JP2002121274A - Thermoplastic elastomer, its application and method for producing the elastomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic elastomer excellent in moisture permeability and especially excellent in flexibility and mechanical properties at high temperatures, in particular, resistance to loss of firmness at high temperature. SOLUTION: This thermoplastic elastomer contains a polyether component (A) as a constituent unit, wherein the C/O ratio of a polyoxyalkylene (CnH2nO) constituting the polyether constituent unit is 2.0-2.5, the polyether component accounts for 50-95 wt.% of the thermoplastic elastomer and the glass transition temperature of the thermoplastic elastomer is <=-20 deg.C. Especially, the polyether component (A) and a polyester component (B) in this elastomer are preferably linked via a polyisocyanate component (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic elastomer containing a polyether component (A) as a constituent unit and a method for producing the same. The present invention also relates to a fiber made of a thermoplastic elastomer having excellent water absorption and moisture release properties, and a fabric made of the fiber. Further, the present invention relates to an elastomer sheet comprising a thermoplastic elastomer containing a polyether component (A) as a constituent unit and having both excellent moisture permeability and water stopping property, and a method for producing the same. The present invention also relates to a moisture-permeable waterproof fabric having both excellent moisture permeability and waterproofness, and to clothing, tents, and shoes comprising the same. In addition, the present invention is a molded article used in the medical, hygiene or pharmaceutical fields, particularly infusions, containers such as blood transfusion bags, infusion set tubes, blood transfusion circuit tubes, tubes such as catheters, or these. The present invention relates to a molded article for medical use such as an injection molded part such as an instrument stopper.

[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 the field of various industrial products and the like. Among them, polyester-based thermoplastic elastomer (TPEE) is excellent in mechanical strength, heat resistance, abrasion resistance, and bending fatigue resistance, and is used in a wide range of industrial fields mainly in the automobile field. There are two types of polyester-based thermoplastic elastomers (TPEE), a polyester-polyether type and a polyester-polyester type. The polyester-polyether type is mainly used. The polyester / polyether type is obtained, for example, by transesterification using dimethyl terephthalate, 1,4-butanediol and polytetramethylene glycol as starting materials, followed by a polycondensation reaction in a vacuum.
That is, it is a multi-block copolymer in which a condensate of 1,4-butanediol and terephthalic acid is used as a hard segment, and a condensate of polytetramethylene glycol and terephthalic acid is used as a soft segment.

However, this type of polyester-based thermoplastic elastomer has disadvantages such as a higher hardness than a normal rubber region, lacking flexibility, and a large compression set at the time of large deformation and high temperature, and lacking in sag resistance. There is a need for improvement. When imparting flexibility to a polyester-based thermoplastic elastomer, it is necessary to reduce the amount of a hard segment component that performs physical crosslinking. However, in this case, the conventional technology as disclosed in Japanese Patent Application Laid-Open No. 2-88632 has a problem that the blockability of the hard segment component is reduced, and as a result, the melting point is reduced and the mechanical properties at high temperatures are reduced. was there. As for the sag resistance, as disclosed in JP-A-52-121699, there is a technique of improving the degree of polymerization by increasing the degree of polymerization, but there is a limit, and compatibility with flexibility is impossible. Met.

On the other hand, in the sanitary field or the garment field, attention has been paid to materials having excellent moisture permeability. As disclosed in JP-A-59-111847, by specifying the composition and amount of the soft segment, excellent moisture permeability can be obtained. Further, as disclosed in Japanese Patent Application Laid-Open No. 62-290714, a thermoplastic urethane elastomer is also known as a material having excellent moisture permeability. However, these materials disclosed conventionally have insufficient moisture permeability, and improvement thereof is desired. Furthermore, urethane resins using paraphenylene diisocyanate, which are commonly used, have a problem of discoloration due to light, and improvement is desired. Various studies have been made to obtain a composite sheet using a polyester resin instead of the polyurethane resin. However, since the polyester resin has a lower solubility in a solvent than the polyurethane resin, the processing method itself is restricted in nature. As disclosed in Japanese Patent Application Laid-Open No. H8-31233, a method of manufacturing a porous film, such as applying a solution of a polyester-based elastomer onto a substrate while heating, solidifying by cooling, and then performing wet film formation, is known. is there.

[0005] It is known that a fiber made of a material having excellent water absorption and moisture release properties is excellent in sweat absorption properties, is excellent in sweat treatment performance, and can provide a dry touch and silky fabric. Conventionally, polyurethane-based elastic fibers have been used. Attention has been focused on elastic fibers made of ester-based elastomers. However, since these materials have high hydrophobicity, when they are used as fabrics, their hygroscopicity is limited, so that dry-touched fabrics cannot be provided.

[0006] Materials having excellent water absorption and moisture release properties include ester elastomers having a specified soft segment composition and amount as disclosed in JP-A-59-111847 and JP-A-62-290714. Although a thermoplastic urethane elastomer is known, its hygroscopicity and drying property are still insufficient. As the material of the film or sheet, the above-mentioned polyester-based thermoplastic elastomer is known (for example, see JP-A-57-133302). However, there is room for improvement in flexibility of a film or sheet made of this elastomer. There is a problem that it is difficult to provide the film to a field requiring elasticity, and a film or sheet having both heat resistance and mechanical properties such as strength and flexibility has not been known. The moisture-permeable waterproof fabric that has both moisture-permeability and waterproof performance has the function of releasing water vapor from sweat from the body to the outside of clothes, preventing rain from entering the clothes,
In order to impart these functions, a material obtained by coating or laminating a cloth with a polyamino acid urethane resin, a polyurethane resin, a polytetrafluoroethylene resin or the like is well known. However, a fabric coated with a normal polyurethane resin has a poor moisture permeability, and thus has a drawback that it becomes stuffy when worn. In order to solve this problem, there has been proposed a method of applying a mixture of a polyurethane resin and wood powder having hygroscopicity (Japanese Patent Application Laid-Open No. 9-13277). In addition, a fabric laminated with a microporous film of polytetrafluoroethylene is excellent in moisture permeability and waterproofness, but the pores are clogged with dust and the like, and there is a drawback that moisture permeability is reduced, and the texture is also low. It is hard and its wearability is poor, especially for clothing, and its use is limited.

[0007] Conventionally, plastic molded products used in the medical, health and hygiene or pharmaceutical fields are different from metals and glasses in that they are lightweight, hard to break, and can be processed into various shapes such as films and tubes. They are widely used due to their advantages such as extremely low price and use in disposable applications. As physical properties, it is required to withstand sterilization treatments such as high-pressure steam sterilization, radiation sterilization, and ethylene oxide gas sterilization, and to easily treat waste after use. Further, depending on the application, transparency of the material is also required.

[0008] Polyethylene resins are generally excellent in impact resistance, flexibility, and transparency, but because of their low melting point temperature, high-pressure steam sterilization at 110 ° C or higher alone is difficult. Therefore, it is necessary to lower the sterilization temperature or prolong the sterilization time. Increasing the density of the resin improves heat resistance,
On the other hand, transparency and flexibility must be sacrificed. Polypropylene resins have a higher softening point temperature and higher heat resistance than polyethylene resins, but have a high elastic modulus and therefore can be used alone for flexible bags, films, tubes, etc. Insufficient impact strength. Therefore, it must be used as a blend with other soft resins or elastomer resins or as a multilayer molded product. Ethylene-vinyl acetate copolymer is excellent in transparency and flexibility, but has low heat resistance, and there is a problem that the acetic acid component is eluted by heating or sterilization treatment.
It is necessary to separately perform cross-linking by irradiating an electron beam.
To solve these problems, medical materials using various cyclic polyolefin-based resins such as norbornene-based resins and cross-linked cyclic polyolefin-based resins have been disclosed in Japanese Unexamined Patent Publication No. Hei.
This is disclosed in, for example, JP-A-337164 and JP-A-5-317411. In addition, there is a concern about the use of polyvinyl chloride resin because it generates dioxin which adversely affects the environment during disposal.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and a first object of the present invention is to provide a thermoplastic elastomer excellent in moisture permeability and light resistance and a method for producing the same. Is to do. The second object is that the blockability of the hard segment component and the soft segment component is high, the flexibility and the mechanical properties at high temperatures are excellent, especially the sag resistance at high temperatures, and the moisture permeability, coating liquid processability, An object of the present invention is to provide a thermoplastic elastomer excellent in light resistance and a method for producing the same.

Another object of the present invention is to provide a fiber made of a thermoplastic elastomer having excellent hygroscopicity and moisture release properties, and a cloth made of the fiber. Another object of the present invention is to provide a film or sheet having excellent moisture permeability, waterproofness, and flexibility in view of the above-mentioned problems of the related art. Another object of the present invention is to provide a moisture-permeable waterproof fabric excellent in moisture permeability, waterproofness, and wearability in view of the above-mentioned problems of the prior art. The purpose of the present invention is to provide excellent clothing, tents and shoes. Also, the present invention provides flexibility, heat resistance,
Medical molded articles made of a thermoplastic elastomer having excellent sterilization resistance and excellent steam sterilization properties, in particular, containers such as infusion bags, infusion set tubes, blood circuit tubes, tubes such as various catheters, and instruments thereof. It is an object of the present invention to provide an injection molded article such as a stopper. The moisture permeability in the present invention means that moisture is absorbed from one surface and released from the other surface.

[0011]

Means for Solving the Problems That is, the present invention provides
(1) Polyether component (A) is contained as a structural unit
Thermoplastic elastomer, the above polyether
Polyoxyalkylene (-C_nH _2nO
-) Having a carbon / oxygen atomic ratio of 2.0 to 2.5,
The polyether content in the plastic elastomer is 50 to
95% by weight, glass transition of thermoplastic elastomer
A thermoplastic resin having a temperature of -20 ° C or lower.
Lastomer, (2) Polyether component (A)
That they are linked by the cyanate component (C)
The thermoplastic elastomer according to the above (1),
(3) The number average molecular weight of the polyether component (A) is 50
The above (1) or 0 to 5000,
(2) the thermoplastic elastomer according to (2),
The polyester component (A) is composed of a polyethylene glycol component.
In any one of the above (1) to (3),
The thermoplastic elastomer described in (5) as a structural unit
A polyester component (B) is contained;
(B) having a number average molecular weight of 500 to 10,000
The method according to any one of (1) to (4), wherein
Thermoplastic elastomer, (6) Polyelite as a structural unit
The polyester component (B) contains a stell component (B).
Is a short-chain polyester component represented by the following general formula (1).
Represented by the following general formula (2) with 50 to 100% by weight per minute.
That the long-chain polyester component comprises 50 to 0% by weight.
The heat according to any one of (1) to (5), which is characterized by:
Plastic elastomer, -CO-R₁-CO-OR_Two-O- (1) (However, R₁ Is a divalent aromatic hydrocarbon having 6 to 12 carbon atoms
And / or a divalent alkylene group having 2 to 10 carbon atoms
Or a divalent aliphatic cyclic hydrocarbon group having 6 to 12 carbon atoms, R
_Two Is an alkylene group having 2 to 8 carbon atoms and / or 6 to 6 carbon atoms.
And 12 divalent aliphatic cyclic hydrocarbon groups. ) -CO-R_Three-CO-OR_Four-(2) (However, R_Three Is a divalent aromatic hydrocarbon having 6 to 12 carbon atoms
And / or a divalent alkylene group having 2 to 10 carbon atoms
Or a divalent aliphatic cyclic hydrocarbon group having 6 to 12 carbon atoms, R
_Four Is -R_FiveComposed of a repeating unit represented by -O-
R_FiveIs an alkylene group having 2 to 8 carbon atoms. ),
(7) mole number of aromatic dicarboxylic acid residue: aliphatic dica
The ratio of the number of moles of the rubonic acid residue is from 100: 0 to 40:60.
The dicarboxylic acid component is a polyester component (B).
(5) or (6).
Thermoplastic elastomer, (8) aliphatic chain diol residue
The number of moles of the group: the ratio of the number of moles of the aliphatic cyclic diol residue is
The diol component of 100: 0 to 40:60 is polyes
(5) wherein the tellur component (B) is constituted.
-The thermoplastic elastomer according to any one of (7),
(9) 40 to 90% by weight of the polyester component (B)
Before being characterized as polybutylene terephthalate
The thermoplastic elastomer according to any one of the above (5) to (8)
Tomer, (10) polyisocyanate component (C)
Aliphatic or alicyclic polyisocyanate component or isocyanate
Polyisocyanates in which the nate group is not directly attached to the aromatic ring
(2)-characterized in that it comprises a nate component
(9) The thermoplastic elastomer according to any one of (1),
(11) The polyisocyanate component (C) is one of the following:
A diisocyanate component represented by the general formula (3)
Described in any one of the above (2) to (10),
-O-CO-NH-R₆-NH-CO-O- (3) (where R₆Is an alkylene group having 2 to 15 carbon atoms,
Aliphatic cyclic hydrocarbon group, phenylene group, methylene group or
A group in which an alkylene group and a phenylene group are bonded
You. ), (12) Polyether component (A) as a structural unit
Wherein the water swelling ratio of the thermoplastic elastomer is 50 to 200% by weight.
%, And the storage elastic modulus at 40 ° C. of the thermoplastic elastomer is
1 × 10⁶Pa ~ 25 × 10⁶Pa, and the glass transition temperature of the thermoplastic elastomer is -20 ° C or lower.
(13) Polyether component (A) is contained as a constituent component
The thermoplastic elastomer is any of the above (1) to (11)
Or the thermoplastic elastomer according to 1 above.
The thermoplastic elastomer according to the above (12), wherein (1)
4) Polyether (a) and polyisocyanate compound
A first step of producing a prepolymer by reacting with (c)
Reacts the prepolymer with the polyester (b).
(2) to (2), characterized by comprising a second step of
(13) The thermoplastic elastomer according to any one of (1)
Manufacturing method, (15) any one of the above (1) to (13)
Characterized by comprising the thermoplastic elastomer described in (1).
And (16) the fiber of (15).
(17) Any of the above (1) to (13)
Characterized by being made of the thermoplastic elastomer according to (1).
Elastomer film or sheet, (18) poly
Ether (a) and polyisocyanate compound (c)
A first step of reacting to produce a prepolymer;
The second step of reacting the repolymer with the polyester (b)
Is obtained by continuous molding.
Elastomeric film or sheet
(19) Elast according to (17) or (18) above
Fabric on at least one side of the mer film or sheet
(20) a moisture-permeable and waterproof fabric characterized by being laminated.
At least one side of the fabric is any one of the above (1) to (13)
A composition comprising the thermoplastic elastomer according to claim 1.
(21) the cloth, which is coated with
(19) wherein the fabric is made of an elastic fiber;
Is the moisture-permeable waterproof cloth according to (20), (22) the moisture-permeable waterproof cloth.
The moisture permeability of the fabric is 2000g / m²・ 24 hours or more
In any one of the above (17) to (21),
The described elastomer film or sheet or transparent
(23) any of the above (20) to (22)
Characterized by being constituted by the moisture-permeable waterproof fabric according to item 1.
Clothing, tents or shoes, and (24) above (1) to
The thermoplastic elastomer according to any one of (11)
Molded articles for medical use characterized by being molded using
I do.

The thermoplastic elastomer of the present invention contains a polyether component (A) as a structural unit. And
Carbon / oxygen atomic ratio of the polyoxyalkylene that constitutes the polyether component _{(A) (-C n H 2n} O-) is 2.0
It is preferably 2.5. When the carbon / oxygen atom ratio is greater than 2.5, the affinity between the obtained elastomer and water is reduced, and the moisture permeability or moisture absorption is reduced.
On the other hand, when the ratio is more than 2.5, the steam sterilization property of the medical molded article manufactured using the elastomer becomes poor. As such a polyether component (A), polyethylene glycol having the above carbon / oxygen atom ratio of 2.0 is preferable.
The carbon / oxygen atom ratio may be adjusted to 2.5 or less by mixing with a polyether having an oxygen atom ratio of, for example, 3.0 or more. Examples of the polyether component having a carbon / oxygen atom ratio of 3.0 or more include polypropylene glycol (for example, poly 1,3 propylene glycol, poly 1,2
Propylene glycol), polytetramethylene glycol, polyhexamethylene glycol, poly (ethylene glycol-tetramethylene glycol) copolymer, poly (ethylene glycol-propylene glycol) copolymer, and the like.

The polyether component (A) preferably has a number average molecular weight of 500 to 5,000, more preferably 500 to 3,000.
000 is more preferred. If the number average molecular weight is less than 500, the flexibility of the obtained elastomer may decrease, and the moisture permeability or moisture release property may decrease. Conversely, if the number average molecular weight is larger than 5,000, the compatibility with other components, for example, the polyester component (B) decreases, the degree of polymerization of the obtained elastomer does not increase, and sufficient mechanical strength cannot be obtained. Sometimes. More preferably, the number average molecular weight is from 1,000 to 2,000. The number average molecular weight of the polyether component (A) is a numerical value corresponding to the average molecular weight of the polyether (a) described below.

Further, the thermoplastic elastomer of the present invention comprises:
The polyether component (A) occupies 40 to 95% by weight, preferably 50 to 9% by weight of the thermoplastic elastomer.
5% by weight. 50% by weight of polyether component (A)
If it is smaller than this, the storage modulus increases (the flexibility decreases), the molecular mobility decreases, and the moisture permeability or moisture release property decreases. Conversely, if the polyether component (A) is more than 95% by weight, sufficient mechanical strength cannot be obtained. Preferably, the polyether component (A) is 55 to 90% by weight, more preferably 60 to 90% by weight.

Further, the thermoplastic elastomer of the present invention comprises:
Glass transition temperature is −20 ° C. or less. When the glass transition temperature is higher than −20 ° C., sufficient rubber elasticity cannot be obtained at a low temperature, molecular mobility decreases, and moisture permeability or moisture release property also decreases. Preferably, the glass transition temperature is -30C or lower. The glass transition temperature in the present invention means a temperature at which a local maximum due to micro-Brownian motion of a thermoplastic elastomer appears among local maxima of loss tangent (tan δ) obtained by viscoelasticity measurement. The glass transition temperature is measured by a viscoelastic spectrometer (for example, RSA-II manufactured by Rheometric Scientific).

The thermoplastic elastomer of the present invention preferably contains a polyester component (B) as a structural unit, and the polyester component (B) is a short-chain polyester component represented by the following general formula (1). 50-100
What consists of 50% by weight of the long-chain polyester component represented by the following general formula (2) by weight and 50% by weight is preferable. When the short-chain polyester component is less than 50% by weight,
The melting point of the polyester component (B) is lowered, which may adversely affect the mechanical strength of the obtained elastomer at high temperatures. —CO—R ₁ —CO—O—R ₂ —O— (1) (where R ₁ is a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms and / or a divalent aromatic hydrocarbon group having 2 to 10 carbon atoms) An alkylene group or an aliphatic cyclic hydrocarbon group, and R ₂ is an alkylene group having 2 to 8 carbon atoms and / or a divalent aliphatic cyclic hydrocarbon group having 6 to 12 carbon atoms.) —CO—R ₃ —CO —OR ₄ − (2) (where R ₃ is a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms and / or a divalent alkylene group having 2 to 10 carbon atoms or an aliphatic cyclic hydrocarbon group) , R ₄ is composed of a repeating unit represented by -R ₅ -O-, R ₅ is an alkylene group having 2 to 8 carbon atoms.)

The short-chain polyester component is obtained by reacting an aromatic dicarboxylic acid or an ester thereof and / or an aliphatic dicarboxylic acid or an ester thereof with a low molecular weight diol. In addition, the long-chain polyester component,
It is obtained by reacting an aromatic dicarboxylic acid or an ester thereof and / or an aliphatic dicarboxylic acid or an ester thereof with a high molecular weight diol. As the aromatic dicarboxylic acid or an ester thereof, for example, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid,
Paraphenylenedicarboxylic acid, dimethyl terephthalate,
Examples thereof include dimethyl isophthalate, dimethyl orthophthalate, dimethyl naphthalene dicarboxylate, and dimethyl paraphenylenedicarboxylate. These may be used alone or in combination of two or more. Examples of the aliphatic dicarboxylic acid or its ester include succinic acid, adipic acid, suberic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimethyl succinate, dimethyl adipate, suberic acid Examples thereof include dimethyl, dimethyl sebacate, dimethyl 1,2-cyclohexanedicarboxylate, and dimethyl 1,4-cyclohexanedicarboxylate. These may be used alone or in combination of two or more. The molar ratio between the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid constituting the polyester component (B) is preferably from 100: 0 to 40:60. When the molar ratio of the aliphatic dicarboxylic acid is 60 or more, the melting point of the polyester component (B) becomes low, which may adversely affect the high-temperature mechanical strength of the obtained elastomer.

Examples of the low molecular weight diol include aliphatic chain diols and aliphatic cyclic diols. Examples of the aliphatic chain diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 1,5-pentanediol. , 1,6-hexanediol, diethylene glycol, triethylene glycol components and the like. These may be used alone or in combination of two or more. Examples of the aliphatic cyclic diol include 1,4-cyclohexanedimethanol, 1,2-cyclohexanediol,
Examples thereof include a 1,4-cyclohexanediol component, and these may be used alone or in combination of two or more.

In the above formula (2), R ₅ represents, for example, an alkylene group having 2 to 8 carbon atoms, and the component composed of repeating units represented by —R ₅ —O— The same diol components as those containing R ₂ can be mentioned, and examples of R ₄ include polyethylene glycol,
Poly (1,3-propylene glycol), poly (1,2
-Propylene glycol), polytetramethylene glycol, polyhexamethylene glycol, poly (ethylene glycol-tetramethylene glycol) copolymer, poly (ethylene glycol-propylene glycol) copolymer, and the like. Each of these may be used alone or two or more of them may be used in combination. In the general formula (2), R ₄ is a component composed of repeating units represented by —R ₅ —O—, and has a number average molecular weight of 500.
~ 5000 are preferred. When the number average molecular weight is less than 500, the blocking property of the polyester component (B) is lowered and the melting point is lowered, so that the mechanical strength at high temperature of the elastomer may be lowered. In some cases, the degree of polymerization of the elastomer does not increase because of low compatibility with the polyether, and a fiber having sufficient strength may not be obtained. More preferably 500 to
2000.

The molar ratio between the aliphatic chain diol and the aliphatic cyclic diol constituting the polyester component (B) is 10
0: 0 to 40:60 is desirable. When the molar ratio of the aliphatic cyclic diol is 60 or more, the melting point of the polyester component (B) is increased, which may adversely affect the solubility of the obtained elastomer in a solvent. Preferably,
90:10 to 40:60. It is preferable that 40 to 90% by weight of the polyester component (B) is polybutylene terephthalate. When the content of polybutylene terephthalate is less than 40% by weight, the melting point of the polyester component (B) is lowered, which may adversely affect the high-temperature mechanical strength of the obtained elastomer. Conversely, if the content of polybutylene terephthalate is more than 90% by weight, the crystallinity of the polyester component becomes strong, which may adversely affect the solubility of the obtained elastomer in a solvent. More preferably, the polyester component (B) 40 to
80% by weight, more preferably 50 to 75% by weight
It is.

As the solvent for dissolving the elastomer,
Although not particularly limited, for example, N, N-dimethylformamide (DMF), N-methylpyrrolidone (NMP),
Examples include polar solvents such as N, N-dimethylacetamide, methyl ethyl ketone (MEK), dioxane, and toluene. As the high molecular weight diol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, poly (ethylene glycol-tetramethylene glycol) copolymer, ethylene oxide-tetrahydrofuran copolymer, poly (ethylene glycol-propylene glycol) Copolymers and the like.

The polyester component (B) has a number average molecular weight of usually 500 to 10,000,
0 is preferred. When the number average molecular weight is less than 500, the blockability of the polyester component (B) in the elastomer is reduced, the melting point is reduced, and the mechanical strength of the obtained elastomer at high temperatures may be reduced. Conversely, if the number average molecular weight is greater than 10,000, the compatibility with the polyether component (A) is low, so that the degree of polymerization of the obtained elastomer does not increase, and an elastomer having sufficient strength may not be obtained. Most preferably, those having a number average molecular weight of 500 to 2,000 are used. The number average molecular weight of the polyester component (B) is
Usually, it is a numerical value corresponding to the average molecular weight of the polyester (b). The number average molecular weight in the present invention was measured under the following measurement conditions. Apparatus: HLC 8020 series manufactured by Tosoh Corporation Column: Shodex HFIP 806M 2 solvents: Hexafluoroisopropanol (addition of 0.005N sodium trifluoroacetate) Standard: Polymethyl methacrylate Standard Temperature: 23 ° C

The thermoplastic elastomer containing the polyether component (A) of the present invention as a constitutional unit can be obtained by a known method. For example, the above-mentioned aromatic dicarboxylic acid or its ester and / or the aliphatic dicarboxylic acid or its ester together with an excess of the above-mentioned low molecular weight diol and optionally the above-mentioned high molecular weight diol together with a catalyst such as tetrabutyl titanate In the presence of, for example, the ester exchange reaction is performed by heating at 160 to 200 ° C. Subsequently, the above thermoplastic elastomer can be obtained by performing a polycondensation reaction under reduced pressure, for example, at 240 to 250 ° C.

In particular, the thermoplastic elastomer of the present invention
One in which the polyether component (A) is bound by a polyisocyanate component (C), or one in which the polyether component (A) and the polyester component (B) are bound by a polyisocyanate component (C) preferable. The thermoplastic elastomer used in the present invention preferably contains a urethane binding component represented by the general formula (3) as the polyisocyanate component (C). —O—CO—NH—R ₆ —NH—CO—O— (3) (where R ₆ is an alkylene group, a phenylene group, or a methylene or alkylene group having a carbon number of 2 to 15 and a phenylene group bonded thereto. Thing.)

Examples of the thermoplastic elastomer containing a urethane-binding component represented by the above general formula (3) include those obtained by a polyaddition reaction between a compound having a hydroxyl group at a molecular terminal and an isocyanate compound. ,
Thermoplastic polyurethane elastomer, polyetherester elastomer obtained by chain extension with isocyanate compound, polyetheramide elastomer obtained by chain extension with isocyanate compound, or polyester (b) and polyether (a) with polyisocyanate (c) Ester elastomers reacted are exemplified.

In short, as the thermoplastic elastomer which achieves the above-mentioned invention, preferable examples include, for example, a polyether component (A), a short-chain polyester component represented by the general formula (1) and a polyether component represented by the general formula (2). A block copolymer with a polyester component (B) comprising 50 to 100% by weight of the short-chain polyester component and 50 to 0% by weight of the long-chain polyester component, which is composed of a repeating long-chain polyester component. Wherein the polyether component (A) and the polyester component (B) are represented by the general formula (3)
And a thermoplastic elastomer composition bonded by a polyisocyanate component (C).

In order to obtain a thermoplastic elastomer bound by the polyisocyanate component (C), the polyether (a) and the polyester (b) may be reacted with the polyisocyanate compound (c). The structure of the polyisocyanate compound (c) is not particularly limited as long as it is a compound having two or more isocyanate groups in the same molecule, but when an isocyanate in which the isocyanate group is directly bonded to an aromatic ring is used, Considering that it becomes yellow and becomes difficult to use for applications requiring light resistance, isocyanates in which an aliphatic / alicyclic or isocyanate group is not directly bonded to an aromatic ring are more preferred. It is preferable that the average number of isocyanate groups per molecule of the polyisocyanate compound (c) is in the range of 2.0 to 2.2. Examples of the isocyanate compound having an average number of isocyanate groups of 2.0 include, for example, aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate, methylene diisocyanate, 1,2-ethylene diisocyanate, 3-propylene diisocyanate, 1,4-butane diisocyanate, 1,5-pentamethylene diisocyanate, 1,
Aliphatic diisocyanate such as 6-hexamethylene diisocyanate, octamethylene diisocyanate, lysine diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, hydrogenated 4,4 ′ -Alicyclic diisocyanates such as phenylmethane diisocyanate and hydrogenated xylene diisocyanate; diisocyanates in which isocyanate groups such as xylene diisocyanate and tetramethyl xylene diisocyanate are not directly bonded to aromatic rings; Further, by mixing an isocyanate compound having an average number of isocyanate groups of 2.0 with an isocyanate compound having an average number of isocyanate groups exceeding 2.2, the average number of isocyanate groups per molecule is in the range of 2.0 to 2.2. Such a configuration may be used.

Isocyanate compound polymeric MD having an average number of isocyanate groups per molecule of more than 2.2
I is typical, and as a commercially available product, for example, "Millionate MR200" (average isocyanate group number: 2.8) manufactured by Nippon Polyurethane Co., Ltd. can be mentioned. In addition, triphenylmethane triisocyanate (average number of isocyanate groups 3.0), tris (isocyanate phenyl), thiophosphate (average number of isocyanate groups 3.0), hexamethylene triisocyanate (average number of isocyanate groups 3.0), lysine ester triisocyanate (Average number of isocyanate groups 3.0), 1,8-diisocyanate-4-isocyanatomethyloctane (average number of isocyanate groups 3.0), 1,6,11-udecan triisocyanate (average number of isocyanate groups 3.0) and the like. .

The molar amount of the isocyanate group contained in the polyisocyanate compound (c) used in the present invention is determined by the amount of the group containing active hydrogen contained in the polyether (a) and the polyester (b) used in the present invention (the above isocyanate). 0.60 of the molar amount of the group capable of reacting with
It is preferably about 1.05 times. If the molar ratio is less than 0.60, the molecular weight of the obtained elastomer will be low, and sufficient mechanical strength may not be obtained. Conversely, if the molar ratio is greater than 1.05, the resulting elastomer will have more by-products such as unstable allophanate groups or burette groups, which will result in lowering of the moldability of the resulting elastomer and with time. In some cases, the deterioration of physical properties becomes remarkable. A more preferable molar ratio is 0.80 to 1.01. In this case, an allophanate group or a burette group is hardly generated, and the molecular weight of the obtained elastomer is increased, so that the physical properties are also excellent.

The thermoplastic elastomer of the present invention, in which the polyether component (A) and the polyester component (B) are bonded by the polyisocyanate component (C), comprises the polyether (a) and the polyisocyanate compound (c). And a second step of reacting the prepolymer with a polyester (b) having hydroxyl groups at both ends by a first step of producing a prepolymer having both ends isocyanated. It is preferably manufactured.

The above-mentioned polyester (b) and polyether (a) usually have hydroxyl groups at both ends, but may have a carboxyl group at 5 equivalent% or less. At this time, when both of the terminal functional groups reacting with the diisocyanate compound are hydroxyl groups, a urethane binding component of the general formula (3),
When one is a hydroxyl group and the other is a carboxyl group, they are bonded by the urethane bonding component of the general formula (4). In the case where the terminal functional group of the polyester-based copolymer is a carboxyl group in these urethane binding components, the compound represented by the general formula (5)
May be partially contained by the diisocyanate compound. _{-O-CO-NH-R 6} -NH-CO- (4) (R 6 are as defined _{above) -CO-NH-R 6 -NH} -CO- (5) (R 6 are as defined above)

The polyester (b) preferably has 95 equivalent% or more of hydroxyl groups at the molecular terminals. A hydroxyl group and a carboxyl group can be considered as the terminal functional groups of the polyester (b). When the hydroxyl group is less than 95 equivalent%, the polyisocyanate compound (c) is used.
, The degree of polymerization of the thermoplastic elastomer does not increase, and sufficient mechanical strength may not be obtained. The terminal functional group of the polyester (b) can be quantified using an acid value and a hydroxyl value. The acid value and the hydroxyl value can be measured by the following methods, but the values guaranteed by the manufacturer may be used as they are. Acid value: After the sample is dissolved in a benzyl alcohol / chloroform mixed solvent, neutralization titration is performed using a phenol red indicator to obtain an acid value. Hydroxyl value: A sample and succinic anhydride are dissolved in a mixed solvent of nitrobenzene / pyridine and reacted for 10 hours, and the reaction solution is reprecipitated with methanol. The obtained reaction product is subjected to the above-mentioned acid value measurement to obtain a hydroxyl value.

In the first step, the molar amount of the isocyanate group contained in the polyisocyanate compound (c) is 1 mol of the molar amount of the group containing active hydrogen capable of reacting with the isocyanate group contained in the polyether (a). The molar ratio is preferably from 1.2 to 2.2, and more preferably from 1.2 to 2.2.
2.0. If the molar ratio is less than 1.1, both ends of the resulting prepolymer cannot be completely isocyanated, which may hinder the reaction in the second step. Conversely, if the molar ratio exceeds 2.2, unreacted isocyanate compound (c) remains, causing a side reaction during the reaction in the second step, and causing a side reaction product such as an allophanate group or a burette group. And the resulting elastomer may have reduced moldability and reduced physical properties. In the first step, the reaction temperature is 100 to 240 ° C.
Is preferred. If the reaction temperature is lower than 100 ° C., the reaction may not proceed sufficiently. Conversely, if the reaction temperature exceeds 240 ° C., the polyether (a) may be decomposed. More preferably, the reaction temperature is between 160C and 220C.

In the second step, the prepolymer produced in the first step is reacted with the polyester (b).
Here, the molar amount of the isocyanate group contained in the polyisocyanate compound (c) is the same as the molar amount of the group containing the active hydrogen contained in the polyether (a) and the active hydrogen contained in the polyester polymer (b). It is preferably 0.60 to 1.05 of the total molar amount with the molar amount of the group to be contained, and the ratio of the more preferable molar amount is 0.80 to 1.01 times. By doing so, side reactions are less likely to occur,
The molecular weight of the obtained elastomer is increased and the physical properties are also excellent. In the second step, the reaction temperature is 10
0-240 ° C is preferred. If the reaction temperature is lower than 100 ° C., the reaction may not proceed sufficiently. Conversely, if the reaction temperature exceeds 240 ° C., the prepolymer may be decomposed and an elastomer having sufficient strength may not be obtained. More preferably, the reaction temperature is between 160 and 220C. here,
The polyester (b) may be separately melted by heating and added to the prepolymer using a pump or the like, or the polyester (b) may be heated and melted by an extruder and then added to the prepolymer.

The above reaction is preferably a bulk reaction. By this reaction method, the reactivity in the second step is particularly improved. In addition, a single-screw or twin-screw extruder is used as the reaction equipment, but is not particularly limited. Preferably, a co-rotating twin-screw extruder and a co-rotating twin-screw extruder are used, and more preferably, a co-rotating mesh twin-screw extruder is used from the viewpoint of the efficiency of stirring and mixing. By using this equipment, the reactivity in the second step is particularly improved. In order to continuously perform the reaction between the first step and the second step, it is preferable to use a tandem type extruder. A catalyst can be used during the stirring and mixing. Such catalysts include stannous diacyl, stannous tetraacyl, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate, tin dioctanoate, tin tetraacetate, triethyleneamine, diethyleneamine, triethylamine, metal naphthenate, Preferred are metal octylate, triisobutylaluminum, tetrabutyltitanate, calcium acetate, germanium dioxide, antimony trioxide and the like. Two or more of the above catalysts may be used in combination.

As described above, the prepolymer having both ends isocyanated, which is obtained by reacting the polyether (a) with the polyisocyanate compound (c), is reacted with the polyester (b) having hydroxyl groups at both ends. And the polyether component (A) and the polyester component (B) are surely linked to the polyisocyanate component (C) without the chain extension of the polyether (a) and the polyester (b) alone by the polyisocyanate compound (c). Thus, a thermoplastic elastomer comprising a block copolymer bonded by the above is obtained. Further, the prepolymer partially reacts with the polyester (b) to form a compatibilizer between the polyether (a) and the polyester (b), and the compatibility between the polyether (a) and the polyester (b). Can be converted to an elastomer even in the case where the value is poor. By controlling the equivalentity of the polyether (a), the polyester (b) and the isocyanate compound (c), for example, by reacting an excess of the polyester (b) with the prepolymer in the second step, The terminal of the obtained thermoplastic elastomer can be a polyester component (B). This makes it possible to increase the melting point, and improves the moldability or high-temperature properties of the thermoplastic elastomer.

A stabilizer may be used in the thermoplastic elastomer of the present invention during or after its production. Examples of such a stabilizer include 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] Hindered phenolic antioxidants such as undecane; tris (2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, 2-t-butyl-
α- (3-t-butyl-4-hydroxyphenyl) -p
-Cumenyl bis (p-nonylphenyl) phosphite,
Dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythryltetrakis (3-laurylthiopropionate)
And heat stabilizers such as ditridecyl 3,3'-thiodipropionate.

Further, the thermoplastic elastomer of the present invention may contain a cell nucleating agent, a fiber, and a fiber as long as practicality is not impaired.
Additives such as inorganic fillers, flame retardants, ultraviolet absorbers, antistatic agents, other inorganic substances, and higher fatty acid salts may be added. The above-mentioned cell nucleating agent generally has a particle diameter of 50.
It is preferably 0 μm or less, for example, calcium carbonate,
Examples include talc, clay, magnesium oxide, zinc oxide, carbon black, silicon dioxide, titanium oxide, baking soda, citric acid, orthoboric acid, and alkaline earth metal salts of fatty acids. Examples of the fibers include glass fibers, carbon fibers, boron fibers, silicon carbide fibers, alumina fibers, amorphous fibers, inorganic fibers such as silicon-titanium-carbon fibers, and organic fibers such as aramid fibers.

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. Examples of the ultraviolet absorber include pt
-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 sulfanates and the like. Examples of the above-mentioned other inorganic substances include barium sulfate, alumina, and silicon oxide. Examples of the higher fatty acid salt include sodium stearate, barium stearate, sodium palmitate and the like.

The thermoplastic elastomer of the present invention may be mixed with other thermoplastic resins and rubber components to modify its properties before use. Examples of such a 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, EPDM), polychloroprene, butyl rubber, acrylic rubber, Examples thereof 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 thermoplastic elastomer of the present invention is a commonly used press molding,
A molded article can be formed by a molding method such as extrusion molding, injection molding, blow molding and the like. Although the molding temperature varies depending on the melting point of the elastomer and the molding method, 160 to 250 ° C is suitable. If the temperature is lower than 160 ° C., it is difficult to obtain a uniform molded product because the fluidity of the ester elastomer is low. On the other hand, if the temperature exceeds 250 ° C., the elastomer is decomposed and it is difficult to obtain an elastomer having sufficient strength. The thermoplastic elastomer of the present invention is suitably used for molded articles such as automobile parts, electric and electronic parts, industrial parts, sporting goods, medical supplies, and sanitary goods.

Examples of the automobile parts include boots such as constant velocity joint boots and rack and pinion boots; ball joint seals; safety belt parts; bumper fascias; emblems;
As the electric and electronic components, for example, a wire covering material,
Gears, rubber switches, membrane switches, tact switches, O-rings, and the like. 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 sports equipment include shoe soles,
Ball game balls, moisture-permeable waterproof clothing, and the like. Examples of the medical supplies include containers such as bags for transfusions and blood transfusions, tubes for transfusion sets, tubes for transfusion circuits, tubes such as catheters, and stoppers for these devices. Examples of the sanitary articles include a dehumidifier, an aromatic, a diaper, a sanitary article, and the like. In addition to the above uses, it can be suitably used as an elastic fiber, an elastic sheet, a composite sheet, a hot melt adhesive, a material for polymer alloy with other resins, and the like.

The fiber of the present invention comprises the above-mentioned thermoplastic elastomer. The fiber of the present invention may be a composite fiber of the above-mentioned thermoplastic elastomer and another fiber, but preferably contains 10% by weight or more of the thermoplastic elastomer. If the content is less than 10% by weight, the moisture absorption and moisture release properties of the thermoplastic elastomer may not be sufficiently exhibited. The fiber of the present invention can be produced by spinning the thermoplastic elastomer according to a conventional method. That is, fibers can be produced from the thermoplastic elastomer obtained as described above by a conventionally known dry spinning method, wet spinning method, melt spinning method, or the like. The form may be either stable or filament. The melt spinning method is preferable because thin denier can be achieved.Specifically, a method in which the thermoplastic elastomer is pelletized once and then melt-spun, or the thermoplastic elastomer obtained by melt polymerization is directly spun through a spinneret. Can be adopted. From the viewpoint of spinning stability, a method of spinning directly by polymerization is preferred. The unstretched yarn obtained by melt spinning may be subjected to heat treatment or drawing heat treatment.

The fabric of the present invention comprises fibers made of the above-mentioned thermoplastic elastomer. The fabric of the present invention is:
A combination of the fiber made of the thermoplastic elastomer and the fiber made of another resin may be used. When the fabric does not contain fibers made of a thermoplastic elastomer, the hanging fabric has low moisture absorption and sweat absorption properties, and when this fabric is used for clothing, a sticky feeling due to sweat occurs.

As a method for forming a film or sheet, known film forming methods such as a T-die method, an inflation method, a solution casting method (dry coagulation method), and a wet coagulation method can be used. The film or sheet may or may not be stretched. The unstretched film or sheet is obtained, for example, by melt extrusion on a casting drum. A uniaxially stretched film or sheet, for example, is usually obtained by sandwiching an unstretched sheet between two different pairs of pinch rolls and pulling the sheet in its length direction in a heated state, whereby it is strongly oriented only in the uniaxial direction. . In this case, the rotational speed ratio between the roll on the take-up side and the roll on the pay-out side becomes the stretching ratio.
A biaxially stretched film or sheet is usually obtained by stretching an unstretched sheet simultaneously or sequentially in a biaxial direction to orient in that direction. In the case of sequential biaxial stretching, the stretching order may be the order of the sheet in the longitudinal direction and the width direction, or the reverse. Furthermore, in simultaneous biaxial or sequential biaxial stretching, stretching in the longitudinal direction and the width direction can be performed twice or more. The stretching ratio in the longitudinal direction and width direction of the film or sheet can be arbitrarily set according to the degree of orientation, strength, elastic modulus, etc. of the target film or sheet, but is preferably 2.5 to 5. 0
Doubled. Either the stretching ratio in the longitudinal direction or the stretching direction in the width direction may be higher, and may be the same. Further, after biaxial stretching, heat treatment of the sheet or film can be performed.
This heat treatment can be performed by any conventionally known method, such as in an oven or on a heated roll. The heat treatment may be performed while relaxing the film or sheet in the longitudinal direction and / or the width direction.

The elastomer film or sheet of the present invention can be produced by molding the thermoplastic elastomer pellets obtained by the above-mentioned production method by a known method. Following production of the elastomer, it is preferred that the thermoplastic elastomer in the molten state be continuously molded through a die. The first reason is that since the thermoplastic elastomer constituting the elastomer film or sheet of the present invention easily absorbs moisture, the method of pelletizing and then molding separately requires very little moisture control of the pellets to obtain a uniform molded body. And the preparation for molding becomes complicated. The second reason is that if the amount of soft segments is increased to improve the flexibility and moisture permeability of the elastomer film or sheet, coalescence of the pellets is likely to occur, resulting in poor handling during molding. This is because

The layer of the thermoplastic elastomer composition of the present invention may be a single layer or a multilayer of two or more layers. As the two or more layers, any of a polyamide resin, a polyester resin and the like may be laminated. The laminated film or sheet of the present invention is obtained by laminating a fabric on at least one surface of the above-mentioned elastomer film or sheet, but the type of the fabric and laminating means are not particularly limited.

The fabric used in the present invention includes a nonwoven fabric and a woven / knitted fabric. The nonwoven fabric is not particularly limited, for example, a nonwoven fabric obtained in a dry process such as a needle punch method, a spunlace method, a spun bond method or a melt blow method, a nonwoven fabric obtained in a wet process such as a papermaking method, A nonwoven fabric obtained by combining a dry process and a wet process, or a laminate of the nonwoven fabric obtained by both processes can be used. The fibers constituting these nonwoven fabrics are not particularly limited, but, for example, cotton,
Natural fibers such as hemp and wool, cellulose-based regenerated fibers, synthetic fibers such as polyamide-based, polyester-based, polyolefin-based, polystyrene-based, polyacryl-based, and polyvinyl alcohol-based fibers, and inorganic fibers such as pulp and glass fiber. These fibers can be used alone or as a mixture. Among them, polyolefin-based, polyester-based, and polyamide-based synthetic fibers are preferably used because of their excellent durability. The woven or knitted fabric is not particularly limited, but in the case of a woven fabric, in addition to the original weaves of plain weave, twill weave, and satin weave, there are also a change weave and a weaving weave. Circular knitting and the like are given. The fibers constituting these woven or knitted materials are not particularly limited, but semi-synthetic fibers such as polyamide-based, polyester-based, polyacrylonitrile-based, polyvinyl alcohol-based synthetic fibers and triacetate, or nylon 6 / cotton, polyethylene Blend fibers such as terephthalate / cotton and the like. The cloth is not particularly limited, but preferably has elasticity. As an advantage of having elasticity, for example, in the case of clothing,
It has good fit to the body and good followability, and is very easy to operate.

The method of coating the fabric with the thermoplastic elastomer of the present invention is not particularly limited. For example, an adhesive laminating method of bonding the elastomer film or sheet to the fabric using an adhesive, or a heat-sealing method of applying heat by heating. A fusion method or the like can be used. Among them, industrially, at the time of extrusion molding of an elastomer film or sheet, extrusion lamination is performed by laminating a fabric on the elastomer film or sheet while the elastomer film or sheet has heat fusibility and pressing both with a roll or the like. The method is preferably used.

The moisture permeable waterproof fabric of the present invention is manufactured in this manner, and the moisture permeable waterproof fabric of the present invention has a moisture permeability of JIS Z
It is a value measured according to 0208. Moisture permeability of moisture-permeable waterproof fabric of the present invention is 2000g / m ² · 24 hours or more, preferably 4000g / m ² · 24 hours or more, more preferably 6000g / m ² · 24 hours or more. If the above moisture permeability is less than 2000 g / m ² · 24 hours, sufficient air permeability cannot be obtained. For example, when used for clothing, water vapor is condensed, and when it comes into direct contact with the skin, it gives a feeling of wetness or stickiness. Discomfort tends to increase. The thickness of the moisture-permeable waterproof fabric of the present invention is preferably 0.0% because it is easily broken when it is too thin, and the moisture permeability decreases when it is too thick.
5 to 5 mm, more preferably 0.05 to 3 mm,
More preferably, it is 0.1 to 2 mm.

The molded article for medical use of the present invention can be obtained by press molding, extrusion molding (tube molding, inflation molding, T-die molding, etc.) injection molding, blow molding, vacuum molding, compression molding generally using the thermoplastic elastomer of the present invention. It can be manufactured by forming into a molded body by a molding method such as calender molding, solution casting and the like. The molding temperature varies depending on the melting point of the elastomer constituting the medical molded article and the molding method, but is suitably 250 ° C. or lower. If it exceeds 250 ° C,
The elastomer decomposes and it is difficult to obtain an elastomer having sufficient strength. The form of the medical molded article of the present invention is, for example, an injection molded article such as a film, a sheet, a tube, a bag, or a stopper of those devices.

The present invention also relates to a thermoplastic elastomer containing a polyether component (A) as a constituent unit, wherein the thermoplastic elastomer has a water swelling ratio of 50 to 200% by weight, and the thermoplastic elastomer is stored at 40 ° C. Elastic modulus is 1
A ^{× 10 6 Pa~25 × 10 6 Pa} , to provide a thermoplastic elastomer, wherein the glass transition temperature of the thermoplastic elastomer is -20 ° C. or less.

The thermoplastic elastomer of the present invention preferably has a water swelling ratio of 50 to 200% by weight. The water swelling rate is greatly affected by the amount of polyether contained in the thermoplastic elastomer and the affinity between polyether and water. When the water swelling ratio is less than 50% by weight, the affinity between the obtained elastomer and water is reduced, and the moisture permeability may be reduced. If it is more than 200% by weight, the physical properties of the elastomer at the time of moisture absorption are remarkably reduced, and may not be practically usable. More preferably, it is 60 to 150% by weight. The water swelling ratio of the thermoplastic elastomer is measured as follows. A test piece (sheet: 50 mm x 50 mm x 1 mm) is placed in a desiccator containing a desiccant (silica gel) and dried sufficiently, and the weight of the test piece is measured (W0). After immersing the test piece, the weight is measured (W1) Water swelling ratio = (W1−W0) / W0 × 100 (% by weight)

The thermoplastic elastomer of the present invention comprises 40
It is preferable that the storage modulus at 1 ° C. is 1 × 10 ^{6 to} 25 × 10 ⁶ Pa. The storage modulus is greatly affected by the amount of polyether contained in the thermoplastic elastomer. When the storage modulus is less than 1 × 10 ⁶ Pa, it is difficult to obtain sufficient mechanical strength. Conversely, when the storage elastic modulus is larger than 25 × 10 ⁶ Pa, the molecular mobility may be low and the moisture permeability may be low. A preferred range of storage modulus is 5 × 10 ⁶ to 15 × 10
⁶ Pa. The thermoplastic elastomer of the present invention is produced by the above production method, or is easily produced by selecting a thermoplastic elastomer satisfying the above conditions from the thermoplastic elastomer produced by the above production method. You.

[0054]

The thermoplastic elastomer of the present invention has a soft segment composed of a specific polyether component, thereby increasing the affinity with water and promoting the adsorption of water molecules. Further, by having a specific glass transition temperature and a soft segment amount, the molecular mobility of the elastomer is enhanced, and the diffusion of water molecules is promoted. These molecular designs result in an elastomer material having a very high moisture permeability that has never been seen before. Furthermore, by using an aliphatic / alicyclic isocyanate or an isocyanate in which an isocyanate group is not directly bonded to an aromatic ring, an elastomer material having excellent light resistance can be obtained. Further, the thermoplastic elastomer of the present invention exhibits properties as an elastomer when the crystals formed by the short-chain polyester component constitute cross-linking points. In particular, it is composed of a portion rich in a short-chain polyester component and a portion rich in a polyether component in a molecule. The short-chain polyester component is easier to crystallize than it is, and as a result, a strong cross-linking point is formed, resulting in an elastomer material having both flexibility and mechanical properties at high temperatures.

The water absorption / hygroscopicity of the fiber is governed by the adsorption of water molecules to the fiber surface, and the moisture release is governed by the diffusion of water molecules in the fiber and evaporation from the surface on the low water vapor pressure side. The thermoplastic elastomer used in the present invention has a specific soft segment composition to enhance affinity with water, and promotes adsorption of water molecules. Furthermore, by having a specific glass transition temperature and a soft segment amount, the molecular mobility of the elastomer is increased,
Promotes the diffusion of water molecules. Due to these molecular designs, in the present invention, the fiber and the fabric made of the above-mentioned thermoplastic elastomer become a fiber and a fabric having extremely high water absorption and moisture release properties which have not been obtained so far.

The elastomer film or sheet of the present invention has a soft segment composed of a specific polyether component, thereby increasing the affinity with water and promoting the adsorption of water molecules. Further, by having a specific glass transition temperature and a soft segment amount, the molecular mobility of the elastomer is enhanced, and the diffusion of water molecules is promoted. These molecular designs result in an elastomer material having a very high moisture permeability that has never been seen before. Further, the thermoplastic elastomer constituting the elastomer film or sheet of the present invention exhibits properties as an elastomer by the fact that crystals formed by the short-chain polyester component constitute crosslinking points. In particular, it is composed of a portion rich in a short-chain polyester component and a portion rich in a polyether component in a molecule. The short-chain polyester component is easier to crystallize than it is, and as a result, a strong cross-linking point is formed, resulting in an elastomer material having both flexibility and mechanical properties at high temperatures.

The thermoplastic elastomer composition to be laminated on the moisture-permeable waterproof fabric of the present invention contains carbon / polyether of the constituent polyether.
By setting the oxygen atom ratio to 2.0 to 2.5, the polarity of the resin layer increases, the affinity with water increases, and high moisture permeability is exhibited. Further, by making the polyether component occupying 50 to 95% by weight in the thermoplastic elastomer and making the glass transition temperature of the thermoplastic elastomer −20 ° C. or lower, the diffusivity of water vapor in the resin is improved, and high moisture permeability is obtained. Demonstrate. By laminating such a thermoplastic elastomer composition, the moisture-permeable waterproof fabric of the present invention has high moisture permeability and waterproofness, and is useful for applications such as clothing, tents, and shoes.

The molded article for medical use of the present invention is made of a thermoplastic elastomer having the following characteristics, and thus has a very high steam sterilization property. The constituent thermoplastic elastomer has a soft segment composed of a specific polyether component, thereby enhancing affinity with water and promoting adsorption of water molecules. Further, by having a specific glass transition temperature and a soft segment amount, the molecular mobility of the elastomer is enhanced, and the diffusivity of water molecules is promoted. Due to these molecular designs, it is an elastomer material having extremely high moisture permeability that has never been seen before.

The constituent thermoplastic elastomer is:
Crystals formed by the short-chain polyester component constitute crosslink points, thereby exhibiting properties as an elastomer. In particular, it is composed of a portion rich in a short-chain polyester component and a portion rich in a polyether component in a molecule. This is an elastomeric material in which the short-chain polyester component is more easily crystallized, and as a result, a strong cross-linking point is formed, and both flexibility and mechanical properties at high temperatures are compatible. as a result,
The molded article for medical use has excellent flexibility, heat resistance, and sterilization resistance.

The thermoplastic elastomer of the present invention has a specific water swelling ratio, thereby increasing the affinity for water and promoting the adsorption of water molecules. Further, by having a specific storage modulus and a glass transition temperature, the molecular mobility of the elastomer is enhanced, and the diffusion of water molecules is promoted. These molecular designs result in an elastomer material having a very high moisture permeability that has never been seen before. Further, the thermoplastic elastomer of the present invention exhibits properties as an elastomer when the crystals formed by the short-chain polyester component constitute cross-linking points. In particular, it is composed of a portion rich in a short-chain polyester component and a portion rich in a polyether component in a molecule. The short-chain polyester component is easier to crystallize than it is, and as a result, a strong cross-linking point is formed, resulting in an elastomer material having both flexibility and mechanical properties at high temperatures.

Among the objects and objects of the present invention, the provision of an elastomer having excellent flexibility and mechanical properties at a high temperature, particularly excellent sag resistance at a high temperature, and a method for producing the same are described by the invention of Part I described above. The invention is also solved by the invention of Part II described below. Reference Examples 1 to 6, Examples 1 to 31, Comparative Examples 1 to 16 and Tables 1 to 7 are used in the description of specific embodiments of the invention of Part I, and Part II is used.
For the description of specific embodiments of the invention, Examples 32-35,
Comparative Examples 21 to 22 and Tables 11 to 12 are used.
Therefore, in the description of the present invention, all of the following from the description to the specific embodiments of the present invention are descriptions of Part II of the present invention.

[0062] In view of the above, the present invention of Part II discloses an ester having high blockability between a hard segment component and a soft segment component, and having excellent flexibility and mechanical properties at high temperatures, especially excellent set resistance at high temperatures. It is an object to provide a method for producing an elastomer, an ester elastomer, a method for producing an amide elastomer, and an amide elastomer. The objects and objects of the Part II invention are achieved by the following solutions.

(1) The polyester (S) and the polymer (T) having hydroxyl groups at both ends of the molecule are represented by the general formula (5)
1); -O-CO-NH -R 1 '-NH-CO-O- (51) ( In the formula, R ^1' is an alkylene group having from 2 to 15 carbon atoms, -
C ₆ H ₄ —, —C ₆ H ₄ —CH ₂ —, or —C ₆ H ₄ —CH ₂
—C ₆ H ₄ — (however, —C ₆ H ₄ — represents a phenylene group). ) Or a group represented by the general formula (5)
2); - O-CO- NH-R 2 '-NH-CO-
(52) (wherein, R ² ′ is an alkylene group having 2 to 15 carbon atoms, —C ₆ H ₄ —, —C ₆ H ₄ —CH ₂ —, or —
C ₆ H ₄ —CH ₂ —C ₆ H ₄ — (provided that —C ₆ H ₄ — represents a phenylene group). ) Is a method for producing an ester elastomer for obtaining an ester elastomer which is a block copolymer bonded by an isocyanate component (U) comprising a group represented by the following general formula (A): ^{53); -CO-R 3 '} -CO-O-R 4'-O- (53) ( wherein, R ³ 'represents a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms .R ⁴ ′ represents an alkylene group having 2 to 8 carbon atoms) as a repeating unit, and a polymer (T) having hydroxyl groups at both ends of the molecule
Has a glass transition temperature of 20 ° C. or less and a number average molecular weight of 50
0 to 5000, wherein the ester elastomer is 100 to 100 parts by weight of the component consisting of the polyester (S) and 50 to 2,000 parts by weight of the component consisting of the polymer (T) having hydroxyl groups at both ends of the molecule. Wherein the isocyanate component (U) is composed of 10 to 100 parts by weight, and the step of producing the ester-based elastomer comprises the step of combining the polymer (T) having hydroxyl groups at both ends of the molecule with the diisocyanate compound (U ′). A method for producing an ester-based elastomer, comprising two steps: a step of reacting to produce a prepolymer, and a step of reacting the prepolymer with polyester (S).

(2) The polymer (T) has the general formula (5)
^{4); -R 5 '-O-} (54) ( wherein, R ^5' is to be a polyether comprising the repeating unit a group represented by) represents an alkylene group having 2 to 10 carbon atoms. The method for producing an ester-based elastomer according to (1), which is characterized in that: (3) The polymer (T) is represented by the general formula (55); -R ⁶ ′ -O—CO—R ⁷ ′ —CO—O— (55) (where R ⁶ ′ and R ⁷ ′ are the same or (1) an aliphatic polyester having a repeating unit represented by a group represented by the following formula (1): Table with ^{-R 8 '-CO-O- (} 56) ( wherein, R ^8' represents an alkylene group having 2 to 10 carbon atoms.); (4) a polymer (T) is the general formula (56) (1) The method for producing an ester-based elastomer according to (1), wherein the polylactone comprises a group to be formed as a repeating unit. (5) Polymer (T) of the general formula ^{(57); -R 9 '-} O-CO-O- (57) ( wherein, R ^9' represents an alkylene group having 2 to 10 carbon atoms.) (1) The method for producing an ester-based elastomer according to (1), which is a polycarbonate comprising a group represented by the following formula as a repeating unit. (6) The above (1), (2), (3), (4) or (5)
An ester elastomer produced by the method for producing an ester elastomer described in the above.

(7) The polyamide (P) and the polymer (T) having hydroxyl groups at both ends of the molecule are represented by the general formula (58): -O-CO-NH-R ¹⁰ '-NH-CO-O- ( 58) (wherein, R ¹⁰ ′ is an alkylene group having 2 to 15 carbon atoms, —
C ₆ H ₄ —, —C ₆ H ₄ —CH ₂ —, or —C ₆ H ₄ —CH
₂ -C ₆ H ₄ - (where, -C ₆ H ₄ - represents a phenylene group.) Represents the. ) Or a group represented by the general formula (5)
9); -O-CO-NH -R 11 '-NH-CO-NH- (59) ( wherein, R ^11' is an alkylene group having from 2 to 15 carbon atoms, -
_{C 6 H 4 -, - C} 6 H 4 -CH 2 -, or, -C ₆ H ₄ -C
H ₂ -C ₆ H ₄ - (where, -C ₆ H ₄ - represents a phenylene group.) Represents the. The method for producing an amide-based elastomer for obtaining an amide-based elastomer which is a block copolymer bonded by an isocyanate component (Q) consisting of a group represented by the following formula (A):
Formula ^{(60); -CO-R 12} '-CO-NH-R 13'-NH- (60) ( wherein, R ¹² 'and R ^13' are the same or different, having from 2 to 12 carbon atoms . group represented by representing the alkylene group), or the following general formula ^{(61); -CO-R 14} '-NH- (61) ( wherein, R ^14' represents an alkylene group having 2 to 12 carbon atoms The polymer (T) having a hydroxyl group at both ends of the molecule is represented by the following formula:
Glass transition temperature is 20 ° C or less, number average molecular weight is 500 ~
5000, and the amide-based elastomer is:
100 to 100 parts by weight of the polyamide (P) component, 50 to 2,000 parts by weight of the polymer (T) having hydroxyl groups at both ends of the molecule, and 10 to 100 parts by weight of the isocyanate component (Q). The step of producing an amide elastomer comprises reacting a polymer (T) having hydroxyl groups at both ends of the molecule with a diisocyanate compound (Q ') to produce a prepolymer, and Polymer and polyamide (P)
And a method for producing an amide-based elastomer.

(8) The polymer (T) has the general formula (5)
^{4); -R 5 '-O-} (54) ( wherein, R ^5' is to be a polyether comprising the repeating unit a group represented by) represents an alkylene group having 2 to 10 carbon atoms. The method for producing an amide-based elastomer according to (7), which is characterized in that: (9) Polymer (T) of the general formula ^{(55); -R 6 '-} O-CO-R 7 -CO-O- (55) ( wherein, R ^6' and R ⁷ 'are the same or different (7) a process for producing an amide-based elastomer according to (7), wherein the repeating unit is an aliphatic polyester having a group represented by an alkylene group having 2 to 10 carbon atoms. Table with ^{-R 8 '-CO-O- (} 56) ( wherein, R ^8' represents an alkylene group having 2 to 10 carbon atoms.); (10) Polymer (T) of the general formula (56) (7) The method for producing an amide-based elastomer according to (7), wherein the lactone is a polylactone having a repeating unit as a repeating unit. (11) Polymer (T) of the general formula ^{(57); -R 9 '-} O-CO-O- (57) ( wherein, R ^9' represents an alkylene group having 2 to 10 carbon atoms.) (7) The method for producing an amide-based elastomer according to (7), which is a polycarbonate having a group represented by the following formula as a repeating unit. (12) An amide-based elastomer produced by the method for producing an amide-based elastomer according to (7), (8), (9), (10) or (11).

In the present invention, the polyester (S) is
Formula ^{(53); -CO-R 3} '-CO-O-R 4'-O- (53) ( wherein, R ³ 'is a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms R ⁴ ′ represents an alkylene group having 2 to 8 carbon atoms.) As a repeating unit. The polyester (S) can be obtained by reacting an aromatic dicarboxylic acid or an ester-forming derivative thereof with a low molecular weight diol.

The aromatic dicarboxylic acids and their ester-forming derivatives are not particularly restricted but include, for example, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate, and orthophthalic acid. And dimethyl naphthalenedicarboxylate and dimethyl paraphenylenedicarboxylate. These may be used alone or in combination of two or more. Among these, naphthalenedicarboxylic acid and dimethyl naphthalenedicarboxylate are particularly preferred because the set resistance at high temperatures of the ester elastomer produced by the present invention is greatly improved. The low molecular weight diol is not particularly limited, and examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 5-pentanediol, 1,6-hexanediol and the like. These may be used alone or in combination of two or more.

The above polyester (S) can be polymerized by a known method. For example, the polyester (S ) Can be obtained. In the polymerization for obtaining the polyester (S), a polyol having hydroxyl groups at both ends of the molecule may be used in order to improve the compatibility with the polymer (T) having hydroxyl groups at both ends of the molecule. The polyol having a hydroxyl group at both ends of the molecule is not particularly limited, and for example, a polyol having a glass transition temperature of 20 ° C. or less and a number average molecular weight of 500 to 5,000 is preferable. Examples of such a polyol include polyether, aliphatic polyester, polylactone, polycarbonate and the like. Among these, it is particularly preferable to use a polyol having the same component as the polymer (T).

The proportion occupied by the component comprising a polyol having hydroxyl groups at both ends of the molecule in the polyester (S) is not particularly limited, and may be, for example, 5 to 50% by weight in the polyester (S). preferable. When the content is less than 5% by weight, the effect of improving the compatibility with the polymer (T) becomes small. If it exceeds 50% by weight, the melting point of the polyester (S) becomes low, which may adversely affect the mechanical strength of the ester elastomer at high temperatures. Particularly preferably, it is 10 to 30% by weight. The number average molecular weight of the polyester (S) is not particularly limited, and is preferably, for example, 500 to 5,000. If it is less than 500, the blockability of the ester-based elastomer is reduced, and the mechanical strength at high temperatures may be adversely affected. If it exceeds 5,000, the compatibility with the polymer (T) becomes low, so that the degree of polymerization of the ester elastomer does not increase, and an elastomer having sufficient strength may not be obtained. More preferably, it is 1000-3000. The intrinsic viscosity of the polyester (S) is not particularly limited, and is preferably, for example, 0.05 to 0.5. If it is less than 0.05, the blockability of the ester-based elastomer becomes low, which may adversely affect the mechanical strength at high temperatures. If it exceeds 0.5, the compatibility with the polymer (T) becomes low, so that the degree of polymerization of the ester elastomer does not increase, and an elastomer having sufficient strength may not be obtained. More preferably, 0.1 to 0.1.
3. In this specification, the intrinsic viscosity is
It means a value measured at 25 ° C. using orthochlorophenol as a solvent.

In the present invention, the polymer (T) having a hydroxyl group at both ends of the molecule has a glass transition temperature of 20 ° C. or less and a number average molecular weight of 500 to 5,000. When the glass transition temperature of the polymer (T) exceeds 20 ° C., the obtained ester-based elastomer becomes hard,
An elastomer having good rubber elasticity cannot be obtained. Preferably, it is 0 ° C. or lower, more preferably −20 ° C.
It is as follows. The number average molecular weight of the polymer (T) is 50
If it is less than 0, the flexibility of the obtained ester elastomer will be lost, and if it exceeds 5,000, the reactivity with the diisocyanate compound (U ') will be low, and the degree of polymerization of the ester elastomer will not be increased, and sufficient strength will be obtained. Cannot be obtained. Preferably it is 500-3000, More preferably, it is 500-2000. The polymer (T) is not particularly limited as long as it satisfies the above conditions. For example, polyether, polylactone, aliphatic polyester, polycarbonate, polyolefin, polybutadiene, polyisoprene, polyacrylate, polysiloxane and the like are preferable. . Among them, polyethers, aliphatic polyesters, polylactones, and polycarbonates are more preferable because their reactivity is particularly excellent. It is not particularly restricted but includes Suitable polyether as the polymer (T), for example, the general formula ^{(54); -R 5 '-} O- (54) ( wherein, R ^5' is C2-10 It is preferable that the polyether is a polyether having a group represented by the following formula:

The polyether comprising a group represented by the general formula (54) as a repeating unit is not particularly limited, and examples thereof include polyethylene glycol, poly-1,3-propylene glycol, poly-1,2-propylene glycol, and polyether. Examples include tetramethylene glycol and polyhexamethylene glycol. Among these, polytetramethylene glycol is preferable because of its excellent mechanical properties and weather resistance.
"PTHF" (trade name) manufactured by Company F, "PTM" manufactured by Mitsubishi Chemical Corporation
G "(product name). The number average molecular weight of the polyether is preferably from 500 to 5,000. If it is less than 500, the flexibility of the obtained ester elastomer may be lost, and if it exceeds 5,000, the reactivity with the diisocyanate compound (U ') becomes low, and the degree of polymerization of the ester elastomer does not increase. It is difficult to obtain an elastomer having sufficient strength. More preferably, it is 500 to 3000, and still more preferably 500
~ 2000.

The aliphatic polyester suitable as the polymer (T) is not particularly limited, and may be, for example, a compound represented by the following general formula (55): -R ⁶ '-O-CO-R ⁷ ' -CO-O- (55) ( In the formula, R ⁶ ′ and R ⁷ ′ are the same or different and each represent an alkylene group having 2 to 10 carbon atoms). The aliphatic polyester having a group represented by the general formula (55) as a repeating unit is not particularly limited, and examples thereof include those obtained by a polycondensation reaction between an aliphatic dicarboxylic acid and an aliphatic diol. Can be The aliphatic dicarboxylic acid is not particularly limited,
For example, oxalic acid, malonic acid, succinic acid, glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Sebacic acid and the like. Further, other various dicarboxylic acids can be used in combination within a range that does not impair the physical properties of a molded article obtained from the resulting ester elastomer. These may be used alone or in combination of two or more.

The aliphatic diol is not particularly restricted but includes, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol and neopentyl glycol. , 1,5-pentanediol, 1,6-hexanediol and the like. In addition, other various diols can be used in combination within a range that does not impair the physical properties of a molded article obtained from the resulting ester elastomer. These may be used alone or in combination of two or more. As the aliphatic polyester, commercially available products include, for example, "Nipporan 4009" manufactured by Nippon Polyurethane Co., Ltd.
“Nipporan 4010”, “Nipporan 4070” (all are trade names) and the like. The aliphatic polyester preferably has a number average molecular weight of 500 to 5,000. If it is less than 500, the flexibility of the obtained ester elastomer tends to be lost, and if it exceeds 5,000, the reactivity with the diisocyanate compound (U ') decreases, and the degree of polymerization of the ester elastomer does not increase, and It is difficult to obtain a strong elastomer. More preferably, it is 500 to 3000, and still more preferably 500
~ 2000.

The polylactone suitable as the polymer (T) is not particularly limited.
^{6); -R 8 '-CO} -O- (56) ( wherein, R ^8' that is a polylactone comprising as repeating units a group represented by represents) an alkylene group having 2 to 10 carbon atoms. Is preferred. The polylactone having the group represented by the general formula (56) as a repeating unit is not particularly limited, and examples thereof include those obtained by ring-opening polymerization of lactone. The lactone is not particularly limited, and for example, those having 3 to 10 carbon atoms are preferably used. Particularly, caprolactone is preferred. These may be used alone or in combination of two or more. As the polylactone, as a commercial product, for example, “TONE polyol” manufactured by Union Carbide Co., Ltd.
(Product name) and the like. The polylactone preferably has a number average molecular weight of 500 to 5,000. 5
If it is less than 00, the flexibility of the obtained ester elastomer tends to be lost, and if it exceeds 5,000, the reactivity with the diisocyanate compound (U ') becomes low, and the degree of polymerization of the ester elastomer does not increase, and It is difficult to obtain a strong elastomer. More preferably, 500 to
3000, and more preferably 500 to 2,000.

The polycarbonate suitable as the polymer (T) is not particularly limited. For example, the polycarbonate represented by the general formula (5)
^{7); -R 9 '-O} -CO-O- (57) ( wherein, R ^9' is a polycarbonate comprising a repeating unit a group represented by represents) an alkylene group having 2 to 10 carbon atoms. Preferably, there is. The polycarbonate comprising a group represented by the above general formula (57) as a repeating unit is not particularly limited, and examples thereof include those obtained by ring-opening polymerization of an aliphatic carbonate.

The aliphatic carbonate is not particularly limited, and for example, those having 4 to 10 carbon atoms are preferably used. Particularly, propylene carbonate, tetramethylene carbonate, and hexamethylene carbonate are preferred. Examples of the commercially available polycarbonate include "Nipporan 981" (trade name) manufactured by Nippon Polyurethane Co., Ltd. The polycarbonate preferably has a number average molecular weight of 500 to 5,000. 5
If it is less than 00, the flexibility of the obtained ester elastomer tends to be lost, and if it exceeds 5,000, the reactivity with the diisocyanate compound (U ') becomes low, and the degree of polymerization of the ester elastomer does not increase, and It is difficult to obtain a strong elastomer. More preferably, 500 to
3000, and more preferably 500 to 2,000.

The ester elastomer in the present invention is a block copolymer comprising the above-mentioned polyester (S) and a polymer (T) having a hydroxyl group at both ends of the above-mentioned molecule bonded by an isocyanate component (U). In order to obtain an ester-based elastomer which is a block copolymer in which the polyester (S) and the polymer (T) having hydroxyl groups at both ends of the molecule are bonded by an isocyanate component (U), the polyester (S) ) And a polymer (T) having hydroxyl groups at both ends of the molecule may be reacted with a diisocyanate compound (U ′) represented by the following general formula (62). The polyester (S) and the polymer (T) usually have hydroxyl groups at both ends, but may partially have a carboxyl group. At this time, when both terminal functional groups that react with the diisocyanate compound (U ′) are hydroxyl groups, they are bound by an isocyanate component (U) consisting of a group represented by the following general formula (51), and When the functional group is a hydroxyl group and the other terminal functional group is a carboxyl group, they are bonded by an isocyanate component (U) comprising a group represented by the following general formula (52). In the case where the terminal functional groups in the polyester (S) and the polymer (T) are a carboxyl group and a carboxyl group, a small amount of a portion bonded by an isocyanate component comprising a group represented by the following general formula (63) It is considered to be included.

-O-CO-NH-R ¹ '-NH-CO-O- (51) -O-CO-NH-R ² ' -NH-CO- (52) OCN-R ¹⁵ '-NCO (62) ^{) -CO-NH-R 16 '} -NH-CO- (63) the general formula (51), (52), (62) and (63)
In the above, R ¹ ′, R ² ′, R ¹⁵ ′ and R ¹⁶ ′ represent an alkylene group having 2 to 15 carbon atoms, —C ₆ H ₄ —, —C ₆ H ₄ —CH
₂ -, _{or, -C 6 H 4 -CH 2 -C} 6 H 4 - ( where, -C ₆
H ₄ — represents a phenylene group. ). Also, R
^{1 ', R 2', R} 15 ' and R ^16' is alkyl substituted phenylene group, may be such a combination of an alkylene group and a phenylene group.

The above diisocyanate compound (U ′) is
The structure is not particularly limited as long as it is a compound having two isocyanate groups in the same molecule. Further, a compound having three or more isocyanate groups may be used as long as the fluidity of the obtained ester elastomer is maintained. These may be used alone or in combination of two or more. Examples of the diisocyanate compound (U ′) include aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; 1,2-ethylene diisocyanate;
1,3-propylene diisocyanate, 1,4-butane diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate,
Examples thereof include aliphatic diisocyanates such as 1,3-cyclohexane diisocyanate, isophorone diisocyanate, and hydrogenated 4,4'-diphenylmethane diisocyanate.

The ester-based elastomer of the present invention contains 100 to 100 parts by weight of the component composed of the polyester (S) and 50 to 2000 parts of the component composed of the polymer (T).
Parts by weight, and 10 to 100 parts by weight of the isocyanate component (U). If the amount of the component comprising the polymer (T) is less than 50 parts by weight, the ester elastomer cannot have sufficient flexibility, and if it exceeds 2,000 parts by weight, sufficient mechanical strength cannot be obtained. Preferably it is 200 to 1000 parts by weight. When the amount of the isocyanate component (U) is less than 10 parts by weight, the ester elastomer does not become a high molecular weight substance and has low mechanical strength. If it exceeds 100 parts by weight, the flexibility of the ester-based elastomer becomes inferior. Preferably 3
0 to 70 parts by weight. In the method for producing an ester-based elastomer of the present invention, the step of producing an ester-based elastomer comprises the step of reacting a polymer (T) having a hydroxyl group at both ends of the molecule with a diisocyanate compound (U ') to produce a prepolymer; And a step of reacting the prepolymer with the polyester (S) in two steps.

The advantages of the manufacturing method of the present invention are the following two points. (1) Normally, it is difficult for different polymer components to react with each other due to insufficient compatibility. For example, the reaction of the polyester (S), the polymer (T), and the diisocyanate compound (U ′) used in the present invention is as follows:
When the three components are simultaneously mixed and reacted, in a normal case, the polyester (S) and the polymer (T) are not bonded to each other but the polyester (S) or the polymer (T) is a diisocyanate compound (U ') Only causes a chain extension reaction, and a blend of the two polymers is formed, and a block copolymer cannot be obtained. However, according to the production method of the present invention, the terminal isocyanate group of the prepolymer composed of the polymer (T) and the polyester (S) can be surely reacted, and a block copolymer can be obtained. At this time, as described below,
In order to improve the reactivity, the reaction equipment and the reaction temperature are important factors.

(2) In the second step, by reacting an excess amount of the polyester (S) with the prepolymer in a molar amount, the block copolymer capped with a polyester having a hard segment at the end is obtained. Obtainable. The physical properties of the elastomer differ greatly depending on the type of terminal of the block copolymer. In the case of a segment comprising a polymer (T) having a soft segment at the end,
It is thought that this segment does not contribute to the development of rubber elasticity at all, but also lowers the melting point of the hard segment crystal, lowers creep resistance and mechanical strength at high temperatures as an elastomer. If the end is a hard segment,
Conversely, it is considered that the elastomer has improved creep resistance and mechanical strength at high temperatures. The production method of the present invention
It is suitable for obtaining a block copolymer whose terminal is sealed with polyester which is a hard segment which can be expected to improve creep resistance as an elastomer and mechanical strength at high temperatures.

The details of the manufacturing method of the present invention will be described below. First, in the first step, it is preferable to react an excess of the diisocyanate compound (U ′) in a molar amount with respect to the polymer (T). The molar amount of the diisocyanate compound (U ′) is 1.1 relative to the polymer (T).
Particularly preferred is -2.2 times. If the ratio is less than 1.1 times, both ends of the resulting prepolymer may not be completely isocyanated, which may hinder the second-stage reaction. 2.2
If it exceeds twice, unreacted diisocyanate compound (U ') remains, which may cause a side reaction at the time of the second stage reaction. More preferably, it is 1.2 to 2.0 times. In the first step, the reaction temperature is 10
0-240 ° C is preferred. If the temperature is lower than 100 ° C., the reaction may not proceed sufficiently.
The polymer (T) decomposes. More preferably, 120 ° C
１６０160 ° C. In the second step, the prepolymer is mixed and reacted with the polyester (S) in a molar amount of 0.9 to 3.0 times. In order to obtain a block copolymer capped with a polyester having a hard segment at the end, it is preferable to react a molar amount of excess polyester (S) with the prepolymer. The molar amount of the polyester (S) is
It is particularly preferred that the ratio be 1.2 to 3.0 times. If the ratio is less than 1.2 times, a block copolymer having a soft segment at the end may be partially formed. If it exceeds 3.0 times,
The flexibility of the ester elastomer may be poor. More preferably, it is 1.25 to 2.0 times.

The structure of the obtained block copolymer can be controlled by the composition ratio of the polyester (S) and the polymer (T). For example, when the hard segment is represented by A and the soft segment is represented by B, polyester (S)
Is twice the molar amount of the prepolymer, AB
An A-type block copolymer is obtained. When the molar amount of the polyester (S) is 1.5 times the prepolymer, an ABABA type block copolymer can be obtained. Further, when the molar amount of the polyester (S) is 1.25 times the prepolymer, an ABABABABA type block copolymer is obtained. By reacting the block copolymer obtained by the above-described method with the block copolymer terminated with a polyester having a hard segment and a diisocyanate compound (U ′) and further increasing the molecular weight, creep resistance,
An ester-based elastomer having extremely excellent mechanical strength at high temperatures can be obtained. Unless the terminal is a hard segment, in order to obtain a high-molecular-weight ester-based elastomer, it is necessary to react 0.9 to 1.2 times the molar amount of polyester (S) with respect to the prepolymer. Is preferred. If it is less than 0.9 times or more than 1.2 times, it is difficult to increase the molecular weight.

In the case of using a prepolymer in which both ends are not completely isocyanated in the second-stage reaction, the polyester (S) is obtained by preliminarily reacting a molar excess of the diisocyanate compound (U '). By reacting the above-mentioned prepolymer with a reaction product of a polyester (S) having isocyanate groups at both ends, a high-molecular-weight ester-based elastomer can be obtained. The molar amount of the diisocyanate compound (U ') used in this series of reactions is preferably 0.9 to 1.2 times the total molar amount of the polymer (T) and the polyester (S). If it is less than 0.9 times or more than 1.2 times, it is difficult to increase the molecular weight. In the second step, the reaction temperature is preferably from 180 to 260 ° C. 180
When the temperature is lower than 0 ° C, the polyester (S) does not melt, so that the reaction is difficult and it is difficult to obtain a high molecular weight polymer. When the temperature exceeds 260 ° C, the prepolymer and the diisocyanate compound (U ') are decomposed, and the strength is lowered. It is difficult to obtain sufficient polymer. More preferably, it is 200 to 240 ° C.

In the production method of the present invention, a catalyst can be used during the above reaction. Examples of the catalyst include diacyl stannous, tetraacylstannic, dibutyltin oxide, dibutyltin dilaurate, dimethyltin malate, tin dioctanoate, tin tetraacetate, triethyleneamine, diethyleneamine, triethylamine,
Preferred are metal naphthenate, metal octylate, triisobutylaluminum, tetrabutyltitanate, calcium acetate, germanium dioxide, antimony trioxide and the like. These may be used alone or in combination of two or more. The above reaction method is preferably a bulk reaction. By this reaction method, the reactivity in the second step is particularly improved. Further, an extruder can be used as the reaction equipment. As the extruder, a co-directional twin screw extruder is preferable. By using this equipment, the reactivity of the second stage is particularly improved. In order to continuously perform the reaction between the first stage and the second stage, it is preferable to use a tandem type extruder.

A stabilizer may be used in the method for producing an ester elastomer of the present invention. Further, a stabilizer may be added to the ester elastomer produced by the method for producing an ester elastomer of the present invention. The stabilizer is not particularly limited, and may be, 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-
Hindered phenolic antioxidants such as dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane; tris (2,4-di-t-butylphenyl) phosphite, trilaurylphospho Fight, 2-t
-Butyl-α- (3-t-butyl-4-hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipro And heat stabilizers such as pionate, pentaerythryltetrakis (3-laurylthiopropionate), and ditridecyl 3,3'-thiodipropionate. These may be used alone or in combination of two or more.

The present invention (2) is an ester elastomer produced by the method for producing an ester elastomer of the present invention (1). The ester-based elastomer of the present invention (2) is produced by the method for producing an ester-based elastomer of the present invention (1), and has a high blockability between a hard segment component and a soft segment component, flexibility and high temperature. And excellent in mechanical properties, especially resistance to sag at high temperatures. The ester-based elastomer of the present invention (2) is an additive such as a fiber, an inorganic filler, a flame retardant, an ultraviolet absorber, an antistatic agent, an inorganic substance, or a higher fatty acid salt within a range that does not impair the utility during or after the production. May be added. These may be used alone or in combination of two or more.
The fibers are not particularly limited and include, for example, 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. Is mentioned. The inorganic filler is not particularly restricted but includes, for example, calcium carbonate, titanium oxide, mica, talc and the like. The flame retardant is not particularly limited. For example, hexabromocyclododecane, tris- (2,3-
Dichloropropyl) phosphate, pentabromophenyl allyl ether and the like.

The ultraviolet absorber is not particularly restricted but includes, for example, p-tert-butylphenyl salicylate, 2-hydroxy-4-methoxybenzophenone,
-Hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4,5-trihydroxybutyrophenone and the like. The antistatic agent is not particularly limited, and includes, for example, N, N-bis (hydroxyethyl) alkylamine, alkyl allyl sulfonate, alkyl sulfanate and the like. The inorganic substance is not particularly limited, and examples thereof include barium sulfate, alumina, and silicon oxide.

The higher fatty acid salt is not particularly restricted but includes, for example, sodium stearate, barium stearate, sodium palmitate and the like. The ester-based elastomer of the present invention (2) may be mixed with other thermoplastic resins, rubber components and the like to modify its properties before use. The thermoplastic resin is not particularly limited, and examples thereof include polyolefin, modified polyolefin, polystyrene, polyvinyl chloride, polyamide, polycarbonate, polysulfone, and polyester. The rubber component is not particularly limited. For example, natural rubber, styrene-butadiene copolymer, polybutadiene, polyisoprene, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer (EPM, EP
DM), polychloroprene, butyl rubber, acrylic rubber, silicone 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 (2) 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. 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., the fluidity of the ester elastomer becomes low, so that it is difficult to obtain a uniform molded product,
If the temperature exceeds 280 ° C., the ester elastomer is decomposed, and it is difficult to obtain an ester elastomer having sufficient strength.

The molded article obtained by using the ester elastomer of the present invention (2) is suitably used for, for example, automobile parts, electric and electronic parts, industrial parts, sports goods, medical goods and the like. The above-mentioned automobile parts are not particularly limited, and include, for example, boots such as constant velocity joint boots and rack and pinion boots; ball joint seals; safety belt parts; bumper fascia; emblem; The electric and electronic components are not particularly limited, and include, for example, wire covering materials, gears, rubber switches, membrane switches, tact switches,
O-ring and the like. The industrial parts are not particularly limited, and include, for example, a hydraulic hose, a coil tube, a sealing material, a packing, a V-belt, a roll, a vibration damping material,
Shock absorbers, couplings, diaphragms,
Examples include a binder for a bonded magnet. The sports equipment is not particularly limited, and includes, for example, shoe soles and ball for ball games. The medical supplies are not particularly limited, and include, for example, containers such as transfusion bags and transfusion bags, infusion set tubes, transfusion circuit tubes, catheters and other tubes, and stoppers for these devices. In addition to the above uses, it can be suitably used as an elastic fiber, an elastic sheet, a composite sheet, a film, a composite film, a foam, a hot melt adhesive, a binder, a material for alloying with other resins, and the like.

The ester elastomer of the present invention (2) is excellent in flexibility and high-temperature properties for the following reasons. That is, different polymer components are usually incompatible with each other due to insufficient compatibility.
In the above, the polyester (S) and the polymer as the soft segment component are controlled by controlling the reaction between the polyester (S) as the hard segment component and the polymer (T) as the soft segment component and the diisocyanate compound (U ′). (T). As a result, an ester elastomer having high blockability between the hard segment component and the soft segment component is produced. In the ester-based elastomer, the crystal formed by the polyester component constitutes a cross-linking point and exhibits properties as an elastomer. The ester-based elastomer of the present invention (2) is composed of a polyester-rich portion and a soft segment-rich portion in the molecule, and the polyester component is more crystalline than the conventional ester-based elastomer having 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. Furthermore, the presence of the soft segment-rich portion increases the molecular weight between crosslink points, resulting in a highly flexible elastomeric material.

In the present invention (3), the polyamide (P) and the polymer (T) having hydroxyl groups at both ends of the molecule are represented by the general formula (58): -O-CO-NH-R ¹⁰ '-NH-CO —O— (58) (wherein, R ¹⁰ ′ is an alkylene group having 2 to 15 carbon atoms;
C ₆ H ₄ —, —C ₆ H ₄ —CH ₂ —, or —C ₆ H ₄ —CH ₂
—C ₆ H ₄ — (however, —C ₆ H ₄ — represents a phenylene group). ) Or a group represented by the general formula (5)
9); -O-CO-NH -R 11 '-NH-CO-NH- (59) ( wherein, R ^11' is an alkylene group having from 2 to 15 carbon atoms, -
C ₆ H ₄ —, —C ₆ H ₄ —CH ₂ —, or —C ₆ H ₄ —CH ₂
—C ₆ H ₄ — (however, —C ₆ H ₄ — represents a phenylene group). The method for producing an amide-based elastomer for obtaining an amide-based elastomer which is a block copolymer bonded by an isocyanate component (Q) comprising a group represented by the following formula: ^{60); -CO-R 12 '} -CO-NH-R 13'-NH- (60) ( wherein, R ¹² 'and R ^13' are the same or different, an alkylene group having 2 to 12 carbon atoms . representing a group represented by), or the following general formula ^{(61); -CO-R 14} '-NH- (61) ( wherein, R ^14' represents an alkylene group having 2 to 12 carbon atoms. ) Is a repeating unit, and the polymer (T) having hydroxyl groups at both ends of the molecule is:
Glass transition temperature is 20 ° C or less, number average molecular weight is 500 ~
5000, and the amide-based elastomer is:
100 to 100 parts by weight of the polyamide (P) component, 50 to 2,000 parts by weight of the polymer (T) having hydroxyl groups at both ends of the molecule, and 10 to 100 parts by weight of the isocyanate component (Q). The step of producing an amide elastomer comprises the steps of reacting a polymer (T) having hydroxyl groups at both ends of the molecule with a diisocyanate compound (Q ') to produce a prepolymer; Polymer and polyamide (P)
And amide-based elastomers.

In the present invention (3), the polyamide (P)
The general formula ^{(60); -CO-R 12} '-CO-NH-R 13'-NH- (60) ( wherein, R ¹² 'and R ^13' are the same or different, 2 carbon atoms Or a group represented by the following general formula (61): —CO—R ¹⁴ ′ —NH— (61) (wherein, R ¹⁴ ′ has 2 to 12 carbon atoms) (Representing an alkylene group)) as a repeating unit.

The polyamide (P) can be obtained by polycondensation of a diamine and a dicarboxylic acid or by ring-opening polymerization of a lactam. The diamine is not particularly limited, and includes, for example, ethylenediamine, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, and the like. These may be used alone or in combination of two or more.

The dicarboxylic acid is not particularly restricted but includes, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like. Further, other various dicarboxylic acids can be used in combination within a range that does not impair the physical properties of the molded article obtained from the amide-based elastomer to be produced. These may be used alone or in combination of two or more. The lactam is not particularly limited and includes, for example, valerolactam, caprolactam, dodecalactam and the like. These may be used alone or in combination of two or more.

The polyamide (P) can be polymerized by a known method. For example, polyamide (P) can be obtained by heating hexamethylenediamine with an equivalent amount of dicarboxylic acid at 260 ° C. in the presence of a catalyst to perform a polycondensation reaction. Also, ε-
Polyamide (P) can be obtained by heating caprolactam at 260 ° C. in the presence of a catalyst to perform ring-opening polymerization. The polyamide (P) obtained by the above method is not particularly limited, and for example, 4-nylon, 6-nylon, 6,6-nylon, 11-nylon, 12-nylon, 6,10-nylon, 6, 12-
Nylon and the like. In the polymerization for obtaining the polyamide (P), a polyol having hydroxyl groups at both ends of the molecule may be used in order to improve the compatibility with the polymer (T) having hydroxyl groups at both ends of the molecule.

The polyol having a hydroxyl group at both terminals of the above molecule is not particularly limited. For example, a polyol having a glass transition temperature of 20 ° C. or less and a number average molecular weight of 500 to 5,000 is preferable. Examples of such a polyol include polyether, aliphatic polyester, polylactone, polycarbonate and the like. Among these, it is particularly preferable to use a polyol having the same component as the polymer (T). The proportion occupied by the component composed of a polyol having hydroxyl groups at both ends of the molecule in the polyamide (P) is not particularly limited, and is preferably, for example, 5 to 50% by weight in the polyamide (P). When the content is less than 5% by weight, the effect of improving the compatibility with the polymer (T) becomes small. If it exceeds 50% by weight, the melting point of the polyamide (P) becomes low, which may adversely affect the mechanical strength of the amide-based elastomer at high temperatures. Particularly preferably, it is 10 to 30% by weight.

The number average molecular weight of the polyamide (P) is not particularly limited, and is preferably, for example, 500 to 5,000. If it is less than 500, the blockability of the amide-based elastomer becomes low, which may adversely affect the mechanical strength at high temperatures. If it exceeds 5,000, the compatibility with the polymer (T) becomes low, so that the degree of polymerization of the amide-based elastomer does not increase, and it is difficult to obtain an elastomer having sufficient strength. More preferably, it is 1000-3000. The intrinsic viscosity of the polyamide (P) is not particularly limited, and is preferably, for example, 0.05 to 0.5. If it is less than 0.05, the blockability of the amide-based elastomer becomes low, which may adversely affect the mechanical strength at high temperatures. If it exceeds 0.5, the compatibility with the polymer (T) becomes low, so that the degree of polymerization of the amide-based elastomer does not increase, and it is difficult to obtain an elastomer having sufficient strength. More preferably, it is 0.1 to 0.3.

In the present invention (3), the polymer (T) having hydroxyl groups at both ends of the molecule has a glass transition temperature of 20.
C. or lower and a number average molecular weight of 500 to 5000. Examples of such a polymer (T) include those similar to those described in the first aspect of the invention. The amide-based elastomer in the present invention (3) is a block copolymer in which the polyamide (P) and the polymer (T) having a hydroxyl group at both terminals of the molecule are bound by an isocyanate component (Q). In order to obtain an amide-based elastomer which is a block copolymer in which the polyamide (P) and the polymer (T) having hydroxyl groups at both ends of the molecule are bound by an isocyanate component (Q), the polyamide (P) ) And a polymer (T) having hydroxyl groups at both ends of the molecule, and the following general formula (64)
May be reacted with the diisocyanate compound (Q ').

The polyamide (P) preferably has an amino group at both terminals, but may partially have a carboxyl group or a hydroxyl group. In addition, the above polymer (T)
Usually has a hydroxyl group at both terminals, but may partially have a carboxyl group or an amino group. At this time, when both terminal functional groups that react with the diisocyanate compound (Q ′) are hydroxyl groups, they are bound by an isocyanate component (Q) consisting of a group represented by the following general formula (58), and When the functional group is an amino group and the other terminal functional group is a hydroxyl group, they are bonded by an isocyanate component (Q) comprising a group represented by the following general formula (59). In addition, when the terminal functional groups in the polyamide (P) and the polymer (T) are an amino group and an amino group, a small amount of a portion bonded by an isocyanate component comprising a group represented by the following general formula (65) It is considered to be included. In the case of an amino group and a carboxyl group, it is considered that a small amount of a part bound by an isocyanate component consisting of a group represented by the following general formula (66) is also contained. In the case of a carboxyl group and a carboxyl group, it is considered that a small amount of a portion bonded by an isocyanate component consisting of a group represented by the following general formula (67) is also contained. When it is a carboxyl group and a hydroxyl group,
It is considered that a small amount of a part bound by an isocyanate component comprising a group represented by the following general formula (68) is also contained.

—O—CO—NH—R^Ten'-NH-CO-O- (58) -O-CO-NH-R¹¹'-NH-CO-NH- (59) OCN-R¹⁷'-NCO (64) -NH-CO-NH-R¹⁸'-NH-CO-NH- (65) -NH-CO-NH-R¹⁹'-NH-CO- (66) -CO-NH-R²⁰'-NH-CO- (67) -CO-NH-R^{twenty one}'-NH-CO-O- (68) The above general formulas (58), (59), (64), (65),
In (66), (67) and (68), R^Ten´, R
¹¹´, R¹⁷´, R¹⁸´, R¹⁹´, R²⁰'And R ^{twenty one}´
An alkylene group having 2 to 15 carbon atoms, -C₆H_Four-, -C₆H_Four
-CH_Two-Or -C₆H_Four-CH_Two -C₆H_Four-(But
And -C₆H_Four-Represents a phenylene group. ).
Also, R^Ten´, R¹¹´, R¹⁷´, R¹⁸´, R¹⁹´, R²⁰
'And R^{twenty one}´ is an alkyl-substituted phenylene group, alkylene
Or a combination of phenylene and phenylene groups
Good. The diisocyanate compound (Q ') of the present invention
1. The diisocyanate compound (U ′) described in 1.
Similar ones can be mentioned.

The amide-based elastomer in the present invention (3) is characterized in that the component consisting of the polymer (T) is 50 to 2,000 per 100 parts by weight of the component consisting of the polyamide (P).
Parts by weight, 10 to 100 parts by weight of the isocyanate component (Q). If the amount of the component comprising the polymer (T) is less than 50 parts by weight, the amide-based elastomer cannot have sufficient flexibility, and if it exceeds 2,000 parts by weight, sufficient mechanical strength cannot be obtained. Preferably 2
It is 00 to 1000 parts by weight. When the amount of the isocyanate component (Q) is less than 10 parts by weight, the amide-based elastomer does not become a high molecular weight substance but has low mechanical strength. If it exceeds 100 parts by weight, the flexibility of the amide-based elastomer becomes inferior. Preferably 30 to
70 parts by weight.

In the method for producing an amide elastomer of the present invention (3), the step of producing the amide elastomer comprises:
A polymer (T) having hydroxyl groups at both ends of the molecule and a diisocyanate compound (Q ′) to react with each other to produce a prepolymer; and a step of reacting the prepolymer with a polyamide (P). It is characterized by comprising a process. The advantage of the production method of the present invention (3) is that
The following two points. (1) Normally, it is difficult for different polymer components to react with each other due to insufficient compatibility. For example, the reaction of the polyamide (P), the polymer (T) and the diisocyanate compound (Q ′) used in the present invention (3) is as follows:
When the three components are simultaneously mixed and reacted, in a normal case, the polyamide (P) and the polymer (T) are not bonded to each other, and the polyamides (P) or the polymers (T) are not bonded to each other. ') Only causes a chain extension reaction, and a blend of the two polymers is formed, and a block copolymer cannot be obtained. However, according to the production method of the present invention (3), the polymer (T)
Can reliably react the terminal isocyanate group of the prepolymer comprising with the polyamide (P), and a block copolymer can be obtained. At this time, as described later, in order to improve the reactivity, the reaction equipment and the reaction temperature are important factors.

(2) In the second step, an excess amount of the polyamide (P) is reacted with the prepolymer in a molar amount to form a block copolymer capped with a polyamide having a hard segment at the end. Obtainable. The physical properties of the elastomer differ greatly depending on the type of terminal of the block copolymer. In the case of a segment composed of a polymer (T) having a soft segment at the end, not only does this segment not contribute to the development of rubber elasticity, but also the melting point of the hard segment crystal is lowered, the creep resistance as an elastomer, It is considered that the mechanical strength decreases. Conversely, when the terminal is a hard segment, it is considered that the elastomer has improved creep resistance and mechanical strength at high temperatures. The production method of the present invention (3) is suitable for obtaining a block copolymer whose end is a polyamide which is a hard segment in which the creep resistance as an elastomer and the improvement in mechanical strength at high temperatures can be expected. I have.

The details of the production method of the present invention (3) will be described below. First, in the first step, the diisocyanate compound (Q ′) in molar excess relative to the polymer (T) is used.
Is preferably reacted. The molar amount of the diisocyanate compound (Q ′) is 1.1 to the polymer (T).
Particularly preferred is -2.2 times. If the ratio is less than 1.1 times, both ends of the resulting prepolymer cannot be completely isocyanated, and the second-stage reaction is inhibited. If it exceeds 2.2 times, unreacted diisocyanate compound (Q ') remains, so that a side reaction is caused during the second stage reaction. More preferably, it is 1.2 to 2.0 times.

In the first step, the reaction temperature is
100-240 ° C is preferred. If it is less than 100 ° C.,
When the reaction does not proceed sufficiently and exceeds 240 ° C., the polymer (T) is decomposed. More preferably, from 120 ° C to 160
° C. In the second step, the prepolymer is mixed and reacted with the polyamide (P) in a molar amount of 0.9 to 3.0 times. In order to obtain a block copolymer capped with a polyamide having a hard segment at the end, it is preferable to react an excess of the polyamide (P) in a molar amount with respect to the prepolymer. Polyamide (P)
Is particularly preferably 1.2 to 3.0 times the molar amount of the prepolymer. When the ratio is less than 1.2 times, a block copolymer having a soft segment at the end is partially formed. If it exceeds 3.0 times, the flexibility of the amide-based elastomer becomes inferior. More preferably, 1.25 to
2.0 times. The structure of the obtained block copolymer is
It can be controlled by the composition ratio of the polyamide (P) and the polymer (T). For example, if the hard segment is A,
When the soft segment is represented as B, polyamide (P)
Is twice the molar amount of the prepolymer, AB
An A-type block copolymer is obtained. When the molar amount of the polyamide (P) is 1.5 times the prepolymer, an ABABA type block copolymer is obtained. Further, when the molar amount of the polyamide (P) is 1.25 times the prepolymer, an ABABABABA type block copolymer is obtained.

A block copolymer obtained by the above-mentioned method and capped with a polyamide whose terminal is a hard segment;
By reacting with the diisocyanate compound (Q ') and further increasing the molecular weight, an amide-based elastomer having extremely excellent creep resistance and high-temperature mechanical strength can be obtained. Unless the terminal is a hard segment, in order to obtain a high molecular weight amide-based elastomer, a molar amount of 0.9 to
It is preferable to react 1.2 times the polyamide (P). If it is less than 0.9 times or more than 1.2 times, it is difficult to increase the molecular weight.

In the case of using a prepolymer in which both ends are not completely isocyanated in the second-stage reaction, the polyamide (P) is obtained by reacting a molar amount of excess diisocyanate compound (Q ') in advance. By reacting a reaction product of a polyamide (P) having isocyanate groups at both ends with the above prepolymer,
A high molecular weight amide-based elastomer can be obtained.
The molar amount of the diisocyanate compound (Q ') used in this series of reactions is preferably 0.9 to 1.2 times the total molar amount of the polymer (T) and the polyamide (P). If it is less than 0.9 times or more than 1.2 times, it is difficult to increase the molecular weight. In the second step, the reaction temperature is preferably from 180 to 280 ° C. 180
If the temperature is lower than ℃, the polyamide (P) does not melt,
The reaction is difficult and it is difficult to obtain a high molecular weight polymer.
If it exceeds 80 ° C., the prepolymer and the diisocyanate compound (Q ′) are decomposed, and it is difficult to obtain a polymer having sufficient strength. More preferably, it is 200 to 260 ° C.

In the production method of the present invention (3), a catalyst can be used during the above reaction. Examples of the catalyst include those similar to the catalyst described in the present invention (1). The above reaction method is preferably a bulk reaction. By this reaction method, the reactivity in the second step is particularly improved. Further, an extruder can be used as the reaction equipment. As the extruder, a co-directional twin screw extruder is preferable. By using this equipment, the reactivity of the second stage is particularly improved. Further, in order to continuously perform the first-stage and second-stage reactions, it is preferable to use a tandem-type extruder. In the method for producing an amide-based elastomer of the present invention (3), the above-mentioned stabilizer may be used. Further, the above-mentioned stabilizer may be added to the amide-based elastomer produced by the method for producing an amide-based elastomer of the present invention (3).

The present invention (4) is an amide elastomer produced by the method for producing an amide elastomer of the present invention (3). The amide-based elastomer of the present invention (4) is produced by the method for producing an amide-based elastomer of the present invention (3),
The blockability of the hard segment component and the soft segment component is high, and it is excellent in flexibility and mechanical properties at high temperatures, especially resistance to sag at high temperatures. The amide-based elastomer of the present invention (4) may be any of the above-mentioned fibers, inorganic fillers, flame retardants, ultraviolet absorbers, antistatic agents, inorganic substances, higher fatty acid salts and the like as long as the practicality is not impaired during or after the production. Additives may be added. These may be used alone or in combination of two or more.

The amide elastomer of the present invention (4) is
It may be mixed with the above-mentioned other thermoplastic resins, rubber components and the like to modify the properties thereof before use. The amide-based elastomer of the present invention (4) can be obtained by press molding generally used,
A molded article can be formed by a molding method such as extrusion molding, injection molding, blow molding and the like. The molding temperature varies depending on the melting point of the amide-based elastomer and the molding method.
C is suitable. When the temperature is lower than 160 ° C., the fluidity of the amide-based elastomer becomes low, so that it is difficult to obtain a uniform molded product. When the temperature exceeds 280 ° C., the amide-based elastomer is decomposed, and it is difficult to obtain an amide-based elastomer having sufficient strength. . The molded article obtained by using the amide-based elastomer of the present invention (4) is suitably used for, for example, the above-mentioned automobile parts, electric and electronic parts, industrial parts, sports goods, medical goods and the like. In addition to the above uses, it can be suitably used as an elastic fiber, an elastic sheet, a composite sheet, a film, a composite film, a foam, a hot melt adhesive, a binder, a material for alloying with other resins, and the like.

The amide-based elastomer of the present invention (4) is
Excellent flexibility and high temperature properties for the following reasons. That is,
Usually, different polymer components have insufficient compatibility,
Although it is difficult to react with each other, the present invention (3)
Wherein the polyamide (P) and the soft segment component are formed by controlling the reaction between the polyamide (P) as the hard segment component and the polymer (T) as the soft segment component and the diisocyanate compound (Q ′). It became possible to bond with the polymer (T). As a result, an amide elastomer having high blockability between the hard segment component and the soft segment component is produced. In the amide-based elastomer, the crystal formed by the polyamide component constitutes a cross-linking point, thereby exhibiting properties as an elastomer.
The amide-based elastomer of the present invention (4) is composed of a polyamide-rich portion and a soft segment-rich portion in the molecule, and the polyamide component is more crystalline than the conventional amide-based elastomer having 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. Furthermore, the presence of the soft segment-rich portion increases the molecular weight between crosslink points, resulting in a highly flexible elastomeric material.

[0116]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples. In addition, various physical properties were measured using the following methods unless otherwise specified. Number average molecular weight: gel permeation chromatography (HLC 8020 series manufactured by Tosoh Corporation) Column; Shodex HFIP 806M 2 solvents; hexafluoroisolopanol (0.005N sodium trifluoroacetate added) Standard sample: Polymethyl methacrylate polyester Acid value: After dissolving the sample in a benzyl alcohol / chloroform mixed solvent, neutralization titration was performed using a phenol red indicator to obtain an acid value. Hydroxyl value of polyester: A sample and succinic anhydride are dissolved in a mixed solvent of nitrobenzene / pyridine and reacted for 10 hours. The hydroxyl value was used.
The acid value and hydroxyl value of the polyether and the isocyanate value (NCO value) of the isocyanate compound adopted the manufacturer's guaranteed values. Glass transition temperature: Viscoelastic spectrometer (RSA-II manufactured by Rheometric Scientific F.)
At a heating rate of 3 ° C./min, a frequency of 1.61 Hz, a strain of 0.05%, and a sample: rectangular piece (thickness 0.5 mm, width 3 m)
m). Melting point: Using a differential scanning calorimeter (DSC), heating rate 10
Measured in ° C / min. Surface hardness: The surface hardness was measured at 23 ° C. using an A-type spring according to JIS K6301. Tensile properties: Tensile strength and tensile elongation at room temperature were measured according to JIS K6301. Compression set: 100 in accordance with JIS K6301
It measured at 25 degreeC with the amount of compression strains of 25%. Moisture permeability: JISZ0208 and ASTM F372-7
The measurement was performed on a film having a thickness of 100 μm in accordance with No. 3. Light fastness: Black panel temperature 63 ° C with 1mm thick sheet
Exposure for 80 hours in a carbon arc type fade tester, surface hardness and color difference meter (color analyzer, TC-1800M
K-II Measured by Tokyo Denshoku Co., Ltd. (JISK)
7105), and the difference was determined before and after irradiation.

The solubility was determined by the following method.
15 g of an elastomer was added to 85 g of N, N-dimethylformamide (DMF), and the solubility was examined under stirring at 120 ° C. for 1 hour. ：: soluble △: slightly soluble ×: hardly soluble The stability of the solution was determined by the following method. The solution used for the dissolution test was stored at 80 ° C. for 1 hour and judged. ：: stable △: solution solidifies as sol ×:
Insolubles precipitate immediately

[0118]

EXAMPLES Reference Example 1 Synthesis of Polyester (b-1) 100 parts by weight of dimethyl terephthalate, 102 parts by weight of 1,4-butanediol, 0.3 part by weight of tetrabutyl titanate as a catalyst,
0.3 parts by weight of 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and tris (2,4-di-t −
Then, 0.3 parts by weight of (butylphenyl) phosphite was added, and 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 proceeded, the temperature was raised to 240 ° C. for 20 minutes, and the pressure was reduced. The polymerization system reached a reduced pressure of 2 Torr or less in 15 minutes. As a result of a polycondensation reaction for 10 minutes in this state, 112 parts by weight of white polyester was obtained. This polyester (b-1) has a number average molecular weight of 2,000,
The acid value and the hydroxyl value were 5.0 (μeq / g), respectively.
And 1000 (μeq / g).

Reference Example 2 Synthesis of Polyester (b-2) 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 1000 (PTHF1000 manufactured by BASF) ) 48 parts by weight,
0.3 parts by weight of tetrabutyl titanate as a catalyst and 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) as a stabilizer
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 maintained at 200 ° C. for 3 hours under nitrogen to carry out a transesterification reaction. The progress of the transesterification reaction was confirmed by measuring the amount of methanol distilled off. After the transesterification proceeded, the temperature was raised to 240 ° C. for 20 minutes, and the pressure was reduced. The polymerization system reached a reduced pressure of 2 Torr or less in 15 minutes. As a result of a polycondensation reaction for 30 minutes in this state, 160 parts by weight of white polyester was obtained. This polyester (b-2) has a number average molecular weight of 5000, an acid value and a hydroxyl value of 5.0 (μeq / g) and 4 respectively.
00 (μeq / g).

Reference Example 3 Synthesis of Polyester (b-3) 100 parts by weight of dimethyl terephthalate, 38 parts by weight of dimethyl adipate, 1,
102 parts by weight of 4-butanediol, 0.3 part by weight of tetrabutyl titanate as a catalyst, 1,3,5 as a stabilizer
-Trimethyl-2,4,6-tris (3,5-di-t-
Butyl-4-hydroxybenzyl) benzene 0.3 parts by weight and tris (2,4-di-t-butylphenyl) phosphite 0.3 parts by weight were added, and the reaction system was heated to 200 ° C. under nitrogen.
For 3 hours to carry out a transesterification reaction. The progress of the transesterification reaction was confirmed by measuring the amount of methanol distilled off. After the transesterification proceeded, the temperature was raised to 240 ° C. for 20 minutes, and the pressure was reduced. The polymerization system is 1
In 5 minutes, the degree of pressure reduction reached 2 Torr or less. In this state, 1
As a result of performing the polycondensation reaction for 0 minutes, white polyester 1
28 parts by weight were obtained. This polyester (b-3)
Has a number average molecular weight of 2200, an acid value and a hydroxyl value,
6.0 (μeq / g) and 900 (μeq / g
g).

Reference Example 4 Synthesis of Polyester (b-4) 100 parts by weight of dimethyl terephthalate, 83 parts by weight of 1,4-butanediol,
30 parts by weight of cyclohexane dimethanol, 0.3 parts by weight of tetrabutyl titanate as a catalyst, 1,1 as a stabilizer
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene
3 parts by weight, tris (2,4-di-t-butylphenyl)
0.3 parts by weight of phosphite was added, and the reaction system was heated under nitrogen for 2 hours.
The mixture was kept at 00 ° C. for 3 hours to carry out transesterification. The progress of the transesterification reaction was confirmed by measuring the amount of methanol distilled off. After transesterification proceeds, 2
The temperature was raised to 240 ° C. in 0 minutes, and the pressure was reduced. The polymerization system reached a reduced pressure of 2 Torr or less in 15 minutes. As a result of performing a polycondensation reaction in this state for 5 minutes, 136 parts by weight of white polyester was obtained. This polyester (b-
4) has a number average molecular weight of 1,000, an acid value and a hydroxyl value of 4.0 (μeq / g) and 1900 (μe
q / g).

Reference Example 5 Synthesis of Polyester (b-5) 100 parts by weight of dimethyl terephthalate, 43 parts by weight of dimethyl isophthalate,
156 parts by weight of 1,4-butanediol, 0.3 parts by weight of tetrabutyl titanate as a catalyst, and 1 part by weight as a stabilizer
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene
3 parts by weight, tris (2,4-di-t-butylphenyl)
0.3 parts by weight of phosphite was added, and the reaction system was heated under nitrogen for 2 hours.
The mixture was kept at 00 ° C. for 3 hours to carry out transesterification. The progress of the transesterification reaction was confirmed by measuring the amount of methanol distilled off. After transesterification proceeds, 2
The temperature was raised to 240 ° C. in 0 minutes, and the pressure was reduced. The polymerization system reached a reduced pressure of 2 Torr or less in 15 minutes. As a result of a polycondensation reaction for 15 minutes in this state, 120 parts by weight of white polyester was obtained. This polyester (b-
5) has a number average molecular weight of 3200, an acid value and a hydroxyl value of 7.0 (μeq / g) and 625 (μeq), respectively.
/ G).

Reference Example 6 Synthesis of Polyester (b-6) 100 parts by weight of dimethyl terephthalate, 11 parts by weight of dimethyl isophthalate,
103 parts by weight of 1,4-butanediol, 17 parts by weight of cyclohexanedimethanol, 0.3 parts by weight of tetrabutyl titanate as a catalyst, and 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-
0.3 parts by weight of 4-hydroxybenzyl) benzene and 0.3 parts by weight of tris (2,4-di-t-butylphenyl) phosphite are added, and the reaction system is kept under nitrogen at 200 ° C. for 3 hours to carry out transesterification. The reaction was performed. The progress of the transesterification reaction was confirmed by measuring the amount of methanol distilled off. After the transesterification progresses, 24
The temperature was raised to 0 ° C., and the pressure was reduced. The polymerization system reached a reduced pressure of 2 Torr or less in 15 minutes. As a result of a polycondensation reaction for 10 minutes in this state, 120 parts by weight of white polyester was obtained. This polyester (b-6) had a number average molecular weight of 2,600, an acid value and a hydroxyl value of 7.0 (μeq / g) and 770 (μeq / g), respectively.

Example 1 As a polyether (a),
Number average molecular weight 1000, hydroxyl value 2000 (μeq /
g), 300 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g) and 87.5 parts by weight of 4,4′-diphenylmethane diisocyanate having an NCO value of 8000 (μeq / g) as a polyisocyanate compound (c) The polyester (b) was supplied from the first barrel of an extruder (L / D = 58, manufactured by Toshiba Machine Co., Ltd.), and was fed from the fifth barrel of the extruder.
-1) 100 parts by weight were supplied by using a forced side feeder and melt-mixed, containing 62% by weight of a polyether component having a carbon / oxygen atomic ratio of 2.0, and having a glass transition temperature of-
A pellet of the thermoplastic elastomer of the present invention at 30 ° C. was obtained. The kneading temperature was 200 ° C. The NCO value refers to the number of terminal NCOs per gram and is represented by 1 / MX (isocyanate group number). Press molding using the obtained thermoplastic elastomer pellets (press temperature 2
(20 ° C.) to produce a 2 mm thick sheet and a 100 μm thick sheet, and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 1.

Example 2 Polyethylene glycol was added to 2
Pellets of a thermoplastic elastomer were obtained in the same manner as in Example 1 except that the amount was changed to 86 parts by weight and further that the amount of 4,4'-diphenylmethane diisocyanate was changed to 83 parts by weight. A 2 mm thick sheet and 10 mm were formed by press molding (press temperature 230 ° C.) using the obtained pellets.
A sheet having a thickness of 0 μm was prepared, and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 1.

Example 3 As polyether (a),
Number average molecular weight 1000, hydroxyl value 2000 (μeq /
g), 240 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g), a number average molecular weight of 1,000, and a hydroxyl value of 20.
Pellets of thermoplastic elastomer were obtained in the same manner as in Example 1 except that 60 parts by weight of polytetramethylene glycol having 00 (μeq / g) and an acid value of 0 (μeq / g) were used. A 2 mm thick sheet and 10 mm were formed by press molding (press temperature 230 ° C.) using the obtained pellets.
A sheet having a thickness of 0 μm was prepared, and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 1.

Example 4 As a polyether (a),
Number average molecular weight 1000, hydroxyl value 2000 (μeq /
g), 210 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g), a number average molecular weight of 1,000, and a hydroxyl value of 20.
Pellets of thermoplastic elastomer by the same method as in Example 1 except that the polyether obtained by equimolar copolymerization of ethylene oxide and tetrahydrofuran was used, with an acid value of 0 (μeq / g) and an acid value of 0 (μeq / g). I got Using the obtained pellets, a 2 mm thick sheet and a 100 μm thick sheet were prepared by press molding (press temperature 230 ° C.), and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 1.

Example 5 As polyether (a),
Number average molecular weight 1500, hydroxyl value 1300 (μeq /
g), a polyethylene glycol having an acid value of 0 (μeq / g) was changed to 450 parts by weight, and 4,4′-diphenylmethane diisocyanate was changed to 87.5 parts by weight in the same manner as in Example 1. A thermoplastic elastomer pellet was obtained. Using the obtained pellets, a 2 mm thick sheet and a 100 μm thick sheet were prepared by press molding (press temperature: 220 ° C.), and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 1.

Example 6 As polyether (a),
Number average molecular weight 1000, hydroxyl value 2000 (μeq /
g), 160 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g) and 45 parts by weight of 4,4′-diphenylmethane diisocyanate having an NCO value of 8000 (μeq / g) as a polyisocyanate compound (c) are twin-screw extruder. (L / D = 58, manufactured by Toshiba Machine Co., Ltd.), and 100 parts by weight of the polyester polymer (b-2) was supplied from the fifth barrel of the extruder using a forced side feeder. Melt mixing was performed to obtain pellets of the thermoplastic elastomer of the present invention. The kneading temperature was 200 ° C.
Using the obtained thermoplastic elastomer pellets, a 2 mm thick sheet and a 100 μm thick sheet were prepared by press molding (press temperature: 220 ° C.), and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 1.

Example 7 Dimethyl terephthalate 100
Parts by weight, 102 parts by weight of 1,4-butanediol, 170 parts by weight of polyethylene glycol having a number average molecular weight of 1000, 0.3 parts by weight of tetrabutyl titanate as a catalyst,
0.3 parts by weight of 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and tris (2,4-di-t −
Then, 0.3 parts by weight of (butylphenyl) phosphite was added, and 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 proceeded, the temperature was raised to 240 ° C. for 20 minutes, and the pressure was reduced. The polymerization system reached a reduced pressure of 2 Torr or less in 20 minutes. As a result of performing a polycondensation reaction for 6 minutes in this state,
283 parts by weight of a thermoplastic elastomer were obtained. A 2 mm thick sheet and a 100 μm thick sheet were prepared by press molding (press temperature 230 ° C.) using the obtained thermoplastic elastomer, and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 1.

Example 8 As polyether (a),
Number average molecular weight 1000, hydroxyl value 2000 (μeq /
g), 273 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g) and 79.5 parts by weight of 4,4′-diphenylmethane diisocyanate having an NCO value of 8000 (μeq / g) as a polyisocyanate compound (c) are biaxially mixed. The polyester (b) was supplied from a first barrel of an extruder (L / D = 58, manufactured by Toshiba Machine Co., Ltd.), and was fed from a fifth barrel of the extruder.
-3) 100 parts by weight were supplied using a forced side feeder and melt-mixed to obtain pellets of the thermoplastic elastomer of the present invention. The kneading temperature was 200 ° C. Using a pellet of the obtained thermoplastic elastomer, a 2 mm-thick sheet and 1
A sheet having a thickness of 00 μm was prepared, and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 1.

Example 9 As polyether (a),
Number average molecular weight 1000, hydroxyl value 2000 (μeq /
g), 600 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g), and 175 parts by weight of 4,4′-diphenylmethane diisocyanate having an NCO value of 8000 (μeq / g) as a polyisocyanate compound (c) are twin-screw extruder. (L / D = 58, manufactured by Toshiba Machine Co., Ltd.), and the polyester (b-) was supplied from the fifth barrel of the extruder.
4) 100 parts by weight were supplied using a forced side feeder and melt-mixed to obtain pellets of the thermoplastic elastomer of the present invention. The kneading temperature was 200 ° C. Using a pellet of the obtained thermoplastic elastomer, a 2 mm-thick sheet and 10
A sheet having a thickness of 0 μm was prepared, and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 1.

Example 10 The polyether (a) used had a number average molecular weight of 1,000 and a hydroxyl value of 2,000 (μeq).
/ G), 156 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g) and 47 parts by weight of 4,4′-diphenylmethane diisocyanate having an NCO value of 8000 (μeq / g) as a polyisocyanate compound (c) are biaxially extruded. From the first barrel of the extruder (L / D = 58, manufactured by Toshiba Machine Co., Ltd.), and the polyester (b-
5) 100 parts by weight were supplied using a forced side feeder to perform melt mixing to obtain pellets of the thermoplastic elastomer of the present invention. The kneading temperature was 200 ° C. Using a pellet of the obtained thermoplastic elastomer, a 2 mm-thick sheet and 10
A sheet having a thickness of 0 μm was prepared, and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 1.

Example 11 As a polyether (a), a number average molecular weight of 1,000 and a hydroxyl value of 2,000 (μeq)
/ G), 231 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g) and 67 parts by weight of 4,4′-diphenylmethane diisocyanate having an NCO value of 8000 (μeq / g) as a polyisocyanate compound (c) are twin-screw extruded. From the first barrel of the extruder (L / D = 58, manufactured by Toshiba Machine Co., Ltd.), and the polyester (b-
6) 100 parts by weight were supplied using a forced side feeder and melt-mixed to obtain pellets of the thermoplastic elastomer of the present invention. The kneading temperature was 200 ° C. Using a pellet of the obtained thermoplastic elastomer, a 2 mm-thick sheet and 10
A sheet having a thickness of 0 μm was prepared, and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 1.

[Comparative Example 1] Polyethylene glycol was added to 5
Pellets of a thermoplastic elastomer were obtained in the same manner as in Example 1 except that the amount was changed to 0 parts by weight, and that 4,4'-diphenylmethane diisocyanate was further changed to 25 parts by weight. A 2 mm thick sheet and 10 mm were formed by press molding (press temperature 220 ° C.) using the obtained pellets.
A sheet having a thickness of 0 μm was prepared, and various physical properties were measured. The results are shown in Table 1.

[Comparative Example 2] As polyether (a),
Number average molecular weight 1000, hydroxyl value 2000 (μeq /
g) Thermoplastic elastomer pellets were obtained in the same manner as in Example 1 except that 300 parts by weight of polytetramethylene glycol having an acid value of 0 (μeq / g) was used. Using the obtained pellets, a 2 mm thick sheet and a 100 μm thick sheet were prepared by press molding (press temperature: 220 ° C.), and various physical properties were measured. The results are shown in Table 1.

[Comparative Example 3] As polyether (a),
Number average molecular weight 600, hydroxyl value 3300 (μeq /
g), 360 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g) and 162.5 parts by weight of 4,4′-diphenylmethane diisocyanate having an NCO value of 8000 (μeq / g) as the polyisocyanate compound (c). Except for the above, a thermoplastic elastomer pellet was obtained in the same manner as in Example 1. Using the obtained pellets, a 2 mm thick sheet and a 100 μm thick sheet were prepared by press molding (press temperature: 220 ° C.), and various physical properties were measured. The results are shown in Table 1.

[Comparative Example 4] As polyether (a),
Number average molecular weight 1000, hydroxyl value 2000 (μeq /
g), 180 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g), a number average molecular weight of 1,000, and a hydroxyl value of 20
Pellets of a thermoplastic elastomer were obtained in the same manner as in Example 1 except that 120 parts by weight of polytetramethylene glycol having a value of 00 (μeq / g) and an acid value of 0 (μeq / g) were used. A 2 mm thick sheet and 10 mm were formed by press molding (press temperature 230 ° C.) using the obtained pellets.
A sheet having a thickness of 0 μm was prepared, and various physical properties were measured. The results are shown in Table 1.

Comparative Example 5 A polyether (a), a polyester (b), and a polyisocyanate compound (c) were all mixed and supplied from the first barrel in the same manner as in Example 1. Melt mixing was performed, but a clay-like material was obtained, and no thermoplastic elastomer was obtained.

[Table 1]

Example 12 As a polyether (a), a number average molecular weight of 1,000 and a hydroxyl value of 2,000 (μeq)
/ G), 300 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g), and 62.3 parts by weight of hexamethylene diisocyanate having an NCO value of 11,900 (μeq / g) as a polyisocyanate compound (c), were fed into a twin-screw extruder ( The polyester (b-1) 1 is supplied from a first barrel of Toshiba Machine Co., Ltd., L / D = 58) and from the fifth barrel of the extruder.
00 parts by weight was supplied by using a forced side feeder and melt-mixed to obtain pellets of the thermoplastic elastomer of the present invention. The kneading temperature was 200 ° C. The resulting thermoplastic elastomer pellets were press-molded (press temperature: 220 ° C.) to form a 1,2 mm thick sheet and a 100 mm thick sheet.
A sheet having a thickness of μm was prepared, and various physical properties were measured. Also,
The solubility was evaluated using the pellet as it was.
The results are shown in Table 2.

Example 13 The procedure of Example 12 was repeated except that polyethylene glycol was changed to 286 parts by weight, hexamethylene diisocyanate was further added to 59 parts by weight, and tin octoate was added to 0.3 parts by weight. A pellet of a plastic elastomer was obtained. Using the obtained pellets, a 1,2 mm-thick sheet and a 100 μm-thick sheet were prepared by press molding (a press temperature of 230 ° C.).
Various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 2.

Example 14 As a polyether (a), a number average molecular weight of 1,000 and a hydroxyl value of 2,000 (μeq)
/ G), 240 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g), a number average molecular weight of 1,000, and a hydroxyl value of 2
Pellets of thermoplastic elastomer were obtained in the same manner as in Example 12, except that 60 parts by weight of polytetramethylene glycol having a molecular weight of 000 (μeq / g) and an acid value of 0 (μeq / g) was used. Using the obtained pellets, a 1,2 mm thick sheet and a 100 µm thick sheet were prepared by press molding (press temperature: 230 ° C), and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 2.

Example 15 The polyether (a) used had a number average molecular weight of 1,000 and a hydroxyl value of 2,000 (μeq).
/ G), 210 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g), a number average molecular weight of 1,000, and a hydroxyl value of 2
Example 12 except that 000 (μeq / g), an acid value of 0 (μeq / g) and 90 parts by weight of a polyether obtained by equimolar copolymerization of ethylene oxide and tetrahydrofuran were used.
A pellet of a thermoplastic elastomer was obtained in the same manner as in the above. Using the obtained pellets, a 2 mm thick sheet and a 100 μm thick sheet were prepared by press molding (press temperature 230 ° C.), and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 2.

Example 16 The polyether (a) used had a number average molecular weight of 1500 and a hydroxyl value of 1300 (μeq).
/ G) and a thermoplastic elastomer by the same method as in Example 12 except that polyethylene glycol having an acid value of 0 (μeq / g) was changed to 450 parts by weight and hexamethylene diisocyanate was changed to 62.3 parts by weight. Was obtained. Using the obtained pellets, a 1,2 mm thick sheet and a 100 µm thick sheet were prepared by press molding (press temperature: 220 ° C), and various physical properties were measured.
The solubility was evaluated using the pellets as they were. The results are shown in Table 2.

Example 17 The polyether (a) used had a number average molecular weight of 1,000 and a hydroxyl value of 2,000 (μeq).
/ G), 160 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g), and 32 parts by weight of hexamethylene diisocyanate having an NCO value of 11,900 (μeq / g) as a polyisocyanate compound (c), were mixed with a twin-screw extruder (Toshiba). (L / D = 58, manufactured by Machinery Co., Ltd.), and the polyester polymer (b-
2) 100 parts by weight were supplied using a forced side feeder and melt-mixed to obtain pellets of the thermoplastic elastomer of the present invention. The kneading temperature was 200 ° C. Using the obtained thermoplastic elastomer pellets, a 1,2 mm thick sheet and a 100 μm thick sheet were prepared by press molding (press temperature: 220 ° C.), and various physical properties were measured.
The solubility was evaluated using the pellets as they were. The results are shown in Table 2.

Example 18 Dimethyl Terephthalate 10
0 parts by weight, 102 parts by weight of 1,4-butanediol, 170 parts by weight of polyethylene glycol having a number average molecular weight of 1000, 0.3 parts by weight of tetrabutyl titanate as a catalyst, 1,3,5-trimethyl-2,2 as a stabilizer 4,6
0.3 parts by weight of tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (2,4-di-
0.3 parts by weight of (t-butylphenyl) phosphite was added, and the reaction system was maintained at 200 ° C. for 3 hours under nitrogen to carry out a transesterification reaction. The progress of the transesterification reaction was confirmed by measuring the amount of methanol distilled off. After the transesterification proceeds, the temperature is raised to 240 ° C. in 20 minutes,
A decompression operation was performed. The polymerization system reached a reduced pressure of 2 Torr or less in 20 minutes. As a result of performing a polycondensation reaction in this state for 6 minutes, 283 parts by weight of a thermoplastic elastomer was obtained.
The obtained thermoplastic elastomer was press-molded (press temperature: 230 ° C.) to form a 1,2 mm thick sheet and a 10 mm thick sheet.
A sheet having a thickness of 0 μm was prepared, and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 2.

Example 19 As polyether (a), the number average molecular weight was 1,000 and the hydroxyl value was 2,000 (μeq).
/ G), 273 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g), and 56.6 parts by weight of hexamethylene diisocyanate having an NCO value of 11900 (μeq / g) as a polyisocyanate compound (c). (L / D = 58, manufactured by Toshiba Machine Co., Ltd.)
From the fifth barrel of the extruder, the polyester (b-3)
100 parts by weight were supplied using a forced side feeder and melt-mixed to obtain pellets of the thermoplastic elastomer of the present invention. The kneading temperature was 200 ° C. The resulting thermoplastic elastomer pellets were press-molded (press temperature 220 ° C.) using a 1,2 mm thick sheet and a 10 mm thick sheet.
A sheet having a thickness of 0 μm was prepared, and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 2.

Example 20 The polyether (a) used had a number average molecular weight of 1,000 and a hydroxyl value of 2,000 (μeq).
/ G), 600 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g), and 124.6 parts by weight of hexamethylene diisocyanate having an NCO value of 11,900 (μeq / g) as a polyisocyanate compound (c). (L / D = 58, manufactured by Toshiba Machine Co., Ltd.), and the polyester (b-) was supplied from the fifth barrel of the extruder.
4) 100 parts by weight were supplied using a forced side feeder and melt-mixed to obtain pellets of the thermoplastic elastomer of the present invention. The kneading temperature was 200 ° C. Using the obtained thermoplastic elastomer pellets, a 1,2 mm thick sheet and a 100 μm thick sheet were prepared by press molding (press temperature: 220 ° C.), and various physical properties were measured.
The solubility was evaluated using the pellets as they were. The results are shown in Table 2.

Example 21 The polyether (a) used had a number average molecular weight of 1,000 and a hydroxyl value of 2,000 (μeq).
/ G), 156 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g), and 34 parts by weight of hexamethylene diisocyanate having an NCO value of 11900 (μeq / g) as a polyisocyanate compound (c) were mixed with a twin-screw extruder (Toshiba Machine Co., Ltd.). L / D = 58) from the first barrel of the extruder, and the polyester (b-5) 100
The parts by weight were supplied using a forced side feeder and melt-mixed to obtain pellets of the thermoplastic elastomer of the present invention. The kneading temperature was 200 ° C. Press molding (press temperature 220 ° C.) using the obtained thermoplastic elastomer pellets, a 1,2 mm thick sheet and 100 μm
Thick sheets were prepared and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 2.

Example 22 The polyether (a) used had a number average molecular weight of 1,000 and a hydroxyl value of 2,000 (μeq).
/ G), 231 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g) and 48 parts by weight of hexamethylene diisocyanate having an NCO value of 11900 (μeq / g) as a polyisocyanate compound (c) were mixed with a twin-screw extruder (Toshiba Machine Co., Ltd.). L / D = 58) from the first barrel, and the polyester (b-6) 100 from the fifth barrel of the extruder.
The parts by weight were supplied using a forced side feeder and melt-mixed to obtain pellets of the thermoplastic elastomer of the present invention. The kneading temperature was 200 ° C. Press molding (press temperature 220 ° C.) using the obtained thermoplastic elastomer pellets, a 1,2 mm thick sheet and 100 μm
Thick sheets were prepared and various physical properties were measured. The solubility was evaluated using the pellets as they were. The results are shown in Table 2.

[Comparative Example 6]
Pellets of thermoplastic elastomer were obtained in the same manner as in Example 12, except that the amount was changed to 0 parts by weight and the amount of 4,4'-diphenylmethane diisocyanate was changed to 25 parts by weight. Using the obtained pellets, a 1,2 mm thick sheet and a 100 µm thick sheet were prepared by press molding (press temperature: 220 ° C), and various physical properties were measured.
The results are shown in Table 2.

[Comparative Example 7] As polyether (a),
Number average molecular weight 1000, hydroxyl value 2000 (μeq /
g), 300 parts by weight of polytetramethylene glycol having an acid value of 0 (μeq / g), and 87.5 parts by weight of 4,4′-diphenylmethane diisocyanate were used. A pellet was obtained. Press molding (press temperature 220 ° C.) using the obtained pellets, a 1,2-mm thick sheet and 10
A sheet having a thickness of 0 μm was prepared, and various physical properties were measured. The results are shown in Table 2.

[Comparative Example 8] As polyether (a),
Number average molecular weight 600, hydroxyl value 3300 (μeq /
g), 360 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g) and 162.5 parts by weight of 4,4′-diphenylmethane diisocyanate having an NCO value of 8000 (μeq / g) as the polyisocyanate compound (c). Except for the above, a thermoplastic elastomer pellet was obtained in the same manner as in Example 12. Using the obtained pellets, a 1,2 mm thick sheet and a 100 µm thick sheet were prepared by press molding (press temperature: 220 ° C), and various physical properties were measured. The results are shown in Table 2.

[Comparative Example 9] As polyether (a),
Number average molecular weight 1000, hydroxyl value 2000 (μeq /
g), 180 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g), a number average molecular weight of 1,000, and a hydroxyl value of 20
In the same manner as in Example 12 except that 120 parts by weight of polytetramethylene glycol having an acid value of 0 (μeq / g) and 0 (μeq / g) and 87.5 parts by weight of 4,4′-diphenylmethane diisocyanate were used. A thermoplastic elastomer pellet was obtained. Using the obtained pellets, a 1,2 mm thick sheet and a 100 µm thick sheet were prepared by press molding (press temperature: 230 ° C), and various physical properties were measured. The results are shown in Table 2.

Comparative Example 10 A polyether (a), a polyester (b), and a polyisocyanate compound (c) were all mixed and supplied from a first barrel.
Melt mixing was performed in the same manner as in Example 12,
A clay was obtained, and no thermoplastic elastomer was obtained.

[Table 2]

Example 23 The thermoplastic elastomer pellets obtained in Example 1 were dried in an oven at 80 ° C. for 10 hours, and then spun at a spinning temperature of 210 using an ordinary melt spinning machine.
The melt-spinning was performed at a spinning speed of 600 m / min and a discharge rate of 40 g / min to obtain an undrawn yarn of 600 denier / 10F. The obtained undrawn yarn was drawn at a drawing speed of 200 m / min and a draw ratio of 3 times, and then passed through a heat-treated plate at 120 ° C., and subjected to a 50% heat shrink treatment to obtain a thermoplastic elastomer elastic yarn. Using the above-mentioned thermoplastic elastomer elastic yarn, a basis weight of 50
(G / m ² ) fabric was produced. The obtained woven fabric was evaluated by the following methods, and the results are shown in Table 3. [Water absorption] Cut out the woven fabric to 10 cm x 10 cm,
After being left for 24 hours in an atmosphere of 0% RH, the mass was measured and defined as an initial weight (WO). Next, this sample was immersed in distilled water at 23 ° C. for 10 hours, and excess water was removed with a filter paper. Then, the mass was measured and defined as the water absorption weight (Wl). Water absorption (%) = Wl / WO × 100. [Moisture Release Characteristics (Drying Time)] The woven fabric used for measuring the water absorption was attached to a drying time measuring apparatus, left in an atmosphere of 23 ° C. and 50% RH, and the time until natural drying was measured.

Example 24 50% by weight of the thermoplastic elastomer elastic yarn obtained in Example 23 and an ether-based polyurethane elastic yarn (ESPA (70 denier) manufactured by Toyobo)
Using 0% by weight, a woven fabric having a basis weight of 50 (g / m ² ) was prepared.
Evaluation was performed in the same manner as in Example 23, and the results are shown in Table 3.

[Comparative Example 11] A woven fabric having a basis weight of 50 (g / m ² ) was prepared using an ether-based polyurethane elastic yarn (ESPA (70 denier) manufactured by Toyobo), and evaluated in the same manner as in Example 23. Table 3 shows the results.

[Table 3]

Example 25 The polyether (a) used had a number average molecular weight of 1,000 and a hydroxyl value of 2,000 (μeq).
/ G), 300 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g) and 87.5 parts by weight of 4,4′-diphenylmethane diisocyanate having an NCO value of 8000 (μeq / g) as a polyisocyanate compound (c). 100 parts by weight of the polyester (b-1) is supplied from a first barrel of a screw extruder (manufactured by Toshiba Machine Co., L / D = 58), and 100 parts by weight of the polyester (b-1) is supplied from a fifth barrel of the extruder using a forced side feeder. The mixture was melt-mixed to obtain pellets of the thermoplastic elastomer of the present invention. The kneading temperature was 200 ° C. (Production of Elastomer Film) The obtained ester-based elastomer composition was dried at 80 ° C. for 8 hours and then molded by a T-die method. The molding temperature was adjusted to 200 ° C., and the extrusion rate and the take-off speed were adjusted so that the thickness of the elastomer film became 30 μm. The molten elastomer was extruded between release papers and wound up into a film. The moisture permeability of the obtained film was evaluated. (Production of laminated sheet) The obtained ester-based elastomer composition was dried at 80 ° C for 8 hours, and then molded by a T-die method. The molding temperature is 200 ° C, the extrusion rate and the take-off speed are
The thickness of the elastomer film was adjusted to 30 μm. The molten elastomer was extruded between a release paper and a nonwoven fabric ("ELTAS E01050" manufactured by Asahi Kasei Corporation), and was rolled up to form a laminated sheet. The resulting sheet was evaluated for moisture permeability and waterproofness.

Example 26 The polyether (a) used had a number average molecular weight of 1500 and a hydroxyl value of 1330 (μeq).
/ G), 1000 parts by weight of polyethylene glycol having an acid value of 0 (μeq / g), and 178.5 parts by weight of 4,4′-diphenylmethane diisocyanate having an NCO value of 8000 (μeq / g) as a polyisocyanate compound (c). 100 parts by weight of the polyester (b-1) is supplied from a first barrel of a screw extruder (manufactured by Toshiba Machine Co., L / D = 58), and 100 parts by weight of the polyester (b-1) is supplied from a fifth barrel of the extruder using a forced side feeder. And melt-mix it, and set the die of the twin-screw extruder to a width of 4
Film forming was performed as a 50 mm T-die. The kneading temperature was 200 ° C. The extrusion amount and the take-off speed were adjusted so that the thickness of the elastomer film became 30 μm.
The molten elastomer was extruded between a release paper and a nonwoven fabric ("ELTAS E01050" manufactured by Asahi Kasei Corporation), and was rolled up to form a laminated sheet. The resulting sheet was evaluated for moisture permeability and waterproofness. Each physical property was measured using the following method. Waterproof: glass tube (inner diameter 40 mm, height 100
(0 mm), a resin-laminated fabric is stuck to one side using a sealing material. A glass tube is set up on a filter paper with the side of the fabric attached down. Colored water is added to the tube, and after 24 hours, the color of the filter paper is checked. If it is not colored
It was judged to be waterproof.

[Comparative Example 12] Pelletization of an elastomer was attempted in Example 26, but the pellets could not be formed into pellets due to severe coalescence of the pellets.

[Table 4]

[Example 27] [Production of polyester (b)] Dimethyl terephthalate 1
00 parts by weight, 102 parts by weight of 1,4-butanediol, 12 parts by weight of polytetramethylene glycol having a number average molecular weight of about 650 ("PTHF650" manufactured by BASF), 0.06 parts by weight of tetrabutyl titanate as a catalyst, and a stabilizer 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
0.01 parts by weight of benzene and tris (2,4-di-t
(Butylphenyl) phosphite (0.01 part by weight) was added, and the reaction system was maintained at 200 ° C. for 1 hour under nitrogen 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. and the pressure was reduced at the same time. As a result of performing the polycondensation reaction for 40 minutes, 37 kg of a white polyester-based copolymer was obtained. (Production of thermoplastic elastomer composition) First, 100 parts by weight of polyethylene glycol having a number average molecular weight of 1,000, 4,4'-diphenylmethane diisocyanate 2
2 parts by weight of a twin-screw extruder (L / D = 2 manufactured by Berstorf)
Using 5), a prepolymer was prepared by kneading (residence time: 200 seconds) at 200 ° C. Subsequently, the twin-screw extruder
The melted ester copolymer (22 parts by weight) and the prepolymer were kneaded at 180 ° C. to obtain a thermoplastic elastomer composition. (Production of resin laminated fabric) After drying the obtained ester-based elastomer composition at 80 ° C. for several hours, a polyester-based nonwoven fabric (Asahi Kasei Co., Ltd.) "Estal E0101"
5)) were supplied in an overlapping manner, and pressed between the laminating rolls to produce a resin laminated fabric. About the obtained resin laminated fabric, moisture permeability, waterproofness, and dew condensation were evaluated.

Example 28 Production of Polyester (b) Dimethyl Terephthalate 1
00 parts by weight, 102 parts by weight of 1,4-butanediol, 0.06 part by weight of tetrabutyl titanate as a catalyst, and 1,3,5-trimethyl-2,4,6-tris (3,5-di- t-butyl-4-hydroxybenzyl)
0.01 parts by weight of benzene and tris (2,4-di-t
(Butylphenyl) phosphite (0.01 part by weight) was added, and the reaction system was maintained at 200 ° C. for 1 hour under nitrogen 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. and the pressure was reduced at the same time. As a result of performing the polycondensation reaction for 25 minutes, 35 kg of a white polyester-based copolymer was obtained. (Production of thermoplastic elastomer composition) First, 100 parts by weight of polyethylene glycol having a number average molecular weight of 1500, 4,4'-diphenylmethane diisocyanate 2
9 parts by weight of a twin-screw extruder (L / D = 2 manufactured by Berstorf)
Using 5), the mixture was kneaded at 200 ° C. to prepare a prepolymer. Subsequently, 13 parts by weight of the melted ester-based copolymer and the prepolymer were kneaded at 180 ° C. by a twin-screw extruder to obtain a thermoplastic elastomer composition. (Production of moisture-permeable waterproof fabric) After drying the obtained ester-based elastomer composition at 80 ° C. for several hours, a polyurethane non-woven fabric (Kanebo Co., Ltd.) was used while the melt-extruded film was in a heat-fusible state by the T-die method. (“Espansione”) manufactured by Nippon Kayaku Co., Ltd.), and pressed between laminating rolls to produce a resin laminated fabric. The properties of the resin-laminated fabric were evaluated in the same manner as in Example 27, and the results are shown in Table 5.

[Example 29] [Production of polyester (b)] The same operation as in Example 28 was carried out except that the polycondensation time was changed to 40 minutes, to obtain 34 kg of a polyester-based copolymer. (Production of thermoplastic elastomer composition) First, 100 parts by weight of polyethylene glycol having a number average molecular weight of 1,000, 25 parts by weight of polytetramethylene glycol,
27 parts by weight of 4′-diphenylmethane diisocyanate was kneaded (residence time: 200 seconds) at 200 ° C. using a twin-screw extruder (L / D = 25, manufactured by Berstorf) to produce a prepolymer. Subsequently, 27 parts by weight of the molten ester-based copolymer and the prepolymer were kneaded at 180 ° C. by a twin-screw extruder to obtain a thermoplastic elastomer composition. (Production of moisture-permeable waterproof fabric) After drying the obtained ester-based elastomer composition at 80 ° C for several hours, while the melt-extruded sheet is in a state of heat-sealing property by the T-die method, the ester-based nonwoven fabric ( (Thickness: 0.29 mm) was supplied in layers, and sandwiched between laminating rolls to produce a resin laminated fabric.
The properties of the resin laminated fabric were evaluated in the same manner as in Example 27,
Table 5 shows the results.

Comparative Example 13 The procedure of Example 28 was repeated, except that polytetramethylene glycol was used instead of polyethylene glycol when preparing the thermoplastic elastomer composition.

Comparative Example 14 The procedure of Example 27 was repeated, except that the time of polycondensation was changed to 150 minutes instead of 40 minutes when preparing the polyester (b).
A thermoplastic elastomer composition could not be obtained.

Comparative Example 15 A commercially available urethane-based elastomer was dried at 80 ° C. for several hours and then used in Example 27 while the melt-extruded film was in a state of heat-sealing property by a T-die method. The same polyester-based nonwoven fabric was supplied repeatedly, and pressed between the laminating rolls to produce a resin laminated fabric. The properties of the resin-laminated fabric were evaluated in the same manner as in Example 27, and the results are shown in Table 5.

[Table 5] Each physical property was measured using the following method. Glass transition temperature: measured by the method described in the text. Condensation: Cover the glass container containing warm water at 40 ° C so that the resin surface of the resin-laminated fabric is on the inside. This container is left for 1 hour in a thermo-hygrostat at 10 ° C. and 60% RH. One hour later, the amount of water droplets adhering to the resin surface was measured, and the dew condensation was evaluated based on this amount.

Example 30 The sheets obtained in Examples 1 to 11 and Comparative Examples 1 to 4 were measured for sterilization resistance and easy sterilization. The results are shown in Table 6.

[Table 6] Sterilization resistance: 121 ° C., 2 mm thick sheet, gauge pressure 1 at
The autoclave was subjected to high-pressure steam sterilization under the conditions of m and 60 minutes, cooled naturally to room temperature, and examined for tensile properties by the above method. Tensile properties: Tensile strength and tensile elongation at room temperature were measured according to JIS K6301. Easy sterilization: Bacillus stearothermophilus can be
After culturing at 35 ° C for about 20 hours in nton Broth, Mueller Hinton
The number of bacteria was adjusted to about 10 ⁴ / ml with Broth. 1
One drop of this bacterial solution was dropped on a filter paper of cm ² and air-dried, and then the filter paper was wrapped with a 100 μm-thick film and sealed. This was subjected to high-pressure steam sterilization at 121 ° C., 1 atm, and 20 minutes. Place the sterilized filter paper on Mueller Hinton Ager,
The growth of the bacteria after culturing at 5 ° C. for about 20 hours was examined.い な い indicates that the fungus did not grow, and x indicates that it did.

Example 31 Examples 1 to 7 and Comparative Example 1
The water swelling ratio / weight% and the storage elastic modulus (40 ° C.) / Pa of the sheets obtained in Comparative Examples 1 to 5 and Comparative Example 16 were measured, and the results shown in Table 7 were obtained.

[Comparative Example 16] As a thermoplastic elastomer, polyurethane elastomer AM manufactured by Nippon Milactran Co., Ltd.
Using 3P9029, press molding (press temperature 200
° C) to prepare a 2 mm thick sheet and a 100 µm thick sheet, and various physical properties were measured.

[Table 7] The storage elastic modulus and glass transition temperature in this example are:
It was measured under the following conditions. Measuring device: RSA-I manufactured by Rheometric Scientific
I Measurement temperature: -100 ° C to 200 ° C Heating rate: 3 ° C / min Frequency: 1.61 Hz Strain: 0.05% The water swelling ratio of the thermoplastic elastomer was measured as follows. A test piece (sheet: 50 mm x 50 mm x 1 mm) was placed in a desiccator containing a desiccant (silica gel) and dried sufficiently, and then the weight of the test piece was measured (W0). 24 hours in ion-exchanged water at a water temperature of 23 ° C. After immersing the test piece, the weight was measured (W1) Water swelling ratio = (W1−W0) / W0 × 100 (% by weight)

Example 32 Dimethyl terephthalate 10
0 parts by weight, 102 parts by weight of 1,4-butanediol, 12 parts by weight of polytetramethylene glycol having a number average molecular weight of about 650 (“PTHF650” (trade name) manufactured by BASF), 0.3 parts by weight of tetrabutyl titanate as a catalyst Parts, 1,3,5-trimethyl-2,4,6 as stabilizer
0.3 parts by weight of tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (2,4-di-
0.3 parts by weight of (t-butylphenyl) phosphite was added, and the reaction system was maintained at 200 ° C. for 3 hours under nitrogen to carry out a transesterification reaction. The progress of the transesterification reaction was confirmed by measuring the amount of methanol distilled off. After the transesterification proceeded, a pressure reduction operation was performed simultaneously with the temperature increase.
The polymerization system reached a reduced pressure of 240 ° C. and 2 mmHg or less in 20 minutes, and 120 parts by weight of white polyester (S) having a number average molecular weight of 1500 was obtained. 177.8 parts by weight of polytetramethylene glycol having a number average molecular weight of 1000 (“PTHF1000” (trade name) manufactured by BASF, glass transition temperature −56 ° C.) having a number average molecular weight of 1000 as the polymer (T);
4,4'-diphenylmethane diisocyanate 55.6
Parts by weight were kneaded (residence time: 200 seconds) at 150 ° C. using a co-directional twin screw extruder (manufactured by Berstorf Co.), and 100 parts by weight of the polyester (S) was introduced from a side feeder into the kneader. Kneading (residence time 200 seconds)
Thus, pellets of the ester-based elastomer were 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 11.

[Example 33] Dimethyl terephthalate 10
0 parts by weight, 102 parts by weight of 1,4-butanediol, 0.25 parts by weight of tetrabutyl titanate as a catalyst, and 1,3,5-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 maintained at 200 ° C. for 3 hours under nitrogen to carry out a transesterification reaction. The progress of the transesterification reaction was confirmed by measuring the amount of methanol distilled off. After the transesterification proceeded, a pressure reduction operation was performed simultaneously with the temperature increase. The polymerization system is
In 20 minutes, a white polyester (S) 12 having a reduced pressure of 240 ° C. and 5 mmHg or less and having a number average molecular weight of 1200 is obtained.
0 parts by weight were obtained. As the polymer (T), 562.5 parts by weight of poly-1,2-propylene glycol having a number average molecular weight of 3000 (“PPG3000” (trade name), manufactured by Mitsui Chemicals, Inc., glass transition temperature: −54 ° C.); 62.5 parts by weight of diphenylmethane diisocyanate was heated at 150 ° C.
(Residence time: 200 seconds), and 100 parts by weight of the polyester (S) is introduced from a side feeder into the kneader.
The mixture was kneaded at 210 ° C. (residence time: 200 seconds) to obtain pellets of the ester elastomer. Using the obtained pellets, a 2 mm thick sheet was prepared by press molding (press temperature 230 ° C.), and various physical properties were measured. Table 1 shows the results.
1 is shown.

[Comparative Example 21] 100 parts by weight of the polyester (S) used in Example 33 and a number average molecular weight of about 300
Poly-1,2-propylene glycol (“PPG3000” (trade name) manufactured by Mitsui Chemicals, Inc .; glass transition temperature −5)
(4 ° C.) 562.5 parts by weight were melted using a co-rotating twin-screw extruder (manufactured by Berstorf Co.), and then 62.5 parts by weight of 4,4′-diphenylmethane diisocyanate was press-fitted.
The mixture was kneaded at 0 ° C. (residence time: 400 seconds), but no elastomer was obtained.

[Table 11] In Table 11, with respect to Comparative Example 21, no elastomer was obtained, so that various physical properties could not be measured.

Example 34 Hexamethylenediamine 1
28 parts by weight, 146 parts by weight of adipic acid, 0.3 parts by weight of phosphoric acid 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, 0.3 parts by weight of tris (2,4-di-t-butylphenyl) phosphite.
3 parts by weight were added, and the reaction system was maintained at 260 ° C. for 20 minutes under nitrogen to carry out a polycondensation reaction. 238 parts by weight of a white polyamide (P) having a number average molecular weight of 1500 was obtained. As the polymer (T), polytetramethylene glycol having a number average molecular weight of 1,000 (“PTHF100” manufactured by BASF)
0 "(trade name), glass transition temperature -56 ° C) 177.8
Parts by weight, and 55.6 parts by weight of 4,4'-diphenylmethane diisocyanate are kneaded at 150 ° C. using a co-axial twin screw extruder (manufactured by Berstorf Co.) (residence time 200 seconds).
Then, 100 parts by weight of the polyamide (P) was sufficiently melted, and then introduced from a side feeder.
(Residence time 200 seconds) to obtain pellets of the amide-based elastomer. Using the obtained pellets, a sheet having a thickness of 2 mm was produced by press molding (press temperature: 260 ° C.), and various physical properties were measured. Table 12 shows the results.

Example 35 ε-caprolactam 100
Parts by weight, 0.25 parts by weight of phosphoric acid as a catalyst, and 1,3,5-trimethyl-2,4,6-tris (3,5
-Di-t-butyl-4-hydroxybenzyl) benzene (0.3 part by weight) and tris (2,4-di-t-butylphenyl) phosphite (0.3 part by weight) were added, and the reaction system was heated to 200 ° C. under nitrogen. For 20 minutes to effect ring-opening polymerization. Further, excess hexamethylenediamine was added thereto, and the mixture was maintained at 200 ° C. for 3 hours. Then, the excess hexamethylenediamine was removed under reduced pressure to obtain 120 parts by weight of white polyamide (P) having a number average molecular weight of 1200. 562.5 parts by weight of poly-1,2-propylene glycol having a number average molecular weight of 3000 (“PPG3000” (trade name) manufactured by Mitsui Chemicals, Inc., glass transition temperature −54 ° C.) having a number average molecular weight of 3000 as the polymer (T);
4,4'-diphenylmethane diisocyanate 62.5
Parts by weight were kneaded (residence time: 200 seconds) at 150 ° C. using a co-directional twin-screw extruder (manufactured by Berstorf Co.), and 100 parts by weight of the polyamide (P) was sufficiently melted. It was introduced from a feeder and kneaded at 215 ° C. (residence time 200 seconds) to obtain amide-based elastomer pellets. Using the obtained pellets, a 2 mm thick sheet was prepared by press molding (press temperature 230 ° C.), and various physical properties were measured. Table 12 shows the results.

[Comparative Example 22] 100 parts by weight of the polyamide (P) used in Example 35 and a number average molecular weight of about 3000
Poly-1,2-propylene glycol (“PPG3000” (trade name) manufactured by Mitsui Chemicals, Inc .; glass transition temperature −54
C.) 562.5 parts by weight were melted using a co-rotating twin-screw extruder (manufactured by Berstorf Co.), and 62.5 parts by weight of 4,4'-diphenylmethane diisocyanate was press-fitted.
The mixture was kneaded at 400C (residence time: 400 seconds), but no elastomer was obtained.

[Table 12] In Table 12, with respect to Comparative Example 22, no elastomer was obtained, so that various physical properties could not be measured.

The various physical properties shown in Tables 11 and 12 were measured by the following methods. (1) Glass transition temperature (Tg), melting point Measurement was performed at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC). (2) Surface hardness According to JIS K6301, 23 ° C with A type spring
Was used to measure the surface hardness. (3) Tensile modulus (E ') The dynamic viscoelastic spectrum was measured at 10 Hz while changing the temperature, and the E' at room temperature (23 ° C) and high temperature (150 ° C) were measured.
Was evaluated. (4) Tensile properties Tensile strength and tensile elongation at room temperature (23 ° C.) were evaluated according to JIS K6301. (5) Compression set In accordance with JIS K 6301, the compression set was measured at 100 ° C. with a compression set of 25%.

From the above results, since the method for producing an ester-based elastomer of the invention (1) of Part II of the present invention has the above-described constitution, an ester-based elastomer having a high blockability of a polyester component can be obtained. As a result, it is understood that it is possible to obtain an ester elastomer having both flexibility and mechanical properties at a high temperature. In addition, since the method for producing an amide elastomer of Part II invention (3) has the above-described constitution, it is possible to obtain an amide elastomer having a high blockability of a polyamide component, and as a result, flexibility and high temperature It can also be understood that it becomes possible to obtain an amide-based elastomer having both of the above mechanical properties.

[0179]

According to the present invention, the affinity with water is high,
A thermoplastic elastomer having excellent molecular mobility and excellent moisture permeability can be obtained. Further, according to the present invention, it has high affinity for water, excellent molecular mobility, high blockability of short-chain polyester component, excellent moisture permeability, and also achieves both flexibility and mechanical properties at high temperatures. The obtained thermoplastic elastomer can be obtained. Further, according to the present invention, a thermoplastic elastomer having good solution coating properties can be obtained by using a short-chain polyester component as a copolymer. Furthermore, by using an isocyanate component in which an aliphatic / alicyclic or isocyanate group is not directly bonded to an aromatic ring, a thermoplastic elastomer excellent in light resistance can be obtained.

Further, according to the present invention, by using a thermoplastic elastomer having high affinity for water and excellent molecular mobility, an elastic yarn and a fabric comprising the thermoplastic elastomer excellent in water absorption and moisture release can be obtained. Can be obtained. According to the present invention, it is possible to obtain a thermoplastic elastomer having high affinity for water, excellent molecular mobility, and excellent moisture permeability. Further, according to the present invention, it has high affinity for water, excellent molecular mobility, high blockability of short-chain polyester component, excellent moisture permeability, and has both flexibility and mechanical properties at high temperatures. A thermoplastic elastomer can be obtained. Further, the film or sheet of the present invention has both high moisture permeability and waterproofness. According to the present invention, the affinity with water is high, the molecular mobility is excellent, the blocking property of the short-chain polyester component is high, and the moisture permeability is excellent,
Moreover, by using a thermoplastic elastomer that has both flexibility and mechanical properties at high temperatures, flexibility, heat resistance,
A medical molded article made of a thermoplastic elastomer having excellent sterilization resistance and excellent steam sterilization properties can be obtained. According to the present invention, it is possible to obtain a thermoplastic elastomer having high affinity for water, excellent molecular mobility, and excellent moisture permeability. Further, according to the present invention, it has high affinity for water, excellent molecular mobility, high blockability of short-chain polyester component, excellent moisture permeability, and has both flexibility and mechanical properties at high temperatures. A thermoplastic elastomer can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C08J 5/18 CFF C08J 5/18 CFF // C08L 71:02 C08L 71:02 75:08 75:08 ( 72) Inventor Akihiko Fujiwara 2-1 Momoyama, Shimamoto-cho, Mishima-gun, Osaka Sekisui Chemical Industry Co., Ltd. (72) Inventor Yasuhiro Nakaya 2-1 Momoyama, Shimamoto-cho, Mishima-gun, Osaka Sekisui Chemical Co., Ltd. (72) Inventor Shoji Nozato 2-1 Momoyama, Shimamoto-cho, Mishima-gun, Osaka Fukushima Chemical Industry Co., Ltd. F-term (reference) GB72 GB74 JA05A JB16A JD04 JD05 JK07A YY00A 4J005 AA02 4J029 AA03 AB01 AC01 AC02 AD01 AD07 AD10 AE01 AE02 AE03 AE06 BA02 BA03 BA04 BA05 BA08 BA10 BD03A BD04A BD07A BF09 BF18 BF25 BF27 BF28 CA02 CA04 CA06 CB04A CB05A CB06A CC05A CD03 HA01 HB01 HB02 JE182 4J034 BA03 BA07 DA01 DB04 DB07 DF01 DF16 DF20 DF21 DF22 DG02 DG03 DG04 DG06 DG09 HC12 HC07 HC12 HC07 HC64 HC65 HC67 HC71 HC73 JA01 JA42 KA01 KB02 KC07 KC13 KC16 KC17 KC18 KC23 KD02 KD04 KD05 KD12 KE02 PA03 QA05 QB03 QB04 QB14 QB15 RA02 RA03 RA05 RA09 RA12 RA14

Claims (24)

[Claims] 1. A thermoplastic elastomer containing the polyether component (A) as a constituent unit, wherein the polyoxyalkylene (—C _n H) constituting the polyether component is used.
_2nO- ), the carbon / oxygen atom ratio is 2.0 to 2.5, the polyether component in the thermoplastic elastomer is 50 to 95% by weight, and the glass transition temperature of the thermoplastic elastomer is -20C. A thermoplastic elastomer characterized by the following. 2. The thermoplastic elastomer according to claim 1, wherein the polyether component (A) is bound by a polyisocyanate component (C). 3. The thermoplastic elastomer according to claim 1, wherein the polyether component (A) has a number average molecular weight of from 500 to 5,000. 4. The polyether component (A) comprises a polyethylene glycol component.
The thermoplastic elastomer according to any one of the above. 5. A polyester component (B) as a structural unit
Wherein the number average molecular weight of the polyester component (B) is from 500 to 10,000.
5. The thermoplastic elastomer according to any one of the above items 4. 6. A polyester component (B) as a structural unit
The polyester component (B) is composed of 50 to 100% by weight of a short-chain polyester component represented by the following general formula (1) and 50 to 100% by weight of a long-chain polyester component represented by the following general formula (2). The thermoplastic elastomer according to any one of claims 1 to 5, comprising 0% by weight. —CO—R ₁ —CO—O—R ₂ —O— (1) (where R ₁ is a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms and / or a divalent aromatic hydrocarbon group having 2 to 10 carbon atoms) An alkylene group or a divalent aliphatic cyclic hydrocarbon group having 6 to 12 carbon atoms, R
₂ is an alkylene group having 2 to 8 carbon atoms and / or 6 to 6 carbon atoms.
And 12 divalent aliphatic cyclic hydrocarbon groups. _{) -CO-R 3 -CO-O} -R 4 - (2) ( where, R ₃ is a divalent alkylene divalent aromatic hydrocarbon group and / or 2 to 10 carbon atoms having from 6 to 12 carbon atoms Or a divalent aliphatic cyclic hydrocarbon group having 6 to 12 carbon atoms, R
₄ is composed of a repeating unit represented by -R ₅ -O-, R ₅ is an alkylene group having 2 to 8 carbon atoms. ) 7. The ratio of the number of moles of aromatic dicarboxylic acid residues to the number of moles of aliphatic dicarboxylic acid residues is 100: 0 to 4.
7. The thermoplastic elastomer according to claim 5, wherein the dicarboxylic acid component having a ratio of 0:60 constitutes the polyester component (B). 8. The ratio of the number of moles of the aliphatic chain diol residue to the number of moles of the aliphatic cyclic diol residue is from 100: 0 to 4.
The diol component having a ratio of 0:60 is a polyester component (B).
The method according to any one of claims 5 to 7, wherein
Item 10. The thermoplastic elastomer according to item 8. 9. The thermoplastic elastomer according to claim 5, wherein 40 to 90% by weight of the polyester component (B) is polybutylene terephthalate. 10. The polyisocyanate component (C) comprises an aliphatic or alicyclic polyisocyanate component or a polyisocyanate component whose isocyanate group is not directly bonded to an aromatic ring. The thermoplastic elastomer according to any one of the above. 11. The thermoplastic elastomer according to claim 2, wherein the polyisocyanate component (C) comprises a diisocyanate component represented by the following general formula (3). —O—CO—NH—R ₆ —NH—CO—O— (3) (where R ₆ is an alkylene group having 2 to 15 carbon atoms, a divalent aliphatic cyclic hydrocarbon group, a phenylene group, a methylene group or It is a group in which an alkylene group and a phenylene group are bonded.) 12. A thermoplastic elastomer containing the polyether component (A) as a constituent unit, wherein the thermoplastic elastomer has a water swelling ratio of 50 to 200% by weight, and the storage elastic modulus at 40 ° C. of the thermoplastic elastomer is 1 ×. 10 ⁶ Pa~25 a × ¹⁰ 6 Pa, a thermoplastic elastomer having a glass transition temperature of the thermoplastic elastomer is characterized in that at -20 ° C. or less. 13. The thermoplastic elastomer according to claim 12, wherein the thermoplastic elastomer containing the polyether component (A) as a constituent is the thermoplastic elastomer according to any one of claims 1 to 11. Elastomer. 14. A first step of producing a prepolymer by reacting a polyether (a) and a polyisocyanate compound (c), and the prepolymer and a polyester (b)
14. The method for producing a thermoplastic elastomer according to any one of claims 2 to 13, comprising a second step of reacting the thermoplastic elastomer. A fiber comprising the thermoplastic elastomer according to any one of claims 1 to 13. 16. A fabric comprising the fiber of claim 15. 17. An elastomer film or sheet comprising the thermoplastic elastomer according to claim 1. Description: 18. A first step of producing a prepolymer by reacting a polyether (a) with a polyisocyanate compound (c), and the prepolymer and a polyester (b)
And an elastomer film or sheet obtained by continuous molding after the second step. 19. A moisture-permeable waterproof fabric comprising a laminate of the elastomer film or sheet according to claim 17 and at least one surface thereof. 20. The fabric according to claim 1, wherein at least one side surface of the fabric is provided.
A fabric, which is coated with the composition containing the thermoplastic elastomer according to any one of claims 13 to 13. 21. The moisture-permeable waterproof cloth according to claim 19, wherein the cloth is made of elastic fibers. 22. The moisture permeable waterproof fabric has a moisture permeability of 2000 g.
/ Claim 1, characterized in that m is 2 ^· 24 hours or more
22. The elastomer film or sheet or the moisture-permeable waterproof fabric according to any one of 7 to 21. 23. A garment comprising the moisture-permeable waterproof fabric according to any one of claims 20 to 22.
Tent or shoes. 24. A medical molded article formed by using the thermoplastic elastomer according to claim 1. Description: