JPH07138418A - Olefinic elastomer composition - Google Patents

Abstract

PURPOSE:To obtain a subject composition thermally fusible with various resins and having a practically sufficient physical properties by blending an ethylene-(meth)acrylate copolymer with an ethylene-alpha-olefin copolymer and a specific hydrogenated block copolymer. CONSTITUTION:This composition is obtained by blending (A) 20-80wt.% of a copolymer of ethylene and (meth)acrylate (preferably ethyl acrylate) of the formula (R1 is H or methyl; R2 is H or a 1-10C alkyl) with 20-80wt.% of a copolymer selected from (B) an ethylene-alpha-olefin copolymer (preferably an ethylene-propylene copolymer rubber) and (C) a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of a polymer block consisting mainly of a vinyl aromatic compound (preferably styrene) and a polymer block consisting mainly of a conjugated diene compound (preferably butadiene or isoprene) so as to hydrogenate >=50% of an aliphatic double bond based on the conjugated diene compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin elastomer composition having an improved heat fusion property to a resin.

[0002]

2. Description of the Related Art In recent years, composite moldings of a resin and a rubber-like soft resin have been used in the fields of automobile parts, building material parts, precision equipment parts, sundries and the like. Co-extrusion molding, insert extrusion molding, simultaneous injection molding, insert injection molding, and the like are available as manufacturing techniques for such composite molded products.
In order to obtain a good composite in these methods, there is a method of using an adhesive or a method of increasing the mutual affinity of the resins used. The method using an adhesive has already been industrially used, but it is necessary to check it in advance each time to select an adhesive, and since the number of steps increases, it is not always the best method. I can not say. On the other hand, in the method of increasing the mutual affinity of the resins used, the mutual resins do not always adhere to each other. That is, the present situation is that bonding can be achieved only by combining a specific resin and a specific rubber-like soft resin. Therefore, the present situation is that a universal rubber-like soft resin that can adhere to any resin has not appeared. For example, when a composite molded product of polycarbonate and a rubber-like soft resin is manufactured by such a molding method, very few resins can be heat-sealed with the polycarbonate. Currently, usable resins are limited to some resins having compatibility with polycarbonate such as polyester elastomer. However, the polyester elastomer is inferior in weather resistance and thus cannot be used for outdoor applications, and has the drawback that it has no degree of freedom in hardness (there is no low-hardness product), and thus its use range is limited. Therefore, in order to obtain a composite molded product of a polycarbonate resin and a rubber-like soft resin, it has been essential to use an adhesive. However, the use of the adhesive has a drawback that the manufacturing cost is naturally high. In addition, the conventional solvent-based adhesive,
There is also a drawback that cracks and the like occur in the polycarbonate resin. An object of the present invention is to provide a resin composition which solves the above-mentioned conventional problems and can be heat-fused with various resins and which has practically sufficient physical properties.

[0003]

As a result of earnest studies, the present inventors were able to solve the above-mentioned conventional problems. That is, the present invention is based on the total weight of the following components (a) and (b) and / or (c): (a) ethylene;

[0004]

Embedded image CH ₂ ═C (R ₁ ) —COOR ₂

A copolymer 2 with a (meth) acrylate represented by the formula: wherein R ₁ represents hydrogen or a methyl group, and R ₂ represents hydrogen or an alkyl group having 1 to 10 carbon atoms.
0 to 80% by weight of (b) an ethylene-α-olefin copolymer and (c) at least one vinyl aromatic compound-based polymer block A as a main component and at least one conjugated diene compound as a main component. From a group consisting of hydrogenated block copolymers in which at least 50% by weight of aliphatic double bonds based on the conjugated diene compound are hydrogenated by hydrogenating a block copolymer comprising An olefin-based elastomer composition comprising at least one selected 20 to 80% by weight.

The present invention also provides the components (a) 20 to 8 described above.
The above-mentioned olefin elastomer composition comprises 0% by weight and 80 to 20% by weight of the component (b).

The present invention further relates to the above-mentioned component (a) 20-
The above-mentioned olefin elastomer composition comprises 80% by weight and 80 to 20% by weight of the component (c).

Furthermore, the present invention provides the above-mentioned (a) component 2
The above-mentioned olefinic elastomer composition is obtained by blending 0 to 80% by weight of (b) component 0.1 to 79.9% by weight and (c) component 0.1 to 79.9% by weight. Is.

In the present invention, the content of the acrylic ester comonomer in the component (a) is 10 to 40% by weight.
The above-mentioned olefin elastomer composition is provided.

Further, in the present invention, the component (b) comprises an ethylene-propylene copolymer, an ethylene-propylene-non-conjugated diene copolymer, an ethylene-butene copolymer (a polymer having polyethylene at both ends as a main component). (Including a triblock copolymer) and at least one selected from the group consisting of ethylene-butene-non-conjugated diene polymers,
The above-mentioned olefin elastomer composition is provided.

Furthermore, the present invention provides the above-mentioned olefinic elastomer composition, wherein the conjugated diene compound before hydrogenation in the component (c) is butadiene and / or isoprene. A small amount of polyester elastomer or polyamide elastomer may be added to the olefin elastomer composition.

The present invention will be described in more detail below. As described above, the present invention has practically satisfactory physical properties,
An olefin-based elastomer composition (hereinafter, simply referred to as a composition) that can be heat-fused with various resins. Examples of the resin that can be heat-fused with the composition of the present invention include resins having a melting point of 200 ° C. or less or amorphous resins. Specifically, examples of the resin having a melting point of 200 ° C. or lower include olefin resins such as propylene resin and ethylene resin. Examples of the amorphous resin include vinyl chloride resin, carbonate resin, sulfone resin, phenylene ether resin, ABS resin, styrene resin, and acrylic ester resin.

This composition uses (a) an ethylene-acrylic acid ester copolymer as an essential component, and (b) an ethylene-α-olefin copolymer and / or (c) a hydrogenated block copolymer. It is constituted by blending. Hereinafter, each component will be described in detail.

(A) Ethylene- (meth) acrylate
Polymer The composition of the present invention uses (a) an ethylene- (meth) acrylate copolymer as its essential component. here,
The (meth) acrylate that can be used has 1 to 1 carbon atoms.
Methacrylic acid methyl ester, acrylic acid methyl ester, acrylic acid ethyl ester and the like having 10 are listed, and among them, acrylic acid ethyl ester is preferable. If the number of carbon atoms exceeds 10, cold resistance is deteriorated and flexibility is lost, which is not preferable. The content of the (meth) acrylate comonomer as described above is 10 to 40% by weight, preferably 15 to 30% by weight, based on the copolymer (a). When the content of the (meth) acrylate comonomer is less than 10% by weight, the heat fusion property to the resin exemplified above, for example, the polycarbonate resin is hardly exhibited. On the other hand, if it exceeds 40% by weight, the strength of the composition decreases, which is not preferable. The blending amount of the ethylene- (meth) acrylate copolymer is 20 to 80% by weight, preferably 30 to 80% by weight, based on the total weight of the components (a) and (b) and / or (c). . When it is less than 20% by weight or exceeds 80% by weight, the heat fusion property to the resin is hardly exhibited. Further, if it is used in an amount of more than 80% by weight, it becomes difficult to adjust hardness, which is not preferable.

(B) Ethylene-α-olefin Copolymer (b) The ethylene-α-olefin copolymer that can be used as one component of the composition of the present invention is, for example, ethylene-propylene copolymer rubber or ethylene-propylene copolymer rubber. Propylene-non-conjugated diene rubber, ethylene-butene copolymer rubber (including triblock copolymer with a polymer mainly composed of polyethylene at both ends), ethylene-butene-non-conjugated diene polymer rubber and other olefins as the main component Amorphous random elastic copolymers can be used, and these can be used as a mixture if necessary. Among them, ethylene-propylene copolymer rubber is preferable. The component (b) has the role of adjusting the hardness of the composition in addition to improving the heat fusion property of the composition of the present invention to the resin. The Mooney viscosity of the component (b) is not particularly limited and can be determined according to the desired strength of the composition of the present invention, but the Mooney viscosity ML _{1 + 4} (100 ° C.) = 10 to 10 is preferable. 100.

(C) Hydrogenated Block Copolymer Next, the (c) hydrogenated block copolymer that can be used as one component of the composition of the present invention is disclosed in JP-A-63-112649. Which is obtained by hydrogenating a block copolymer comprising at least one vinyl aromatic compound-based polymer block A and at least one conjugated diene compound-based polymer block B , A-B, A-B-A, B-A-B-A, A
It is a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as -BABA. The hydrogenated block copolymer (c) contains a vinyl aromatic compound in an amount of 6 to 60% by weight, preferably 10 to 5%.
It is preferable to contain 0 wt%.

Further referring to the block structure,
The polymer block A mainly composed of at least one vinyl aromatic compound is a homopolymer of a vinyl aromatic compound,
Alternatively, it is composed of a copolymer containing a vinyl aromatic compound in an amount of more than 50% by weight, preferably 70% by weight or more. Also, at least 1 hydrogenated
Polymer block B mainly composed of individual conjugated diene compounds
Is a homopolymer of a conjugated diene compound, or a conjugated diene compound is more than 50% by weight, preferably 70% by weight.
It is composed of a copolymer containing the above. Further, the polymer block A containing at least one vinyl aromatic compound as a main component and the polymer block B containing at least one hydrogenated conjugated diene compound as a main component are the molecular chains in the respective polymer blocks. The distribution within is not particularly limited, and may be, for example, random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-shaped, or any combination thereof. Good.

(C) As the vinyl aromatic compound constituting the hydrogenated block copolymer, for example, one or more selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and the like. Of these, styrene is the most preferable. The conjugated diene compound before hydrogenation constituting the hydrogenated conjugated diene compound is, for example, one or more of butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butyldiene, or the like. Two or more kinds are selected, and among them, butadiene, isoprene and a combination thereof are preferable.

Here, at least 50% of the aliphatic double bond based on the conjugated diene compound must be hydrogenated. The reason for defining this value is weather resistance. The hydrogenation rate of the aromatic double bond based on the vinyl aromatic compound is not particularly limited, but is usually 98% or more.

The above-mentioned (c) hydrogenated block copolymerization has the role of improving the heat fusion property to the resin of the composition of the present invention, adjusting the hardness, and improving the permanent set in the intermediate temperature range (around 70 ° C.). Have.

Blending Ratio As described above, the composition of the present invention uses (a) an ethylene-acrylic acid ester copolymer as an essential component, and (b) an ethylene-α-olefin copolymer, or It is obtained by blending the hydrogenated block copolymer (c), or by blending the above components (a), (b) and (c) together. Here, when the mixing ratio of each component is clearly shown, (a) ethylene- (meth) acrylate in a two-component system is based on the total weight of the components (a) and (b) and / or (c). Copolymer 20 to 80% by weight, preferably 30 to 80% by weight,
(B) 80 to 20% by weight, preferably 80 to 30% by weight of ethylene-α-olefin copolymer, or (c) 80 to 20% by weight of hydrogenated block copolymer, preferably 70 to 2
It is 0% by weight. In the three-component system, (a) ethylene- (meth) acrylate copolymer 20 to 80% by weight, preferably 30 to 80% by weight, (b) ethylene-α.
-Olefin copolymer 0.1 to 79.9 wt%, preferably 5 to 75 wt%, more preferably 20 to 50 wt%, (c) hydrogenated block copolymer 0.1 to 79.9 wt% , Preferably 5 to 75% by weight, more preferably 20
~ 50% by weight. In the case of a two-component system, if the component (b) or (c) is used in an amount of less than 20% by weight or more than 80% by weight, the heat fusion property to the resin becomes difficult to be exhibited. In the case of a two-component system, if the component (c) is used in an amount of less than 20% by weight, it becomes difficult to adjust the hardness of the composition.

Further, in the present invention, in addition to the above-mentioned components, an inorganic filler may be added and blended, if necessary. This inorganic filler is effective not only for cost reduction as an extender but also for improving the appearance (gloss) of the molded product. As the inorganic filler added here, for example, calcium carbonate, talc, clay, carbon black, magnesium hydroxide, mica, barium sulfate, natural silicic acid,
Examples thereof include synthetic silicic acid, titanium oxide, magnesium oxide and zinc oxide. In the present invention, the amount of these inorganic fillers is not particularly limited and may be arbitrarily added depending on the purpose (heat fusion force to resin, mechanical strength, etc.), but usually in the resulting composition. To 0 to 50
% By weight.

In the present invention, a non-aromatic softening agent for rubber can be added as a softening agent, if necessary. Here, the non-aromatic softening agent for rubber is a softening agent for a mineral oil type rubber, which is generally called a process oil or extender oil used for increasing the softening amount of rubber, improving processability, and has a total carbon number of paraffin chains. Paraffinic occupies 50% or more of carbon number, naphthene ring carbon number is 3 of total carbon number
A naphthene type of 0 to 45% is preferable. The blending amount of the softening agent is not particularly specified in the present invention,
It may be optionally added depending on the purpose (heat fusion strength to resin, hardness), but it is usually from 0 to 70% by weight based on the resulting composition.

Furthermore, if necessary, the composition of the present invention contains a flame retardant, glass fiber, carbon fiber, nylon fiber,
Antioxidants, heat resistance stabilizers, UV absorbers, hindered amine stabilizers, colorants and the like can be added.

As the method for producing the composition of the present invention, a method used for producing a usual resin composition or a rubber composition can be adopted, and a single-screw extruder, a twin-screw extruder, a Banbury mixer, a heating roll, It can be produced by uniformly compounding the components using a melt-kneader such as various kneaders. The set temperature of the processing equipment can be arbitrarily selected from 120 ° C to 300 ° C. Therefore, if the effect of the composition of the present invention of heat fusion to the resin is exhibited,
There is no limitation on the manufacturing method.

The composition of the present invention can be molded by using a generally used thermoplastic resin molding machine, and various molding methods such as injection molding, extrusion molding, blow molding and calender molding are possible. .

[0027]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

The resin composition of the present invention was manufactured as follows. First, each component will be described. (1) (a) ethylene- (meth) acrylate copolymer component (a-1) an ethylene-ethyl acrylate copolymer (ethylene acrylate amount 10% by weight, NUC6221 (manufactured by Nippon Unicar Co., Ltd.)) as a component (a -1). Component (a-2) An ethylene-ethyl acrylate copolymer (ethylene acrylate amount 15% by weight, DPDJ6182 (manufactured by Nippon Unicar Co., Ltd.)) was used as a component (a-2). (Component a-3) Ethylene-ethyl acrylate copolymer (ethylene acrylate amount 25% by weight, WN930 (manufactured by Nippon Unicar Co., Ltd.)) was used as component (a-3). (Component a-4) ethylene-ethyl acrylate copolymer (ethylene acrylate amount 5% by weight, NUC8027
(Manufactured by Nippon Unicar Co., Ltd.) was used as the component (a-4).

(2) (b) Ethylene-α-olefin copolymer (Component b-1) Mooney viscosity ML _{1 + 4} (100 ° C.) = 6
3 ethylene-propylene copolymer rubber (EP961S
P, manufactured by Nippon Synthetic Rubber Co., Ltd., was used as the component (b-1). (Component b-2) ethylene-butene-1 copolymer rubber (E
BM2021P, manufactured by Japan Synthetic Rubber Co., Ltd., as a component (b-
2).

(3) (c) Hydrogenated block copolymer (Component c-1) Polystyrene-Hydrogenated isoprene-Polystyrene structure, bound styrene content 30%
(Septon 4055, manufactured by Kuraray Co., Ltd.) as a component (c-
1) (hydrogenation rate 99%). (Component c-2) Polystyrene-has a structure of hydrogenated butadiene-polystyrene, and has a bound styrene content of 30%.
(Tuftec H1272G (no oil extension), manufactured by Asahi Kasei Co., Ltd.) was used as the component (c-2) (hydrogenation rate 99%).

Subsequently, each of the above components was mixed at a mixing ratio shown in Tables 1 to 3 with a twin screw extruder having a diameter of 37 mm.
Melt kneading was carried out under the condition of 230 ° C. As shown in Tables 1 to 3, Examples 1 to 13 and Comparative Example 1 are based on each composition.
~ 8 compositions were prepared. The hardness, tensile strength, elongation, 100% modulus and compression set of each of the obtained compositions were measured. The results are shown in Tables 1 to 3. The test methods used for various evaluations are as follows. (1) Hardness The hardness was measured by the JIS A type method described in JIS K6301. (2) Tensile strength It was measured by the method described in JIS K6301. 1 sample
A mm-thick press-formed sheet was used, and the test piece was a No. 3 dumbbell. (3) Elongation It was measured by the method described in JIS K6301. (4) 100% modulus Measured by the method described in JIS K6301. (5) Compression set Measured by the method described in JIS K6301. The conditions were 70 ° C. × 22 hours.

Next, length 150 mm, width 25 mm, thickness 4 mm
The resin plate of was prepared by injection molding. The resins used for making the resin plate are as follows. Vinyl chloride resin (VDV003 manufactured by Riken Vinyl Industry Co., Ltd.
0A) Polysulfone (Uder P-1 manufactured by Daigin Amoco Co., Ltd.)
700) Modified polyphenylene ether (Zylon X9102 manufactured by Asahi Kasei Corporation) ABS (JSR ABS38 manufactured by Japan Synthetic Rubber Co., Ltd.) Polystyrene (Stylon G807 manufactured by Asahi Kasei Corporation)
3) Polymethylmethacrylate (Delpet SR8200 manufactured by Asahi Kasei Corporation) Polycarbonate (Upilon S- manufactured by Mitsubishi Gas Chemical Co., Inc.)
3000) High-density polyethylene (110J manufactured by Idemitsu Petrochemical Co., Ltd.) Polypropylene (RB110 manufactured by Tokuyama Soda Co., Ltd.). The injection conditions were the recommended injection molding conditions for each resin.

The resin plate thus prepared was inserted into a mold, and the various compositions of the present invention obtained as described above were injection molded to obtain test pieces as shown in FIGS. 1 and 2. Created. In addition, the composition of each of Examples 1 to 13 and Comparative Examples 1 to 8 was injection-molded to a polycarbonate resin plate to prepare a test piece. A test piece obtained by injection-molding only the composition was prepared. The injection molding conditions are described below. Injection molding conditions Molding machine: FS-120 manufactured by Nissei Plastic Industry Co., Ltd. Molding temperature: 200 ° C. or 250 ° C. Injection speed: 55 mm / sec Injection pressure: 1400 kg / cm ² Holding pressure: 400 kg Injection time: 6 sec Cooling time: 45 seconds

Subsequently, the 180-degree peel strength of each test piece was measured. The measurement was performed by bending the composition of the present invention from the paper portion as shown in FIG. 3 and pulling both ends of the resin plate and the composition in the directions of the arrows. Tables 1 to 3 show measurement results of test pieces including a resin plate of polycarbonate.
Table 4 and Table 5 show the measurement results of test pieces including other resin plates.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

Regarding the results shown in Tables 1 to 3 : Table 1: A composition comprising the ethylene-ethyl acrylate copolymer as the component (a) and the ethylene-α-olefin copolymer rubber as the component (b), It was revealed that the heat fusion property to the polycarbonate resin was excellent. However, the ethylene acrylate content of the component (a) ethylene-ethyl acrylate copolymer is less than 10% (Comparative Example 1).
Does not exhibit heat-sealing properties, and ethylene-
It was also found that the resin compositions containing no α-olefin copolymer rubber (Comparative Examples 2 and 3) also did not exhibit heat fusion properties. Table 2: It was revealed that when the amount of the ethylene-ethyl acrylate copolymer as the component (a) was 20 to 80% by weight based on the weight of the composition, the heat fusion property to the polycarbonate resin was excellent. . In addition, ethylene (b) component
A composition excellent in heat fusion property could not be obtained only with the α-olefin copolymer rubber (Comparative Example 6). Table 3: The composition containing the ethylene-ethyl acrylate copolymer as the component (a) and the hydrogenated block copolymer as the component (c) has excellent heat fusion property to the polycarbonate resin and further has a compression set. Was found to be improved. Further, a composition comprising the ethylene-ethyl acrylate copolymer as the component (a), the ethylene-α-olefin copolymer rubber as the component (b) and the hydrogenated block copolymer as the component (c) is also a polycarbonate resin. It was revealed that the heat fusion property was excellent.

Regarding the results shown in Tables 4 and 5, Tables 4 and 5: Compositions containing the ethylene-ethyl acrylate copolymer as the component (a) and the hydrogenated block copolymer as the component (c) were various resins. It was found that the heat fusion property to In particular, it has been found that the heat-sealing property to vinyl chloride resin, sulfone resin, styrene resin, carbonate resin, ethylene resin, and propylene resin is excellent.

[0042]

The olefin-based elastomer composition obtained by the present invention is an epoch-making composition which is heat-fused with various resins and has practically sufficient physical properties. Therefore, since the adhesive, which has been indispensable in the conventional manufacturing process, is not used, the cost can be greatly reduced.

[Brief description of drawings]

FIG. 1 is a plan view of a test piece composed of the composition of the present invention and various resin plates.

FIG. 2 is a cross-sectional view of a test piece composed of the composition of the present invention and various resin plates.

FIG. 3 is a diagram for explaining a method of measuring 180-degree peel strength.

[Explanation of symbols]

 1 Test piece 2 Composition of the present invention 3 Resin plate 4 Paper A Heat-sealed part

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Toshiaki Izumida 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Sanryo Gas Chemical Co., Ltd. (72) Katsumi Yoshida 5-6-2, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Sanryo Gas Chemical Co., Ltd.

Claims (7)

[Claims] 1. A total of the following components (a) and (b) and / or (c), and (a) ethylene and the general formula: CH ₂ ═C (R ₁ ) —COOR ₂ ( In the formula, R ₁ represents hydrogen or a methyl group, and R ₂ represents hydrogen or an alkyl group having 1 to 10 carbon atoms) and a copolymer with (meth) acrylate represented by 20 to 80% by weight.
And (b) an ethylene-α-olefin copolymer and (c)
A conjugated block copolymer comprising at least one vinyl aromatic compound-based polymer block A and at least one conjugated diene compound-based polymer block B is hydrogenated to obtain the conjugated diene compound. 20 to 80% by weight of at least one kind selected from the group consisting of hydrogenated block copolymers in which at least 50% by weight of aliphatic double bonds based on Elastomer composition. 2. The (a) component 20 to 80 according to claim 1.
The olefinic elastomer composition according to claim 1, which comprises 80% by weight and 80 to 20% by weight of the component (b). 3. The (a) component 20 to 80 according to claim 1.
The olefin elastomer composition according to claim 1, which comprises 80% by weight and 80% by weight of the component (c). 4. The (a) component 20 to 80 according to claim 1.
% Of component (b) and 0.1 to 79.9% by weight of component (c).
The olefin-based elastomer composition described in 1. 5. The olefinic elastomer composition according to claim 1, wherein the content of the acrylic ester comonomer in the component (a) is 10 to 40% by weight. 6. The component (b) is an ethylene-propylene copolymer, an ethylene-propylene-non-conjugated diene copolymer, an ethylene-butene copolymer (triblock copolymer with a polymer mainly composed of polyethylene at both ends). The olefin elastomer composition according to any one of claims 1 to 4, which is at least one selected from the group consisting of a polymer) and an ethylene-butene-nonconjugated diene polymer. 7. The olefin elastomer composition according to any one of claims 1 to 4, wherein the conjugated diene compound before hydrogenation in the component (c) is butadiene and / or isoprene.