JPH05320471A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in heat resistance, impact resistance and moldability by mixing a hydrogenated block polymer of a specified structure with a polyphenylene ether. CONSTITUTION:This resin composition is prepared by mixing 99-1wt.% polyphenylene ether resin with 1-99wt.% hydrogenated block polymer prepared by hydrogenating at least 90% of the double bonds of a linear or branched block polymer comprising 5-35wt.% block segments comprising polystyrene, 30-94wt.% block segments comprising a butadiene (co)polymer comprising 50-100wt.% butadiene and 0-50wt.% other monomers and having a 1,2-vinyl bond content in the butadiene part of 20-90% or polyisoprene and 1-35wt.% block segments comprising polybutadiene having a 1,2-vinyl bond content of 15% or below.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyphenylene ether resin composition, and more particularly to a polyphenylene ether resin composition having excellent impact resistance, heat resistance, processability and chemical resistance.

[0002]

2. Description of the Related Art Polyphenylene ether resin (hereinafter referred to as "P
PE) is a resin that has excellent heat resistance, mechanical strength, electrical properties, etc., but it is not sufficient in moldability and impact resistance. Commonly used. However, the rubber-reinforced polystyrene used in PPE cannot have a high rubber content due to restrictions in its manufacturing process, and the rubber content is generally as low as 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 is used, but the thermal stability of the butadiene block is poor, which causes coloring and deterioration of physical properties during high temperature molding. Further, in recent years, the heat resistance of PPE-based compositions has been energetically improved, and the emergence of a saturated elastomer replacing a highly unsaturated rubber such as a rubber-reinforced polystyrene or a styrene-butadiene-styrene block polymer is strongly desired. ing. As a saturated elastomer, ethylene-propylene copolymer rubber (hereinafter referred to as "EP
Rubber)) and hydrogenated products of styrene-butadiene-styrene block polymers (hereinafter referred to as “SEBS”), but EP rubber does not have a segment compatible with PPE, and therefore has a special compatibilization property. There is a problem that a technique is required, and SEBS itself has extremely poor fluidity and gives a PPE composition having poor processability.

[0003]

The present invention has been made against the background of the above-mentioned problems of the prior art. By using a hydrogenated block polymer having a specific structure, heat resistance, impact resistance and molding are improved. An object is to provide a PPE composition having excellent processability.

[0004]

Means for Solving the Problems The present invention comprises (1) (a) 5 to 35% by weight of a brog segment composed of (A) polystyrene, and (B) 50 to 100 butadiene.
30 to 94% by weight of a block segment consisting of a butadiene (co) polymer or polyisoprene having a 1,2-vinyl bond content of 20 to 90% in the butadiene part and comprising 0 to 50% by weight of other monomers. % And (C) 1,2
90% of unsaturated double bonds of a linear or branched block polymer having 1 to 35% by weight of a block segment consisting of polybutadiene having a vinyl bond content of 15% or less.
% Or more hydrogenated block polymer 1 to 99% by weight, and (b) polyphenylene ether resin 99 to
1% by weight of a resin composition, and

(2) Hydrogenated block polymer (a) 1 to
To 100 parts by weight of a composition composed of 99% by weight and a polyphenylene ether resin of 99 to 1% by weight, (1) at least one polymer selected from the group consisting of a polyolefin resin, a polyamide resin, and a polyester resin 1 to Three
A resin composition containing 100 parts by weight, and

(3) 100 parts by weight of the hydrogenated block polymer (a) as the component (a) is at least selected from the group consisting of acid anhydride groups, carboxyl groups, hydroxyl groups, amino groups, oxazoline groups, and epoxy groups. A modified hydrogenated block polymer (a ′) modified with 0.01 to 20 parts by weight of an unsaturated compound having one kind of functional group is used, and the resin composition according to the above (1) or (2) is used. Is provided.

The present invention will be described in detail below. [1] Description of Hydrogenated Block Polymer of Component (A) of the Present Invention The component (A) of the present invention comprises (A) polystyrene block segments of 1 to 35% by weight, and (B) butadiene 5
It is composed of 0 to 100% by weight and 0 to 50% by weight of other monomers, and the amount of 1,2-vinyl bond in the butadiene portion is 20 to 9%.
Block segment consisting of 0% butadiene (co) polymer or polyisoprene 30 to 98% by weight,
(C) 1 to 35% by weight of a block segment consisting of polybutadiene having a 1,2-vinyl bond content of 15% or less, and at least 1 of each of (A), (B) and (C)
It is a hydrogenated block polymer obtained by hydrogenating 90% or more of the unsaturated double bond of a linear or branched block polymer having one unit. Specifically, an A-B-C type triblock polymer, C-B-A- (A-B-C) n (provided that n ≧ 1).
Type linear or branched block polymer.

The component (A) is a block segment made of polystyrene, which is a part that determines the compatibility with PPE, and must have a certain size or more. Usually, it is desirable that the amount 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 will be insufficient, and there will be no sufficient improvement effect. On the other hand, if it exceeds 35% by weight, the performance of the component (A) as an elastomer is deteriorated and the improvement effect is deteriorated, which is not preferable. The component (A) in the component (A) usually exhibits good properties within the above range, but the molecular weight of the block (A) depends on the molecular weight of the component (B) in the definition based on the composition ratio, and it is incompatible with PPE. The absolute molecular weight for dissolution cannot be defined. The inventors have clarified the molecular weight of the block (A) necessary to be compatible with PPE by proceeding with more 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, it is controlled within the range of 1.5 to 40,000, and the composition ratio is within the above range, so that the most balanced component (a) can be obtained.
If it is less than 12,000, the compatibility with PPE is poor and the impact resistance improving effect is insufficient. The upper limit of the molecular weight of the component (A) is not particularly limited, but it is usually preferably 50,000 or less. If it exceeds 50,000, the moldability tends to decrease, so caution is required.

Here, the hydrogenated block polymer (a) is
C coupled with an ABC type triblock polymer
In the case of a -BA- (A-B-C) n (where n ≧ 1) type linear or branched block polymer, 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 a 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 that directly affects the degree of impact resistance improvement. Recent PPE compositions not only have impact resistance at room temperature, but also at low temperature (-30 ° C).
Impact resistance is also 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 ) budadiene 50 to 100% by weight and other monomers 0 to 50% by weight.
And the amount of 1,2-vinyl bonds in the butadiene part is 2
0-90% butadiene (co) polymer, or (B
₂ ) A 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 1,2-vinyl bond content is usually 20 to 80%, preferably 30 to 60%, more preferably 35 to 50%.
Is. When the 1,2-vinyl bond content is less than 20% or more than 80%, the low-temperature characteristics of the component (B) are extremely low due to the appearance of crystal structures derived from polyethylene chain and polybutene chain, respectively, after hydrogenation. It is not preferable because it decreases to. Further, as the other monomer copolymerizable with butadiene in (B ₁ ), an aromatic vinyl compound,
Examples thereof include diene compounds and acrylic monomers, with styrene, isoprene, butyl acrylate and the like being preferred. 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 amount is less than 1%, no improvement effect due to the copolymerization is observed. When using a monomer that gives a rigid homopolymer such as styrene, 50%
If it is used in excess of this, the glass transition temperature of the B ₂ component after hydrogenation rises, and the low temperature characteristics deteriorate, which is not preferable.
The glass transition temperature of the component (B) is usually -35 ° C or lower, preferably -40 ° C or lower, and more preferably -45.
It is below ℃. When the glass transition temperature is higher than -35 ° C, the low temperature characteristics of the composition are poor.

The component (B) is usually 30 to 30% in the component (A).
It is desirable to occupy 94% by weight, preferably 40 to 90% by weight, more preferably 50 to 85% by weight. Thirty
If it is less than 10% by weight, the elastomer component is insufficient and the impact resistance effect is poor, which is not preferable. If it exceeds 94% by weight, it becomes difficult to ensure compatibility with PPE,
After all, the impact resistance improving effect tends to be inferior, which is not preferable. Similar to the component (A), the detailed study by the inventors has clarified the molecular weight of the component (B) necessary for improving the impact resistance. The weight average molecular weight of the component (B) is usually 50,000 or more, preferably 60 to 200,000, more preferably 8 to 15
The most balanced component (a) can be obtained by controlling the content within the range of 10,000 and the composition ratio within the above range. If it is less than 50,000, the impact resistance improving effect is insufficient, which is not preferable. The upper limit of the molecular weight of the block (B) is not particularly limited, but it is usually preferably 200,000 or less. If it exceeds 200,000, the molding processability of the composition tends to be inferior, so caution is required.

The component (C) has a 1,2-vinyl bond content of 1
It is a block component composed of 5% or less of polybutadiene and has a polyethylene-like structure showing a crystalline melting point by hydrogenation. The component (C) having a polyethylene-like structure after hydrogenation contributes greatly to the excellent impact resistance improving effect of the component (a) of the present invention and good processability. For example, a hydrogenated block polymer (AB diblock type) lacking the component (C) has a poor impact resistance improving effect. Further, the hydrogenated block polymer having the component (A) instead of the component (C) (ABA triblock type) has a sufficient impact resistance improving effect, but the flow of the hydrogenated block polymer itself. Since the property is poor, the molding processability of the PPE composition becomes poor. That is, the present invention provides (C)
It was made possible by discovering the effect of introducing the ingredients.

The 1,2-vinyl bond content of the component (C) is usually 15% or less, preferably 14% or less, more preferably 13% or less. When the 1,2-vinyl bond content exceeds 15%, the crystal melting point derived from the component (C) after hydrogenation is lowered. 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,
2-vinyl bond content exceeds 15% (C) after hydrogenation
A decrease in the crystalline melting point of the component leads to a decrease in the strength of the physical crosslinking point inside the component (a), and the elastomer elasticity of the component (a) deteriorates. Therefore, the impact resistance improving effect of the PPE composition decreases, which is not preferable. The component (C) is usually 1 to 35% by weight, preferably 3 in the component (A).
It is desirable to occupy 30 to 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 impact resistance improving effect 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 deteriorated and the effect of improving impact resistance is inferior, which is not preferable.

The inventors conducted a detailed study of the component (C) as well as the components (A) and (B), and clarified the required molecular weight. The weight average molecular weight of the component (C) is generally 20,000 or more, preferably 0.4 to 40,000, more preferably 0.
The most balanced component (a) can be obtained by controlling the amount within the range of 5 to 25,000 and setting the composition ratio within the above range. Below 0.2 million,
In the component (a), the component (C) cannot form a sufficient crystal structure, resulting in poor impact resistance improving effect, which is not preferable. The upper limit of the molecular weight of the block (C) is not particularly limited, but it is usually preferably 40,000 or less. Four
If it exceeds 10,000, the moldability tends to be poor, so caution is required. The hydrogenation rate of the component (a) is usually 90% or more, preferably 95% or more, more preferably 97% or more. When the hydrogenation rate is less than 90%, the heat resistance and weather resistance are lowered, and the impact resistance improving effect is lowered due to the lowering of the crystal melting point of the component (C).

The component (a) of the present invention may be a mixture of substances having different molecular weights. Specifically, 1 to 50% by weight of the component (a) (a-1) having a weight average molecular weight of less than 80,000, and the component (a-2) 9 having a weight average molecular weight of 80,000 or more (a-2) 9
It is a mixture consisting of 9 to 50% by weight, and has a low molecular weight (e-
The compounding of 1) makes it excellent in moldability. The component (a-1) is the component (a) having a total weight average molecular weight of less than 80,000, preferably 40,000 to less than 80,000, and more preferably 50 to 75,000. Since the component (a-1) is added mainly for the purpose of improving the fluidity, it is necessary to satisfy all the conditions of the necessary molecular weights of the components (A), (B) and (C) described above. Absent. The component (a-2) has a weight average molecular weight of 80,000 or more, preferably 8 to 60.
And more preferably 90-400,000 (a) component.
Since the main purpose of the component (a-2) is to improve impact resistance, it is necessary to satisfy all 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 5-45 / 95-55, particularly preferably 5-30 / 95-70. If the content of (a-1) is less than 1% by weight, there is no fluidity improving effect. Also, (a-1) is 5
When it is used in an amount of more than 0% by weight, the impact resistance improving effect is poor, which is not preferable.

The hydrogenated block polymer (ii) can be obtained by subjecting block C, block B and block A to living anion polymerization in the above-mentioned order in an organic solvent, and further hydrogenating this block polymer. Specifically, 1,3-butadiene is used, for example, with an organic lithium compound such as sec-butyllithium as an initiator, under vacuum or under a high-purity nitrogen stream, and an organic solvent such as benzene or cyclohexane as a polymerization solvent in the first stage. Is polymerized to polymerize the low vinyl polybutadiene block to be the block C. Then, 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 was further added to polymerize the polystyrene block to be the block A, and CB-
A block polymer composed of A can be obtained. By adding a coupling agent when the polymerization is completed, CB
A -A- (A-B-C) 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 obtain the molecular weight of 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 step can be determined by subtracting the molecular weight values of the first step and the second step from the molecular weight values obtained by GPC measurement of the sample in which the polymerization is completed. The hydrogenated block polymer of the present invention is prepared by dissolving the block polymer thus obtained in an inert solvent,
It can be obtained by hydrogenation in the presence of a hydrogenation catalyst under a hydrogen pressure 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]

[Chemical 1] (In the formula, 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 and a hydrogen atom, and n represents the degree of polymerization.) Of the polyphenylene ether resin Specific examples include poly (2,6-dimethylphenylene-1,4-ether) and poly (2,6-
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).
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), etc., and their copolymers, and their styrene compound graft copolymers. Be done. Particularly preferred are polymers obtained from 2,6-dimethylphenol and copolymers obtained from 2,6-dimethylphenol and 2,3,6-trimethylphenol.

The amounts of the components (a) and (b) in the composition of claim 1 (hereinafter referred to as composition 1) are usually (a) / (b) = 1 to 99% by weight / 99 to 1 weight%
Therefore, it can be applied in a wide range from coin resin to soft resin. When the resin composition of the present invention is used as a coin resin, the amounts of (a) and (b) used are preferably (a) 1 to 70% by weight and (b) 99 to 30% by weight. More preferably, (a) 1 to 60% by weight, (b) 99 to
It is within the range of 40% by weight. If (a) is less than 1% by weight, the impact resistance improving effect is poor. When the content of (a) exceeds 99% by weight, the performance of the composition obtained is comparable to the performance of (a) alone, and it is meaningless to make a composition.

The composition according to claim 2 (hereinafter referred to as composition 2) comprises a polyolefin resin, a polyamide resin and a polyester resin as the components (a), (b) and (c). It is a multi-component composition using at least one polymer selected. Specific examples of the component (c) include polyethylene, polypropylene, polymethylpentene, nylon 6, nylon 6.6, nylon 4.6, polyethylene terephthalate, polybutylene terephthalate, and polycarbonate. The amount of component (c) used is usually (a)
1 to 300 parts by weight, preferably 5 to 250 parts by weight, and more preferably 1 to 100 parts by weight of (b).
It is 0 to 200 parts by weight. When the amount of the component (c) used is less than 1% by weight, there is no difference in performance from the system in which the component (c) is not added, which is meaningless. If the component (c) is used in an amount of more than 300 parts by weight, impact resistance and rigidity will be insufficient, which is not preferable. The usage ratio of (a) and (b) is usually (i) / (b) = 1 to 99 / with respect to the portion excluding the component (c).
99-1 (% by weight), preferably 1-80 / 99-2
0, more preferably 1 to 70/99 to 30, and 1 to 40% by weight of the component (a), particularly preferably 100 parts by weight of the total of (a), (b) and (c). 1 to
It is desirable to select it in the range of 30% by weight. The component (a) in the portion excluding the component (c) is 1% by weight.
If it is less than 1, the impact resistance is poor. On the other hand, when the amount of the component (a) exceeds 99% by weight, the amount of PPE in the composition becomes insufficient, and the heat resistance, rigidity, etc. decrease, which is not preferable.

In the present invention, a polystyrene resin such as polystyrene, styrene-α-methylstyrene copolymer, styrene-P-methylstyrene copolymer,
Styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, HIPS resin, ABS resin,
You may mix | blend an appropriate amount of AES resin etc. Styrene-based resin has excellent compatibility with PPE,
It is possible to greatly improve the processability of the PE-based composition.
The amount of the polystyrene resin used is not particularly limited, but the glass transition temperature (T
Use in large amounts should be avoided, as g) will decrease and heat resistance will decrease. Normally, it is desirable to adjust the Tg of the composition to be in the range of 120 to 190 ° C. by blending with a polystyrene resin.

Next, the composition according to claim 3 (hereinafter referred to as composition 3) will be described in detail. Composition 3 is
As the component (a), with respect to 100 parts by weight of the component (a), an acid anhydride group, a carboxyl group, a hydroxyl group, an amino group,
Unsaturated compounds having at least one functional group selected from the group of oxazoline groups and epoxy groups 0.01-
20 parts by weight of the modified hydrogenated block polymer (a ′) bonded by graft polymerization or the like is used. The method for obtaining the modified hydrogenated block polymer (a ′) is a method for producing a hydrogenated block polymer by a known grafting reaction of an unsaturated compound having a functional group, for example, in the presence of a radical generator, specifically, an organic peroxide. The polymer and the unsaturated compound having a functional group can be industrially and simply produced by a method of heating, melting and mixing. Hydrogenated block polymer (ii)
The following can be mentioned as a monomer for adding a functional group to. Examples of the acid anhydride group-containing monomer include acid anhydride compounds such as maleic anhydride, itaconic anhydride, and citraconic anhydride. Examples of the carboxyl group-containing monomer include monoamides such as unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, monoalkyl esters represented by the following general formula (II), etc. Is mentioned.

[0024]

[Chemical 2] (In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 2 to 6 carbon atoms, R ₃ is a phenylene group, a cyclohexylene group, an alkylene group having 2 to 6 carbon atoms, or an unsaturated hydrocarbon group. Examples of the hydroxyl group-containing monomer include a hydroxyl group-containing vinyl compound represented by the following general formula (III).

[0025]

[Chemical 3] (In the formula, R ₁ and R ₂ are the same as described above) Examples of the epoxy group-containing monomer include epoxy group-containing vinyl compounds represented by the following general formulas (IV) to (V).

[0026]

[Chemical 4] (In the formula, R ₄ represents a hydrogen atom, a methyl group or a lower alkyl substituted with a glycidyl ester group.)

[0027]

[Chemical 5] Examples of the amino group-containing monomer (wherein R ₄ is the same as above) include vinyl monomers having an amino group or a substituted amino group represented by the following formula (VI).

[0028]

[Chemical 6] (In the formula, R ₅ represents a hydrogen atom, a methyl group or an ethyl group, and R ₆ represents an alkyl group having 1 to 12 carbon atoms and 2-1 to 2 carbon atoms.
2 represents an alkanoyl group having 2 carbon atoms, a phenyl group having 6 to 12 carbon atoms, a cycloalkyl group, or a derivative thereof. )
Specific examples of the amino group-containing monomer include acrylic acid such as aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, and cyclohexylaminoethyl methacrylate. Or esters of methacrylic acid, vinylamines such as N-vinyldiethylamine and N-acetylvinylamine, allylamines such as allylamine, methallylamine, N-methylallylamine, acrylamide, methacrylamide, N-methylacrylamide and the like (meth) Examples thereof include acrylamides and aminostyrenes such as P-aminostyrene. Moreover, vinyl oxazoline is mentioned as an oxazoline group containing monomer. Preferred examples of these functional group-containing monomers include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, hydroxyethylene methacrylate, hydroxypropyl methacrylate, Examples thereof include hydroxyethyl acrylate, hydroxypropyl acrylate, dimethylaminoethyl methacrylate, vinyloxazoline and the like. Further, as the functional group-containing monomer, a substituted arylmaleimide compound represented by the following general formula (VII) is also an example of preferable examples.

[0029]

[Chemical 7] (In the formula, R ₇ is —OH, —OCH ₃ , —Cl, —COO.
It is a functional group selected from H and -NO ₂ and is attached to the o-, m-, or p-position of the benzene nucleus. ) This general formula (V
A preferred example of the substituted arylmaleimide compound represented by II) is N- (o-carboxylphenyl).
Maleimide, N- (p-carboxylphenylmaleimide), N- (p-chlorophenyl) maleimide, N-
(M-hydroxyphenyl maleimide), N- (p-hydroxyphenyl) maleimide and the like.

The amount of the unsaturated compound having a functional group to be graft-polymerized is usually 0.01 to 20 parts by weight, based on 100 parts by weight of the unmodified hydrogenated block polymer (a).
The amount is preferably 0.02 to 15 parts by weight, more preferably 0.05 to 10 parts by weight. If it is less than 0.01 part by weight, the concentration of the functional group introduced is too low to be effective. 20
If the amount is more than parts by weight, problems such as gelation due to chemical reaction between introduced functional groups and thermal stability are likely to occur, which is not preferable. The modified hydrogenated block polymer (a ′) is produced by mixing the hydrogenated block polymer (a), an unsaturated compound having a functional group and an auxiliary agent for activating the graft reaction with a mixture such as a twin-screw extruder. The method of kneading with and the grafting reaction during kneading is industrially the simplest.
Organic peroxides are most preferred as the activation aid used. Specifically, one having a one-minute half-life temperature of 150 ° C. or higher is preferable in the manufacturing process, and for example, 2,5-
Di-methyl-2,5-di-benzoyl-peroxyhexane, n-butyl-4,4-di-t-butylperoxyvalerate, dicumyl peroxide, t-butylperoxybenzoate, di-t- Butyl peroxy-di-
Isopropylbenzene, t-butylcumyl peroxide, 2,5-di-methyl-2,5-di-t-butylperoxyhexane, di-t-butylperoxide, 2,
5-di-methyl-2,5-di-t-butylperoxyhexyne-3 and the like are examples of preferable ones. The amount of organic peroxide used is usually the active oxygen concentration in the organic peroxide.
It is desirable to be in a range of equimolar to 3 times the molar amount of the unsaturated bond in the compounded functional group-containing unsaturated compound. If it is less than equimolar, the reaction rate of the grafting reaction is low. When it is used in an amount of 3 times by mole or more, a side reaction other than the grafting reaction, for example, a cross-linking reaction proceeds and gelation easily occurs, which is not preferable. Composition 3 is characterized by the introduction of a functional group into PPE.
It is the point that the compatibility with other components, specifically, polyester resin and polyamide resin is improved. Therefore, in the composition 3, a composition showing more excellent performance can be obtained in the system using the component (c).

The resin composition of the present invention can be obtained by melt-kneading with an extruder, a kneader, a Banbury mixer or the like. In producing the resin composition of the present invention, the respective components may be mixed at once,
It is also possible to use a divided mixing method in which a part or the whole of at least one kind is pre-mixed and then the remaining components are added and mixed. Further, when using the resin composition of the present invention, glass fiber, carbon fiber, metal fiber, glass beads, glass flakes, worstrite, calcium carbonate, talc, barium sulfate, mica, potassium titanate, aramid fiber, two Fillers such as molybdenum sulfide and fluororesins can be added alone or in combination. Among these fillers, glass fiber and carbon fiber 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 the range of 5 to 150 parts by weight with respect to 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 and 2
-(1-Methylcyclohexyl) -4,6-dimethylphenol, 2,2-methylene-bis- (4-ethyl-6)
-T-butylphenol), 4,4'-thiobis- (6
-T-butyl-3-methylphenol), dilaurylthiodipropionate, antioxidants such as tris (di-nonylphenyl) phosphite, pt-butylphenyl salicylate, 2,2'-dihydroxy-4- Methoxybenzophenone, 2- (2'-hydroxy-4'-n-
Octoxyphenyl) benzotriazole and other UV absorbers, paraffin wax, stearic acid, hardened oil,
Lubricants such as stearamide, methylenebis stearamide, 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, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A and other flame retardants, stearoamidopropyldimethyl-β-hydroxyethylammonium nitrate and other antistatic agents, titanium oxide, carbon black, etc. Colorants, pigments, lubricants, and the like. The resin composition of the present invention can be molded into various molded articles by injection molding, sheet molding, vacuum molding, profile molding, foam molding, blow molding, stampable molding, or the like. The obtained molded product can be used for exterior / interior members of automobiles, various electric / electronic-related parts, housings and the like by utilizing its excellent properties.

[0033]

EXAMPLES The present invention will be described more specifically below with reference to examples. In the examples, parts and% are based on weight unless otherwise specified. The 1,2-vinyl bond content of polybutadiene in the examples was calculated by the Morello method using infrared analysis. 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 pellets, a test piece for measuring physical properties was molded using an injection molding machine at a molding temperature of 280 ° C.

[0035]

[Physical property evaluation method] Impact resistance: Measured in accordance with ASTM D-256 at 23 ° C with a 1/4 "notch. Solvent resistance: 1% strain is applied to a test piece (1/8" UL bar), After soaking in kerosene and leaving it for 48 hours, the state of breakage and cracks was observed and evaluated in the following four grades. ⊚: No breakage or cracking occurred. ◯: A small crack has occurred. Δ: Large cracks have occurred. X: Fracture surface impact strength: 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 Δ: Ductile to conformable fracture ×: Brittle fracture Workability (MFR): using sufficiently dried pellets, 28
It was measured at 0 ° C. and a load of 10 kg (unit: g / 10 minutes).

(A) used in Examples and Comparative Examples,
Description of components (b) and (c) Component (a) is a hydrogenated block polymer of H-1 to H-12 shown in Tables 1 and 2. In the table, H-5 and H-6 are
These are examples of modified hydrogenated block copolymers (a ′) obtained by grafting 100 parts by weight of hydrogenated block polymers with 1 part of maleic anhydride and allyl glycidyl ether. Further, in Tables 3 and 4, H-13 and H-14 are blends of the component (a) having different molecular weights. H-13 is
H-3 and block (A) 30% by weight, block (B) 5
5% by weight, 15% by weight of block (C), 70/30 (wt.) Of a hydrogenated block polymer having a weight average molecular weight of 55,000.
%). H-14 is 65/35 (wt%) of H-4 and the above-mentioned low molecular weight hydrogenated block polymer.
%).

Component (A) A-1 is 2,6-xylenol, cupric bromide and di-n-butylamine as catalysts, and a polymerization reaction is carried out in a toluene solution at 30 ° C. while blowing oxygen. It is the obtained polyphenylene ether. [Η] of A-1 (chloroform, 30 ° C) was 0.40. A-2 is 50% by weight of the above A-1
And polystyrene (Mitsui Toatsu Co., Ltd., Topolex 5)
00-51) is a composition in which 50% by weight is blended, and the glass transition temperature after mixing is 142 ° C.
3 is 50% by weight of A-1 and rubber-modified polystyrene (Mitsubishi Flex Tech Co., Ltd., Cuflex HF-76).
It is a composition in which 50% by weight is blended, and the glass transition temperature after mixing is 145 ° C.

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

Examples 1 to 18 (compounding recipes and evaluation results are shown in Tables 3 and 4) are resin compositions of the present invention. By adding a hydrogenated block polymer having a specific structure, A composition having excellent impact resistance, chemical resistance, and moldability has been obtained. In Comparative Examples 1 to 6, the hydrogenated block polymers used are 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 the composition ratio of the block (A) are less than the ranges of the present invention, and the compatibility with PPE is insufficient and the impact resistance and surface impact are poor. Comparative Example 2 is block (C)
Is an example in which the molecular weight and the composition ratio are less than the range of the present invention. Inferior surface impact strength. Comparative Example 3 is an example in which the molecular weight and composition ratio of the block (B) are below the range of the present invention.
Since it has a low molecular weight as a whole, it is excellent in workability, but inferior in impact resistance and surface impact. Comparative Example 4 is an example lacking the block (C). Good workability, but poor impact resistance and surface impact.
In Comparative Example 5, the block (A) was used instead of the block (C).
Is an example with both ends attached. Good impact resistance and surface impact, but poor workability.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

EFFECTS OF THE INVENTION In order to improve the impact resistance of polyphenylene ether resin compositions, various rubbery polymers have been studied so far. However, the balance of impact resistance, molding processability and thermal stability has been studied. It is difficult to obtain an excellent composition. The present invention, by using a hydrogenated block polymer having a specific structure, to obtain a polyphenylene ether-based resin composition having an excellent balance of impact resistance, molding processability, and thermal stability, in particular instrument panel core It is suitable as a material for large molded products such as wood and automobile exterior / interior products, and has great industrial value.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Reference number within the agency FI Technical display location C08L 71/12 LQP 9167-4J 77/00 LQS 9286-4J LQV 9286-4J 101/00 LSY 7242-4J (72 ) Inventor Toshio Teramoto 2-11-24 Tsukiji, Chuo-ku, Tokyo, Japan Synthetic Rubber Co., Ltd.

Claims (3)

[Claims] 1. (A) 5 to 35% by weight of a block segment (A) polystyrene, and (B) butadiene 50
-100% by weight and other monomers 0-50% by weight,
And the amount of 1,2-vinyl bonds in the butadiene portion is 20 to 90
% Of butadiene (co) polymer or polyisoprene block segment 30 to 94% by weight and (C) 1,2-vinyl bond content of 15% or less polybutadiene block segment 1 to 35% by weight. Resin composition comprising 1 to 99% by weight of a hydrogenated block polymer obtained by hydrogenating 90% or more of an unsaturated double bond of a linear or branched block polymer, and 99 to 1% by weight of a (b) polyphenylene ether resin. .. 2. A hydrogenated block polymer (a) 1-99.
(C) at least one polymer 1 to 300 selected from the group consisting of (C) a polyolefin-based resin, a polyamide-based resin, and a polyester-based resin, based on 100 parts by weight of a composition composed of 100% by weight of a polyphenylene ether resin and 99 to 1% by weight of a polyphenylene ether resin.
A resin composition containing 1 part by weight. 3. 100 parts by weight of the hydrogenated block polymer (a) as the component (a) is added with an acid anhydride group, a carboxyl group,
A modified hydrogenated block polymer (a ′) modified with 0.01 to 20 parts by weight of an unsaturated compound having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, an oxazoline group, and an epoxy group. The resin composition according to claim 1, which is used.