JP2001213931A - Ester-based elastomer and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ester-based elastomer excellent in flexibility and mechanical characteristics, particularly in resistance to flattening at a high temperature and to provide a method for manufacturing the same. SOLUTION: The ester-based elastomer comprises a block copolymer of a polyester-based copolymer (A) comprising a recurring unit of a short chain polyester component and a recurring unit of a long chain polyester component, the short chain polyester component accounting for 50-100 wt.% and the long chain polyester component accounting for 50-0 wt.%, with a polyester (B) composed of a recurring unit represented by the formula: -R3-O-, wherein R3 is a 2-8C alkylene group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ester elastomer having excellent flexibility and mechanical properties at high temperatures, especially excellent sag resistance at high temperatures, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, due to increasing awareness of environmental issues,
The replacement of recyclable materials in various industrial fields is accelerating. As a rubber material, thermoplastic elastomer (TPE) has been attracting attention for a long time, and has been used for various applications in fields such as automobiles and various industries.

[0003] Among them, polyester-based elastomer (TPEE) is excellent in mechanical strength, heat resistance, abrasion resistance and flex fatigue resistance, and is used in a wide range of industrial fields mainly in the automobile field. However, TPEE has the drawbacks that it has a higher hardness than ordinary rubber regions and lacks flexibility, and has a large compression set at the time of large deformation and high temperature and lacks set resistance, and its improvement is desired. .

When imparting flexibility to TPEE, it is necessary to reduce the proportion of hard segment components responsible for physical crosslinking. Such a method is disclosed in, for example, JP-A-2-886.
No. 32 is proposed. However, there was a problem that the blockability of the hard segment component was reduced, and as a result, the melting point was lowered and the mechanical properties at high temperatures were lowered. A technique of improving sag resistance by increasing the degree of polymerization is disclosed in, for example,
Although it is disclosed in JP-A-121699, there is a limit,
In addition, compatibility with flexibility was impossible.

[0005]

SUMMARY OF THE INVENTION In view of the above, the present invention has a high blockability of a hard segment component and a soft segment component, and is excellent in flexibility and mechanical properties at high temperatures, especially resistance to sag at high temperatures. It is an object of the present invention to provide an ester-based elastomer and a method for producing the same.

[0006]

The ester elastomer according to the first aspect of the present invention comprises a short-chain polyester component represented by the general formula (1) and a long-chain polyester component represented by the general formula (2). A polyester-based copolymer (A) comprising 50 to 100% by weight of the short-chain polyester component and 50 to 0% by weight of the long-chain polyester component, and a repeating unit represented by the general formula (3). A block copolymer with a polyether (B) composed of units, wherein the polyester copolymer (A) and the polyether (B) are an isocyanate component (C) represented by the general formula (4): And the polyester-based copolymer (A) is 100 parts by weight, and the polyether (B) is 50 to 1000 parts by weight and the isocyanate component (C) is 10 to 200 parts by weight. Characterized in that it is composed of parts.

The ester elastomer of the present invention is a block copolymer of a polyester copolymer (A) and a polyether (B), wherein the polyester copolymer (A) and the polyether (B) are It is bonded by the isocyanate component (C).

The polyester copolymer (A) is composed of a repetition of a short-chain polyester component represented by the general formula (1) and a long-chain polyester component represented by the general formula (2). As such a copolymer, for example, a known polyether elastomer obtained by reacting an aromatic dicarboxylic acid with a low molecular weight diol and a polyether can be used.

-CO-R ⁰ -CO-OR ¹ -O- ... (1) -CO-R ⁰ -CO-OR ² -... (2)

In the general formulas (1) and (2), R ⁰ represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, R ¹ represents an alkylene group having 2 to 8 carbon atoms, and R ^{2 represents} is, -R ⁵ -O-
(Wherein, R ⁵ represents an alkylene group having 2 to 8 carbon atoms), and has a number average molecular weight of 50.
0 to 5000 components are shown.

Examples of the aromatic dicarboxylic acid constituting the polyester copolymer (A) include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate, Examples thereof include dimethyl orthophthalate, dimethyl naphthalenedicarboxylate, and dimethyl paraphenylenedicarboxylate.

The low molecular weight diol constituting the polyester copolymer (A) includes, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4 -Butanediol, neopentylglycol, 1,5-pentanediol, 1,6-hexanediol and the like, which may be used alone or in combination of two or more.

The polyether constituting the polyester copolymer (A) includes, for example, polyethylene glycol, poly-1,3-propylene glycol, poly1,
Examples thereof include 2-propylene glycol, polytetramethylene glycol, polyhexamethylene glycol, and the like.
Among these, polytetramethylene glycol is preferable in terms of excellent mechanical properties and weather resistance, and commercially available products include “PTHF” manufactured by BASF and “PTM” manufactured by Mitsubishi Chemical Corporation.
G "and the like.

The number average molecular weight of the above polyether is 50
It is preferably from 0 to 5000, more preferably from 500 to 20.
00. When the number average molecular weight is less than 500, the blocking property of the obtained polyester-based copolymer (A) decreases, the melting point decreases, and the mechanical strength of the ester-based elastomer at a high temperature decreases. When the number average molecular weight exceeds 5000, the degree of polymerization of the ester elastomer does not increase due to low compatibility with the polyether (B), and an elastomer having sufficient strength cannot be obtained.

The polyester copolymer (A) can be polymerized by a known method. Specifically, terephthalic acid dimethyl ester is heated at 200 ° C. in the presence of a catalyst together with a polyether and an excess of low molecular weight diol at 200 ° C. to perform a transesterification reaction, followed by a polycondensation reaction at 140 ° C. under reduced pressure. Thereby, a polyester copolymer (A) can be obtained.

The proportion of the short-chain polyester component in the components of the polyester-based copolymer (A) is 50-1.
00% by weight. 50% by weight of short-chain polyester component
If it is less than 1, the melting point of the polyester copolymer (A) is low, which adversely affects the mechanical strength of the ester elastomer at high temperatures.

The number average molecular weight of the polyester copolymer (A) is preferably from 500 to 5,000. When the number average molecular weight is less than 500, the blockability of the ester-based elastomer becomes low, adversely affecting the mechanical strength at a high temperature. When the number average molecular weight exceeds 5,000, compatibility with the polyether (B) is obtained. , The degree of polymerization of the ester elastomer does not increase, and an ester elastomer having sufficient strength cannot be obtained.

The intrinsic viscosity of the polyester copolymer (A) is preferably from 0.05 to 1.0, more preferably from 0.2 to 0.6. If the intrinsic viscosity is less than 0.05, the blockiness of the ester elastomer becomes low, which adversely affects the mechanical strength at high temperatures. When the intrinsic viscosity exceeds 1.0, the degree of polymerization of the ester elastomer does not increase because of low compatibility with the polyether (B),
An ester elastomer having sufficient strength cannot be obtained.
The intrinsic viscosity is a value measured at 25 ° C. using orthochlorophenol as a solvent.

The above polyether (B) has the general formula -R ³
-O- (wherein, R ³ represents an alkylene group having 2 to 8 carbon atoms) comprised of repeating units represented by.

As such a polyether (B),
The same polyethers as those used for the polymerization of the polyester-based copolymer (A) can be used.

The number average molecular weight of the polyether (B) is preferably from 500 to 3,000. When the number average molecular weight is less than 500, the obtained ester-based elastomer has poor flexibility, and when it exceeds 3000, the crystallinity becomes too high, and the flexibility in a low temperature region becomes poor. More preferably, it is 500 to 1,000.

The ester-based elastomer of the present invention is a copolymer of the above-mentioned polyester-based copolymer (A) and polyether (B), and the polyester-based copolymer (A) and polyether (B) are generally It is bonded by the isocyanate component (C) represented by the formula (4). In order to obtain the ester-based elastomer bonded by the isocyanate component (C), the polyester-based copolymer (A)
And the polyether (B) and the isocyanate compound (D) represented by the general formula (5). The polyester-based copolymer (A) and the polyether (B) usually have hydroxyl groups at both ends, but may partially have a carboxyl group. At this time, the isocyanate compound (D)
When both of the terminal functional groups reacting with the isocyanate component are hydroxyl groups, they are bonded by the isocyanate component (C) of the general formula (4), while when one is a hydroxyl group and the other is a carboxyl group, the isocyanate component of the general formula (6) (C). ^{-O-CO-NH-R 4} -NH-CO-O- ··· (4) -CO-NH-R 4 -NH-CO- ··· (5) -CO-NH-R 4 -NH- CO-O- (6) In addition, when the terminal functional group of the polyester-based copolymer (A) is a carboxyl group, a portion bonded by the isocyanate compound (D) represented by the general formula (6) is also used. It is considered to be included in a small amount.

The structure of the isocyanate compound (D) represented by the general formula (6) used in the present invention is not particularly limited, but the average number of isocyanate groups per molecule of the isocyanate compound is 2.0 to 2.2. Are preferred. The average number of isocyanate groups is 2.0
Examples of the isocyanate compound include aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, and 1,4-butane Diisocyanate, 1,6-
Examples include hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, isophorone diisocyanate, and aliphatic diisocyanates such as hydrogenated 4,4'-diphenylmethane diisocyanate. When an isocyanate compound having an average number of isocyanate groups per molecule of more than 2.2 is used, for example, by mixing with an isocyanate compound having an average number of isocyanate groups of 2.0, the average number of isocyanate groups per molecule is adjusted. Is preferably in the range of 2.0 to 2.2. As an isocyanate compound having an average number of isocyanate groups per molecule of more than 2.0, polymeric MDI is typical, and as a commercially available product, for example, "Millionate MR200" manufactured by Nippon Polyurethane Co., Ltd.
(Average isocyanate group number: 2.8). Other isocyanate compounds having an average number of isocyanate groups exceeding 2.0 include triphenylmethane triisocyanate (average number of isocyanate groups 3.0), tris (isocyanatephenyl) thiophosphate (average number of isocyanate groups 3.0), hexamethylene triisocyanate (Average number of isocyanate groups: 3.0).

The ester-based elastomer of the present invention is prepared by melt-mixing 50 to 1000 parts by weight of the polyether (B) and 10 to 200 parts by weight of the isocyanate compound (D) with respect to 100 parts by weight of the polyester-based copolymer (A). Obtained by If the amount of the polyether (B) is less than 50 parts by weight, the polyester elastomer cannot have sufficient flexibility, and if it is more than 1000 parts by weight, sufficient mechanical strength cannot be obtained. Preferably 100 parts by weight to 7 parts
00 parts by weight. When the amount of the isocyanate component (C) is 1
When the amount is less than 0 parts by weight, the polyester elastomer does not become a high molecular weight substance but has low mechanical strength. If the amount is more than 200 parts by weight, the flexibility of the polyester elastomer becomes inferior. Preferably it is 30 to 170 parts by weight.

In order to improve the reactivity between the polyester copolymer (A) and the polyether (B) and obtain an ester elastomer having excellent mechanical strength, the polyester copolymer (A) Is preferably a hydroxyl group. For example, when the terminal functional group is a carboxyl group,
Due to poor reactivity with isocyanate groups, a polymer having a sufficient high molecular weight cannot be obtained, resulting in poor mechanical strength. Further, since carbon dioxide is generated by the reaction between the carboxyl group and the isocyanate group, it is necessary to take a process countermeasure against foaming.

In order to improve the compatibility between the polyester copolymer (A) and the polyether (B) and obtain an ester elastomer having excellent mechanical strength at high temperatures, the polyester copolymer is used. The proportion of the short-chain polyester component in the components of (A) is 90 to 10
0% by weight, preferably 95 to 100% by weight, and the number average molecular weight of the polyester copolymer (A) is 500
It is preferably set to 5000. More preferably, the short-chain polyester component is 100% by weight, and the number average molecular weight is 1,000 to 3,000.

The equivalent ratio between the isocyanate group of the isocyanate component (C) and the terminal functional group of the polyester copolymer (A) and the polyether (B) is 0.95.
~ 1.1 is preferred. If the equivalent ratio deviates significantly from the above range, a polymer having a sufficient high molecular weight cannot be obtained, resulting in poor mechanical strength.

In the ester elastomer of the present invention, in order to satisfy the amounts of the polyester copolymer (A), polyether (B) and isocyanate component (C), the polyester copolymer (A), The reaction may be carried out by melt-mixing the polyether (B) and the diisocyanate compound (D) at the above weight ratio.

The above polyester copolymer (A), polyether (B) and diisocyanate compound (D)
The reaction can be performed by melt mixing using an extruder. The extrusion temperature is preferably from 180 to 260C, more preferably from 200 to 240C. Extrusion temperature 18
When the temperature is lower than 0 ° C., the reaction is difficult because the polyester copolymer (A) does not melt, and a high molecular weight polymer cannot be obtained. When the temperature exceeds 260 ° C., the polyester copolymer (A) And the diisocyanate compound (D) is decomposed, and a polymer having sufficient strength cannot be obtained.

In the present invention, a catalyst can be used at the time of melt-mixing the polyester copolymer (A) and the polyether (B) with the diisocyanate compound (D). Examples of the catalyst include diacyl stannous,
Tetanacyl stannic, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate, tin dioctanoate, tin tetraacetate, triethyleneamine, diethyleneamine, triethylamine, metal naphthenate,
Metal octylate, triisobutylaluminum, tetrabutyltitanate, calcium acetate, germanium dioxide, antimony trioxide and the like may be used, and these may be used alone or in combination of two or more.

A stabilizer may be used in the above-mentioned ester-based elastomer, for example, 1,3,5-trimethyl-
2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9-bis {2- [3
-(3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane Hindered phenolic antioxidants; tris (2,4-di-t-butylphenyl) phosphite,
Trilauryl phosphite, 2-t-butyl-α- (3
-T-butyl-4-hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite, dimyristyl 3,3'-thiodipropionate, distearyl 3,
Heat stabilizers such as 3′-thiodipropionate, pentaerythryltetrakis (3-laurylthiopropionate), and ditridecyl 3,3′-thiodipropionate are included.

The ester-based elastomer of the present invention may be a fiber, an inorganic filler, a flame retardant, an ultraviolet absorber, an antistatic agent, an inorganic material, or the like, as long as practicality is not impaired during or after the production.
An additive such as a higher fatty acid salt may be added.

Examples of the fiber include glass fiber,
Examples include inorganic fibers such as carbon fiber, boron fiber, silicon carbide fiber, alumina fiber, amorphous fiber, and silicon / titanium / carbon fiber; and organic fibers such as aramid fiber. Examples of the inorganic filler include calcium carbonate, titanium oxide, mica, and talc. Examples of the flame retardant include hexabromocyclododecane, tris- (2,3-dichloropropyl) phosphate, and pentabromophenyl allyl ether.

As the above-mentioned ultraviolet absorber, for example, p-
tert-butylphenyl salicylate, 2-hydroxy-
4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4,5-
Trihydroxybutyrophenone and the like.

Examples of the antistatic agent include N, N
-Bis (hydroxyethyl) alkylamine, alkylallyl sulfonate, alkyl sulfanate and the like. As the inorganic substance, for example, barium sulfate,
Alumina, silicon oxide and the like can be mentioned. Examples of the higher fatty acid salt include sodium stearate, barium stearate, sodium palmitate and the like.

The ester elastomer of the present invention may be mixed with other thermoplastic resins and rubber components to modify its properties before use. Examples of the thermoplastic resin include polyolefin, modified polyolefin, polystyrene, polyvinyl chloride, polyamide, polycarbonate, polysulfone, and polyester.

Examples of the rubber component include natural rubber, styrene-butadiene copolymer, polybutadiene,
Polyisoprene, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer (EPM, EPD
M), polychloroprene, butyl rubber, acrylic rubber,
Examples include silicone rubber, urethane rubber, olefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, PVC-based thermoplastic elastomer, ester-based thermoplastic elastomer, and amide-based thermoplastic elastomer.

The ester-based elastomer of the present invention can be formed into a molded article by a commonly used molding method such as press molding, extrusion molding, injection molding, blow molding and the like. Although the molding temperature varies depending on the melting point of the ester elastomer and the molding method, 160 to 260 ° C is suitable. If the molding temperature is lower than 160 ° C., a uniform molded product cannot be obtained because the fluidity of the ester elastomer is low. If the molding temperature is higher than 260 ° C., the ester elastomer is decomposed, and a sufficient strength of the ester elastomer is obtained. I can't get it.

Molded articles obtained by using the ester elastomer of the present invention include, for example, residential building materials, automobile parts,
It is suitably used for electric and electronic parts, industrial parts, sports goods, medical goods and the like.

As a building material for a house, a roof base material, an outer wall base material, and the like can be given. Examples of automobile parts include boots such as constant velocity joint boots, rack and opinion boots, etc .; ball joint seals; safety belt parts; bumper fascias; emblems; Examples of the electric and electronic components include a wire covering material, gears, a rubber switch, a membrane switch, a tact switch, and an O-ring. Examples of the industrial component include a hydraulic hose, a coil tube, a sealing material, a packing, a V-belt, a roll, a vibration damping material, a shock absorber, a coupling, a diaphragm, and the like.

Examples of the sporting goods include shoe soles and ball for ball games. Examples of the medical supplies include a medical tube, a blood transfusion pack,
Catheters and the like. In addition to the above applications, elastic fibers,
It can be suitably used as an elastic sheet, a composite sheet, a hot melt adhesive, a material for alloying with other resins, and the like.

[0042]

In the ester elastomer of the present invention,
Crystals formed by the short-chain polyester component constitute crosslink points, thereby exhibiting properties as an elastomer. This elastomer is composed of a portion rich in short-chain polyester component and a portion rich in polyether, and the presence of this short-chain polyester component makes it crystallize more than the conventional ester-based elastomer showing the same degree of flexibility. As a result, a strong crosslinking point is formed, resulting in an elastomer material having excellent mechanical properties at high temperatures. Further, the presence of the polyether-rich portion increases the molecular weight between cross-linking points, resulting in a highly flexible elastomer material.

[0043]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

Synthesis of polyester copolymer (I) 100 parts by weight of dimethyl terephthalate, 102 parts by weight of 1,4-butanediol, polytetramethylene glycol having a number average molecular weight of about 650 (“PTHF65” manufactured by BASF)
0 ") 28 parts by weight, 0.3 parts by weight of tetrabutyl titanate as a catalyst, 1,3,5-trimethyl- as a stabilizer
0.3 parts by weight of 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and 0.3 part of tris (2,4-di-t-butylphenyl) phosphite The reaction system was kept at 200 ° C. for 3 hours under nitrogen to carry out transesterification. The progress of the transesterification reaction was confirmed by measuring the amount of methanol distilled off. After the transesterification progresses, 2
The temperature was raised to 40 ° C., and the pressure was reduced. The polymerization system reached a reduced pressure of 2 mmHg or less in 20 minutes. As a result of a polycondensation reaction for 20 minutes in this state, 140 parts by weight of a white polyester-based copolymer (I) was obtained. The average molecular weight of the obtained polyester copolymer (I) was 3,000.

Synthesis of Polyester Copolymer (II) Polyester methylene glycol having a number average molecular weight of about 650 (“PTHF650” manufactured by BASF) was added, except that it was not added. In the same manner as in the synthesis, 112 parts by weight of the polyester copolymer (II) was obtained. The average molecular weight of the obtained polyester copolymer (II) was 3,000.

Synthesis of polyester copolymer (III) 112 weight of polyester copolymer (III) in the same manner as in the synthesis of polyester copolymer (II) except that the polycondensation reaction was changed to 10 minutes. Got a part. The average molecular weight of the obtained polyester copolymer (III) is 120.
It was 0.

Synthesis of Polyester Copolymer (IV) 112 weight of polyester copolymer (IV) in the same manner as synthesis of polyester copolymer (II) except that the polycondensation reaction was changed to 60 minutes. Got a part. The average molecular weight of the obtained polyester copolymer (IV) was 8,000.

Synthesis of Polyester Copolymer (V) 112 weight of polyester copolymer (V) in the same manner as synthesis of polyester copolymer (II) except that the polycondensation reaction was changed to 5 minutes. Got a part. The average molecular weight of the obtained polyester copolymer (V) was 300.

Synthesis of Polyester Copolymer (VI) 100 parts by weight of dimethyl naphthalenedicarboxylate, 1,4
-81 parts by weight of butanediol, having a number average molecular weight of about 650
Polytetramethylene glycol (PTM manufactured by Mitsubishi Chemical Corporation)
G650) 12 parts by weight, 0.3 parts by weight of tetrabutyl titanate as a catalyst, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4) as a stabilizer
-Hydroxybenzyl) benzene 0.3 parts by weight, and
0.3 parts by weight of tris (2,4-di-t-butylphenyl) phosphite was added, and the reaction system was heated at 210 ° C. under nitrogen for 3 hours.
The transesterification reaction was performed while keeping the time. The progress of the transesterification reaction was confirmed by measuring the amount of methanol distilled off. After the transesterification reaction proceeded, the temperature was raised to 250 ° C. in 20 minutes, and a pressure reduction operation was performed. The polymerization system is 20
Minutes, the degree of reduced pressure reached 2 mmHg or less. 20 in this state
After performing the polycondensation reaction for 130 minutes, 130 parts by weight of a white polyester-based copolymer (VI) was obtained. The average molecular weight of the obtained polyester copolymer (VI) was 1,300.

Synthesis of Polyester Copolymer (VII) Polyester methylene glycol having a number average molecular weight of about 650 (“PTHF650” manufactured by BASF) was not added except that polyester copolymer (VI) was added. 118 parts by weight of a polyester copolymer (VII) were obtained in the same manner as in the synthesis. The obtained polyester copolymer (VI
The average molecular weight of I) was 1200.

Synthesis of polyester copolymer (VIII) 118 weight of polyester copolymer (VIII) in the same manner as in synthesis of polyester copolymer (VII) except that the polycondensation reaction was changed to 60 minutes. Got a part. The average molecular weight of the obtained polyester copolymer (IV) is 80.
00.

Example 1 100 parts by weight of a polyester copolymer (I), polytetramethylene glycol having a number average molecular weight of about 1000 (“PTHF10” manufactured by BASF)
00 ") 250 parts by weight and 45 parts by weight of 4,4'-diphenylmethane diisocyanate were melt-kneaded using a twin-screw extruder (L / D = 40 manufactured by Berstorf Co.) to obtain ester elastomer pellets. . The raw materials were supplied from the polyester copolymer (I) and the polytetramethylene glycol extruded feed material port, and from the injection port provided with 4,4′-diphenylmethane diisocyanate in the fourth cylinder. The extrusion temperature was 200 ° C. An elastomer pellet was obtained.

Example 2 Elastomer pellets were obtained in the same manner as in Example 1 except that the polyester copolymer (II) was used instead of the polyester copolymer (I).

Example 3 Elastomer pellets were obtained in the same manner as in Example 1 except that the polyester copolymer (III) was used instead of the polyester copolymer (I).

Comparative Example 1 Elastomer pellets were obtained in the same manner as in Example 1, except that the polyester copolymer (IV) was used instead of the polyester copolymer (I).

Comparative Example 2 An elastomer pellet was obtained in the same manner as in Example 1 except that the polyester copolymer (V) was used instead of the polyester copolymer (I).

Example 4 Polyester copolymer (V
I) 100 parts by weight of polytetramethylene glycol having a number average molecular weight of about 1000 (“PTHF100” manufactured by BASF)
0 ") 500 parts by weight and 15045 parts by weight of 4,4'-diphenylmethane diisocyanate are melt-kneaded using a twin-screw extruder (L / D = 40 manufactured by Berstorf Co.)
Ester elastomer pellets were obtained. The raw materials were supplied from the polyester-based copolymer (VI) and the polytetramethylene glycol extruded feed material port, and 4,4′-diphenylmethane diisocyanate was supplied from the injection port provided in the fourth cylinder. The extrusion temperature was 222 ° C. An elastomer pellet was obtained.

Example 5 Polyester-based copolymer (V
Elastomer pellets were obtained in the same manner as in Example 1, except that the polyester copolymer (VII) was used instead of I).

(Comparative Example 3) Polyester copolymer (V
Elastomer pellets were obtained in the same manner as in Example 1 except that the polyester copolymer (VIII) was used in place of I).

The pellets obtained in the above Examples and Comparative Examples were press-molded (press temperature: 230 ° C.) to produce a sheet having a thickness of 2 mm, and the following items were evaluated using the sheet, and the results were shown in Table. 2 is shown. (1) Glass transition temperature (Tg), melting point Differential scanning calorimeter (“D” manufactured by TA Instruments
SC2920 ”) at a heating rate of 10 ° C./min. (2) Surface hardness According to JIS K 7215, the surface hardness (H
_D D) was measured. (3) Compression set In accordance with JIS K 6301, the compression set was measured at 100 ° C. with an amount of compression set of 25%, and the set resistance was evaluated. (4) Tensile properties Tensile strength and tensile elongation at room temperature (23 ° C.) were evaluated according to JIS K6301.

[0061]

[Table 1]

[0062]

The ester elastomer of the present invention has the above constitution and is an ester elastomer having a high blockability of a short-chain polyester component, so that it has flexibility and mechanical properties at high temperatures. Excellent in sag resistance especially at high temperatures. The ester-based elastomer can be easily produced by the production method of the present invention using an extruder or the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J029 AA03 AC03 AD01 BA02 BA03 BA04 BA05 BA08 BA09 BA10 CB04A CB05A CB06A CC05A JE182 KE02 KE05 4J034 BA07 DA01 DB03 DB04 DB07 DF01 DF16 DF21 DF22 DG02 DH03 DG03 HC03 DG04 HC12 HC13 HC17 HC22 HC46 HC52 HC61 HC64 HC65 HC67 HC71 HC73 JA01 KA01 KB02 KC07 KC17 KC18 KC22 KD02 KD04 KD05 KD12 KE02 QA05 QB14 QB15 RA02 RA03 RA10 RA12 RA14

Claims (5)

[Claims] 1. A short-chain polyester component represented by the general formula (1) and a long-chain polyester component represented by the general formula (2) repeated, wherein the short-chain polyester component is 50 to 100% by weight, The long-chain polyester component is 5
0 to 0% by weight of a polyester copolymer (A);
A block copolymer with a polyether (B) composed of a repeating unit represented by the general formula (3), wherein the polyester copolymer (A) and the polyether (B) are:
It is bound by the isocyanate component (C) represented by the general formula (4), and the polyether (B) 50 to 10 is used based on 100 parts by weight of the polyester copolymer (A).
00 parts by weight and isocyanate component (C) 10 to 200
An ester-based elastomer characterized by being composed of parts by weight. —CO—R ⁰ —CO—O—R ¹ —O— (1) —CO—R ⁰ —CO—O—R ² — (2) —R ³ —O— (( 3) -O-CO-NH- R 4 -NH-CO-O- ··· (4) wherein, R ⁰ represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, R ¹ , R ³ represents an alkylene group having 2 to 8 carbon atoms, and R ⁴ represents an alkylene group having 2 to 15 carbon atoms or a phenylene group. R ² represents a component having a number average molecular weight of 500 to 5000, which is composed of a repeating unit represented by —R ⁵ —O— (wherein, R ⁵ represents an alkylene group having 2 to 8 carbon atoms)] 2. The ester-based elastomer according to claim 1, wherein the polyester-based copolymer (A) has a number average molecular weight of 500 to 5,000. 3. The polyether (B) having a number average molecular weight of 5
3. The composition according to claim 1, wherein the number is from 0.00 to 3000.
The ester-based elastomer according to the above. 4. The polyester-based copolymer (A) has an intrinsic viscosity of 0.05 to 1.0.
Or the ester-based elastomer according to 2 or 3. 5. A mixture of a short-chain polyester component represented by the general formula (1) and a long-chain polyester component represented by the general formula (2), wherein the short-chain polyester component is 50 to 100% by weight, The long-chain polyester component is 5
0 to 0% by weight of a polyester copolymer (A) 10
0 parts by weight, 50 to 1000 parts by weight of a polyether (B) composed of a repeating unit represented by the general formula (3), and 10 to 200 parts by weight of an isocyanate compound (D) represented by the general formula (5) A method for producing an ester-based elastomer, comprising melt-mixing parts. —CO—R ⁰ —CO—O—R ¹ —O— (1) —CO—R ⁰ —CO—O—R ² — (2) —R ³ —O— (( 3) —CO—NH—R ⁴ —NH—CO— (5) [wherein, R ⁰ represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ¹ and R ³ represent R ⁴ represents an alkylene group having 2 to 15 carbon atoms or a phenylene group; R ² represents a component having a number average molecular weight of 500 to 5000, which is composed of a repeating unit represented by —R ⁵ —O— (wherein, R ⁵ represents an alkylene group having 2 to 8 carbon atoms)]