JP2001316575A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition excellent in heat adhering property with both of a polyamide resin and polyester resin, especially under a high temperature atmosphere, and having a good flexibility and molding property, and a laminated material based on the same. SOLUTION: This thermoplastic elastomer containing 3-components consisting of [the component (A)] a thermoplastic polyester-based elastomer, [the component (B)] a thermoplastic polyamide 6-based elastomer and [the component (C)] a polymer having >=2 epoxy groups and/or acid anhydride groups in 1 molecule is provided by setting (70/30)-(30/70) range weight ratio of the component (A) to component (B) as the component (A)/component (B), and also 0.1-30 pt.wt. content of the component (C), when the total amount of the components (A) and (B) is made as 100 pts.wt. The laminated material of the same with the polyamide resin and/or polyester resin is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide resin such as polyamide 6, polyamide 6, 6 and polyamide MXD6 and a polyester resin such as polyethylene terephthalate, polybutylene terephthalate and copolyester, which are excellent in heat-sealing property and flexible. TECHNICAL FIELD The present invention relates to a thermoplastic elastic composition having good moldability and moldability and a laminate based on the composition.

[0002]

2. Description of the Related Art Polyamide resins are widely used in industrial equipment and household goods, particularly gas containers and gas piping, because of their excellent toughness, heat resistance, wear resistance and gas barrier properties. On the other hand, polyester resins such as polybutylene terephthalate have excellent heat resistance, chemical resistance, and mechanical properties, and are widely used in the field of resin bottles and food packaging. In order to further expand applications in these fields, application to containers such as carbonated beverages and packaging for fresh foods which can be stored for a long period of time by improving gas barrier properties is being studied. Since the gas barrier properties of the polyester resin are insufficient for use in such applications, a composite with a resin having excellent gas barrier properties such as a polyamide resin has been attempted for improvement.

[0003] However, since the polyester resin and the polyamide resin do not fuse with each other, a composite using an adhesive or the like has been proposed. However, the adhesive strength is high at the time of a sterilization process in food applications or a high temperature process such as retort cooking. And there is a problem that the film is easily peeled off.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned situation, and has been made to improve the heat-fusing property with both polyamide resin and polyester resin, especially the property of maintaining the adhesive force under a high-temperature atmosphere. It is an object of the present invention to provide a thermoplastic elastomer composition which is excellent and has good flexibility and moldability.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, it has been found that a specific thermoplastic elastic composition is not melted with a polyamide resin and a polyester resin. The inventors have found that the adhesiveness is excellent, the flexibility and the moldability are good, and the present invention has been completed. That is, the gist of the present invention is a thermoplastic polyester-based elastic body (hereinafter, referred to as a thermoplastic polyester elastic body)
A component (A)), a thermoplastic polyamide 6-based elastic body (hereinafter, referred to as a “component (B)”), and two or more epoxy groups and / or acid anhydride groups in one molecule. A thermoplastic elastomer composition containing three components of a polymer (hereinafter, referred to as “component (C)”), wherein the weight ratio of component (A) to component (B) is component (A) / component (B ) As 70/30 ~
30/70, component (A) and component (B)
Is 100 parts by weight, the content of component (C) is 0.1 to 30 parts by weight in the thermoplastic elastomer composition.

Another gist of the present invention is that a polyamide 6-based thermoplastic elastomer of the component (B) comprises a polymer block mainly composed of polyamide 6 and a polymer block mainly composed of aliphatic polyether. The above thermoplastic elastomer composition is a polyamide 6-polyether block copolymer constituted. Another aspect of the present invention is a polyamide 6,
A layer made of at least one kind of polyamide resin selected from the group consisting of polyamide 6,6 and polyamide MXD6, or a layer made of at least one kind of polyester resin selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate and copolymerized polyester Also present in a laminate obtained by laminating a layer made of the above thermoplastic elastomer composition, and polyethylene terephthalate on one surface of the layer made of the thermoplastic elastic composition,
A layer made of at least one polyester resin selected from the group consisting of polybutylene terephthalate and a copolymerized polyester, and on the other surface, at least one polyamide resin selected from the group consisting of polyamide 6, polyamide 6,6 and polyamide MXD6 The present invention also exists in a laminate in which layers made of are laminated.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described in detail. [1] Composition The thermoplastic elastomer composition of the present invention contains components (A) to (C), and has a Shore-D hardness according to ASTM-D2240 of 60 or less, preferably 5 or more and 55 or more.
Or less, particularly preferably in the range of 10 to 50, and the flexural modulus is 200 MPa or less, preferably 5 to 190 M
It is preferably Pa or less, particularly preferably in the range of 10 to 180 MPa. If the Shore-D hardness and the flexural modulus are less than the above ranges, the moldability tends to be inferior, and if it exceeds the above ranges, the flexibility tends to be inferior.

(1) Compounding material component (A): Thermoplastic polyester-based elastic body The thermoplastic polyester-based elastic body of the component (A) used in the present invention is an aromatic polyester as a hard segment and a polyalkylene as a soft segment. Those using ether glycol or aliphatic polyester are preferred.

Among them, preferred is a polyester polyether block copolymer using a polyalkylene ether glycol as a soft segment. The content of the polyalkylene ether glycol component is 5 to 90% by weight in the block copolymer. Is more preferably 20 to 85% by weight, more preferably 50 to 80% by weight. A block copolymer having a polyalkylene ether glycol component content exceeding 90% by weight is generally difficult to produce by polycondensation.

The polyester polyether block copolymer comprises i) an aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, ii) an aromatic dicarboxylic acid or an alkyl ester thereof, and iii) a number average molecular weight. 400-6
It can be obtained by polycondensing an oligomer obtained by an esterification reaction or a transesterification reaction with a polyalkylene ether glycol of 000 as a raw material.

As the aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, those usually used as raw materials for polyesters, in particular, raw materials for thermoplastic polyester-based elastomers can be used. For example, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-
Butanediol, 1,4-cyclohexanediol,
Examples thereof include 1,4-cyclohexanedimethanol, and among them, 1,4-butanediol and ethylene glycol are preferable, and 1,4-butanediol is particularly preferable. One or a mixture of two or more of these diols can be used.

As the aromatic dicarboxylic acid, those generally used as a raw material of polyester, particularly a raw material of a polyester-based elastic material can be used. For example, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid can be used. Acids and the like. Of these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferred, and terephthalic acid is particularly preferred. Further, two or more of these aromatic dicarboxylic acids may be used in combination.

When an alkyl ester of an aromatic dicarboxylic acid is used, the above-mentioned dimethyl ester or diethyl ester of the aromatic dicarboxylic acid is used. Preferred are dimethyl terephthalate and 2,6-dimethylnaphthalate. In addition to the above components, a small amount of trifunctional alcohol or tricarboxylic acid or an ester thereof may be copolymerized, and an aliphatic dicarboxylic acid such as adipic acid or a dialkyl ester thereof can also be used as a copolymerization component.

As the polyalkylene ether glycol, those having a number average molecular weight of 400 to 6,000 are usually used, but those having a number average molecular weight of 500 to 4,000 are preferred, and those having a number average molecular weight of 600 to 3,000 are particularly preferred. . If the number average molecular weight is less than 400, the blockability of the copolymer will be insufficient, while if it exceeds 6,000, phase separation tends to occur in the system and the physical properties of the polymer tend to decrease. Here, the “number average molecular weight” is measured by gel permeation chromatography (GPC). GPC
POLYMER for calibration
LABORATORIES (UK) POLYTETRAHYDRO
A FURAN calibration kit may be used.

The polyalkylene ether glycol used here includes, for example, polyethylene glycol, poly (1,2- and 1,3-propylene ether)
Glycol, poly (tetramethylene ether) glycol, poly (hexamethylene ether) glycol and the like can be suitably used. Particularly preferred is polytetramethylene ether glycol.

Commercially available thermoplastic polyester-based elastomers include "Primalloy" manufactured by Mitsubishi Chemical Corporation, "Pelprene" manufactured by Toyobo Co., Ltd. and "Hytrel" manufactured by Toray DuPont. Component (B): Polyamide 6-based thermoplastic elastic body As the polyamide 6-based thermoplastic elastic body, a polyamide polyether having a hard segment composed of an aliphatic polyamide 6 block and a soft segment composed of an aliphatic polyether block is used. Block copolymers (block copolyether amide, block copolyether ester amide, block copolyether ester ether amide, etc.) are preferred, and those in which the aliphatic polyether block mainly comprises polyalkylene ether glycol are preferred.

The aliphatic polyamide 6 block is a polymer mainly composed of a ring-opening polymer of ε-caprolactam,
If necessary, lactams such as ω-laurolactam, aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid One or more of the acids may be copolymerized.

Further, a ring-opened polymer containing one or more lactams such as ω-laurolactam as a main component, and aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid. One or more polycondensates containing two or more main components, or hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, one or more aliphatic diamines such as dodecamethylenediamine and succinic acid, adipic acid, A block composed of a polycondensate or the like mainly containing one or more aliphatic dicarboxylic acids such as sebacic acid and azelaic acid may be contained.

As the kind and the suitable molecular weight range of the polyalkylene ether glycol, those similar to those described in the above section (Component (A)) can be used. The content of the polyether block in the polyamide 6-based thermoplastic elastic material is preferably 10 to 90% by weight. Such a commercially available polyamide 6-based thermoplastic elastic body is, for example, “Grillon ELX” manufactured by Ms Japan Co., Ltd.
"Pebax" manufactured by Toray Industries, "Novamit PAE" manufactured by Mitsubishi Chemical Corporation, "Diamid-PAE" manufactured by Daicel Huls Co., Ltd., "UBE" manufactured by Ube Industries, Ltd.
Polyamide elastomer "and" Glaek A "manufactured by Dainippon Ink and Chemicals, Inc. and the like.

Component (C): Two or more epoxy compounds per molecule
A polymer containing two or more epoxy groups in one molecule of a polymer containing a siloxane group and / or an acid anhydride group is a polymer having two or more oxirane ring structures in one molecule, For example, an epoxy compound of a polymer obtained by epoxidizing two or more double bonds of a polymer having a double bond such as a styrene-diene block copolymer can be exemplified. Commercial products of such a polymer containing two or more epoxy groups include “Epofriend” manufactured by Daicel Chemical Industries, Ltd.

The polymer containing two or more acid anhydride groups in one molecule is a polymer containing two or more acid anhydride groups in one molecule. It can be obtained by modification with an unsaturated carboxylic acid or a derivative thereof using a modification method such as a solution method or a melt kneading method. Preferred polymers containing an acid anhydride group include:
It is a thermoplastic styrene-based elastic material modified with maleic anhydride, particularly preferably a styrene-butadiene-styrene block copolymer (SEBS) modified with maleic anhydride.

Commercial products of such a polymer containing two or more acid anhydride groups include "Clayton FG1901X" manufactured by Shell Chemical Co., Ltd. and "ToughTech M Series" manufactured by Asahi Kasei Corporation. (2) Additional compounding material (arbitrary component) The thermoplastic elastomer composition of the present invention has the purpose and effect of the present invention in addition to the above-mentioned components (A), (B) and (C). Any component can be blended according to the purpose within a range not to impair.

Specifically, fillers such as talc, calcium carbonate, mica and glass fiber, plasticizers such as paraffin oil, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, neutralizers, lubricants, Various additives such as an anti-fogging agent, an anti-blocking agent, a slip agent, a cross-linking agent, a cross-linking auxiliary, a coloring agent, a flame retardant, a dispersant, an antistatic agent, an antibacterial agent, and a fluorescent whitening agent can be added. .

Among them, it is preferable to add at least one of various antioxidants such as phenol, phosphite and thioether. In addition to the above components, propylene-based polymers such as propylene homopolymer, propylene-ethylene block copolymer, and propylene-ethylene random copolymer, low-density polyethylene (branched ethylene polymer), medium-density, and high-density Ethylene polymers such as polyethylene (linear ethylene polymer)
Ethylene and unsaturated compounds such as unsaturated carboxylic acid copolymers or anhydrides thereof (acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, norbornene-5,6
Olefinic resins such as copolymers of dicarboxylic acids and their anhydrides); and thermoplastic resins such as styrene-based resins such as styrene homopolymer, acrylonitrile / styrene resin, and acrylonitrile / butadiene / styrene resin. May be added.

Of these, it is preferable to add a propylene polymer such as a propylene homopolymer, a propylene / ethylene block copolymer, or a propylene / ethylene random copolymer, since the appearance of the molded product is improved. (3) Compounding ratio The compounding ratio of each component constituting the thermoplastic elastomer composition of the present invention is such that the weight ratio of component (A) to component (B) is 70/30 as component (A) / component (B). ~ 30/70,
When the total amount of the components (A) and (B) is 100 parts by weight, the amount of the component (C) is 0.1 to 30 parts by weight.

The more preferable range of (A) / (B) is 6
It is 5/35 to 35/65, especially 60/40 to 40/60. The amount of component (C) is preferably 1 to 20 parts by weight. The ratio of component (A) / component (B) is 70
When the amount of the component (A) is larger than 30/30, the heat-fusibility of the thermoplastic elastic composition to the polyamide resin is inferior.
When it is less than 70, the heat-fusibility of the thermoplastic elastic composition to the polyester resin is inferior.

When the compounding ratio of the component (C) exceeds 30 parts by weight when the total amount of the components (A) and (B) is 100 parts by weight, the thermoplastic elastomer composition has a weight ratio to the polyamide resin and the polyester resin. Although it has heat fusibility, the moldability is reduced and the appearance of the molded body is also deteriorated. If the amount is less than 0.1 part by weight, not only the heat sealability of the thermoplastic elastomer composition to the polyester and polyamide resins is deteriorated, but also the molded product is deteriorated and only a molded product having an inferior appearance is obtained.

(4) Compounding method The method for producing the thermoplastic elastomer composition of the present invention from the compounding components such as component (A), component (B) and component (C) includes a melting method and a solution method. And a suspension / dispersion method, and are not particularly limited. Practically, the melt-kneading method is desirable. As a specific method for melt-kneading, a powdery or granular component (A), a component (B), and a component (C) are added at a predetermined mixing ratio and, if necessary, an additional compounding material. After uniformly mixing with the additives described in (1) using a Henschel mixer, a ribbon blender, a V-type blender, or the like, a usual kneading machine such as a Banbury mixer, a kneader, a roll, or a multi-screw kneading extruder such as a single-screw or twin-screw. Can be exemplified.

The melting and kneading temperature of each component is from 100 ° C. to 3 ° C.
In the range of 00 ° C, preferably in the range of 150 ° C to 280 ° C,
Particularly preferably, it is in the range of 180 ° C to 260 ° C. Furthermore, the kneading order and method of each component are not particularly limited, and a method of kneading the components (A) to (C) and the additional compounding materials collectively, and the components (A) to (C) And then kneading the remaining components, including the additional ingredients.

[2] Molding method [0030] The method for producing a molded article using the thermoplastic elastomer composition of the present invention includes (co) extrusion molding, inflation molding, blow molding, rotation molding, and press molding. And various molding methods such as injection molding (insert injection molding, two-color injection molding, core back injection molding, sandwich injection molding, injection press molding). Among them, injection molding, (co) extrusion molding, inflation molding, and blow molding are preferred.

When molding, it is important to use a dried material. The temperature for pre-drying the material is 40 to 150 ° C, preferably 60 to 130 ° C, more preferably 80 to 120 ° C, and the drying time is 1 to 24 hours.
Preferably, the reaction is performed for 1 to 10 hours, more preferably for 2 to 6 hours. Furthermore, it is more effective to carry out the drying under reduced pressure, whereby the drying temperature can be lowered and the drying time can be shortened.

When molding is performed using an undried material, the surface of the molded article may be roughened or the physical properties may be deteriorated. Conditions for molding by the injection molding method include a molding temperature of 100 to 300 ° C., preferably 150 to 280.
° C, particularly preferably 180 to 260 ° C, and an injection pressure of 4.9 to 98 MPa (50 to 1,000 kg / cm
2), preferably 9.8 to 78 MPa (100 to 800 MPa)
kg / cm2).

Further, molded parts other than products such as runners and spools, defective molded products, etc. can be recycled and used. [3] Use The molded article made of the thermoplastic composition of the present invention can be used, for example, as various industrial parts.

More specifically, automobile interior parts such as a steering wheel and an air bag cover, automobile exterior parts such as a bumper and a molding, rack and pinion boots, suspension boots, constant velocity joint boots, automobile functional parts such as a diaphragm, and a vacuum cleaner. Home appliances parts such as bumpers, remote control switches, various rolls and key tops of OA equipment, underwater products such as underwater glasses and underwater camera covers, various cover parts, various grip parts, airtightness, waterproofness, soundproofing, and vibration isolation It can be used for various kinds of industrial parts with packing, curl cord electric wire covering, belts, hoses, tubes, noise reduction gears, and other electric and electronic parts, sporting goods, etc.

[4] Composite molded article Since the composition of the present invention is excellent in heat-sealing properties with other kinds of resins, it should be molded into a molded article by combining with various resins such as polyamide resin. Can be. In particular, it is preferable to use the composition as a laminate such as a laminated film since the excellent fusion property of the composition can be utilized.

(1) Other Resins As the resin to be combined with the composition of the present invention, a hard resin is preferable, whereby a molded article having rigidity but having flexibility at necessary portions can be produced. Can be. As the hard resin, a molded body or a skeleton of the molded body can be formed to maintain the rigidity of the molded body. As long as the resin has a desired mechanical strength, even a thermoplastic resin is a thermosetting resin. Although a resin can be used without particular limitation, a resin having excellent rigidity, heat resistance and adhesiveness is preferable, and a flexural modulus according to JIS-K7203 is 500MP.
a or more, preferably 1,000 MPa or more, particularly preferably 2,000 MPa or more.

Specific examples of such a thermoplastic resin include polyamide resin, acrylic resin, GPPS (polystyrene made of homopolymer), HIPS (impact polystyrene), and ABS resin (acrylonitrile-butadiene-styrene resin). Resins such as styrene and AS resins (acrylonitrile / styrene resin), polyester resins such as PBT (polybutylene terephthalate), PET (polyethylene terephthalate), and polycarbonate;
Polyvinyl chloride, HIPS-modified PPE and nylon-modified P
And modified polyphenylene ethers such as PE.

Of these, polyamide resins and polyester resins are preferred from the viewpoints of gas barrier properties (particularly oxygen barrier properties), chemical resistance, heat resistance and the like. This polyamide resin is usually represented by the following formula (1)

[0039]

Embedded image A linear diamine represented by H ₂ N— (CH ₂ ) _X —NH ₂ (1) (where x is an integer of 4 to 12) and the following formula (2)

[0040]

Embedded image embedded image Condensed with a linear carboxylic acid represented by HO ₂ C— (CH ₂ ) _y —CO ₂ H (2), wherein y is an integer of 2 to 12. However, it can also be obtained by ring-opening polymerization of lactams.

Preferred examples of these polyamide resins include polyamide 6,6, polyamide 6,9, polyamide 6,10, polyamide 6,12, polyamide 6, polyamide 12, polyamide 11, polyamide 4,6 and the like. . In addition, polyamide 6 / 6,6, polyamide 6 / 6,10, polyamide 6/12, polyamide 6 /
Copolymerized polyamides such as polyamide 6,6,6,6 / 6,10, polyamide 6 / 6,6 / 12 and polyamide MXD6 can also be used.
(T; terephthalic acid component), aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid and meta-xylene diamine, or semi-aromatic polyamides obtained from alicyclic diamines, and meta-xylene diamine and the above-mentioned linear carboxylic acids. Polyamides, polyesteramides, and the like can also be used.

Commercially available polyamide resins include "NOVAMID" and "RENY" manufactured by Mitsubishi Engineering-Plastics Corporation. The polyamide resin may be used alone or in combination of two or more. Particularly preferred polyamide resins are polyamide 6, polyamide 6,6 and polyamide MXD6.

As the polyester resin, generally, a thermoplastic polyester produced by polycondensing a dicarboxylic acid or a lower alkyl ester thereof, an acid halide or an acid anhydride derivative with glycol can be used. Suitable aromatic and aliphatic dicarboxylic acids for producing the polyester resin include, for example, oxalic acid,
Malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, p-carboxyphenoacetic acid, p, p'-dicarboxydiphenyl, p, p'-dicarboxydiphenyl Sulfone, p-carboxyphenoxyacetic acid, p-carboxyphenoxypropionic acid, p-carboxyphenoxybutyric acid, p-carboxyphenoxyvaleric acid, p-carboxyphenoxyhexanoic acid, p, p'-dicarboxydiphenylmethane, p, p'-di Carboxydiphenylpropane, p, p'-dicarboxydiphenyloctane, 3-alkyl-4- (β-carboxyethoxy)-
Benzoic acid, 2,6-naphthalenedicarboxylic acid and 2,7
-Naphthalenedicarboxylic acid. Also, a mixture of these dicarboxylic acids can be used. Of these, terephthalic acid is particularly preferred.

Glycols suitable for preparing the above polyester resins are straight-chain alkylene glycols having 2 to 12 carbon atoms, for example ethylene glycol,
1,3-propylene glycol, 1,6-hexylene glycol, 1,10-decamethylene glycol and 1,
12-dodecamethylene glycol and the like. Some or all of these glycols may be replaced with aromatic glycols.

Preferred aromatic glycols include p-
Xylylene glycol, pyrocatechol, resorcinol, hydroquinone, or alkyl-substituted derivatives of these compounds. Also, 1,4-cyclohexanedimethanol can be used. Among them, a linear alkylene glycol having 2 to 4 carbon atoms is preferable. Examples of the polyester resin include polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate, and a preferable polyester resin is polybutylene terephthalate.

Specific examples of the thermosetting resin include polyimide resin, phenol resin, unsaturated polyester resin, urea resin, melamine resin, epoxy resin, diallyl phthalate resin, polyurethane resin, silicon resin, furan resin, poly (p- Hydroxybenzoic acid), maleic acid resin and the like, but preferred are polyimide resin,
Among the unsaturated polyester resins and phenol resins, particularly preferred are phenol resins.

When these resins are used, they have a rubber component,
Filler such as talc, calcium carbonate, mica, glass fiber, plasticizer such as paraffin oil, antioxidant, heat stabilizer, light stabilizer, ultraviolet absorber, neutralizer, lubricant, lubricant, anti-fog agent, anti Various additives such as blocking agents, slip agents, dispersants, coloring agents, antibacterial agents, optical brighteners and the like can be blended as necessary, but in particular, reinforcing agents such as glass fibers and other Those with a filler added are preferred.

(2) Compounding method As a method for obtaining a composite molded article, the molding method described in the section of [2] Molding method can be used without any particular limitation. In particular, coextrusion molding, inflation The molding method and the blow molding method are preferable because the excellent heat-fusibility and processability of the composition of the present invention can be utilized.

[0049]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples unless it exceeds the gist. [1] Evaluation method Various evaluations in Examples and Comparative Examples were performed by the following methods.

(1) Heat-fusibility (peel strength) Thermoplastic polyester-based elastomer (component (A)), polyamide 6-based thermoplastic elastomer (component (B)), and two or more epoxies in one molecule The thermoplastic elastomer composition obtained by melt-kneading a polymer (component (C)) containing an acid anhydride group or an acid anhydride group at a weight ratio shown in Table 2 was mixed with a 30 mmφ and 20 m
Two-layer co-extrusion small sheet molding machine having a cylinder of mφ (die opening width 50 mm, thickness 3 mm, die temperature: 23
0 ° C (PA6 resin), 240 ° C (PBT resin), 250
(PA-MXD6 resin)) to form a laminate with a polyamide resin or a polyester resin.

Using a strip test piece having a width of 25 mm and a length of 100 mm punched from the laminate, the skin material layer (composition layer) and the base material layer (polyamide resin or polyester resin layer) were pulled in the direction of 180 ° C. A tensile test was performed at a speed of 200 mm / min, and the peel strength (unit: kgf / 25 mm) of the fused surface of the skin material layer / base material layer was measured. The measurement was performed at ambient temperatures of 23 ° C., 100 ° C., and 150 ° C., and the retention of adhesive strength at high temperatures was also evaluated.

(2) Flexural Modulus Using an injection molding machine, a bending test sample (width 10 mm, length 90 mm, thickness 4 mm) was formed at 230 ° C., and the crosshead speed was 2 mm at a distance between fulcrums of 64 mm.
/ Min. Was evaluated for the flexural modulus (unit: MPa) and used as an index of flexibility.

(3) Shore-D hardness Measured according to ASTM D2240. (4) Formability (Roll Adhesion and Drawdown Property) At the time of molding using the extrusion molding machine of the above (1), adhesion to a roll (a surface temperature of 30 ° C.), drawdown property, and a molded article Was evaluated according to the criteria shown in Table 1.

[0054]

[Table 1]

[2] Raw Materials (1) Thermoplastic Elastic Layer Component (A) : Thermoplastic Polyester Elastic Material Polybutylene terephthalate is used as a hard segment,
Polyester polyether block copolymer having polytetramethylene ether glycol having a number average molecular weight of 2000 as a soft segment (content of polytetramethylene ether glycol: 65% by weight, flexural modulus 36MP)
a, density 1.09 g / cm ³ , melting peak temperature by differential scanning calorimetry 181.7 ° C., JIS-A hardness 90) Component (B) : Polyamide 6-based thermoplastic elastic material “Grillon ELX211” manufactured by EMS Japan Co., Ltd.
2 ) Component (C) : a polymer containing two or more epoxy groups and / or acid anhydride groups in one molecule C-1: "Epofriend" manufactured by Daicel Chemical Industries, Ltd.
CT129 "(epoxidized diene-based block copolymer obtained by epoxidizing a styrene butadiene-styrene block copolymer (oxirane oxygen concentration 2.5% by weight)) C-2:" Clayton FG1901 manufactured by Shell Chemical Co., Ltd. "
X "(maleic anhydride-modified SEBS) (2) Hard resin layer Polyamide 6 resin (PA6) " Novamid 1020CA2 "manufactured by Mitsubishi Engineering-Plastics Corporation (flexural modulus 2550MP)
a) Polyamide MXD6 resin (PA-MXD6) "Nylon MXD6 MX nylon 6121" (flexural modulus of elasticity: 4400 MPa) manufactured by Mitsubishi Gas Chemical Co., Ltd. Polybutylene terephthalate resin (PBT) manufactured by Polyplastics "Duranex 60"
0JP "[3] Examples and Comparative Examples Table 2 (Examples) and Table 3 (Comparative Examples) show the evaluation results of the samples prepared according to the above methods.

[4] Evaluation of Results The following points were found from Examples and Comparative Examples shown in Tables 2 and 3. (1) The thermoplastic elastic body compositions of Examples 1 to 12 containing the thermoplastic elastic body (A) and the polyamide 6-based thermoplastic elastic body (B) at a specific ratio specified in the present invention are a polyamide resin and It has excellent heat-fusibility with polyester resin, especially excellent maintainability of adhesive strength in a high-temperature atmosphere, and has good flexibility and moldability. (2) In Comparative Example 1 which does not contain the component (B) and the component (C), it can be seen that the heat fusibility to the polyester resin is excellent, but the heat fusibility to the polyamide resin is not. (3) In Comparative Example 2, which does not contain the component (A) and the component (C), the heat-fusing property to the polyamide resin is excellent, but the heat-fusing property to the polyester resin does not exist, and the flexibility is insufficient. is there. (4) In Comparative Examples 3 and 4 in which the blending ratio of the component (A) is low and the blending ratio of the component (B) is high, the heat fusibility to the polyamide resin is excellent, but the heat fusibility to the polyester resin is excellent. Is inferior. (5) In Comparative Examples 5 and 6, in which the blending ratio of the component (A) is large and the blending ratio of the component (B) is small, the heat-fusing property to the polyester resin is excellent, but the heat-fusing property to the polyamide resin is Is inferior. (6) In Comparative Example 7, which does not contain the component (C), the heat-fusing property with respect to the polyamide resin is excellent, but the heat-fusing property with respect to the polyester resin does not exist, and the moldability is poor. (7) In Comparative Examples 8 and 9, in which the proportion of the component (C) is large, the heat sealability to the polyamide resin and the polyester resin is excellent, but the appearance of the molded product is poor.

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

Industrial Applicability The thermoplastic elastomer composition of the present invention has excellent heat-fusibility with a polyamide resin and a polyester resin, particularly excellent adhesive strength maintenance property under a high temperature atmosphere, and good flexibility and moldability. is there.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 101/06 C08L 101/06 F-term (Reference) 4F100 AK41A AK41B AK41C AK41J AK42B AK42C AK48A AK48B AK48C AK48J AK53A AK54A AK73 AL01A AL01B AL01C AL05A AL06 AL09A BA01 BA02 BA03 BA10B BA10C BA15 DA01 EH23 GB16 GB23 JB16A JK06 JK07 JK07A JK12 JK13 JK17 JL01 JL12 YY00A 4J002 BC04Y BP01Y CD18Y CF10WCL07X01 GM01 010

Claims (5)

[Claims] 1. A thermoplastic polyester-based elastic body (hereinafter referred to as “elastic body”).
A component (A)), a thermoplastic polyamide 6-based elastic body (hereinafter, referred to as a “component (B)”), and two or more epoxy groups and / or acid anhydride groups in one molecule. A thermoplastic elastomer composition containing three components of a polymer (hereinafter, referred to as “component (C)”), wherein the weight ratio of component (A) to component (B) is component (A) / component (B ) As 70/30 ~
30/70, component (A) and component (B)
Is a thermoplastic elastomer composition having a component (C) content of 0.1 to 30 parts by weight when the total amount of the components is 100 parts by weight. 2. The polyamide 6-based thermoplastic elastic body of the component (B) comprises a polyamide 6-based polymer block and an aliphatic polyether-based polymer block. The thermoplastic elastomer composition according to claim 1, which is a polyether block copolymer. 3. At least one member selected from the group consisting of polyamide 6, polyamide 6,6 and polyamide MXD6.
A laminate comprising a layer composed of a kind of polyamide resin and a layer composed of the thermoplastic elastic composition according to claim 1 or 2 laminated thereon. 4. A layer comprising at least one polyester resin selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate and copolymerized polyester, and a layer comprising the thermoplastic elastomer composition according to claim 1 or 2. A laminated body formed by laminating. 5. A layer comprising the thermoplastic elastomer composition according to claim 1, wherein one surface of the layer comprises at least one polyester resin selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate and copolymerized polyester. A laminate comprising: a layer made of at least one polyamide resin selected from the group consisting of polyamide 6, polyamide 6,6 and polyamide MXD6 on the other surface.