JP3114269B2 - Thermoplastic elastomer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION This invention relates to mechanical strength, transparency,
The present invention relates to a thermoplastic elastomer composition having excellent heat resistance, flexibility and high frequency fusion, and more specifically, a hydrogenated diene copolymer having excellent rubber properties and ethylene-vinyl acetate having good high frequency fusion. The present invention relates to a high-frequency fusing thermoplastic elastomer composition mainly composed of a copolymer and a polyolefin resin.

[0002]

2. Description of the Related Art Conventionally, an ethylene-vinyl acetate copolymer has been known as a material which can be fused by high frequency. The requirement is satisfied by using. However, ethylene-vinyl acetate copolymers cannot be used for applications that require high-frequency fusing properties and flexibility and require heat resistance.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and is a thermoplastic elastomer which is excellent in heat resistance, flexibility, mechanical strength and transparency and which can be fused by high frequency. It is intended to provide a composition.

[0004]

According to the present invention, there is provided (a) at least one hydrogenated diene copolymer selected from the group consisting of (a-1), (a-2) and (a-3) below. Coalescing 10-90
% By weight, (a-1); vinyl aromatic compound polymer block (A)
(A)-(B) block copolymer consisting of a conjugated diene polymer or a random copolymer block (B) of a vinyl aromatic compound and a conjugated diene, or, if necessary, conjugated with a vinyl aromatic compound (A)-(B)-(C) block copolymer comprising a taper block (C) in which a vinyl aromatic compound gradually increases in a diene, or (A)-comprising a vinyl aromatic polymer block (A)
(B)-(A) a block copolymer wherein the ratio of vinyl aromatic compound / conjugated diene is 5 to 60/9 by weight.
5 to 40, the bond content of the vinyl aromatic compound in the component (A) and the component (C), which is optionally formed, is 3 to 3
Component (A) has a vinyl aromatic compound bond content of at least 3% by weight, and component (B) has a conjugated diene moiety having a vinyl bond content of 6 % by weight.
0% or more of the block copolymer or the block copolymer unit is (A) via a coupling agent residue;
(B) or (C) a block copolymer bonded to a polymer unit consisting of at least one polymer block and having a polymer molecular chain extended or branched, and hydrogenated;
A hydrogenated diene copolymer in which at least 80% of the double bonds of the conjugated diene portion are saturated and the number average molecular weight is 50,000 to 600,000. (A-2); having one or more polymer blocks (D), (E) and (F) in the molecule, respectively (provided that (D) is a vinyl aromatic compound containing 90% by weight or more of a vinyl aromatic compound) (E) a conjugated diene polymer block having a vinyl bond content of 30 to 70%,
(F) indicates a polybutadiene polymer block having a vinyl bond content of less than 30%), the content of the polymer block (D) in the block copolymer is 10 to 50% by weight, and the content of the polymer block (E) is The block copolymer having a content of 30 to 80% by weight and the content of the polymer block (F) of 5 to 30% by weight, or the block copolymer unit is formed of the above (D), (D) E) or (F) is bonded to a polymer unit consisting of at least one polymer block, and the block copolymer in which the polymer molecular chain is extended or branched is hydrogenated to form a double conjugated diene moiety. At least 80% of the bonds are saturated and have a number average molecular weight of 4
A hydrogenated diene copolymer having a molecular weight of 10,000 to 700,000. (A-3): a polybutadiene polymer block (G), a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene copolymer block having a vinyl bond content of 20% or less, wherein the vinyl bond in the conjugated diene portion is It consists of a polymer block (H) having a content of 25 to 95%, and the block structure is [(G)-(H)-(G)] p or [(G)-(H)] q (where p is 1 or more, and q represents an integer of 2 or more), or a block copolymer in which the molecular chain of the polymer is extended or branched via a coupling agent residue. Hydrogenated polymer, at least 80% of the double bonds of the conjugated diene portion are saturated, and the number average molecular weight is 50,000 to
A hydrogenated diene copolymer having a molecular weight of 600,000. (B) 10 to 90% by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 10% by weight or more, and (C) 0 to 35% by weight of a polyolefin resin [
(A) + (b) + (c) = 100% by weight].

[0005] The thermoplastic elastomer composition of the present invention will be described below for each constituent element. Component (A ) Component (A) is composed of at least one hydrogenated diene copolymer selected from the group consisting of (A-1), (A-2) and (A-3). The compounding amount is 1 in the total composition.
It is 0 to 90% by weight, preferably 15 to 80% by weight, more preferably 20 to 75% by weight. If the amount of the component (a) is less than 10% by weight, the flexibility is inferior, while 90% by weight.
If it exceeds, the heat resistance will be poor. Here, the component (a) will be further described as (a-1), (a-2), and (a-3).

Component (A-1): (A-1) Styrene, t-butylstyrene, and vinyl aromatic compounds used in the hydrogenated diene copolymer
α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p
-Aminoethylstyrene, vinylpyridine and the like, and styrene and α-methylstyrene are particularly preferred. The conjugated diene used in the (a-1) hydrogenated diene copolymer includes 1,3-butadiene, isoprene,
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3
-Hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like, and are hydrogenated diene copolymers which can be used industrially and have excellent physical properties. In order to obtain, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, and 1,3-butadiene is more preferable.

The (a-1) hydrogenated diene copolymer of the present invention comprises a vinyl aromatic polymer block (A) and a conjugated diene polymer or a random copolymer of a vinyl aromatic compound and a conjugated diene. (A) consisting of blocks (B)
(A)-(B)-(C) comprising a (B) block copolymer or, if necessary, a vinyl aromatic compound and a tapered block (C) in which the vinyl aromatic compound among the conjugated dienes gradually increases. (A)-comprising a block copolymer or a vinyl aromatic polymer block (A)
(B)-(A) It is composed of a block copolymer. First, the ratio of vinyl aromatic compound / conjugated diene in all monomers is 5-60 / 95-40, preferably 7-50 / 9 by weight ratio.
It needs to be 3 to 50. When the content of the vinyl aromatic compound is less than 5% by weight, the obtained hydrogenated diene-based copolymer is easily blocked when pelletized, and when blended with another resin, the molded appearance is inferior.
On the other hand, when the content of the vinyl aromatic compound exceeds 60% by weight, it becomes resinous, and when blended with another resin,
The effect of improving impact resistance, particularly low-temperature impact resistance, is insufficient.

The total amount of the vinyl aromatic compound polymer block (A) and the optional taper block (C) is 3 to 50% by weight, preferably 5 to 40% by weight of the whole block copolymer. % By weight, more preferably 5%
-25% by weight, and the component (A) is at least 3% by weight,
Preferably it is 5 to 15% by weight. When the component (A) or the total amount of the component (A) and the component (C) is less than 3% by weight, when the obtained hydrogenated diene-based copolymer is pelletized, it becomes easy to block, and other resins are used. When blended with other resins, the molding appearance is inferior. On the other hand, when it exceeds 50% by weight, it becomes resinous, and when blended with other resins, the effect of improving the impact resistance is insufficient, and especially the low-temperature impact resistance is insufficient. Further, the vinyl bond content of the conjugated diene portion in the random copolymer block (B) of the conjugated diene polymer or the vinyl aromatic compound and the conjugated diene is 60%.
Or more, preferably 70% or more, more preferably 80%
That is all. If the vinyl bond content is less than 60% , the effect of improving softness on the resin is reduced.

The (A)-(B) block copolymer, (A)-(B)-(C) block copolymer or (A)-(B)-(A) block copolymer May be a block copolymer having a polymer molecular chain extended or branched as represented by the following general formula via a coupling agent residue. [(A)-(B)] n-X, [(A)-(B)-(C)] n-X, or [(A)-(B)-(A)] n-X , N is an integer of 2 to 4, and X represents a residue of a coupling agent.) Examples of the coupling agent in this case include diethyl adipate, divinylbenzene, tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, and butyl. Trichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2-dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate,
1,2,4-benzene triisocyanate and the like can be mentioned.

Furthermore, the (a-1) hydrogenated diene copolymer of the present invention contains at least 80%, preferably 90% or more, more preferably 95% or more of double bonds in the conjugated diene portion of the block (B). It is necessary that 〜100% is hydrogenated and saturated, and if it is less than 80%, heat resistance, weather resistance and ozone resistance are inferior. Furthermore, (A-1) of the present invention
The hydrogenated diene copolymer has a number average molecular weight of 50,000 to 60.
If it is less than 50,000, the mechanical strength and heat resistance of the elastomer composition are reduced, while if it exceeds 600,000, the fluidity and processability are reduced and the surface appearance is reduced. And so on. It should be noted that (A) of the present invention
1) The hydrogenated diene copolymer has a melt flow rate measured at 230 ° C. under a load of 12.6 kg of preferably 0.1.
g / 10 minutes or more, more preferably 0.5 g / 10 minutes or more, and if less than 0.1 g / 10 minutes, pelletization becomes difficult. The (a-1) hydrogenated diene copolymer used in the present invention can be obtained, for example, by the method disclosed in JP-A-3-72512.

Component (a-2): The aromatic vinyl compound and conjugated diene used in the component (a-2) are the same as those used in the component (a-1). Here, the polymer block (D) constituting the (a-2) hydrogenated diene copolymer is a polymer block of an aromatic vinyl compound or 90% by weight of an aromatic vinyl compound.
80 of the conjugated diene portion of the copolymer with the conjugated diene
% Or more are hydrogenated polymer blocks. If the content of the aromatic vinyl compound in the polymer block (D) is less than 90% by weight, weather resistance is undesirably reduced. The content of the polymer block (D) is 10 to 50% by weight, preferably 15 to 50% by weight.
The number average molecular weight of the polymer block (D) is preferably 5,000 to 70,000. When the content of the polymer block (D) is 10% by weight or less, the improvement in heat resistance is insufficient, while when it exceeds 50% by weight, flexibility is reduced.

The content of the polymer block (E) constituting the (a-2) hydrogenated diene copolymer is 30 to 80% by weight, preferably 35 to 70% by weight, and the vinyl bond content is 30 to 80% by weight. It is a conjugated diene polymer block having 90%, preferably 40 to 70%, a number average molecular weight of 30,000 to 300,000, and hydrogenated at least 80% of a double bond of a conjugated diene portion. The polymer block (E) becomes a polymer block in which ethylene and butene-1 are randomly copolymerized by hydrogenating the double bond of the conjugated diene portion by 100%. If the vinyl bond content of polybutane in the conjugated diene block before hydrogenation, which becomes the polymer block (E), is less than 30%, the hydrogenation results in the formation of polyethylene chains and loss of rubbery properties. %, The hydrogenation increases the glass transition temperature and loses rubbery properties, which is not preferred. When the content of the polymer block (E) in the block copolymer before hydrogenation is less than 30% by weight, the flexibility is reduced, while the content is 80% by weight.
If it exceeds, the workability is reduced.

Further, the content of the polymer block (F) constituting the hydrogenated diene copolymer of the component (a-2) is 5 to 30% by weight, preferably 5 to 25% by weight, and the vinyl bond content. Has a double bond of less than 30%, preferably 3 to 20%, and a number average molecular weight of preferably 10,000 to 300,000 in the butadiene portion of the polybutadiene block.
It is a polymer block hydrogenated by 0% or more. When the vinyl bond content of the polybutadiene before hydrogenation in the polymer block (F) is 30% or more, the resinous properties are lost when hydrogenated, and the properties of the thermoplastic elastomer as the block copolymer are lost. . If the content of the polymer block (F) in the block copolymer before hydrogenation is less than 5% by weight, the mechanical strength decreases, while if it exceeds 30% by weight, the flexibility is poor, which is not preferable. (A-2) of the present invention
The number average molecular weight of the hydrogenated diene copolymer is 40,000 to 700,000,
It is preferably from 50,000 to 500,000, and if it is less than 40,000, the mechanical strength and heat resistance of the obtained composition are reduced. On the other hand, if it exceeds 700,000, the fluidity and processability are reduced, and the surface appearance is reduced. Will be.

The block copolymer constituting the component (A-2) is formed by coupling at least one of the polymer blocks (D), (E) and (H) via a coupling agent residue. It may be a block copolymer bonded to a polymer unit composed of a block and having a polymer molecular chain extended or branched, for example, as represented by the following general formula. [(D)-(E)-(F)] n-X or [(D)-(E)-(F)] X [(D)-(E)] wherein n is 2-4 Integer and X represent a coupling agent residue, and the coupling agent used is the same as that used in the component (A-1). Used in the present invention (a
2) The hydrogenated diene copolymer is disclosed in, for example, JP-A-2-133.
It can be obtained by the method disclosed in Japanese Patent Publication No. 406.

Component (a-3): The vinyl aromatic compound and the conjugated diene used in the component (a-3) are the same as those used in the component (a-1). Here, the hydrogenated diene copolymer which is the component (a-3) used in the present invention has a vinyl bond content of 20%.
The following polybutadiene polymer block (G) and conjugated diene polymer block or vinyl aromatic compound
A conjugated diene copolymer block comprising a polymer block (H) in which the vinyl bond content of the conjugated diene portion is 25 to 95%, and the block structure is [(G)-(H)
-(G)] p or [(G)-(H)] q (where p
Is an integer of 1 or more, and q is an integer of 2 or more.) A linear or branched block copolymer represented by the following formula: .

The block (G) in the component (a-3) becomes a crystalline block having a structure similar to ordinary low density polyethylene (LDPE) by hydrogenation. The vinyl bond content in the block (G) is at most 20%, preferably at most 18%, more preferably at most 15%. When the vinyl bond content of the block (G) exceeds 20%, the crystal melting point after hydrogenation drops remarkably, and (a-3)
It is not preferable because the mechanical properties of the components are inferior. The block (H) is a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene copolymer block, and is a rubbery ethylene-butene copolymer block or a vinyl aromatic compound-ethylene-butene block by hydrogenation. A polymer block having a structure similar to that of the copolymer is obtained.

The amount of the vinyl aromatic compound used in the block (H) is at most 35% by weight, preferably at most 30% by weight, more preferably at most 25% by weight of the monomers constituting the block (H). % Or more, and if it exceeds 35% by weight, the glass transition temperature of the block (H) increases, and the mechanical properties of the component (A-3) are inferior. The vinyl bond content of the butadiene portion of the block (H) is 25 to 95%, preferably 25 to 75%, more preferably 25 to 55%, and is less than 25% or 95%.
%, It is not preferable because after hydrogenation, it shows a crystal structure derived from a polyethylene chain and a polybutene-1 chain, respectively, becomes resinous, and has poor mechanical properties of the component (a-3).

(A-3) Block (G) occupying in the component
And the ratio of block (H) is usually block (G)
The content is 5 to 90% by weight, preferably 10 to 85% by weight, and the block (H) 95 to 10% by weight, preferably 90 to 15% by weight. When the content of the block (G) is less than 5% by weight and the content of the block (H) exceeds 95% by weight, the crystalline polymer block is insufficient, and the mechanical properties of the component (A-3) are not preferable. Also, the block (G) is 90% by weight.
When the block (H) is less than 10% by weight,
The hardness of the component (a-3) is undesirably increased.

Further, (a-3) the hydrogenated diene copolymer used in the present invention has at least 80 double bonds of the butadiene portion of the block (G) and the block (H).
%, Preferably 90% or more, more preferably 95 to 1%.
00% must be hydrogenated and saturated,
If it is less than 80%, heat resistance and weather resistance will be poor. The weight average molecular weight of the block (G) and the block (H) is usually 5,000 or more, preferably 10,000.
It is desirable that it is 0 or more, more preferably 15,000 or more, and if it is less than 5,000, the mechanical properties of the component (a-3) are inferior, which is not preferred. (A-3) of the present invention
The number average molecular weight of the hydrogenated diene copolymer is from 50,000 to 600,000,
It is preferably 100,000 to 500,000, and if it is less than 50,000, the mechanical strength, heat resistance, fluidity, and processability of the obtained composition are reduced, and the surface appearance is reduced.
Workability is reduced and surface appearance is reduced.

The (G)-(H)-(G) block copolymer or the (G)-(H) block copolymer which is the block copolymer before hydrogenation is used as a coupling agent residue. A polymer having at least one polymer unit block selected from the above (G) and (H), and having an extended or branched polymer molecular chain represented by the following general formula. There may be. [(G)-(H)] nx [(G)-(H)-(G)] nx (wherein n and X are the same as described above). -1) The same compounds as those used for the component are exemplified. The (a-3) hydrogenated diene-based copolymer used in the present invention can be obtained, for example, by the method disclosed in Japanese Patent Application No. 2-110467.

(B) Component The ethylene-vinyl acetate copolymer used as the component (b) in the present invention is a copolymer having a vinyl acetate content of 10% by weight or more. In particular, in the present invention, it is preferable to use an ethylene-vinyl acetate copolymer having a vinyl acetate content in the range of 15 to 45% by weight. The melt index of such a copolymer is usually from 0.2 to 400 g /
10 minutes (190 ° C., 2.16 kg load), preferably 0.1 min.
5 to 50 g / 10 min. The amount of the (b) ethylene-vinyl acetate copolymer in the composition of the present invention is 10%.
When the content is less than 10% by weight, high-frequency fusion property is inferior, and when it exceeds 90% by weight, flexibility is inferior. Become.

(C) Component (C) The polyolefin-based resin used in the present invention comprises:
A resin obtained from polymerization of one or more monoolefins by either a high-pressure method or a low-pressure method. Here, as the monoolefin, ethylene, propylene,
1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 2-methyl-1-propene, 3-methyl-1-pentene, 5-methyl-1-hexene, and mixtures thereof. And preferably ethylene, propylene, 4-methyl-1-pentene, and more preferably propylene.

The preferred (c) polyolefin resin is
Polyethylene, polypropylene, poly 4-methyl-1-
Pentene, and the copolymer type (c) component includes ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 2-methyl-1-propene, and 3-methyl Examples thereof include polypropylene in which at least one monoolefin selected from the group consisting of -1-pentene and 5-methyl-1-hexene is copolymerized. (C) More preferably, the polyolefin resin is polypropylene or the copolymer type polypropylene. (C) The melt index of the polyolefin resin is
Usually, 0.1 to 70 g / 10 minutes (230 ° C, 2.16 kg
Load), preferably 0.2 to 50 g / 10 min. The amount of the (C) polyolefin resin in the composition of the present invention is 0 to 35% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight, and 1% by weight.
When used as described above, heat resistance and mechanical strength are excellent, but when it exceeds 35% by weight, flexibility is inferior.

The thermoplastic elastomer composition of the present invention comprises:
If necessary, cross-linking such as sulfur cross-linking, peroxide cross-linking, metal ion cross-linking, and silane cross-linking can be performed by a conventionally known method. Further, additives used for ordinary thermoplastic elastomers can be added to the thermoplastic elastomer composition of the present invention as needed. Examples of the additive include a plasticizer such as a phthalate ester, a softener for rubber, a filler or a reinforcing agent such as silica, talc, and glass fiber, and other antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, Lubricants, foaming agents, coloring agents, pigments, nucleating agents, and the like, and mixtures thereof are also included. In addition, if necessary, a rubbery polymer such as SBR, NBR, B
R, EPT, EPR, NR, IR, 1,2-polybutadiene, AR, CR, IIR and the like can be added. In addition, if necessary, a thermoplastic resin other than the above components (a) to (c), for example, a diene resin, a polyvinyl chloride resin, a polyvinyl acetate resin, a polycarbonate resin, a polyacetal resin, a polyamide resin ,
Polyester resins, polyether resins, polysulfone, polyphenylene sulfide, and the like can also be blended.

The thermoplastic elastomer composition of the present invention comprises:
It is kneaded using a usual kneading device, for example, a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader, a ruder, a twin-screw extruder, and the like, but the kneading device may be a closed type or an open type. Although good, a type that can be replaced by an inert gas is preferable.
The kneading temperature is a temperature at which all components to be mixed are melted, and is usually 160 to 250 ° C., preferably 180 ° C.
It is desirable to be in the range of -240 ° C. In addition, the kneading time depends on the type, the amount and the kneading device of the constituent components, and is therefore not generally discussed.However, when a pressure kneader or a Banbury mixer is used as the kneading device,
Usually, it is about 3 to 10 minutes. Further, in kneading, each component may be kneaded all at once, or a multi-stage kneading method in which arbitrary components are kneaded, and then the remaining components are added and kneaded may be employed. The composition of the present invention can be molded into a practically useful molded article by a conventionally known method, for example, extrusion molding, injection molding, hollow molding, compression molding, calendering, or the like. In addition, processing such as painting and plating can be performed as necessary.

The thermoplastic elastomer composition of the present invention comprises:
Excellent high frequency fusion, transparency, heat resistance, impact resistance, workability, flexibility, low temperature characteristics, temperature dependence, compatibility, paintability, printability, hot stamping, deep drawing, hot water resistance,
Utilizing rubber elasticity, rubber touch, flexibility, slip resistance, stress crack resistance, etc., it can be used for various applications. For example, used for sheet applications such as fresh fish trays, fruit and vegetable packs, frozen dessert food containers, food packaging, daily miscellaneous goods packaging, industrial material packaging, various rubber products, resin products, fabrics, lamination of leather products, disposable diapers, etc. Film applications such as elastic tape, hoses, tubes, belts, etc., sports shoes, leisure shoes, fashion sandals, footwear such as leather shoes, TVs, stereos, vacuum cleaners, etc.
Automotive interior and exterior parts applications such as bumper parts, body panels, side seals, road paving materials, waterproof sheets,
Materials for asphalt blending such as pipe coating, other daily necessities, leisure goods, toys, industrial goods,
It can be used for a wide range of applications such as medical devices.

[0027]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention. In the examples, parts and% are by weight unless otherwise specified.
In the examples, the analysis of the copolymer and the evaluation of various physical properties were measured by the following methods. The number average molecular weight was determined in terms of polystyrene using gel permeation chromatography (GPC) at 135 ° C. using trichlorobenzene as a solvent. Using hydrogenation rate ethylene tetrachloride as a solvent, 100 MHz, ¹ H
-Calculated from NMR spectrum.

Tensile properties Measured according to JIS K6301. Heat resistant 2mm square sample 2mm thick, 120 ℃, 30 minutes,
The sample was aged in a gear oven, and the presence or absence of shrinkage of the sample after aging was determined. ○ indicates shrinkage of less than 3%,
Δ indicates that the contraction rate is 3 to 6%, and X indicates that the contraction rate is greater than 6%. Using a multi-light source spectrophotometer manufactured by Suga Test Co., Ltd.
The haze of a 4 mm sheet was measured and judged. The lower the number, the more transparent. Complies with the flexibility JIS K6301, was measured JIS A hardness. A sheet sample of vinyl acetate copolymer, - ethylenically the sheet sample and the high-frequency welding of a high-frequency fusion bonding thickness of about 0.4mm
Using a high-frequency welder (manufactured by Yamamoto Vinyl Co., Ltd.), the high-frequency fusion property was evaluated. The sample subjected to high frequency fusion was evaluated as ○, and the sample not subjected to high frequency fusion was evaluated as ×.

REFERENCE EXAMPLES Various polymers used in the formulations of Examples and Evaluations are as follows. EVA-1; [ Ethylene-vinyl acetate copolymer EVA-1; [Ultracene 760, manufactured by Tosoh Corporation] EVA-2: [Ultracene 710, manufactured by Tosoh Corporation] PP polypropylene [Mitsubishi Yuka Corporation, polypropylene M
A-4] PE polyethylene [Mitsubishi Yuka Co., Ltd., polyethylene YK-
30] Block copolymer of SEBS polystyrene-polybutadiene-polystyrene copolymer obtained by hydrogenating a polybutadiene portion [Clayton G1657 manufactured by Shell Chemical Co., Ltd .; SEB
S-1] Softener Idemitsu Kosan Co., Ltd., paraffin oil, PW380 hydrogenated diene copolymer Hydrogenated diene copolymer (Q1-8) is manufactured by Nippon Synthetic Rubber Co., Ltd. The microstructure, number average molecular weight, and hydrogenation ratio of Q1 to Q8 are as shown in Table 1.

[0030]

[Table 1]

Note) Q-6, which is the component (a-3),
It has a (G)-(H)-(G) structure, and the number average molecular weight of each block is 3.6 × 10 ^{4 for} the block (G) and 16.8 × 10 ⁴ for the block (H). Q-7 is a hydrogenated diene-based copolymer obtained by hydrogenating a random copolymer of styrene and butadiene, and Q-8 is a (a-1) hydrogenated block copolymer. The vinyl bond content of part (B) is outside the scope of the present invention. Examples 1 to 13 and Comparative Examples 1 to 8 Using the formulation shown in Tables 2 to 4, each component was added to a Labo Plastomill whose temperature was adjusted to 190 ° C., and kneaded at 60 rpm for 5 minutes. The mixture was discharged, formed into a sheet with a hot roll, pressed, formed into a square plate having a side of 10 cm, cut out with a dumbbell cutter to obtain a test specimen for measurement, and various physical properties were evaluated. As is clear from Tables 2 and 3, Examples 1 to 13 are compositions of the present invention, and are excellent in tensile properties, heat resistance, transparency, flexibility, and high-frequency fusion property, and the objects of the present invention. Is obtained.

On the other hand, as is clear from Table 4, Comparative Example 1 is an example in which the blending amount of (a) the hydrogenated diene copolymer is less than the range of the present invention, and is excellent in high-frequency fusion property. But poor heat resistance. Comparative Example 2 is an example in which the blending amount of the (b) ethylene-vinyl acetate copolymer is less than the range of the present invention, and is excellent in flexibility but inferior in high-frequency fusion property. Comparative Example 3 is the case where the compounding amount of (c) the polyolefin resin exceeds the range of the present invention, and is excellent in heat resistance, but inferior in high-frequency fusion property and flexibility. Comparative Examples 4 to 6
This is an example using a hydrogenated diene copolymer other than the component (a), and is inferior in mechanical strength, transparency and heat resistance. Comparative Example 7
(C) The amount of the component is large, and a rubber softener is added as a flexibility-imparting agent, which is inferior in heat resistance and high-frequency fusing property. Comparative Example 8 is an example in which the component (a) is not used, and is inferior in flexibility.

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

Industrial Applicability The high-frequency-fusible thermoplastic elastomer composition of the present invention has essentially the properties of a thermoplastic elastomer composition, and has extremely good high-frequency-fusibility, tensile properties, Excellent heat resistance and flexibility. The high frequency fusing thermoplastic elastomer composition of the present invention,
It is a material having excellent properties as described above, and can be suitably used for industrial goods, automobile interior parts, toys, medical supplies and the like, and is a material of high industrial value.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shoji Yanagisawa 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-58-57455 (JP, A) (58 ) Surveyed field (Int.Cl. ⁷ , DB name) C08L 53/02 C08L 23/08 C08L 23/02

Claims (1)

(57) [Claims] (A) 10 to 90% by weight of at least one hydrogenated diene copolymer selected from the group consisting of the following (A-1), (A-2) and (A-3): B-1); vinyl aromatic compound polymer block (A)
(A)-(B) block copolymer consisting of a conjugated diene polymer or a random copolymer block (B) of a vinyl aromatic compound and a conjugated diene, or, if necessary, conjugated with a vinyl aromatic compound (A)-(B)-(C) block copolymer comprising a taper block (C) in which a vinyl aromatic compound gradually increases in a diene, or (A)-comprising a vinyl aromatic polymer block (A)
(B)-(A) a block copolymer, wherein the ratio of vinyl aromatic compound / conjugated diene is 5 by weight.
６０60 / 95〜40, the bond content of the vinyl aromatic compound in the component (A) and the component (C) constituted as required is 3 to 3
Component (A) has a vinyl aromatic compound bond content of at least 3% by weight, and component (B) has a conjugated diene moiety having a vinyl bond content of 6 % by weight.
0% or more of a block copolymer or a block copolymer unit comprising at least one polymer block of the above (A), (B) or (C) via a coupling agent residue. Hydrogenated from a block copolymer in which a polymer molecular chain is extended or branched, which is combined with a united unit, wherein at least 80% of the double bonds of the conjugated diene portion are saturated, and the number average molecular weight is 50,000 to A hydrogenated diene copolymer having a molecular weight of 600,000. (A-2); having one or more polymer blocks (D), (E) and (F) in the molecule, respectively (provided that (D) is a vinyl aromatic compound containing 90% by weight or more of a vinyl aromatic compound) (E) a conjugated diene polymer block having a vinyl bond content of 30 to 70%,
(F) indicates a polybutadiene polymer block having a vinyl bond content of less than 30%), the content of the polymer block (D) in the block copolymer is 10 to 50% by weight, and the content of the polymer block (E) is A block copolymer having a content of 30 to 80% by weight and a polymer block (F) of 5 to 30% by weight, or the block copolymer unit having the above-mentioned (D), (D) (E) or (F), a block copolymer bonded to a polymer unit comprising at least one polymer block and having an extended or branched polymer molecular chain; A hydrogenated diene copolymer in which at least 80% of the bonds are saturated and the number average molecular weight is 40,000 to 700,000. (A-3): a polybutadiene polymer block (G), a conjugated diene polymer block or a vinyl aromatic compound-conjugated diene copolymer block having a vinyl bond content of 20% or less, wherein the vinyl bond in the conjugated diene portion is It consists of a polymer block (H) having a content of 25 to 95%, and the block structure is [(G)-(H)-(G)] p or [(G)-(H)] q (where p is 1 or more, q represents an integer of 2 or more), or a block copolymer in which the molecular chain of the polymer is extended or branched through the coupling agent residue via the block copolymer unit. A hydrogenated diene-based copolymer in which the polymer is hydrogenated to have at least 80% of the double bonds of the conjugated diene portion saturated, and have a number average molecular weight of 50,000 to 600,000. (B) 10 to 90% by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 10% by weight or more, and (C) 0 to 35% by weight of a polyolefin resin [
(A) + (b) + (c) = 100% by weight].