JPH093323A - Thermoplastic elastomer composition excellent in fusibility - Google Patents

Abstract

PURPOSE: To obtain a thermoplastic elastomer compsn. which is excellent in fusibility and is useful since it gives a composite molding when fused to a rigid synthetic resin molding by compounding two specific thermoplastic block elastomers. CONSTITUTION: This compsn., excellent in fusibility and fused to a rigid synthetic resin molding to give a composite molding, comprises 3-100 pts.wt. addition-polymerized thermoplastic block elastomer comprising a polystyrene block and an optionally hydrogenated polybutadiene block and 100 pts.wt. thermoplastic polyetheresteramide block elastomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastic composition having excellent heat-sealing property. More specifically, the present invention provides:
It is useful for the production of composite molded products consisting of a molded body part made of synthetic resin such as engineering plastic with excellent mechanical strength and a molded body part made of a thermoplastic elastic body that is flexible and elastic. The present invention relates to a thermoplastic elastic body composition, particularly a thermoplastic elastic body composition having excellent heat-sealing characteristics for a preformed hard synthetic resin molded body part.

[0002]

2. Description of the Related Art Engineering plastics having mechanical strength superior to conventional ones are widely used as mechanical parts to which a load is applied or structural parts.
Engineering plastics of this type of thermoplastic resin include ABS resin, polyamide, polyacetal,
Polycarbonate, modified polyphenylene oxide, polybutylene terephthalate, polysulfone and wholly aromatic polyester are widely known.

On the other hand, a thermoplastic elastic body (thermoplastic elastomer, thermoplastic elastomer, TPE) molded body is also molded by an injection molding technique having particularly high productivity and is used for many purposes. As is well known, a thermoplastic elastic body (TPE) is a material that exhibits the properties of vulcanized rubber at room temperature, is plasticized at high temperature and can be molded by a plastic processing machine, and has rubber elasticity in its molecule. The flexible component (soft segment) and the molecular constraining component (hard segment) for preventing plastic deformation are shared. Known examples of this type of thermoplastic elastic body (TPE) include styrene-butazine type, polyolefin type, polyurethane type, vinyl chloride type and acrylic acid ester type.

The above-mentioned injection molding method is capable of efficiently molding a molded product having a complicated shape and is suitable for mass production. The injection molding method is applied in the field of engineering plastics, and various injection molding methods are applied. Machine parts and structural parts are manufactured efficiently. In recent years, demands for higher performance and higher functionality of synthetic resin (plastic) parts and members have become strict, and among them, the combination of hard synthetic resin members including engineering plastics and thermoplastic elastic members has been demanded. There is a move to try. In that case, when compounding both completely dissimilar members, it is most efficient and effective to apply the injection molding technology, which is a molding means common to both members, and heat bond both members to each other. Target.

However, in general, a thermoplastic resin such as engineering plastic and a thermoplastic elastic body (TPE) having excellent rubber elasticity are poor in heat fusion, so that it is extremely difficult to firmly and surely bond them. is there.
Therefore, when an attempt is made to composite a thermoplastic resin such as engineering plastic with a thermoplastic elastic body (TPE) to manufacture a composite molded body such as a high-value-added composite part or composite member, unevenness is formed in the composite part of both. Under the present circumstances, it is unavoidable to employ extremely unproductive joining means such as a method of mechanically joining by providing a locking portion, or a method of joining by applying an adhesive to both joining portions.

As described above, a hard thermoplastic resin such as engineering plastic and a thermoplastic elastic body (TP) are used.
The composite technology with E) is uneconomical and inefficient, and leaves many problems in the strength of the joint surface and the sealing property. That is, the method of mechanically joining by providing a locking portion such as uneven fitting has a problem that the structure of the mold is complicated or the number of steps is increased depending on the structure. In some cases, it may not be possible to form a strong bond structure in view of the shape of the final composite molded body. Furthermore, in the mechanical joining method, a composite molded body that is required to have a waterproof effect, for example, the spectacles are made of hard engineering plastic, and the edges of the spectacles that are in contact with the face are soft elastic thermoplastic elastic. In the case of a composite molded body such as underwater glasses formed of a body (TPE), there is a limit that the mechanical joining method described above does not have a sufficient waterproof effect. In addition, the bonding method using an adhesive requires a process such as application of the adhesive, and has a problem that the bonding strength is weak due to deterioration of the adhesive.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art. That is, the present invention is indispensable for manufacturing a composite molded article having a structure in which a portion made of a synthetic resin such as engineering plastic and a portion made of a thermoplastic elastic body (TPE) having excellent rubber elasticity are strongly bonded. The present invention provides a thermoplastic elastic composition having excellent heat fusion properties. Further, the present invention is
A product with high added value by strongly joining a part molded with a hard synthetic resin with excellent mechanical strength and a part molded with a flexible and thermoplastic adhesive composition with excellent heat fusion properties Is to provide. As this type of composite molded product, products (members) such as underwater glasses that require high strength and waterproof performance, and grips such as plastic handsets and handles are made soft with a thermoplastic elastic body. In order to have a packing effect when installing products, plastic automobile headlight covers, etc., products in which thermoplastic elastic body is combined and integrated at the edge of the cover, packing such as air shield, valve parts, flexible joints,
There are power transmission parts such as gears and input / output operation buttons for various control devices, and the like, and the present invention provides various products, members, and parts with high functionality and high added value.

[0008]

The present invention will be summarized as follows.
The present invention is a thermoplastic elastic body composition used for forming a composite molded body by heat-sealing a hard synthetic resin molded body part, wherein the thermoplastic elastic body composition is (i) a polystyrene block. Addition polymerization type thermoplastic block elastic body consisting of hydrogenated or non-hydrogenated polybutadiene block: 3 to 100 parts by weight, (ii) poly (ether ester amide) type thermoplastic block elastic body: ... 100 The present invention relates to a thermoplastic elastomer composition having excellent heat fusion properties, characterized by comprising:

In the present invention, the poly (ether ester amide) type thermoplastic block elastic body of the component (ii) is
It is constituted by one or a combination of two or more elastic bodies having repeating units represented by the following general formulas (1), (2) and (3). The oxyalxin) glycol residue site (the site represented by "G" in the following general formula) constitutes the soft segment, and the sites of other components constitute the hard segment. Therefore, the poly (ether ester amide) -based thermoplastic block elastic body of the component (ii) is a segmented thermoplastic elastomer, or if each segment (hard / soft segment) is regarded as a block unit, the component (i) The “poly (ether ester amide) -based thermoplastic block elastic body” can be referred to as the “addition polymerization-based thermoplastic block elastic body”. The latter name is used in the description of the invention.

General formula (1): --CO--R ¹ --CONH--R ² --NH
^{CO-R 1 -CO-O -G} -O - formula ^{(2): -NH-R 3} -CONH-R 2 -NHCO-R 1 -CO
-O -G -O - Formula _{(3): -CO-C 6} H 4 -NHCO-R 1 -CONH-C 6
H ₄ —CO—O —G —O— (in the above formula, R ¹ = C _{6 to} C ₃₀ divalent aromatic residue, R
Divalent aromatic residue of _{^{2 = C 6 ~C 30, R}} 3 = C 6 ~C 30
Divalent aromatic residue, G = poly (alkylene oxide)
Glycol residue, respectively. )

The technical constitution of the present invention will be described in detail below. INDUSTRIAL APPLICABILITY The present invention provides a synthetic resin molded body having a high hardness (JIS Shore hardness A), such as pre-molded polycarbonate, with a soft rubber excellent in rubber elasticity, which provides a molded body having lower hardness and flexibility than the synthetic resin molded body. It was born from the pursuit of a method for efficiently compounding thermoplastic elastomer (TPE). As described above, even if a thermoplastic elastic body (TPE) having a high elasticity is simply fusion-bonded to the pre-molded synthetic resin molded body having a high hardness by injection molding or the like, the bonding force is extremely low. It is enough.
The greatest feature of the present invention is that a molded body portion made of synthetic resin having high hardness (hard) and a soft thermoplastic elastic body (TP) having high elasticity.
In order to strongly bond the molded body part of E) by heat fusion, as the molded body part of the thermoplastic elastic body, a specific addition polymerization type thermoplastic block elastic body and polycondensation type poly (ether ester amide) are used. ) A thermoplastic elastic composition comprising a thermoplastic block elastic body.

First, the component (i) constituting the thermoplastic elastic composition of the present invention, that is, the addition polymerization type thermoplastic block elastic will be described. The addition polymerization type thermoplastic block elastic body of the present invention is a polystyrene block (hereinafter, referred to as S
May be abbreviated. And a hydrogenated or non-hydrogenated polybutadiene block (hereinafter sometimes abbreviated as B). In the present invention, the addition polymerization type thermoplastic block elastic body is (S
-B) of diblock, or S- (B
-S) n, (where n = 1 to 5) and other triblocks represented by general formulas, and more. The above-mentioned addition-polymerization type thermoplastic block elastic body is known per se, and for example, as a hydrogenated substance, JP-A-1-1.
No. 74550 (here, it is used to improve impact resistance), JP-A-60-260645 (here, for obtaining a polyethylene terephthalate composition for injection molding having a small heat shrinkability). It is used as one component.) And the like. Further, the non-hydrogenated substance is disclosed in JP-A-63-178187 (here, it is used as one component of the pressure-sensitive adhesive composition).

The addition polymerization type thermoplastic block elastic material of the present invention has, for example, a total number average molecular weight of 5,000.
It is preferably in the range of 0 to 500,000, the content of the S block unit is 5 to 70 wt%, and 70% or more of the double bond of the B block unit is hydrogenated. The weight average molecular weight of the S block unit is 5,
2,000 to 125,000, and the B block unit has a weight average molecular weight of 15,000 to 250,000. Incidentally, this type of hydrogenated block elastic body adopted in the present invention is disclosed in the above-mentioned reference,
They are known per se or can be easily produced by a method commonly used by those skilled in the art.

In the present invention, specific examples of the above-mentioned addition polymerization type thermoplastic block elastic body include Lavalon (manufactured by Mitsubishi Yuka Co., Ltd.), Tuftec (manufactured by Asahi Kasei Co., Ltd.) and Kraton G (Shell Chemistry) as hydrogenated substances. As a non-hydrogenated substance, elastomer AR (manufactured by Aron Kasei Co.), Kraton Califlex TR (manufactured by Shell Chemical Co.), JSR
TR (manufactured by Japan Synthetic Rubber Co., Ltd.) and the like.

Next, the component (ii) constituting the thermoplastic elastomer composition of the present invention, that is, a poly (ether ester amide) type thermoplastic elastic body (polyether ester amide type thermoplastic segmented elastic body, poly The ether ester amide-based thermoplastic block elastic body) will be described. The poly (ether ester amide) -based thermoplastic block elastic body of the present invention is composed of one or more elastic bodies having repeating units represented by the following general formulas (1), (2), and (3). It is something. Formula ^{(1): -CO-R 1} -CONH-R 2 -NHCO-R 1 -CO
-O -G -O - formula ^{(2): -NH-R 3} -CONH-R 2 -NHCO-R 1 -CO
-O -G -O - Formula _{(3): -CO-C 6} H 4 -NHCO-R 1 -CONH-C 6
H ₄ —CO—O —G —O— (in the above formula, R ¹ = C _{6 to} C ₃₀ divalent aromatic residue, R
Divalent aromatic residue of _{^{2 = C 6 ~C 30, R}} 3 = C 6 ~C 30
Divalent aromatic residue, G = poly (alkylene oxide)
Glycol residue, respectively. )

The poly (ether ester amide) -based thermoplastic block elastic body used as the component (ii) in the present invention is known in the art, and
It may also be abbreviated as TPEA (thermoplastic polyether ester-amide). Further, hereinafter, those having the repeating unit of the general formula (1) are TPEA-1, and those having the repeating unit of the general formula (2) are TPEA-2, the general formula
A compound having the repeating unit (3) may be abbreviated as TPEA-3. In addition, it goes without saying that in R ¹ , R ² and R ³ of the above-mentioned general formulas and general formulas described later, the carboxyl group and amine group bonded to these aromatic residues are not limited to the para position only. Is.

The poly (ether ester amide) -based thermoplastic block elastic body used as the component (ii) in the present invention is known in the art as described above,
For example, Japanese Examined Patent Publication No. 6-207006 and Japanese Patent Laid-Open No. 4-29.
3923, JP-A-6-279503, and JP-A-63-159432. This type of TPEA generally uses (1) a poly (alkylene oxide) glycol having a desired molecular weight as an essential component of an elastic body (elastomer), and (2) the poly (alkylene oxide) glycol. Using the amide molding component and the dicarboxylic acid component,
It is known as being constituted by connecting by an ester bond. Also, this kind of TPEA
In, it is also known that the poly (alkylene oxide) glycol component constitutes a soft segment and the other components constitute a hard segment. In the industry, the soft segment part, the hard segment part, and the hard segment part are constructed based on what kind of molecular design concept in order to improve various properties such as heat distortion resistance and moldability. Whether or not it is being actively researched.

In the present invention, as the TPEA, those known in the art can be used. As shown in the above general formulas (1) to (3), the hard segment portion has an aromatic residue. The wholly aromatic type having is preferably used. As is well known, TPEA has a general property that it is susceptible to thermal deterioration because the poly (alkylene oxide) glycol component constituting the soft segment has a difficulty in thermal stability. In order to remedy this drawback, it has been proposed that the molecular design of the hard segment should consist of an aliphatic or alicyclic type. However, when these modifying components (aliphatic amine, aliphatic carboxylic acid, etc.) are used, the TP produced is
Although the processing characteristics (melting temperature, flow starting temperature, etc.) of EA can be improved, it causes another drawback that the overall thermal characteristics, mechanical characteristics, chemical resistance, etc. are deteriorated. I will end up. In this sense, the present invention provides the above-mentioned general formulas (1) to (3), in other words, TPEA (1) to (3).
Is adopted.

(1) to (3) adopted in the present invention, that is, TPE
A (1) to (3) are known in the art,
Hereinafter, a method of manufacturing these TPEAs will be slightly supplementarily described.

The poly (ether ester amide) -based thermoplastic block elastic body (TPEA-1) of the general formula (1) is prepared by the following general formula (4) from an aromatic dicarboxylic acid compound and an aromatic diamine compound. Prepared by preparing an aromatic oligoester amide having an aromatic oligoester amide chain shown, and then melt reacting the aromatic oligoester amide with a poly (alkylene oxide) glycol represented by the following general formula (5): It is something.
Examples of the aromatic dicarboxylic acid include phthalic acids such as terephthalic acid and isophthalic acid, biphenylcarboxylic acids such as 4,4′-dicarboxybifer, 3,3
Dicarboxyphenones such as dicarboxybenzofer, dicarboxynaphthalenes such as 1,4-dicarboxynaphthalene are used. The aromatic diacin compound will be described in the following general formula (7). Formula ^{(4): -CO-R 1} -CONH-R 2 -NHCO-R 1 -CO
-General formula (5): OH-G-OH The above-mentioned production method is disclosed in JP-A-6-207006. This production method is a conventional solution polymerization method (JP-A-4-20706).
293923) has been considered in view of difficulty in aligning aromatic amide units, and for this purpose, oligomerization and melting reaction are adopted. In the present invention, even in the solution polymerization method described above, the second (ii)
It goes without saying that it can be used as a component.

The aromatic oligoesteramide represented by the general formula (4) is synthesized from, for example, an aromatic dicarboxylic acid compound and an aromatic diamine compound. Examples of the poly (alkylene oxide) glycol represented by the general formula (5) include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, ethylene oxide and propylene. Examples thereof include oxide copolymers.
The number average molecular weight of this kind of poly (alkylene oxide) glycol may be set based on a desired molecular design concept, but is generally preferably 500 to 10,000.

Poly (ether ester amide) -based thermoplastic block elastic body (TPEA-1) represented by the general formula (1)
Can be prepared as follows according to JP-A-6-207006 (Reference Example 1 and Example 1). (i) Synthesis of Aromatic Orgoester Amide Terephthalic acid monomethyl chloride (MMC) and dehydrated N-methyl-2-pyrrolidone (NMP) are charged into a flask, and MMC is dissolved in NMP. Then, an NMP solution of m-phenylenediamine is added, and the mixture is reacted at 0 to 5 ° C. This gives oligoesteramide (a) with mp = 312 ° C. (ii) Preparation of poly (ether ester amide) The oligo ester amide (a), polytetramethylene glycol (number average molecular weight Mn = 1009), and tetrabutkin titanium as a catalyst were charged in a flask, and methanol was added under heating and reduced pressure. The reaction is carried out while flowing out to prepare an ester amide copolymer (TPEA-1) having rubber elasticity.

The poly (ether ester amide) -based thermoplastic block elastic body (TPEA-2) of the general formula (2) has the following general formula (5) (polyalkylene oxide glycol),
It is prepared by reacting (6) (aromatic carboxylic acid halide), (7) (aromatic diamine), and (8) (aromatic aminocarboxylic acid halide). Formula (5): OH-G -OH general formula (6): XCO -R ¹ -COX general formula _{(7): H 2 N -R} 2 -NH 2 Formula _{(8): XH · H 2} N - R ³ —COX (In the above formula, X represents a halogen atom.) The production method is disclosed in JP-A-4-293923, and as is clear from the above description, conventional aliphatic amines are used. In lieu of the technique of using as a hard segment, an attempt is made to form a hard segment by a wholly aromatic system using an aromatic dicarboxylic acid, an aromatic diamine, and an aromatic aminocarboxylic acid.

Specific examples of the poly (alkylene oxide) glycol represented by the general formula (5) are as described above.
Examples of the aromatic carboxylic acid halide represented by the general formula (6) include terephthalic acid dichloride, isophthalic acid dichloride, 2,6-naphthalenedicarboxylic acid chloride and 1,5
Examples thereof include naphthalene dicarboxylic acid chloride and 4,4′-biphenyldicarboxylic acid chloride.

Specific examples of the aromatic diamine compound represented by the general formula (7) include para-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-diamino Examples thereof include benzene and 2,4-bis (β-amino-t-butyl) toluene.

Specific examples of the aromatic aminocarboxylic acid halide represented by the general formula (8) include para-aminobenzoic acid chloride hydrochloride and meta-aminobenzoic acid chloride hydrochloride.

The poly (ether ester amide) type thermoplastic block elastic body (TPEA-3) of the general formula (3) comprises an aromatic diamide carboxylic acid diester compound represented by the following general formula (9) and a poly (alkylene oxide). It was prepared by melt polycondensation of glycol. Formula _{(9): ROOC-C 6} H 4 -NHCO-R 1 -CONH-C 6
H ₄ —COOR ^{1 The} above-mentioned production method is disclosed in JP-A-6-279583, which is used for melt polycondensation of the diaminodicarboxylic acid dialkyl ester and poly (alkylene oxide) glycol. 0.01% of the resulting polyetheresteramide elastomer at 25 ° C
First, a prepolymer is prepared by dissolving at least g / ml and reacting in the presence of a solvent having a boiling point of 140 to 290 ° C. under normal pressure.
Next, the solvent is removed and bulk melt polymerization is performed to prepare a high molecular weight poly (ether ester amide).

In the general formula (9), the following can be exemplified as R ¹ . _{-C 6 H 4 -, - C} 6
_{H 4 -C 6 H 4 -,} - C 6 H 4 -o-C 6 H 4 -, - C
_{6 H 4 -S-C 6 H} 4 -, - C 6 H 4 -SO 2 -C 6 H
_{4 -, - C 6 H 4} -CO-C 6 H 4 -, - C 6 H 4 -C
_{H 2 -C 6 H 4 -,} - C 10 H 6 - ( disubstituted residues naphthalene), and the like can be exemplified.

Poly (ether ester amide) type thermoplastic block elastic body (TPEA-3) represented by the general formula (3).
Can be prepared as follows according to JP-A-6-279583 (Reference Example 1 and Example 1). (i) Preparation of Prepolymer Butyl aminobenzoate (BAB) was dissolved in N-methyl-2-pyrrolidone (NMP), and a solution prepared by dissolving terephthalic acid dichloride (TPC) in NMP was added. Aromatic diamide dicarboxylic acid diester (a) is prepared by reacting at 5 ° C. for 6 hours at room temperature overnight. Then, the aromatic diamide dicarboxylic acid diester (a)
On the other hand, polytetramethylene glycol (MS = 1031) is charged and reacted, and the solvent (NMP) is completely removed to prepare a prepolymer. (ii) Preparation of poly (ether ester amide) After removing the solvent, the mixture is reacted under heating and reduced pressure to prepare an elastomeric polymer (TPEA-3).

In the present invention, the addition-polymerization thermoplastic block elastic body of the above-mentioned component (i) (an elastic body comprising a polystyrene block and a hydrogenated or non-hydrogenated polybutadiene block) and a poly (of the component (ii) ( (Ether ester amide) -based thermoplastic block elastic material is used in combination with a thermoplastic elastic material composition to strongly bond by heat fusion to the part of the molded article that is pre-configured with a synthetic resin of relatively high hardness It is possible to combine the parts of the molded body composed of a soft thermoplastic elastic body rich in water. That is, both members can be firmly integrated and compounded. Although the reason why the above-mentioned members are strongly joined by heat fusion is not clear, the present inventors presume as follows. That is, in the fusion-bonded portion of these different molded body parts, the hard segment, soft segment, -NHCO-, -NH of the addition polymerization type thermoplastic block elastic body and the poly (ether ester amide) type thermoplastic block elastic body. ₂ , OH
It is considered that the result is that functional groups such as COOH and COOH effectively act on the surface of the hard synthetic resin molding.

The properties of the poly (ether ester amide) thermoplastic block elastic body vary depending on the ratio of the hard segment and the soft segment or the type of the constituent components of each segment, but the general characteristic is Excellent in bending resistance, oil resistance, wear resistance, heat resistance, etc. However, since the hardness is higher than that of a normal elastomer and the flexibility is poor, this point is preferably eliminated by blending with the above-mentioned addition polymerization type thermoplastic block elastic body. Generally, 100 parts by weight of the poly (ether ester amide) -based thermoplastic block elastic body contains 3 parts of the addition polymerization-based thermoplastic block elastic body.
It may be blended up to 100 weight. A thermoplastic elastic material composition having excellent heat fusion properties is prepared by the blending ratio of both components described above. Needless to say, when using both components, it is preferable to use a mixture in which both components are uniformly dispersed in a sea-island shape.

In the present invention, the above-mentioned component (i) (addition polymerization type thermoplastic block elastic body) and component (ii) (polyether ester amide type thermoplastic block elastic body) are basic components. It goes without saying that other elastic body components and other compounding components such as other fillers commonly used in the art may be used. As another thermoplastic elastic body which is an optional compounding component of this kind, any one may be used as long as it has elasticity and a relatively small hardness as compared with the hard synthetic resin described later which is a target of the compounding. For example, hydrogenated or non-hydrogenated polystyrene-polyisoprene block polymers (SIS, hydrogenated SIS), olefin elastomers such as EPR, S
Examples include diene-based elastomers such as BR, urethane-based elastomers, and plasticized polyvinyl chloride with a plasticizer blend and high elasticity. In particular, in order to obtain a composite molded article with high added value, the hardness (JIS Shore hardness A) is 70
It is preferable to use a thermoplastic elastic body having a relatively small hardness of ˜35 degrees.

The above-mentioned addition polymerization type thermoplastic block elastic body of the component (i) and the poly (ether ester amide) type thermoplastic block elastic body of the component (ii) are excellent in heat fusion property. The thermoplastic elastic body composition can be firmly bonded to a molded body portion of a synthetic resin having a relatively higher hardness than the composition by heat fusion to produce a useful composite molded body. The synthetic resin moldings that are the subject of such compounding are polycarbonate, nylon 6, nylon 1
It is manufactured from a thermoplastic engineering plastic such as 1, nylon 12, ABS resin, methacrylic resin or a thermoplastic synthetic resin. Among these synthetic resins, in order to obtain a composite molded article with high added value,
What has hardness of 70 or more may be used.

In the present invention, a molded body part made of a synthetic resin having a high hardness and a molded body part made of a thermoplastic elastic composition having excellent heat-sealing property are firmly joined by heat-sealing. As a method of making it possible, a thermoplastic elastomer composition having excellent rubber elasticity may be heat-fused to a molded article composed of a synthetic resin having a high hardness in advance, or conversely, a thermoplastic resin composition having excellent rubber elasticity in advance may be used. A molded body is formed from the elastic body composition,
A synthetic resin having high hardness may be heat-fused to form a composite body. Then, the technical means for joining the molded body part made of a synthetic resin having a high hardness and the molded body part made of the thermoplastic elastic composition having excellent heat-sealing property by heat fusion are known and commonly used. Either method can be adopted. For example, injection molding, extrusion molding, blow molding, calendar molding, compression molding, transfer molding, etc. may be used as long as the conditions for thermal fusion are set. Of these, it goes without saying that the injection molding method is preferable from the viewpoint of productivity and economy.

[0035]

EXAMPLES Next, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples without departing from the gist thereof.

Example 1 A thermoplastic elastic body composition was prepared as follows. As an addition polymerization type thermoplastic block elastic body, 10 parts of hydrogenated SBS block polymer (trade name "Lavalon" T3427C, manufactured by Mitsubishi Petrochemical Co., Ltd.)) and a poly (ether ester amide) type thermoplastic block elastic body (the TPEA- 100 parts of 1) were blended to obtain a blend in which both components were uniformly dispersed in a sea-island shape. An experiment was conducted in which the thermoplastic elastomer composition prepared as described above was heat-fused to a polycarbonate molded article to form a composite molded article.
That is, the main part of the underwater glasses is molded in advance by injection molding with polycarbonate, and then the thermoplastic elastomer composition is fusion-bonded to the main part of the polycarbonate underwater glasses by injection molding means, and the face contact part is formed. Was formed.
(The entire structure of the underwater glasses is described in Japanese Patent Publication No. 62-23577). The injection molding conditions are: nozzle temperature 235 ° C, cylinder temperature 180 ° C, die bottom temperature 140 ° C, mold temperature 5
The injection pressure is 400 Kg / cm ² at 0 ° C. The joining surface between the polycarbonate and the thermoplastic elastic composition was strongly and completely adhesively fused.

Under the same experiment as described above, a poly (ether ester amide) -based thermoplastic block elastic body (the above TPE
A blend of 30 parts and 50 parts of the hydrogenated SBS block copolymer with 100 parts of A-1) was also completely fused. Further, in Example 1, instead of the polycarbonate, an ABS resin (acryloyltriurea butadiene-styrene resin) (trade name "Denka ABS" GR-100
0, manufactured by Denki Kagaku Kogyo Co., Ltd., or methacrylic resin (trade name “Acrylic PET”, manufactured by Mitsubishi Rayon Co., Ltd.) was used for fusion bonding, the bonding surfaces were also fusion bonded with sufficient strength.

(Example 2) The thermoplastic elastomer composition of the present invention having an excellent heat fusion property was applied to the molding of mechanical parts as disclosed in JP-A-57-144737. In place of the polycarbonate of Example 1, preformed 11-
Put the nylon machine parts into the mold. The other conditions were the same as in Example 1, and when the same thermoplastic elastomer composition was injection-molded and fusion-bonded, the joint surfaces were completely fused. Also, when 12 nylon was used instead of 11 nylon, the joint surface was completely fusion bonded.

Example 3 A thermoplastic elastic composition was prepared as follows. As the addition-polymerization thermoplastic block elastic body, 10 of non-hydrogenated SBS block polymer (trade name “elastomer AR” AR140, manufactured by Aron Kasei Co., Ltd.)
Parts and 100 parts of a poly (ether amide) -based thermoplastic block elastic body (TEPA-3) were blended to obtain a blend in which both components were uniformly dispersed in a sea-island shape. An experiment was carried out in the same manner as in Example 1 to heat-bond the thermoplastic elastic composition prepared as described above to a polycarbonate molded article (underwater glasses) to form a composite molded article. The results were exactly the same as in Example 1, and the bonding surface between the polycarbonate and the thermoplastic elastic composition was strongly adhesively fused. With respect to the thermoplastic elastomer composition of this example, the same modification was obtained when the modified example of Example 1 described in Example 1 and Example 2 were additionally tested.

[0040]

EFFECT OF THE INVENTION The thermoplastic elastic composition of the present invention having excellent heat-sealing property is strongly bonded to a molded body part made of a hard engineering plastic, which has been molded in advance, by heat-sealing. A molded body part made of a soft and flexible thermoplastic elastic body can be formed. INDUSTRIAL APPLICABILITY The thermoplastic elastic composition of the present invention is extremely useful for producing a molded product in which both hard and soft parts are combined. Then, these composite molded bodies can be manufactured efficiently and economically by employing a heat fusion means such as injection molding for the thermoplastic elastomer composition of the present invention.

In particular, the thermoplastic elastomer composition having excellent rubber elasticity and flexibility of the present invention is strongly fusion-bonded by a simple method of heat-fusing an engineering plastic having high hardness such as polycarbonate by injection molding means. Therefore, a composite molded body having new performance and new function can be provided economically and efficiently.

Claims (8)

[Claims] 1. A thermoplastic elastic composition used for forming a composite molded body by heat-sealing to a hard synthetic resin molded body, wherein the thermoplastic elastic composition is (i) a polystyrene block. Addition polymerization type thermoplastic block elastic body consisting of and hydrogenated or non-hydrogenated polybutadiene block: 3 to 100 parts by weight, (ii) poly (ether ester amide) type thermoplastic block elastic body: 100 parts by weight of the thermoplastic elastomer composition having excellent heat-sealing property. 2. A poly (ether ester amide) -based thermoplastic block elastic body is composed of one or more elastic bodies having repeating units represented by the following general formulas (1), (2) and (3). The thermoplastic elastic composition according to claim 1, which is a compound. Formula ^{(1): -CO-R 1} -CONH-R 2 -NHCO-R 1 -CO
-O -G -O - formula ^{(2): -NH-R 3} -CONH-R 2 -NHCO-R 1 -CO
-O -G -O - Formula _{(3): -CO-C 6} H 4 -NHCO-R 1 -CONH-C 6
H ₄ —CO—O —G —O— (in the above formula, R ¹ = C _{6 to} C ₃₀ divalent aromatic residue, R ² = C _{6 to} C ₃₀ divalent aromatic residue, R ³ = C ₆ -C ₃₀ divalent aromatic residue, G = poly (alkylene oxide) glycol residue, respectively.) 3. An aromatic oligo having a poly (ether ester amide) -based thermoplastic block elasticity of the general formula (1) represented by the following general formula (4) from an aromatic dicarboxylic acid compound and an aromatic diamine compound. An aromatic oligoester amide having an ester amide chain is prepared, and then the aromatic oligo ester amide is melt-reacted with the poly (alkylene oxide) glycol represented by the following general formula (5). 2. The thermoplastic elastic composition according to item 2. Formula ^{(4): -CO-R 1} -CONH-R 2 -NHCO-R 1 -CO
-General formula (5): OH-G-OH 4. A poly (ether ester amide) -based thermoplastic block elastic body of the general formula (2) has the following general formula (5):
(Polyalkylene oxide glycol), (6) (Aromatic carboxylic acid halide), (7) (Aromatic diamine), (8)
The thermoplastic elastomer composition according to claim 2, which is prepared by reacting (aromatic aminocarboxylic acid halide). Formula (5): OH-G -OH general formula (6): XCO -R ¹ -COX general formula _{(7): H 2 N -R} 2 -NH 2 Formula _{(8): XH · H 2} N - R ³ -COX (in the above formulas, X is a halogen atom.) 5. A poly (ether ester amide) -based thermoplastic block elastic body represented by the general formula (3) melts an aromatic diamide carboxylic acid diester compound represented by the following general formula (9) and poly (alkylene oxide) glycol. The thermoplastic elastic composition according to claim 2, which is prepared by polycondensation. Formula _{(9): ROOC-C 6} H 4 -NHCO-R 1 -CONH-C 6
H ₄ —COOR ¹ (In the above formula, R ¹ and R ¹ each independently represent a C _{1 to} C ₁₃ aliphatic alkyl group.) 6. The hardness of a hard synthetic resin molding (JIS
The thermoplastic elastomer composition according to claim 1, which has a Shore hardness A) of 70 or more. 7. The thermoplastic elastic composition according to claim 1, wherein the thermoplastic elastic composition has a hardness (JIS Shore hardness A) of 70 or less. 8. The thermoplastic elastomer composition according to claim 1, wherein the hard synthetic resin molded body is a molded body of a resin selected from a polycarbonate resin, a polyamide resin, an ABS resin, a polymethacrylic acid resin and a polyolefin resin. Stuff.