JP2000309621A - Production of ester-based elastomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ester-based elastomer having high-temperature mechanical characteristics, especially high-temperature creep resistance and resistance to fatigue from flexing and high melt viscosity, useful in the field of automobiles by for compounding a polyester-based copolymer, etc., in a molten state. SOLUTION: This polyester-based elastomer is obtained by compounding 100 pts.wt. of a polyester-based copolymer (A) composed of 0-95 wt.% of a short-chain polyester component (i) of formula I (R0 is a 6-12C bifunctional aromatic hydrocarbon; R1 is a 2-8C alkylene) and 50-5 wt.% of a long-chain polyester component (ii) of formula II (R2 is a component which is composed of a repeating unit of the formula R-O and has 500-5,000 number-average molecular weight) with 50-500 pts.wt. of a polyether (B) constituted of a repeating unit of the formula R2O (R2 is a 2-8C alkylene), 10-100 pts.wt. of an isocyanate component (C) of formula III (R4 is a 2-15C alkylene or the like) and 0.01-20 pts.wt. of an epoxy compound (D) in a molten state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ester-based elastomer having excellent mechanical properties at high temperatures, particularly excellent creep resistance and bending fatigue resistance at high temperatures, and having a high melt viscosity suitable for extrusion molding and blow molding. The present invention relates to a method for producing an ester-based elastomer that can be provided.

[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. Thermoplastic elastomer (TP
E) has been attracting attention for a long time because it exhibits rubber elasticity at normal temperature but exhibits plasticity at high temperature and can be molded normally, and is used in various applications in the fields of automobiles, various industries, and the like. became. Among them, polyester-based elastomers (TPEE) have excellent mechanical strength, oil resistance, abrasion resistance, and flex fatigue resistance, and are therefore used in a wide range of industrial fields mainly in the automobile field. However, TPE
E has the disadvantages that it has higher hardness than ordinary rubber and lacks flexibility, and lacks creep resistance due to large compression set at the time of large deformation and high temperature, and its improvement has been desired.

[0003] On the other hand, when a thermoplastic resin is molded by an extrusion molding method or a blow molding method, a high melt viscosity is generally required. However, TPEE has a relatively low melt viscosity. There is a problem that molding failure such as uneven wall thickness occurs even if it is attempted to obtain. With respect to the improvement of the creep resistance of TPEE, attempts to improve the creep resistance by increasing the degree of polymerization have been known (see, for example, JP-A-52-121699). It was desired. As a technique for increasing the melt viscosity of TPEE, a technique of melt-mixing a diepoxy compound (D) and a metal salt of a carboxylic acid with a polyetherester elastic material is disclosed in, for example, JP-A-57-36124.

[0004]

However, according to the study of the present inventors, the polyester elastomer obtained by the method described in the above-mentioned Japanese Patent Application Laid-Open No. Sho 57-36124,
It is presumed to be caused by the metal salt of the carboxylic acid used as the catalyst, but there was an adverse effect such as a decrease in durability, particularly hydrolysis resistance. The present invention has been made in view of the above-mentioned problems relating to the conventional method for producing an ester-based elastomer, and has excellent mechanical properties at high temperatures, in particular, excellent resistance to creep and bending fatigue at high temperatures, and high melt viscosity. It is an object of the present invention to provide a method for producing an ester-based elastomer, which is capable of producing an elastomer.

[0005]

In order to achieve the above object, a method for producing an ester-based elastomer according to the present invention according to claim 1 comprises a short-chain polyester component represented by the following general formula (1): (2) is constituted by repeating the long-chain polyester component, wherein the short-chain polyester component is 50 to 95% by weight, and the long-chain polyester component is 50 to 95% by weight.
100 parts by weight of a polyester copolymer (A), which is 5% by weight; 50 to 500 parts by weight of a polyether (B) composed of a repeating unit represented by the general formula (3); 10 to 100 parts by weight of the isocyanate component (C) and 0.01 to 20 parts by weight of the epoxy compound (D) are melt-mixed.

[0006]

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[0007]

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[0008]

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[0009]

Embedded image The method for producing an ester-based elastomer according to the present invention according to claim 2 is characterized in that 0.01 to 20 parts by weight of the amine compound (E) having two or more active hydrogens is added to the polyester-based copolymer (A) 100 Parts by weight, polyether (B) 50-5
After melt-mixing 00 parts by weight and 10 to 100 parts by weight of the isocyanate component (C), they are added and melt-mixed.

The polyester copolymer (A) used in the present invention is composed of a repeating short-chain polyester component represented by the general formula (1) and a long-chain polyester component represented by the general formula (2). You. As the polyester copolymer (A), for example, a known polyester terelastomer obtained by reacting an aromatic dicarboxylic acid or an ester-forming derivative thereof with a low molecular weight diol and a polyether can be used.

The aromatic dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid and the like, and the ester-forming derivatives thereof include dimethyl terephthalate and isophthalic acid. And dimethyl orthophthalate, dimethyl naphthalenedicarboxylate and dimethyl paraphenylenedicarboxylate.

Examples of the low molecular weight diol for obtaining the polyester copolymer (A) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 4 Butanediol, neopentyl glycol, 1,5-pentanediol, 1,6
-Hexanediol and the like, which may be used alone or in combination of two or more.

Examples of the polyether for obtaining the polyester copolymer (A) include polyethylene glycol, poly 1,3-propylene glycol, poly 1,2 propylene glycol, polytetramethylene glycol,
And polyhexamethylene glycol. Among them, polytetramethylene glycol is preferable in terms of excellent mechanical properties and weather resistance. Examples of commercially available products include "PTHF" manufactured by BASF and "PTMG" manufactured by Mitsubishi Chemical Corporation.

The above polyether has a number average molecular weight of 50.
It is preferable to use one having 0 to 5,000, and more preferably one having 500 to 2,000. When the number average molecular weight is less than 500, the resulting polyester copolymer
The blockability of (A) is lowered and the melting point is lowered, and as a result,
The mechanical strength at a high temperature of the ester elastomer obtained by the present invention is reduced. Further, the number average molecular weight is 5,0
If it exceeds 00, the compatibility with the polyether (B) becomes low, so that the degree of polymerization of the ester elastomer does not increase, and an elastomer having sufficient strength cannot be obtained.

The above polyester copolymer (A) can be polymerized by a known method. In particular,
The aromatic dicarboxylic acid and its ester-forming derivative, together with the polyether and excess low molecular weight diol, are heated to 200 ° C. in the presence of a catalyst to effect a transesterification reaction, followed by a polycondensation reaction at 240 ° C. under reduced pressure. By performing the above, a polyester-based copolymer (A) can be obtained.

The proportion of the short-chain polyester component in the components of the polyester-based copolymer (A) is 50 to 95.
%, Preferably 70 to 90% by weight. When the content of the short-chain polyester component is less than 50% by weight, the melting point of the polyester copolymer (A) is low, which adversely affects the mechanical strength of the ester elastomer at high temperatures. If it exceeds 95% by weight, 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 polyether (B) used in the present invention comprises a repeating unit represented by the above general formula (3).
As such a polyether, for example, the same polyether as that used for obtaining the above-mentioned polyester-based copolymer (A) is suitably used.

The isocyanate component used in the present invention
(C) is represented by the above general formula (4), and its structure is not particularly limited as long as it is a compound having two isocyanate groups in the same molecule.

Examples of the isocyanate component (C) include 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate,
Aromatic diisocyanates such as naphthalene diisocyanate; 1,2-ethylene diisocyanate, 1,3-propylene diisocyanate, 1,4-butane diisocyanate,
Examples thereof include aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, isophorone diisocyanate, and hydrogenated 4,4′-diphenylmethane diisocyanate.

Epoxy compound (D) used in the present invention
Is not particularly limited as long as it has one or more epoxy groups in one molecule. Preferably, an elastomer having two or more epoxy groups in one molecule is used because the melt viscosity of the obtained elastomer can be increased. These are usually classified into polyphenol type, polyglycidylamine type, alcohol type, ester type, alicyclic type and the like.

Specifically, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether,
Glycerol polyglycidyl ether, ethylene polyethylene glycol glycidyl ether, pentaerythritol polyglycidyl ether, N, N'-diglycidylphenylaniline, N, N, N ', N'-tetraglycidyldiaminodiphenylmethane, diglycidyl phthalate, hydrogenated Diglycidyl phthalate, 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexanecarboxylate and the like can be mentioned.

Preferred epoxy compounds (D) include polyethylene glycol diglycidyl ether and pentaerythritol polyglycidyl ether. These may be used alone or in combination of two or more. Commercial products of the epoxy compound (D) include, for example, "Denacol" manufactured by Nagase Kasei, "Araldite" manufactured by Ciba-Geigy, "Epicoat" manufactured by Yuka Shell Epoxy, and the like.

The structure of the amine compound having two or more active hydrogens used in the present invention is not particularly limited. Examples of usable amine compounds include aniline, ethylenediamine, hexamethylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, and diethylaminopropylamine.

Preferred amine compounds include diamine compounds in terms of reactivity and melt viscosity of the resulting elastomer. Specifically, hexamethylenediamine, aliphatic amine compounds such as trimethylhexamethylenediamine and modified products thereof, 3,3′-dimethyl 4,4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylmethane, isophorone diamine Modified, 4,4'-diaminodiphenylmethane, 4,4'-diaminophenyl ether, diaminodiphenylsulfone, toluylenediamine, aromatic amine compounds such as xylenediamine and modified products thereof,
Heterocyclic modified amines such as 1,3'-bis (aminomethyl) cyclohexane and the like can be mentioned. Examples of these commercially available products include "Acmex" manufactured by Nippon Synthetic Chemical Industry Co., Ltd., "Epicure" and "EpoMate" manufactured by Yuka Shell Epoxy Co., Ltd. "Sumicure" manufactured by Sumitomo Chemical Co., Ltd., and "Hardner" manufactured by Ciba Kaigie Co., Ltd.

The ester elastomer of the present invention comprises 50 to 500 parts by weight of the polyether (B), 10 to 100 parts by weight of the isocyanate component (C), and 100 to 100 parts by weight of the polyester copolymer (A). Compound (D)
01 to 20 parts by weight, and preferably also an amine compound
(E) is obtained by melting and mixing 0.01 to 20 parts by weight of (E). As described in detail below, the order of adding the epoxy compound (D) is not particularly limited, but the amine compound (E) is
It is necessary to add the polyester copolymer (A), the polyether (B) and the isocyanate component (C) after melt mixing.

When the amount of the polyether (B) is less than 50 parts by weight with respect to 100 parts by weight of the polyester copolymer (A), the ester elastomer does not have sufficient flexibility, and is not 500 parts by weight. If it exceeds, sufficient mechanical strength cannot be obtained. Preferably, it is 100 to 300 parts by weight.

When the amount of the isocyanate component (C) is less than 10 parts by weight per 100 parts by weight of the polyester copolymer (A), the ester elastomer does not become a high molecular weight polymer and has low mechanical strength. It becomes something, 100
When the amount exceeds the weight part, the ester elastomer becomes inferior in flexibility. Preferably, 30 to 70
Parts by weight.

When the amount of the amine compound having two or more active hydrogens is less than 0.01 part by weight based on 100 parts by weight of the polyester copolymer (A), the ester elastomer has sufficient melt viscosity. If the amount exceeds 20 parts by weight, gelation proceeds depending on the kind of the amine compound, and the melt fluidity is lost. Preferably, 0.1
To 10 parts by weight.

When the amount of the epoxy compound (D) is less than 0.01 part by weight based on 100 parts by weight of the polyester copolymer (A), the ester elastomer cannot obtain a sufficient melt viscosity, If the amount exceeds the weight part, gelation proceeds depending on the type of the epoxy compound (D), and the melt fluidity is lost. Preferably, it is 0.1 to 10 parts by weight.

The above-mentioned polyester copolymer (A), polyether (B), isocyanate component (C), epoxy compound
To melt-mix (D) and the amine compound (E), usually,
An extruder is used. The type of the extruder is not particularly limited, and a single-screw extruder or a twin-screw extruder is used. From the viewpoint of the efficiency of stirring and mixing, preferably, a co-rotating twin-screw extruder or a different-rotating twin extruder is used. A screw extruder is used,
More preferably, a co-rotating meshing twin screw extruder is used.

The extrusion temperature is preferably from 180 to 260 ° C. 1
If the temperature is lower than 80 ° C, the reaction is difficult because the polyester copolymer (A) does not melt, and it is difficult to obtain an ester elastomer as a high molecular weight polymer. (A) and isocyanate are decomposed, and it is difficult to obtain an ester elastomer having sufficient strength. A more preferable range of the melt mixing temperature is 200 to 24.
0 ° C.

In the method for producing the ester elastomer of the present invention, for example, the polyester copolymer (A), the polyether (B), the isocyanate component (C) and the epoxy compound (D) are melt-mixed, and then the amine is added. Compound (E) is supplied and melt-mixed, or the above three raw materials (A)
Are melt-kneaded to supply an amine compound (E), and then an epoxy compound (D) is supplied and melt-kneaded. Amine compound
When (E) is not supplied, the order of addition is not particularly limited as long as the epoxy compound (D) is supplied and melt-mixed until the elastomer formation reaction by the three kinds of raw materials (A) to (C) is completed. Not

When the amine compound (E) is supplied, three kinds of raw materials are used in order to exert the action of the amine compound (E).
That is, it is important that the polyester copolymer (A), the polyether (B) and the isocyanate component (C) are melt-mixed, then added and melt-mixed.

In this case, the polyester copolymer (A), the polyether (B) and the isocyanate component (C) are melt-kneaded in advance, and then the above-mentioned amine compound (E) is supplied and melt-kneaded. D) may be supplied and melt-kneaded, and three kinds of raw materials, (A) to (C) and the epoxy compound (D)
May be melt-kneaded, and then the amine compound (E) may be supplied and melt-kneaded. In some cases, the above three raw materials,
After melt-kneading (A) to (C), the epoxy compound (D) and the amine compound (E) may be simultaneously supplied and melt-mixed.

However, a method of supplying the amine compound (E) before the start of the elastomer formation reaction, for example, any one of the polyester copolymer (A), the polyether (B) and the isocyanate component (C) Raw materials and amine compounds (E)
And the other three raw materials and the four components of the amine compound (E), or the five components to which the epoxy compound (D) is further added, are simultaneously supplied and melt-mixed. In this case, due to the difference in reactivity between each of the polyester copolymer (A), the polyether (B) and the amine compound (E), and the isocyanate component (C), a non-uniform reaction occurs and sufficient mechanical An elastomer showing the proper strength cannot be obtained.

In the present invention, a catalyst may be used at the time of melting and mixing the above components. Examples of the catalyst include stannous diacyl, stannous tetraacyl, dibutyltin oxide,
Dibutyltin dilaurate, 2-ethylhexanetin, dimethyltin malate, tin dioctanoate, tin tetraacetate, triethyleneamine, diethyleneamine, triethylamine, metal salts of naphthenate, metal octylate, triisobutylaluminum, tetrabutyltitanate, calcium acetate , Germanium dioxide, antimony trioxide and the like are preferred. Two or more of the above catalysts may be used in combination.

A stabilizer may be used in the ester elastomer obtained according to the present invention, for example, 1,3,5-
Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-
(Hydroxybenzyl) benzene, 3,9-bis {2- [3- (3
-Tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl {-2,4,8,10-
Hindered phenolic antioxidants such as tetraoxaspiro [5,5] undecane; 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 3,3′-thio Examples thereof include heat stabilizers such as dipropionate, pentaerythryltetrakis (3-laurylthiopropionate), and ditridecyl 3,3'-thiodipropionate.

The ester-based elastomer obtained according to the present invention includes fibers, flame retardants, ultraviolet absorbers, antistatic agents, inorganic fillers, inorganic substances, higher fatty acid salts, etc. within a range that does not impair the utility during or after production. May be added. Examples of the fibers include inorganic fibers such as glass fibers, carbon fibers, boron fibers, silicon carbide fibers, alumina fibers, amorphous fibers, and silicon / titanium / carbon fibers; and organic fibers such as aramid fibers. Examples of the flame retardant include hexabromocyclododecane, tris- (2,3-dichloropropyl) phosphate,
Pentabromophenyl allyl ether and the like, as the 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.

As the above antistatic agent, for example, N, N-
Bis (hydroxyethyl) alkylamine, alkyl allyl sulfonate, alkyl sulfanate and the like can be mentioned. Examples of the inorganic filler include calcium carbonate, titanium oxide, mica, and talc, and examples of the inorganic substance include barium sulfate, alumina, and silicon oxide. As the higher fatty acid salt, for example, sodium stearate, barium stearate,
And sodium palmitate.

The ester-based elastomer of the present invention may be used after mixing thermoplastic resins and rubber components other than those described above to modify the properties thereof. Examples of the thermoplastic resin include polyolefin, modified polyolefin, polystyrene, polyvinyl chloride, polyamide, polycarbonate, polysulfone, and polyester.
As the rubber component, for example, natural rubber, styrene-
Butadiene copolymer, polybutadiene, polyisoprene, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer (EPM, EPDM), polychloroprene, butyl rubber, acrylic rubber, silicon rubber, urethane rubber, olefin-based thermoplastic elastomer, Styrene-based thermoplastic elastomer, PVC-based thermoplastic elastomer, ester-based thermoplastic elastomer, amide-based thermoplastic elastomer, and the like.

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 and blow molding. The molding temperature varies depending on the melting point of the ester-based elastomer and the molding method, but 160 to 280 ° C is suitable. If the temperature is lower than 160 ° C, a uniform molded article cannot be obtained because the fluidity of the ester elastomer is low. If the temperature exceeds 280 ° C, the ester elastomer is decomposed, and it is difficult to obtain an ester elastomer having sufficient strength. Becomes

The molded article obtained by using the ester-based elastomer of the present invention is suitably used for, for example, automobile parts, electric and electronic parts, industrial parts, sports goods, medical goods and the like. Examples of automobile parts include boots such as constant velocity joint boots and rack and opinion boots; ball joint seals; safety belt parts;
Bumper fascia; emblem; mall, and the like. Examples of the electric and electronic components include a wire covering material, gears, a rubber switch, a membrane switch, a tact switch, an O-ring, and the like.

Examples of the sports equipment include shoe soles and balls for ball contact. 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.

(Function) In the method for producing an ester elastomer according to the present invention, a specific amount of the above-mentioned specific polyester copolymer (A), polyether (B) and isocyanate component (C) is melt-mixed, The basic technology is to obtain an elastomer by reacting. Claim 1
In the method for producing an ester-based elastomer according to the present invention, as described above, the reaction proceeds without adding the metal carboxylate as a catalyst by adding the epoxy compound (D) during the elastomer-forming reaction. Therefore, according to the present invention, it is possible to obtain an ester elastomer having a high melt viscosity and without impairing hydrolysis resistance and the like. According to the study of the present inventors, the polyester-based copolymer (A),
In the elastomer obtained by the reaction of the polyether (B) and the isocyanate component (C), bonds having poor durability such as an allohanate bond and a biuret bond are formed in the molecule. In the present invention described in claim 2, attention is paid to the fact that the above-mentioned allohanate bond and biuret bond are easily cleaved by a primary or secondary amine compound.
The above-mentioned allohanate bond and biuret bond were decomposed by allowing an amine compound (E) having at least one compound to act during the production of the elastomer. Furthermore, focusing on the high reactivity between the epoxy compound (D) and the amine compound (E), the amine terminal generated by the decomposition reaction and the epoxy compound
By rapidly reacting (D) with (E), the molecular weight of the elastomer is further increased or a branch is formed. Therefore, according to the present invention described in claim 2,
While the present invention according to claim 1 is common in that a metal carboxylate need not be added as a catalyst, the combination of the amine compound (E) and the epoxy compound (D) increases the molecular weight or branches of the elastomer. With the action of generation,
An ester elastomer having a high melt viscosity and a higher hydrolysis resistance can be obtained. On the other hand, in the present invention, as a raw material, a polyester-based copolymer (A) composed of a repeating unit represented by the above specific general formula, a polyether (B) represented by a specific general formula, and a specific Since the isocyanate component (C) represented by the general formula is used, the ester elastomer obtained by the present invention has a high blockability of the hard segment component and the soft segment component, and the crystal formed by the short-chain polyester component has a crosslinking point. It is considered that the composition as described above shows properties as an elastomer.

In particular, the polyester-based copolymer (A) as an ester-based elastomer is composed of a hard segment having a high proportion of a short-chain polyester component represented by the general formula (1) and a soft segment. Is a general formula
(2) is composed of a portion having a high proportion of the long-chain polyether polyester component, so that the short-chain polyester component is easier to crystallize than the conventional ester-based elastomer having the same degree of flexibility, As a result, a strong crosslinking point is formed, and excellent mechanical properties at high temperatures, particularly creep resistance, can be exhibited.

[0046]

[Glass transition temperature Tg, melting point]

The measurement was performed at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC). [Surface hardness] The surface hardness was measured at 23 ° C according to JIS K7215.

[Tensile Properties] Tensile strength and tensile elongation at room temperature (23 ° C.) were evaluated according to JIS K6301. [Compression Permanent Strain] Based on JIS K6301, the creep resistance was evaluated by measuring the compression set at 25% at 100 ° C.

[Melting temperature] Using a Capillograph 1B manufactured by Toyo Seiki, 220 ° C, 128 ° C
It was measured under the condition of sec- ¹ . [Hydrolysis resistance] Using a pressure cooker tester, a test piece immersed at 120 ° C for 72 hours in accordance with JIS K6301 at room temperature (23 ° C)
Was measured, and evaluated by the retention of the tensile strength before immersion.

Synthesis of Polyester Copolymer (A) 100 parts by weight of dimethyl terephthalate, 1,4-butanediol
102 parts by weight, 48 parts by weight of polytetramethylene glycol having a number average molecular weight of about 1000 (PTHF1000 manufactured by BASF) (hereinafter abbreviated as (b)), 0.3 parts by weight of tetrabutyl titanate as a catalyst, and 1,3,5 as a stabilizer -Trimethyl-2,4,6-
Tris (3,5-di-t-butyl-4-hydroxybenzyl)
0.3 parts by weight of benzene and 0.3 parts by weight of tris (2,4-di-t-butylphenyl) phosphite were added, and the reaction system was placed under nitrogen.
The mixture was kept at 200 ° C. for 3 hours to carry out a transesterification reaction. The progress of the transesterification reaction was confirmed by measuring the amount of methanol distilled out. After the transesterification proceeded, the temperature was raised to 240 ° C. in 20 minutes, and the pressure was reduced. Polymerization system is 20
Minutes, the degree of reduced pressure reached 2 mmHg or less. As a result of a polycondensation reaction for 20 minutes in this state, 160 parts by weight of a white polyester copolymer (a) was obtained.

Example 1 The above-mentioned polyester copolymer
(a) 100 parts by weight, the above polytetramethylene glycol (b)
110 parts by weight, 4,4'-diphenylmethane diisocyanate
36 parts by weight, and as an epoxy compound (D), polyethylene glycol diglycidyl ether (manufactured by Nagase Chemicals,
“Denacol EX811”) was heated at 220 ° C. using a twin-screw extruder (L / D = 40 mm, manufactured by Berstorf).
And melt kneading (residence time 230 seconds) to obtain pellets of the ester elastomer. The extrusion temperature was 220 ° C.

The raw material was supplied from a polyester copolymer.
(a) and polytetramethylene glycol (b) were fed from the raw material feed port of the extruder, and 4,4'-diphenylmethane diisocyanate was fed from the injection port provided in the fourth cylinder to the epoxy compound.
(D) was performed from the inlet provided in the sixth cylinder downstream of these. Using the obtained pellets, a 2 mm-thick ester-based elastomer sheet was prepared by press molding (press temperature: 230 ° C.), and various physical properties were measured. The results are shown in Table 1.

Example 2 As an epoxy compound (D), 2 parts by weight of "Denacol EX811" manufactured by Nagase Kasei and 1 part by weight of pentaerythritol polyglycidyl ether ("Denacol EX411" manufactured by Nagase Kasei) were used. Except for this, pellets of the ester elastomer were obtained in exactly the same manner as in Example 1. Obtained. Using the obtained pellets, a sheet having a thickness of 2 mm was prepared by press molding (press temperature: 230 ° C.), and various physical properties were measured. The results are shown in Table 1.

Example 3 The above polyester copolymer
(a) 100 parts by weight, the above polytetramethylene glycol (b)
110 parts by weight, 4,4'-diphenylmethane diisocyanate
36 parts by weight, 3 parts by weight of polyethylene glycol diglycidyl ether ("Denacol EX811", manufactured by Nagase Kasei Co., Ltd.) as an epoxy compound (D), and 0.5 part by weight of diaminodiphenylmethane as an amine compound (E) having two or more active hydrogens. Twin screw extruder (L / D manufactured by Berstorf)
= 40 mm) and melt kneading at 220 ° C (residence time 23
0 second) to obtain an ester-based elastomer pellet.
Raw materials were supplied by feeding the polyester copolymer (a) and polytetramethylene glycol (b) from the raw material feed port of the extruder.
4′-diphenylmethane diisocyanate was supplied from the inlet provided in the fourth cylinder, and diaminodiphenylmethane was supplied from the inlet provided in the sixth cylinder downstream of these.
"Denacol EX811" was performed from the inlet provided in the eighth cylinder further downstream. Using the obtained pellets, a 2 mm-thick ester-based elastomer sheet was prepared by press molding (press temperature: 230 ° C.), and various physical properties were measured. The results are shown in Table 1.

Example 4 The procedure of Example 3 was repeated, except that 2 parts by weight of "Denacol EX411" manufactured by Nagase Kasei Co., Ltd. was used as the epoxy compound (D).
Ester elastomer pellets were obtained. Using the obtained pellets, a sheet having a thickness of 2 mm was prepared by press molding (press temperature: 230 ° C.), and various physical properties were measured. The results are shown in Table 1.

Example 5 An ester-based elastomer was prepared in the same manner as in Example 3 except that “Denacol EX811” manufactured by Nagase Kasei Co., Ltd. was supplied from the raw material supply port of the extruder as the epoxy compound (D). A pellet was obtained. Press molding using the obtained pellets (press temperature
230 ° C.) to prepare a sheet having a thickness of 2 mm, and various physical properties were measured. The results are shown in Table 1.

Comparative Example 1 Ester elastomer pellets were obtained in exactly the same manner as in Example 1 except that the epoxy compound (D) was not added. Using the obtained pellets, a sheet having a thickness of 2 mm was prepared by press molding (press temperature: 230 ° C.), and various physical properties were measured. The results are shown in Table 1.

Comparative Example 2 Polyester Copolymer (a)
And polytetramethylene glycol (b) and an amine compound (hexamethylenediamine) were supplied from an extruder raw material supply port and 4,4'-diphenylmethane diisocyanate was supplied from an injection port provided in a fourth cylinder. Melt kneading was carried out in exactly the same manner as in Example 3, but no elastomer was obtained.

[0058]

[Table 1]

[0059]

According to the present invention, the method for producing an ester-based elastomer of the present invention has the above-mentioned constitution. According to the present invention, it has both flexibility and mechanical properties at a high temperature, particularly creep resistance, and further has a melt viscosity. It is possible to obtain an ester elastomer which is high and can be suitably used for extrusion molding and blow molding. Further, an amine compound (E) having two or more active hydrogens
In the above method for producing an ester-based elastomer, which is melt-mixed, an ester-based elastomer having a high melt viscosity and a higher hydrolysis resistance can be obtained by the reaction with the epoxy compound (D).

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shigeichi Fukaya 2-1 Hyakuyama, Shimamoto-cho, Mishima-gun, Osaka Sekisui Chemical Co., Ltd. F-term (reference) 4J034 BA07 BA08 CA15 DC02 DC03 DC43 DF01 DF16 DF21 DF22 DG02 DH02 DH06 DK00 HA01 HA07 HC01 HC03 HC12 HC13 JA01 QB15 RA02 RA03 RA08 RA11 RA12 RA14

Claims (2)

[Claims] 1. A short-chain polyester component represented by the following general formula (1) and a long-chain polyester component represented by the following general formula (2):
0 to 95% by weight, and the long-chain polyester component is 50 to 5%.
100% by weight of a polyester copolymer (A), which is 50% by weight, 50 to 500 parts by weight of a polyether (B) composed of a repeating unit represented by the general formula (3), and represented by a general formula (4) And 10 to 100 parts by weight of an isocyanate component (C) and 0.01 to 20 parts by weight of an epoxy compound (D). Embedded image Embedded image Embedded image Embedded image 2. An amine compound having two or more active hydrogens.
(E) 0.01 to 20 parts by weight, 100 parts by weight of the polyester-based copolymer (A), polyether (B) 50 to 500
2. The method for producing an ester elastomer according to claim 1, wherein after melt-mixing 10 to 100 parts by weight of the isocyanate component (C), the mixture is added and melt-mixed.