are also shown in Table 2.

Table 2 Actual 2 Actual 3 Actual 4 Ratio 3 Ratio 4 Formulation A1 (parts)-20 15--A2 (parts) 20----B1 (parts) 50-50 50-B3 (parts)-50- − − C1 (parts) 30 30 − − 100 C2 (parts) − − 35 50 − D1 (parts) 1 11 1 − E (parts) 0.5 0.5 0.5 0.5 0.5 Physical properties Hs (degrees) 87 85 89 95 96 EB ( %) 400 340 450 230 200 TB (kgf / cm ² ) 190 180 200 80 180 Cset (%) 39 39 35 41 70 Oil resistance (%) 24 25 20 36 23 Heat aging resistance (%) 90 87 89 40 98 Resistance Flexural fatigue (cracks) None None None Cutting None

As shown in Table 2, Examples 2 to 4 were all excellent in physical properties. On the other hand, Comparative Example 3 lacked the copolyester C, so that the elongation and strength were small, the heat aging resistance and the bending fatigue resistance were inferior, and the sample was cut three hours after the start in the bending fatigue resistance test. did.

Examples 5 to 7 and Comparative Examples 5 to 7 The thermoplastic elastomer composition of Example 5 was prepared in the same manner as in Example 4 except that the crosslinking agent was omitted in the formulation of Example 4. The same test was performed, and the results are shown in Table 3. In addition, the thermoplastic elastomer compositions of Examples 6 and 7 were produced with the formulations shown in Table 3, and the same tests were performed as described above. The results are shown in Table 3. The test results of Comparative Example 6 consisting of only the polyester resin (PBT) C3 and Comparative Example 7 lacking the copolymerized polyester A are also shown.

Table 3 Actual 5 Ratio 5 Actual 6 Ratio 6 Actual 7 Ratio 7 Formulation A1 (parts) 15---25-A2 (parts)--30---B1 (parts) 50 50 50---B5 ( ----50 50 C1 (part) 35 50--25 50 C3 (part)--20 100--D1 (part)--0.5-11 E (part) 0.5 0.5 0.5 0.5 0.5 0.5 Physical properties Hs (Degree) 82 85 89> 99 76 78 EB (%) 330 440 300 100 340 240 TB (kgf / cm ² ) 120 50 190 580 180 50 Cset (%)--41 90 42 65 Oil resistance (%)-- 12 9 40 40 Heat aging resistance (%)--85 97 97 90 Flexural fatigue resistance (crack)--None-None Cutting

As shown in Table 3, Examples 5 to 7
All exhibited good physical properties. However, since Example 5 was not crosslinked, the hardness, breaking strength, elongation at break, and the like were slightly lower than those of Example 4 which was crosslinked. on the other hand,
Comparative Example 5 lacked the copolyester resin A, so that the breaking strength was significantly reduced. Further, Comparative Example 6 lacked both the copolymerized polyester resin A and the rubber B and was composed of only the polyester resin C, so that the hardness was high, the elongation was small, and the compression set was large. Also,
Comparative Example 7 lacked the copolyester resin A and therefore had low strength and poor flex fatigue resistance, and the sample was cut 0.5 hours after the start of the test.

Examples 8 to 11 The thermoplastic elastomer compositions of Examples 8 to 11 were produced in the same manner as in Example 3 except that the composition was changed to the description in Table 4, and the physical property tests were carried out in the same manner as described above. . Table 4 shows the results.
Shown in

Table 4 Actual 8 Actual 9 Actual 10 Actual 11 Formulation A1 (parts) 20 10--A3 (parts)--8-A4 (parts)---10 B1 (parts)--60 40 B2 (parts) 50---B4 (parts)-60--C1 (parts)-30--C2 (parts) 30-32 50 D1 (parts)-1 1.5 0.5 Sulfur (parts) 1.5---D2 (parts) 1.5- − − Zinc oxide (parts) 15 − − − Stearic acid (parts) 2.0 − − − E (parts) 0.5 0.5 0.5 0.5 Physical properties Hs (degrees) 88 78 69 90 EB (%) 340 400 290 240 TB (kgf / cm) ² ) 220 190 160 170 Cset (%) 38 33 28 40 Oil resistance (%) 15 29 30 10 Heat aging resistance (%) 95 99 95 100 Flexural fatigue resistance (cracks) None None None None

As shown in Table 4 above, Examples 8 to 11
Had good mechanical properties.

[0042]

As described above, the inventions according to the first to third aspects have oil resistance and heat resistance similar to those of polyester resins, are excellent in mechanical strength, and are comparable in flexibility to rubber. And a compression set, and are extremely excellent as a thermoplastic elastomer composition. In particular, the invention described in claim 1 is excellent in flexibility, mechanical strength, and bending fatigue resistance since it is composed of the two components of the copolyester resin A and the rubber B. Claim 2
The invention described in the above, the above-mentioned copolymerized polyester resin A
Since it is constituted by adding polyester resin C to rubber B and rubber B, it is more excellent in mechanical strength and bending fatigue resistance. Further, in the invention described in claim 3, since any one of NBR, hydrogenated NBR and EPDM is used as the rubber B, the compressibility is improved, and the compression set is further reduced.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shigeo Kobayashi 255 Kannonji-cho, Tsu-shi, Mie Pref.

Claims (3)

[Claims] 1. A copolymerized polyester resin 1 containing at least 13 mol% of a copolymer component based on the total of all acid components and all glycol components and having a crystal melting point or softening point of less than 200 ° C.
A thermoplastic elastomer composition obtained by kneading from 90 to 90 parts by weight of rubber and from 10 to 90 parts by weight of rubber. 2. A copolymerized polyester resin 1 containing at least 13 mol% of a copolymer component with respect to the total of all acid components and all glycol components and having a crystal melting point or softening point of less than 200 ° C.
To 90 parts by weight, 10 to 90 parts by weight of rubber and the content of the above copolymer component is less than 13 mol%, and the crystal melting point is 110 to 2 parts.
A thermoplastic elastomer composition obtained by kneading 90 parts by weight or less of a polyester resin at 50 ° C. 3. The thermoplastic elastomer composition according to claim 1, wherein the rubber is one of NBR, hydrogenated NBR and EPDM.