JP3185193B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene ether resin composition, and more particularly to a polyphenylene ether resin composition excellent in impact resistance, heat resistance, workability and chemical resistance.

[0002]

2. Description of the Related Art Polyphenylene ether resin (hereinafter referred to as "P
PE) is a resin with excellent heat resistance, mechanical strength, electrical properties, etc., but it is not sufficient in moldability and impact resistance. Commonly used. However, rubber-reinforced polystyrene used in PPE cannot have a high rubber content due to restrictions in the production process, and generally has a low rubber content of about 5 to 10% by weight. Therefore, sufficient impact resistance cannot be imparted to PPE.
To compensate for this drawback, a method of blending a styrene-butadiene-styrene block polymer has been used, but the thermal stability of the butadiene block is poor, causing coloration at the time of high-temperature molding and deterioration of physical properties. In recent years, the heat resistance of PPE compositions has been energetically improved, and the emergence of saturated elastomers to replace highly unsaturated rubbers such as rubber-reinforced polystyrene and styrene-butadiene-styrene block polymers has been strongly desired. ing. As a saturated elastomer, ethylene-propylene copolymer rubber (hereinafter referred to as “EP
Rubber)) and hydrogenated styrene-butadiene-styrene block polymer (hereinafter referred to as “SEBS”). However, EP rubber does not have a segment compatible with PPE. There is a problem that a technique is required, and that SEBS has very poor fluidity itself and gives a PPE composition having poor processability.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and uses a hydrogenated block polymer having a specific structure to provide heat resistance, impact resistance, and molding resistance. An object of the present invention is to provide a PPE composition having excellent processability.

[0004]

Means for Solving the Problems The present invention relates to (1) (A) (A) a weight average molecule comprising polystyrene.
5 to 35% by weight of block segments having an amount of 12,000 or more, preferably 1.3 to 50,000 , and (B) butadiene 50 to 1
The weight average molecular weight of a butadiene (co) polymer or polyisoprene comprising 00% by weight and 0 to 50% by weight of another monomer and having a 1,2-vinyl bond content of 20 to 90% in a butadiene portion is 50,000 or more, preferably 60,000 to 200,000
30 to 94% by weight of a block segment of (C)
The weight average molecular weight comprising polybutadiene having a 1,2-vinyl bond amount of 15% or less is at least 2,000, preferably at least
1 to 60 % by weight of a hydrogenated block polymer obtained by hydrogenating 90% or more of unsaturated double bonds of a linear or branched block polymer having 0.4 to 40,000 block segments of 1 to 35% by weight, and (B) a resin composition comprising 99 to 40 % by weight of a polyphenylene ether resin, and

(2) 100% by weight of the resin composition of the above (1)
Parts with respect, there is provided a resin composition obtained by adding at least one polymer 1-300 weight parts selected from the group consisting of (c) a polyolefin resin, a polyamide resin, a polyester resin.

[0006]

Hereinafter, the present invention will be described in detail. [1] Description of hydrogenated block polymer of component (A) of the present invention The component (A) of the present invention comprises (A) a block segment of 1 to 35% by weight of polystyrene, and (B) butadiene 5
0 to 100% by weight and 0 to 50% by weight of other monomers, and a 1,2-vinyl bond amount of 20 to 9 in a butadiene portion.
A block segment of 30% to 98% by weight of a butadiene (co) polymer which is 0% or polyisoprene;
(C) a block segment comprising 1 to 35% by weight of a polybutadiene having a 1,2-vinyl bond content of 15% or less, wherein each of (A), (B) and (C) is at least 1%.
This is a hydrogenated block polymer obtained by hydrogenating 90% or more of unsaturated double bonds of a linear or branched block polymer having two or more carbon atoms. Specifically, ABC-type triblock polymer, CBA- (ABC) n (where n ≧ 1)
Type linear or branched block polymers.

The component (A) is a block segment made of polystyrene, which determines the compatibility with PPE, and must have a certain size or more. Usually, it is desirable that the content is in the range of 5 to 35% by weight, preferably 10 to 30% by weight, particularly preferably 15 to 25% by weight in the component (A). If the amount of the component (A) is less than 5% by weight, the compatibility with PPE is insufficient, and there is no sufficient improvement effect. On the other hand, if the content exceeds 35% by weight, the performance of the component (a) as an elastomer decreases, and the improvement effect decreases, which is not preferable. The component (A) in the component (A) generally shows good characteristics within the above range, but the molecular weight of the block (A) depends on the molecular weight of the component (A) and is not compatible with PPE by definition according to the composition ratio. The absolute molecular weight for dissolution cannot be determined. The inventors clarified the molecular weight of the block (A) necessary for compatibility with PPE by proceeding with further detailed studies. The weight average molecular weight of the component (A) is usually 12,000 or more, preferably 1.3 to 50,000,
More preferably, the content is controlled within the range of 1.5 to 40,000, and the composition ratio is within the above range, whereby the component (a) having the best balance can be obtained.
If it is less than 12,000, the compatibility with PPE is poor, and the effect of improving impact resistance is insufficient. The upper limit of the molecular weight of the component (A) is not particularly limited, but is usually preferably 50,000 or less. Care must be taken when the amount exceeds 50,000, since the moldability tends to decrease.

Here, the hydrogenated block polymer (a) is
C coupled with ABC type triblock polymer
In the case of a linear or branched block polymer of the type -BA- (ABC) n (where n ≧ 1), the molecular weight of the block (A) (polystyrene block) in the block polymer Is a value obtained by multiplying the molecular weight of the block (A) of the ABC-type triblock polymer before coupling by an integer n. Therefore, in the case of the coupled hydrogenated block polymer, it is necessary that the molecular weight of the block (A) after coupling is within the above range.

The component (B) is a block segment serving as an elastomer component in the component (A), and is a portion directly affecting the degree of improvement in impact resistance. Recent PPE compositions have not only the impact resistance at room temperature but also the low temperature (−30 ° C.).
) Is strongly required. for that reason,
The component (B) needs to have a glass transition temperature as low as possible. The component (B) of the present invention comprises (B ₁ ) 50 to 100% by weight of butadiene and 0 to 50% by weight of another monomer.
And the amount of 1,2-vinyl bonds in the butadiene portion is 2
0-90% butadiene (co) polymer, or (B
₂ ) Block segment composed of polyisoprene.

Since the 1,2-vinyl bond of the butadiene component in (B ₁ ) has a butene structure after hydrogenation, its content directly affects the glass transition temperature of component (B) after hydrogenation. The amount of 1,2-vinyl bond is usually 20 to 90 %, preferably 30 to 60%, more preferably 35 to 50%.
It is. 1,2-vinyl bond amount is less than 20%, or
If the content exceeds 90 %, the low-temperature properties of the component (B) are unpreferably lowered after hydrogenation due to the appearance of crystal structures derived from polyethylene chains and polybutene chains, respectively. Other monomers copolymerizable with butadiene in (B ₁ ) include aromatic vinyl compounds,
Diene compounds, acrylic monomers and the like are mentioned, and styrene, isoprene, butyl acrylate and the like are preferable examples. The copolymerization amount depends on the properties of the monomer, but is usually 1 to 50%, preferably 1 to 40%, more preferably 1 to 30%. When the copolymerization is less than 1%, no improvement effect due to the copolymerization is observed. When a monomer that gives a rigid homopolymer such as styrene is used, 50%
The glass transition temperature of the B ₂ component after hydrogenation Operation outside increases, undesirably low temperature characteristics deteriorate.
The glass transition temperature of the component (B) is generally -35 ° C or lower, preferably -40 ° C or lower, more preferably -45 ° C.
It is below ° C. When the glass transition temperature is higher than -35 ° C, the low-temperature properties of the composition are poor.

The component (B) usually has a content of 30 to 30 in the component (a).
It is desirable to account for 94% by weight, preferably 40-90% by weight, more preferably 50-85% by weight. 30
If the amount is less than 10% by weight, the elastomer component is insufficient, and the impact resistance effect is poor. On the other hand, if it exceeds 94% by weight, it is difficult to ensure compatibility with PPE,
Again, the impact resistance improving effect tends to be inferior, which is not preferable. Similar to the component (A), the inventors examined the molecular weight of the component (B) necessary for improving the impact resistance through detailed studies. The weight average molecular weight of the component (B) is usually 50,000 or more, preferably 60,000 to 200,000, and more preferably 8 to 15,
The component (a) having the best balance can be obtained by controlling the composition within the range of 10,000 and setting the composition ratio within the above range. If it is less than 50,000, the effect of improving impact resistance is insufficient, which is not preferable. Although the upper limit of the molecular weight of the block (B) is not particularly limited, it is usually preferably 200,000 or less. If the amount exceeds 200,000, care must be taken because the molding processability of the composition tends to be inferior.

The component (C) has a 1,2-vinyl bond content of 1
It is a block component made of polybutadiene of 5% or less, and becomes a polyethylene-like structure showing a crystal melting point by hydrogenation. After hydrogenation, the component (C) having a structure similar to polyethylene greatly contributes to the excellent impact resistance improving effect and the good workability of the component (A) of the present invention. For example, a hydrogenated block polymer (AB diblock type) lacking the component (C) has a poor impact resistance improving effect. A hydrogenated block polymer (ABA triblock type) having the component (A) instead of the component (C) has a sufficient impact resistance improving effect, but the flow of the hydrogenated block polymer itself is high. Poor performance leads to poor molding processability of the PPE composition. That is, the present invention relates to (C)
This was made possible by discovering the effect of introducing the components.

The 1,2-vinyl bond content of the component (C) is usually 15% or less, preferably 14% or less, more preferably 13% or less. If the amount of 1,2-vinyl bond exceeds 15%, the crystal melting point derived from the component (C) after hydrogenation decreases. The component (C) forms a crystal structure inside the component (A). This crystal structure acts as a physical crosslinking point, and the component (a) has elastomer elasticity. 1,
(C) after hydrogenation when the amount of 2-vinyl bonds exceeds 15%
The decrease in the crystalline melting point of the component leads to a decrease in the strength of the physical cross-linking point inside the component (A), and the elastomer elasticity of the component (A) deteriorates. Therefore, the effect of improving the impact resistance of the PPE composition decreases, which is not preferable. Component (C) is usually 1 to 35% by weight, preferably 3% by weight of component (A).
It is desirable to account for about 30% by weight, more preferably 5% to 25% by weight. If it is less than 1% by weight, the component (C) cannot form a sufficient crystal structure, and as a result, the effect of improving impact resistance is poor, which is not preferable. On the other hand, if it exceeds 35% by weight, the performance of the component (a) as an elastomer is lowered, and the effect of improving the impact resistance is poor.

The present inventors have conducted detailed studies on the component (C) as well as the components (A) and (B), and have clarified the required molecular weight. The weight average molecular weight of the component (C) is usually at least 2,000, preferably from 0.4 to 40,000, more preferably from 0.1 to 40,000.
The most balanced component (a) can be obtained by controlling the composition within the range of 5 to 25,000 and the composition ratio within the above range. If less than 22,000,
The component (C) in the component (A) cannot form a sufficient crystal structure, and as a result, the effect of improving the impact resistance is poor. Although the upper limit of the molecular weight of the block (C) is not particularly limited, it is usually preferably 40,000 or less. 4
If the number exceeds 10,000, care must be taken because molding workability tends to be inferior. The hydrogenation rate of the component (a) is usually 90% or more, preferably 95% or more, and more preferably 97% or more. If the hydrogenation rate is less than 90%, heat resistance and weather resistance will be reduced, and the impact resistance improving effect will be reduced due to a decrease in the crystal melting point of the component (C).

The component (A) of the present invention may be a mixture of components having different molecular weights. Specifically, component (A) having a weight average molecular weight of less than 80,000 (1) 1 to 50% by weight, component (A) having a weight average molecular weight of 80,000 or more (A-2) 9
A mixture consisting of 9 to 50% by weight and having a low molecular weight (a
Excellent molding processability due to the combination of 1). The component (A-1) is a component (A) having a total weight average molecular weight of less than 80,000, preferably 40 to 80,000, and more preferably 5 to 75,000. Since the component (a-1) is blended for the purpose of mainly improving the fluidity, it is necessary to satisfy all of the above-mentioned requirements for the molecular weight of the components (A), (B) and (C). Absent. The component (a-2) has a weight average molecular weight of 80,000 or more, preferably 8 to 60.
10,000, more preferably 90,000-400,000 component (a).
Since the main purpose of the component (a-2) is to improve impact resistance, it is necessary to satisfy all of the conditions of the components (A), (B) and (C) described above. The composition ratio of (A-1) and (A-2) is usually A-1 / A-2 = 1 to 50/99 to 5
0, preferably 5 to 45/95 to 55, particularly preferably 5 to 30/95 to 70. If (a-1) is less than 1% by weight, there is no fluidity improving effect. Also, (A-1) is 5
Use of more than 0% by weight is not preferable because the effect of improving impact resistance is poor.

The hydrogenated block polymer (a) is obtained by subjecting block C, block B, and block A to living anion polymerization in an organic solvent in the above order, and further hydrogenating the block polymer. Specifically, for example, an organic lithium compound such as sec-butyllithium is used as an initiator, and an organic solvent such as benzene or cyclohexane is used as a polymerization solvent in a first stage under vacuum or a high-purity nitrogen stream. Is polymerized to polymerize the low vinyl polybutadiene block which becomes the block C. Subsequently, a microstructure modifier such as tetrahydrofuran or diethyl ether, and a second
1,3-butadiene for the stage is added, and the high vinyl polybutadiene block to be the block B is polymerized. After completion of the second-stage polymerization, styrene is further added, and a polystyrene block serving as block A is polymerized.
A block polymer consisting of A in order can be obtained. By adding a coupling agent at the completion of polymerization, C-B
-A- (ABC) n type linear or branched block polymer can be obtained.

At the end of the first stage, an appropriate amount of the polymerization solution is sampled and measured by gel permeation chromatography (GPC) to determine the molecular weight of the block (C). Similarly, the molecular weight of the block B of the second stage is obtained by subtracting the molecular weight value of the first stage from the molecular weight value obtained by GPC measurement of the sample at the end of the second stage. The molecular weight of the block A in the third stage can be determined by subtracting the molecular weight values in the first and second stages from the molecular weight values obtained by GPC measurement of the sample in which polymerization has been completed. The hydrogenated block polymer of the present invention is obtained by dissolving the thus obtained block polymer in an inert solvent, at 20 to 150 ° C,
It is obtained by hydrogenation in the presence of a hydrogenation catalyst under pressurized hydrogen of 1 to 100 kg / cm ² . [2] Description of Component (B) of the Present Invention The component (B) is a polyphenylene ether resin represented by the following general formula (I).

[0019]

Embedded image (Wherein, R ₁ , R ₂ , R ₃ and R ₄ represent the same or different residues such as an alkyl group, an aryl group, a halogen atom, a hydrogen atom, and n represents a degree of polymerization.) Specific examples include poly (2,6-dimethylphenylene-1,4-ether) and poly (2,6-dimethylphenylene-1,4-ether).
Diethylphenylene-1,4-ether), poly (2,
6-dibromophenylene-1,4-ether), poly (2-methyl-6-ethylphenylene-1,4-ether), poly (2-chloro-6-methylphenylene-1,
4-ether), poly (2-methyl-6-isopropylphenylene-1,4-ether), poly (2,6-di-
n-propylphenylene-1,4-ether), poly (2-chloro-6-bromophenylene-1,4-ether), poly (2-chloro-6-ethylphenylene-1,
4-ether), poly (2-methylphenylene-1,4)
-Ether), poly (2-chlorophenylene-1,4-)
Ether), poly (2-phenylphenylene-1,4-)
Ether), poly (2-methyl-6-phenylphenylene-1,4-ether), poly (2-bromo-6-phenylphenylene-1,4-ether), poly (2,4 ')
-Methylphenylphenylene-1,4-ether), poly (2,3,6-trimethylphenylene-1,4-ether), copolymers thereof, and styrene-based compound graft copolymers. Can be Particularly preferred are a polymer obtained from 2,6-dimethylphenol and a copolymer obtained from 2,6-dimethylphenol and 2,3,6-trimethylphenol.

The amounts of the components (a) and (b) used in the composition of the present invention are usually (a) / (b) = 1 to 6
0 percent by weight / 99-40% by weight, can be adapted in a wide range of hard resin to a soft reduction <br/> resin. If the component (a) is less than 1% by weight, the effect of improving impact resistance is poor. (A) component is 6
When the content exceeds 0 % by weight, the performance of the obtained composition is (a)
It does not differ much from the performance of the component alone, and is meaningless as a composition.

In the composition of the present invention containing the component ( c)
Te, (c) component is at least one polymer selected from the group consisting polyolefin resin, polyamide resin, a polyester resin. (C) As the component, specifically, polyethylene, polypropylene, polymethylpentene, nylon 6, nylon 6.6, nylon 4.6,
Representative examples include polyethylene terephthalate, polybutylene terephthalate, and polycarbonate. (C) The amount of components used is usually (a) and (b)
1 to 300 parts by weight, preferably 5 to 250 parts by weight, more preferably 10 to 200 parts by weight based on 100 parts by weight of
Parts by weight. When the use amount of the component (c) is less than 1 part by weight, there is no difference in performance from the system without the component (c), and it is meaningless. If the component (c) is used in an amount exceeding 300 parts by weight, the impact resistance, rigidity and the like will be insufficient.
The usage ratio of (a) and (b) is usually (a) / (b) = 1 to 60/99 to 4 with respect to the portion excluding the (c) component.
0 , and the component (a) is in the range of 1 to 40% by weight, particularly preferably 1 to 30% by weight, based on 100 parts by weight of the total of (A), (B) and (C). It is desirable to choose. If the component (a) in the portion excluding the component (c) is less than 1% by weight, the impact resistance is poor. In addition, (a) component
If it exceeds 60 % by weight, the amount of PPE in the composition is insufficient, and heat resistance and rigidity are undesirably reduced.

In the present invention, polystyrene resins such as polystyrene, styrene-α-methylstyrene copolymer, styrene-P-methylstyrene copolymer,
Styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, HIPS resin, ABS resin,
An appropriate amount of AES resin or the like may be blended. Styrene resin has excellent compatibility with PPE,
The processability of the PE composition can be greatly improved.
Although the amount of the polystyrene resin used is not particularly limited, the glass transition temperature (T
g) is reduced and the heat resistance is reduced, so that large quantities should be avoided. Usually, it is desirable to mix and adjust the composition so that the Tg of the composition is in the range of 120 to 190 ° C. by compounding a polystyrene resin.

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

The resin composition of the present invention can be obtained by melt-kneading with an extruder, kneader, Banbury mixer or the like. In producing the resin composition of the present invention, each component may be mixed at once,
A partial mixing method may be used in which a part or all of the seeds or more are premixed, and the remaining components are added and mixed. Further, when using the resin composition of the present invention, glass fibers, carbon fibers, metal fibers, glass beads, glass flakes, wastolite, calcium carbonate, talc, barium sulfate, mica, potassium titanate, aramid fibers, Fillers such as molybdenum sulfide and fluororesin can be added alone or in combination. Among these fillers, glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more. Usually, these fillers are used in a range of 5 to 150 parts by weight based on 100 parts by weight of the resin composition.

Further, various other compounding agents can be added to the composition of the present invention. Examples of the compounding agent include 2,6-di-t-butyl-4-methylphenol,
-(1-methylcyclohexyl) -4,6-dimethylphenol, 2,2-methylene-bis- (4-ethyl-6
-T-butylphenol), 4,4'-thiobis- (6
-T-butyl-3-methylphenol), antioxidants such as dilaurylthiodipropionate, tris (di-nonylphenyl) phosphite, pt-butylphenyl salicylate, 2,2'-dihydroxy-4- Methoxybenzophenone, 2- (2'-hydroxy-4'-n-
UV absorbers such as octoxyphenyl) benzotriazole, paraffin wax, stearic acid, hardened oil,
Lubricants such as stearamide, methylenebisstearamide, n-butyl stearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride, antimony oxide, ammonium hydroxide, zinc borate, tricresyl phosphate, tris (dichloro) Propyl) phosphate, chlorinated paraffin, flame retardants such as tetrabromobutane, hexabromobenzene, tetrabromobisphenol A, antistatic agents such as stearoamidopropyldimethyl-β-hydroxyethylammonium nitrate, titanium oxide, carbon black, etc. Coloring agents, pigments, lubricants and the like. The resin composition of the present invention can be formed into various molded products by injection molding, sheet molding, vacuum molding, irregular-shaped molding, foam molding, blow molding, stampable molding, or the like. The obtained molded article can be used for exterior and interior members of automobiles, various electric / electronic parts, housings, etc. by utilizing its excellent properties.

[0033]

The present invention will be described more specifically with reference to the following examples. In the examples, parts and% are based on weight unless otherwise specified. In addition, the amount of 1,2-vinyl bonds of the polybutadiene in the examples was calculated by the Morero method using an infrared analysis method. The physical properties of the resin composition of the present invention were evaluated by the following methods.

[0034]

[Molding method] The resin compositions having the compounding ratios shown in Tables 3 and 4 were kneaded and extruded using a twin-screw extruder having a barrel temperature of 280 to 300 ° C to form pellets. After drying the obtained pellet, a test piece for measuring physical properties was molded using an injection molding machine at a molding temperature of 280 ° C.

[0035]

[Method for evaluating physical properties] Impact resistance: Measured at 23 ° C. with a １ ／ ″ notch in accordance with ASTM D-256. Solvent resistance: A 1% strain was applied to a test piece (１ ／ ″ UL bar). After being immersed in kerosene and allowed to stand for 48 hours, the state of occurrence of breakage and cracks was observed and evaluated in four stages as follows. A: No break or crack is generated. ；: Small cracks have occurred. Δ: A large crack has occurred. ×: Impact strength at fracture surface: measured at −30 ° C. using a method according to ISO6603-2. The state of the fracture surface was evaluated in three stages as follows. ◎; ductile fracture △: ductile to malleable fracture ×; brittle fracture Workability (MFR): 28 pellets sufficiently dried
The measurement was performed at 0 ° C. under a load of 10 kg (unit: g / 10 minutes).

(A) used in Examples and Comparative Examples
(B) Description of component (c) The component (a) is a hydrogenated block polymer of H-1 to H- 11 shown in Tables 1 and 2. In Tables 3 and 4, H-
13, H-14 is obtained by blending the components (a) having different molecular weights. H-13 is H-3 and block (A) 30
Weight%, block (B) 55 weight%, block (C) 1
It is a mixture obtained by mixing 5% by weight of a hydrogenated block polymer having a weight average molecular weight of 550,000 at 70/30 (wt%). H
No. -14 is a mixture of H-4 and the above-mentioned low molecular weight hydrogenated block polymer in a ratio of 65/35 (wt%).

The component (A-1) is a polymerization reaction of 2,6-xylenol, cupric bromide and di-n-butylamine as catalysts while blowing oxygen at 30 ° C. in a toluene solution. The obtained polyphenylene ether. [Η] (chloroform, 30 ° C.) of A-1 was 0.40. A-2 is the above A-1 50% by weight.
And polystyrene (Mitsui Toatsu Co., Ltd., Toporex 5
00-51) A composition having a glass transition temperature of 142 ° C. after mixing by blending 50% by weight.
No. 3 is 50% by weight of the above A-1 and rubber-modified polystyrene (Kflex HF-76, manufactured by Mitsubishi Polytech Co., Ltd.)
It is a composition having a glass transition temperature of 145 ° C. after mixing by blending 50% by weight.

The component (c) is as follows. B-1; manufactured by Mitsubishi Yuka Co., Ltd., polypropylene MH8 B-2; manufactured by Nippon Petrochemical Co., Ltd., polyethylene staphrene E791 B-3; manufactured by Polyplastics Co., Ltd., polybutylene terephthalate Duranex XD499 B-4 Nippon Unipet Co., Ltd., polyethylene terephthalate unipet RT543 B-5; Toray Co., Ltd., nylon 6.6 Amilan CM
3006

Examples 1 to 15 (formulations and evaluation results are shown in Tables 3 and 4) are resin compositions of the present invention. A composition excellent in impact resistance, chemical resistance, and moldability is obtained. In Comparative Examples 1 to 5 , the hydrogenated block polymers used were outside the scope of the present invention (the structures of the hydrogenated block polymers are shown in Tables 1 and 2). Comparative Example 1
Is an example in which the molecular weight and composition ratio of the block (A) are less than the ranges of the present invention, and the impact resistance and surface impact are inferior due to insufficient compatibility with PPE. Comparative Example 2 is a block (C)
Is an example in which the molecular weight and the composition ratio are below the range of the present invention. Poor surface impact strength. Comparative Example 3 is an example in which the molecular weight and the composition ratio of the block (B) are less than the range of the present invention.
The workability is excellent due to the low molecular weight as a whole, but the impact resistance and surface impact are poor. Comparative Example 4 is an example in which the block (C) is missing. Good workability, but poor impact resistance and surface impact.
Comparative Example 5 is different from block (A) in place of block (C).
Are examples attached to both ends. Good impact resistance and surface impact, but poor workability.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

In order to improve the impact resistance of a polyphenylene ether-based resin composition, various rubbery polymers have been studied for blending, but the balance of impact resistance, moldability and heat stability has been studied. It is difficult to obtain an excellent composition. The present invention provides a polyphenylene ether-based resin composition having an excellent balance of impact resistance, moldability, and heat stability by using a hydrogenated block polymer having a specific structure. It is suitable as a material for large molded articles such as materials and exterior / interior articles of automobiles, and has great industrial value.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 101/00 C08L 101/00 (72) Inventor Toshio Teramoto 2-11-24 Tsukiji, Chuo-ku, Tokyo Nippon Gosei Rubber Co., Ltd. (56) References JP-A-2-133406 (JP, A) JP-A-2-269138 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 53/02 C08L 23 / 00 C08L 67/02 C08L 71/12 C08L 77/00 C08L 101/00

Claims (3)

(57) [Claims] (1) Weight of (A) polystyrene
Block segments 5 to 3 having an average molecular weight of 12,000 or more
5% by weight, (B) butadiene (co) weight consisting of 50 to 100% by weight of butadiene and 0 to 50% by weight of another monomer, and having a 1,2-vinyl bond amount of 20 to 90% in a butadiene portion. Weight average of coalesced or polyisoprene
30 to 94% by weight of block segments with a size of 50,000 or more
And (C) a polybutadiene having a 1,2-vinyl bond amount of 15% or less and a weight average molecular weight of 2,000 or more.
90% of unsaturated double bonds of a linear or branched block polymer having 1 to 35% by weight of a block segment
1 to 60 % by weight of the hydrogenated block polymer thus hydrogenated, and (b) polyphenylene ether resin 99 to 4
A resin composition comprising 0 % by weight. 2. (A) Weight of (A) Polystyrene
Block segments 5 to 3 having an average molecular weight of 1.3 to 50,000
5% by weight, (B) butadiene (co) weight consisting of 50 to 100% by weight of butadiene and 0 to 50% by weight of another monomer, and having a 1,2-vinyl bond amount of 20 to 90% in a butadiene portion. Weight average of coalesced or polyisoprene
The weight average molecular weight of 30 to 94 % by weight of a block segment having a molecular weight of 60,000 to 200,000 and (C) polybutadiene having a 1,2-vinyl bond amount of 15% or less is 0.4 to 4,
Of unsaturated double bonds of a linear or branched block polymer having 1 to 35% by weight of
% To 60 % by weight of a hydrogenated block polymer which is hydrogenated by at least
A resin composition comprising 40 % by weight. 3. The resin composition 10 according to claim 1 or 2.
A resin composition comprising (C) 1 to 300 parts by weight of at least one polymer selected from the group consisting of a polyolefin-based resin, a polyamide-based resin, and a polyester-based resin with respect to 0 parts by weight.