JP2008274039A - Polyphenylene ether composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an environmentally-favorable resin composition containing no halogen compound, excellent in electric properties, heat resistance, mechanical properties, having good releasability when injection molding, having scarce problem of emitting smoke, adhesion of a flame retardant agent to a mold and the like, and having excellent appearance, impact resistance and flame retardancy. <P>SOLUTION: A polyphenylene ether flame retardant resin composition is constituted by adding a random hydrogenated copolymer (c) having a specific hydrogenated random copolymer block and a polyolefin resin by a specific ratio to a flame retardant resin composed of a polyphenylene ether resin and a condensed phosphoric acid ester. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a flame retardant resin composition that is preferable in terms of environment with excellent impact resistance.

In general, flame retardant methods such as adding halogenated compounds and antimony trioxide have been used as flame retardants for flammable synthetic resins. Improvement of flame retardant methods is desired.
A mixed resin based on polyphenylene ether and styrene resin (hereinafter referred to as modified PPE) can be selected in a range from styrene resin alone to polyphenylene ether alone depending on the mixing ratio of polyphenylene ether and styrene resin. It has excellent properties such as electrical characteristics, dimensional stability, impact resistance, acid resistance, alkali resistance, low water absorption, and low specific gravity. In addition, the modified PPE resin can be flame retardant without using halogen compounds and antimony trioxide, which are said to be harmful, and is excellent in terms of environment and safety and health. High-strength, high-rigidity, high-heat-resistant materials are designed by adding inorganic reinforcing agents and are used in various applications around the world. Examples of applications include electrical / electronic parts, office equipment parts, various types Examples include exterior materials and industrial products.

  For the flame retardant of polyphenylene ether resin or mixed resin of styrene resin (hereinafter referred to as modified PPE resin), monophosphate such as triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, resorcinol and bisphenol A Organic phosphate esters such as condensed phosphate esters made from bifunctional phenols and polyfunctional phenols as raw materials have been used. Among them, the resin composition using the condensed phosphate ester flame retardant is superior in heat resistance compared to the resin composition using the monophosphate ester flame retardant, and is suitable for fuming and molds during injection molding. There are few problems such as adhesion of flame retardants, and it is said that demand is expanding.

  However, condensed phosphate ester flame retardants have improved rigidity, typified by physical properties such as tensile strength, bending strength, and elastic modulus, compared with monophosphate ester flame retardants, but reduced the inherent impact resistance of the resin. Let Moreover, since the flame retardant effect is inferior, it is necessary to add a larger amount. Therefore, since the impact resistance inherent in the resin is further reduced, it is necessary to improve the impact such as adding a large amount of elastomer. In addition, materials for exterior materials such as office machine housings and TV housings that have excellent appearance characteristics, excellent impact properties, and excellent moldability have been desired.

  In general, in modified PPE resins, hydrogenated block copolymers that do not have a random structure that is superior in thermal stability are used as elastomers for impact improvement. Therefore, it is necessary to add in a large amount. As a result, the flame retardancy is lowered, and it is expensive, which is not preferable economically. Patent Documents 1 to 9 disclose techniques for improving the impact properties of modified PPE resins by using a hydrogenated block copolymer not having a random structure and a polyolefin resin in combination, but these are difficult to use as a condensed phosphate ester. Since there was no viewpoint of the flame retardant resin composition containing a flame retardant and the purpose was different, the amount of each added was very large, and the flame retardancy was low.

Patent Document 10 describes that, for the purpose of suppressing flame dripping, the level is increased from rank V-2 to rank V-1 in the UL combustion test by adding a small amount of high-density polyethylene. In addition, it is described that a hydrogenated block copolymer containing a random copolymer block is also used as an impact modifier at that time, but only a hydrogenated block copolymer having no random structure is exemplified. Yes. (Patent Document 10)
On the other hand, modified PPE resins, particularly flame retardant modified PPE containing a flame retardant, are often processed by an injection molding method, but at that time, the problem of mold release from the mold often becomes a problem. This improvement in releasability has been demanded conventionally.

USP 4145377 USP 4166055 USP 4383082 JP 56-51356 A Japanese Unexamined Patent Publication No. 62-179561 Japanese Patent Laid-Open No. 02-169665 Japanese Patent Laid-Open No. 04-7357 Japanese Patent Laid-Open No. 04-279997 JP 06-192561 A JP 2000-26717 A

  The problem of the present invention is that it does not contain a halogen compound, is excellent in heat resistance, mechanical properties, electrical properties, has good releasability at the time of injection molding, has almost no problems such as fuming, adhesion of flame retardant to the mold, It is an environmentally preferable polyphenylene ether resin composition excellent in flame retardancy and impact resistance, and a material suitable for exterior material use excellent in appearance characteristics.

As a result of intensive studies on the technology for achieving the above-mentioned problems, the present inventors have found that a flame retardant resin of a polyphenylene ether resin and a condensed phosphate ester contains a hydrogenated block copolymer having a specific random structure and a polyolefin. The inventors have found that the object can be achieved by adding at a specific ratio, and have reached the present invention.
That is, the present invention
1. (A) 50 to 98 parts by mass of a polyphenylene ether resin or a combination of this with a styrene resin,
(B) Formula (I)

（式中、Ｑ１、Ｑ２、Ｑ３、Ｑ４は、炭素数１から６のアルキル基、または水素を表し、Ｒ１、Ｒ２、Ｒ３、Ｒ４はメチル基、または水素を表す。ｎは１以上の整数を、ｎ１、ｎ２は０から２の整数を示し、ｍ１、ｍ２、ｍ３、ｍ４は、１から３の整数を示す。）
で示される縮合リン酸エステルを主成分とする難燃剤１〜４０質量部、
（ｃ）共役ジエン単量体単位とビニル芳香族単量体単位とからなるブロック共重合体を水素添加して得られる水添共重合体であって、且つ共役ジエン単量体単位とビニル芳香族単量体単位とからなる（非水添）ランダム共重合体ブロックを水素添加して得られる水添ランダム共重合体ブロックを有するランダム水添共重合体１〜１０質量部未満、および（ｄ）ポリオレフィン０〜１０質量部であり、（ａ）＋（ｂ）＋（ｃ）＋（ｄ）の合計１００質量部からなるポリフェニレンエーテル組成物。 Or the following formula (II)

(Wherein Q1, Q2, Q3 and Q4 represent an alkyl group having 1 to 6 carbon atoms or hydrogen, R1, R2, R3 and R4 represent a methyl group or hydrogen. N represents an integer of 1 or more. , N1, and n2 represent integers from 0 to 2, and m1, m2, m3, and m4 represent integers from 1 to 3.)
1 to 40 parts by mass of a flame retardant mainly comprising a condensed phosphate ester represented by
(C) a hydrogenated copolymer obtained by hydrogenating a block copolymer comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit, wherein the conjugated diene monomer unit and the vinyl aromatic 1 to less than 10 parts by mass of a random hydrogenated copolymer having a hydrogenated random copolymer block obtained by hydrogenating a (non-hydrogenated) random copolymer block consisting of a group monomer unit, and (d ) Polyphenylene ether composition comprising 0 to 10 parts by mass of polyolefin and 100 parts by mass in total of (a) + (b) + (c) + (d).

（式中、Ｑ１、Ｑ２、Ｑ３、Ｑ４は、炭素数１から６のアルキル基、または水素を表し、Ｒ１、Ｒ２、Ｒ３、Ｒ４はメチル基、または水素を表す。ｎは１以上の整数を、ｎ１、ｎ２は０から２の整数を示し、ｍ１、ｍ２、ｍ３、ｍ４は、１から３の整数を示す。）
で示される縮合リン酸エステルを主成分とする上記１記載のポリフェニレンエーテル組成物。 2. (B) The flame retardant is
Formula (I)

(Wherein Q1, Q2, Q3 and Q4 represent an alkyl group having 1 to 6 carbon atoms or hydrogen, R1, R2, R3 and R4 represent a methyl group or hydrogen. N represents an integer of 1 or more. , N1, and n2 represent integers from 0 to 2, and m1, m2, m3, and m4 represent integers from 1 to 3.)
2. The polyphenylene ether composition according to 1 above, which comprises a condensed phosphate ester represented by

3. (C) The polyphenylene ether composition according to 1 or 2 above, comprising 1 to less than 7 parts by mass of a random hydrogenated copolymer and (d) 0.5 to 5 parts by mass of a polyolefin-based resin.
4). (C) The polyphenylene ether composition according to 1 or 2 above, comprising 1 to less than 5 parts by mass of a random hydrogenated copolymer.
5. (D) The polyphenylene ether composition according to any one of the above 1 to 3, comprising 0.5 to 3 parts by mass of a polyolefin-based resin.

6). (C) the random hydrogenated copolymer comprises at least one polymer block comprising a polymer block (A) comprising a vinyl aromatic monomer unit, a conjugated diene monomer unit and a vinyl aromatic monomer unit; A hydrogenated copolymer comprising at least one hydrogenated random copolymer block (B) obtained by hydrogenating a random copolymer block consisting of the following: (1) to (4) 6. The polyphenylene ether composition according to any one of 1 to 5 above.
(1) The content of the vinyl aromatic monomer unit is more than 40% by mass and less than 95% by mass with respect to the mass of the (c) random hydrogenated copolymer,
(2) The content of the polymer block (A) is 10 to 50% by mass with respect to the mass of the (c) random hydrogenated copolymer,
(3) The weight average molecular weight is 30,000 to 1,000,000,
(4) The hydrogenation rate of the double bond of the conjugated diene monomer unit is 75% or more.

7). (D) The polyphenylene ether composition according to any one of 1 to 6 above, wherein the polyolefin is low-density polyethylene.
8). (D) The polyphenylene ether composition according to any one of 1 to 6 above, wherein the polyolefin is a linear low density polyethylene.

9. (D) The polyphenylene ether composition according to any one of 1 to 6 above, wherein the polyolefin comprises an ethylene-propylene copolymer.
10. (D) The polyphenylene ether composition according to any one of 1 to 6 above, wherein the polyolefin comprises an ethylene-butene copolymer.

11. (D) The polyphenylene ether composition according to any one of 1 to 6 above, wherein the polyolefin comprises an ethylene-octene copolymer.
12 The polyphenylene ether composition according to any one of 1 to 11 above, wherein the glossiness is 90% or more.

13. (A) The polyphenylene ether composition as described in 12 above, wherein the styrene resin used in combination with the polyphenylene ether resin is polystyrene (styrene homopolymer).
14 14. A molded article obtained by injection molding the polyphenylene ether composition according to 12 or 13 above.

  The present invention

The (a) polyphenylene ether resin used in the present invention is a homopolymer or copolymer having a repeating unit represented by the general formula (III) and / or (IV).

（ここで、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６は独立に炭素１〜４のアルキル基、アリール基、ハロゲン、水素を表す。但し、Ｒ５、Ｒ６は同時に水素ではない。）

(Here, R1, R2, R3, R4, R5, and R6 independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, and hydrogen, provided that R5 and R6 are not hydrogen at the same time.)

  Representative examples of homopolymers of polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-14-phenylene) ether, poly (2,6 -Diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether poly (2,6-di-n-propyl-1,4-phenylene) ether, Poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1, 4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenyle) ) Include homopolymers such as ether.

Of these, poly (2,6-dimethyl-1,4-phenylene) ether is preferable, and 2- (dialkylaminomethyl) -6-methylphenylene ether described in JP-A-63-301222 and the like is preferable. A polyphenylene ether containing a unit or a 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit as a partial structure is particularly preferred.
Here, the polyphenylene ether copolymer is a copolymer having a phenylene ether structure as a main monomer unit. Examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, or 2,6-dimethylphenol and 2 , 3,6-trimethylphenol and a copolymer with o-cresol.

  Particularly preferred in practice, ηsp / c measured with a 30 ° C. chloroform solution is in the range of 0.3 to 0.7, preferably in the range of 0.4 to 0.6, and gel permeation chromatography ( Poly (2,6) having a weight average molecular weight / number average molecular weight in the range of 2.2 to 5.0, preferably in the range of 2.3 to 3.5, based on the molecular weight in terms of polystyrene measured by GPC). -Dimethyl-1,4-phenylene) ether. Such polyphenylene ether is particularly preferable from the viewpoint of molding fluidity.

  In the present invention, a modified polyphenylene ether resin in which a part or all of the polyphenylene ether resin is modified with an unsaturated carboxylic acid or a derivative thereof can be used. This modified polyphenylene ether resin is described in JP-A-2-276823, JP-A-63-108059, JP-A-59-59724, etc., for example, in the presence or absence of a radical initiator. In this method, an unsaturated carboxylic acid or a derivative thereof is melt-kneaded and reacted with a polyphenylene ether resin. Alternatively, it is produced by dissolving polyphenylene ether and unsaturated carboxylic acid or a derivative thereof in an organic solvent in the presence or absence of a radical initiator and reacting in a solution.

Examples of unsaturated carboxylic acids or derivatives thereof include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene 1,2-dicarboxylic acid, and endo-cis-bicyclo (2,2,1)- 5-heptene-2,3-dicarboxylic acid, etc., acid anhydrides, esters, amides, imides, etc. of these dicarboxylic acids, acrylic acid, methacrylic acid, etc., esters of these monocarboxylic acids, amides, etc. . Further, although it is a saturated carboxylic acid, it can be thermally decomposed itself at the reaction temperature when producing the modified polyphenylene ether, and the unsaturated carboxylic acid used in the present invention or a compound that can be a derivative thereof can be used. Examples include malic acid and citric acid. These may be used alone or in combination of two or more.

The styrene resin used in combination with the polyphenylene ether resin in the present invention is a polymer obtained by polymerizing a styrene compound or a compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer. .
The ratio of the polyphenylene ether resin (PPE) and the styrene resin (PS) used in the present invention is preferably in the range of 100/0 to 20/80 by mass ratio. When the PPE ratio is 20 or more, the heat resistance and flame retardancy are excellent, and by using PS together, the molding fluidity is excellent.

  Specific examples of the styrenic compound include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene, and the most preferable is styrene. It is. Examples of the compound copolymerizable with the styrene compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. And used with styrenic compounds. The amount of the copolymerizable compound used is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total amount with the styrene compound.

  Examples of rubbery polymers include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, and ethylene-propylene copolymer rubbers. Specifically, polybutadiene and styrene-butadiene copolymer are particularly preferable. As the rubbery polymer, it is preferable to use partially hydrogenated polybutadiene having an unsaturation degree of 80 to 20% or polybutadiene containing 90% or more of 1,4-cis bonds. Specific examples of the styrene resin include polystyrene and rubber-reinforced polystyrene, styrene-acrylonitrile copolymer (AS resin), rubber-reinforced styrene-acrylonitrile copolymer (ABS resin), other styrene copolymers, and the like. It is done.

  Preference is given to polystyrene and rubber-modified polystyrene. Particularly preferred are polystyrene (styrene homopolymer) and rubber-modified polystyrene having an average rubber particle size of 1.0 μm or less. By using these styrene resins, the surface gloss is good, and the weld line. It is possible to obtain a molded article having an excellent appearance such as being inconspicuous. According to the present invention, a molded article having excellent surface impact and excellent appearance can be obtained, and can be preferably used for various exterior materials.

  In the present invention, the resin composition having excellent surface gloss uses polystyrene (styrene homopolymer) as the styrene resin, or rubber-modified polystyrene having a relatively small rubber particle diameter, or the amount of rubber-modified polystyrene. Can be obtained when there is little. When the surface glossiness is 85% or more, preferably 90% or more, it can be used without coating as an exterior material for various exterior materials, particularly televisions and office machines, and is particularly useful.

The condensed phosphate ester (b) flame retardant used in the present invention is
Formula (I)

で表される。
（式中、Ｑ１、Ｑ２、Ｑ３、Ｑ４は、炭素数１から６のアルキル基、または水素を表し、Ｒ１、Ｒ２、Ｒ３、Ｒ４はメチル基、または水素を表す。ｎは１以上の整数を、ｎ１、ｎ２は０から２の整数を示し、ｍ１、ｍ２、ｍ３、ｍ４は、１から３の整数を示す。）で表される。 Or the following formula (II)

It is represented by
(Wherein Q1, Q2, Q3 and Q4 represent an alkyl group having 1 to 6 carbon atoms or hydrogen, R1, R2, R3 and R4 represent a methyl group or hydrogen. N represents an integer of 1 or more. , N1, and n2 represent integers from 0 to 2, and m1, m2, m3, and m4 represent integers from 1 to 3.

The condensed phosphate ester represented by the formula (II) is considered to be caused by decomposition or dehydration reaction in the melt-kneading when producing the resin composition of the present application, compared to the condensed phosphate ester represented by the formula (I). Black foreign matter is easily generated, and the water absorption of the composition is large.
Among these, preferred condensed phosphate esters are those in which Q1, Q2, Q3 and Q4 in formula (I) are hydrogen or a methyl group, R1 and R2 are hydrogen, R3 and R4 are methyl groups, and the range of n is 1 ~ 3, particularly those containing 50% or more of the phosphoric acid ester in which n is 1, more preferably those having an acid value of less than 0.1. Here, the acid value is a value represented by the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the sample in accordance with JIS K2501. When the condensed phosphoric acid ester acid value is large, the mold is easily corroded at the time of molding, the compound is easily decomposed, so that gas is generated during processing, and further, the electrical characteristics of the composition are deteriorated. There are disadvantages such as.

In the present invention, (b) the condensed phosphate ester as a flame retardant is used in the range of 1 to 40 parts by weight with respect to 100 parts by weight of (a) a polyphenylene ether resin or a combination of this and a styrene resin. A flame retarding effect is obtained when the amount is 1 part by mass or more, and a decrease in mechanical strength or heat resistance is preferable when the amount is 40 parts by mass or less.
These flame retardants are generally commercially available, for example, trade name CR-74 of Daihachi Chemical Co., Ltd.
1, CR-747, CR733S, PX-200 and the like.

  The (c) random hydrogenated copolymer used in the present invention (hereinafter also referred to as component (c) hydrogenated copolymer) is composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit. It comprises a hydrogenated copolymer obtained by hydrogenating a (non-hydrogenated) random copolymer block. As a material using the component (c) hydrogenated copolymer in the present invention, a general hydrogenated styrene elastomer (for example, a hydrogenated block copolymer having a polystyrene-poly (ethylene / butylene) -polystyrene structure) is used. Compared to conventional materials, it is known to be superior in terms of fluidity, wear resistance, scratch resistance, etc. This difference in performance is due to the (non-hydrogenated) random copolymer block part being hydrogenated. It is estimated that this is the effect of the segment. Further, even when the resin composition is extruded, there is little occurrence of scum as compared with a composition containing a conventional styrene elastomer.

The polyphenylene ether composition blended with the component (c) hydrogenated copolymer used in the present invention is not only excellent in the above-mentioned properties, but also has an excellent appearance, particularly surface gloss, conspicuous weld lines, colorability, and flame retardancy. A material excellent in impact resistance can be provided.
The name of each monomer unit constituting the polymer is in accordance with the name of the monomer from which the monomer unit is derived. For example, “vinyl aromatic monomer unit” means a structural unit of a polymer resulting from polymerization of a vinyl aromatic compound as a monomer, and the structure thereof is substituted ethylene derived from a substituted vinyl group. It is a molecular structure in which the two carbons of the group are binding sites. The term “conjugated diene monomer unit” means a structural unit of a polymer produced as a result of polymerizing a monomer, conjugated diene, and its structure is the same as that of an olefin derived from a conjugated diene monomer. It is a molecular structure in which two carbons are binding sites.

The component (c) hydrogenated copolymer in the present invention is a (non-hydrogenated) random copolymer (hereinafter often referred to as “base non-hydrogenated”) containing a conjugated diene monomer unit and a vinyl aromatic monomer unit. A copolymer obtained by hydrogenating a copolymer). Component (c) hydrogenated copolymer in the present invention comprises at least one polymer block (A) (hereinafter referred to as polymer block (A)) composed of vinyl aromatic monomer units, and a conjugated diene unit. At least one hydrogenated random copolymer block (B) obtained by hydrogenating a (non-hydrogenated) random copolymer block comprising a monomer unit and a vinyl aromatic monomer unit (hereinafter referred to as hydrogenated random). Copolymer block (B)). A hydrogenated polymer block (C) obtained by hydrogenating a (non-hydrogenated) polymer block composed of conjugated diene monomer units (hereinafter referred to as hydrogenated polymer block (C)) is also included. Good. However, the vinyl bond amount of the (non-hydrogenated) polymer block comprising conjugated diene monomer units is preferably less than 30%, and the non-hydrogenated polymer comprising conjugated diene monomer units and vinyl aromatic monomer units. The vinyl bond content of the random copolymer block is preferably less than 40%.
The polymer block (A) and the hydrogenated polymer block (C) serve as physical cross-linking points and are therefore referred to as “constrained phase”. On the other hand, the hydrogenated random copolymer block (B) is referred to as “unconstrained phase”.

The component (c) hydrogenated copolymer in the present invention preferably has two or more polymer blocks which are constrained phases. In the present invention, when the hydrogenated copolymer (c) does not have the hydrogenated polymer block (C), the hydrogenated copolymer preferably has at least two polymer blocks (A). In the case where the component (c) hydrogenated copolymer used in the present invention has two or more polymer blocks that are a constrained phase, the mechanical strength of the hydrogenated copolymer is excellent.
When the component (c) hydrogenated copolymer in the present invention does not have the hydrogenated polymer block (C), in the differential scanning calorimetry (DSC) chart obtained for the hydrogenated copolymer, −20 It is preferable that the crystallization peak due to the hydrogenated random copolymer block (B) is substantially absent in the range of ˜80 ° C. Here, “the crystallization peak due to the hydrogenated copolymer block (B) is not substantially present in the range of −20 to 80 ° C.” means that the hydrogenated random copolymer block (B ) Or the peak due to crystallization is observed, but the crystallization peak heat due to the crystallization is preferably less than 3 J / g, more preferably less than 2 J / g, More preferably, it means less than 1 J / g, particularly preferably no crystallization peak heat.

  When the component (c) hydrogenated copolymer of the present invention has a hydrogenated polymer block (C), in the differential scanning calorimetry (DSC) chart, hydrogenation random in the range of −20 to 80 ° C. It is not required that the crystallization peak due to the copolymer block (B) is substantially absent. However, even in the case of having the hydrogenated polymer block (C), in the differential scanning calorimetry (DSC) chart, crystallization caused by the hydrogenated random copolymer block (B) in the range of −20 to 80 ° C. It is preferred that the peak is substantially absent.

  The hydrogenated copolymer having substantially no crystallization peak due to the hydrogenated random polymer block (B) in the range of −20 to 80 ° C. in the differential scanning calorimetry (DSC) chart has good flexibility. Yes, preferred in the present invention. A hydrogenated copolymer having substantially no crystallization peak due to the hydrogenated random copolymer block (B) in the range of −20 to 80 ° C. as described above is a vinyl bond amount adjusting agent as described later. Or obtained by conducting a polymerization reaction under conditions as described later using a regulator as described later for adjusting random copolymerizability between the conjugated diene and the vinyl aromatic compound (non-hydrogenated). It can be obtained by hydrogenating the copolymer.

In the case of having a hydrogenated polymer block (C), in the differential scanning calorimetry (DSC) chart, regarding the crystallization peak due to the hydrogenated polymer block (C), the crystallization peak temperature is 30 ° C. or higher, preferably It preferably has a crystallization peak in the temperature range of 45 to 100 ° C, more preferably 50 to 90 ° C. The crystallization peak heat quantity is preferably 3 J / g or more, preferably 6 J / g or more, and more preferably 10 J / g or more.
The crystallization peak temperature and the crystallization peak calorie can be measured using a differential scanning calorimeter.

The content of the vinyl aromatic monomer unit in the component (c) hydrogenated copolymer in the present invention is preferably more than 40% by mass and less than 95% by mass with respect to the hydrogenated copolymer. . The component (c) hydrogenated copolymer of the present invention preferably has a vinyl aromatic monomer unit content in the above range, and is excellent in flexibility, low temperature characteristics, and the like. From the viewpoint of flexibility and low temperature characteristics, the content of the vinyl aromatic monomer unit is more preferably more than 40% by weight and 80% by weight or less, particularly preferably more than 45% by weight and 70% by weight or less, most preferably. Is more than 45 mass% and 60 mass% or less. In particular, when the component (c) hydrogenated copolymer does not have the hydrogenated polymer block (C), the content of the vinyl aromatic monomer unit is preferably more than 40% by mass and 90% by mass or less, More preferably, it exceeds 45 mass% and is 85 mass% or less, More preferably, it exceeds 50 mass% and is 80 mass% or less.
Since the content of the vinyl aromatic monomer unit in the component (c) hydrogenated copolymer is substantially equal to the content of the vinyl aromatic monomer unit in the base non-hydrogenated copolymer, the vinyl aromatic monomer The content of the body unit with respect to the component (c) hydrogenated copolymer is determined as the content with respect to the base non-hydrogenated copolymer. The content ratio of the vinyl aromatic monomer unit to the component (c) hydrogenated copolymer is measured using an ultraviolet spectrophotometer using the base non-hydrogenated copolymer as a specimen.

In the component (c) hydrogenated copolymer in the present invention, the content of the polymer block (A) is in the range of 5 to 50% by mass relative to the component (c) hydrogenated copolymer. Since the content of the polymer block (A) is in the above range, the component (c) hydrogenated copolymer of the present invention is excellent in toughness, flexibility and low temperature characteristics. Preferably it is 10-45 mass%, More preferably, it is 15-40 mass%.
In the present invention, the content of the polymer block (A) with respect to the component (c) hydrogenated copolymer is substantially equal to the content of the polymer block (A) with respect to the base non-hydrogenated copolymer. The content of component (A) with respect to component (c) hydrogenated copolymer is determined as the content of polymer block (A) with respect to the base non-hydrogenated copolymer. Specifically, a method of oxidatively decomposing a base non-hydrogenated copolymer with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF et al., J. Polymer Sci. 1, 429 (1946). ), The mass of the vinyl aromatic polymer block component obtained by the method described below (hereinafter often referred to as the “osmium tetroxide decomposition method”) (excluding vinyl aromatic polymer components having an average degree of polymerization of about 30 or less). Is obtained from the following equation.
Content (% by mass) of vinyl aromatic polymer block (A) = (mass of vinyl aromatic polymer block (A) in base non-hydrogenated copolymer / mass of base non-hydrogenated copolymer) × 100.

In the case of directly measuring the content of the polymer block (A) with respect to the component (c) hydrogenated copolymer, the component (c) hydrogenated copolymer is used as a specimen, and a nuclear magnetic resonance apparatus (NMR) is used. (Y. TANAKA, et al., RUBBER CHEMISTRY
and TECHNOLOGY 54, 685 (1981); hereinafter referred to as “NMR method”).
The content of the polymer block (A) determined by the osmium tetroxide decomposition method (referred to as “Os value”) and the content of the polymer block (A) determined by the NMR method (“Ns value”) Are referred to as correlations. As a result of investigations using various copolymers by the present inventors, it was found that the relationship is expressed by the following formula.
Os value = −0.012 (Ns value) 2 + 1.8 Ns value) −13.0

  Accordingly, in the present invention, when the content (Ns value) of the polymer block (A) with respect to the component (c) hydrogenated copolymer is determined by the NMR method, the Ns value is converted into an Os value based on the above formula. To do. The content of the hydrogenated random copolymer block (B) in the component (c) hydrogenated copolymer of the present invention is not particularly limited. However, in the case where the component (c) hydrogenated copolymer of the present invention does not have the hydrogenated polymer block (C), the hydrogenated random copolymer block (B) of the hydrogenated random copolymer block (B) is used from the viewpoint of flexibility and low temperature characteristics. The content is preferably 30 to 95% by mass, more preferably 40 to 92% by mass, and particularly preferably 50 to 90% by mass with respect to the component (c) hydrogenated copolymer. On the other hand, when the component (c) hydrogenated copolymer of the present invention has a hydrogenated polymer block (C), the content of the hydrogenated random copolymer block (B) is preferably 30 to 90 mass. %, More preferably 40 to 88% by mass, particularly preferably 50 to 86% by mass.

  As described above, the hydrogenated random copolymer block (B) is obtained by hydrogenating a (non-hydrogenated) random copolymer block composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit. It is done. Content of hydrogenated random copolymer block (B) is calculated | required from the addition amount of the conjugated diene monomer and vinyl aromatic monomer unit at the time of manufacturing the said (non-hydrogenated) random copolymer block. . The content ratio of the hydrogenated random copolymer block (B) to the component (c) hydrogenated copolymer is the content ratio of the above (non-hydrogenated) random copolymer block to the base non-hydrogenated copolymer. Since the content of the hydrogenated random copolymer block (B) with respect to the component (c) hydrogenated copolymer is almost the same, the content of the above (non-hydrogenated) random copolymer block with respect to the base non-hydrogenated copolymer Calculate as a rate.

The content of the hydrogenated polymer block (C) in the component (c) hydrogenated copolymer in the present invention is not particularly limited. However, from the viewpoint of flexibility and low temperature characteristics, the content of the hydrogenated polymer block (C) is preferably 0 to 50% by mass, more preferably 10 to 50%, based on the component (c) hydrogenated copolymer. % By mass, more preferably 12 to 45% by mass, particularly preferably 15 to 40% by mass.
As described above, the hydrogenated polymer block (C) is obtained by hydrogenating a (non-hydrogenated) polymer block composed of conjugated diene monomer units. The content of the hydrogenated polymer block (C) is determined from the amount of the conjugated diene monomer added when the (non-hydrogenated) polymer block is produced. The content of the hydrogenated polymer block (C) with respect to the component (c) hydrogenated copolymer is substantially equal to the content of the (non-hydrogenated) polymer block with respect to the base non-hydrogenated copolymer. The content of the hydrogenated polymer block (C) with respect to the component (c) hydrogenated copolymer is determined as the content of the (non-hydrogenated) polymer block with respect to the base non-hydrogenated copolymer.

  The weight average molecular weight of the component (c) hydrogenated copolymer in the present invention is preferably 30,000 to 1,000,000. The component (c) hydrogenated copolymer of the present invention has an excellent balance between mechanical strength and molding processability because the weight average molecular weight is in the above range. From the viewpoint of the balance between mechanical strength and impact absorbability and moldability, the weight average molecular weight of the component (c) hydrogenated copolymer of the present invention is more preferably 50,000 to 800,000, still more preferably 10 It is 10,000 to 500,000, particularly preferably 150,000 to 400,000. In particular, when the component (c) hydrogenated copolymer of the present invention has a hydrogenated polymer block (C), it is preferably more than 100,000 and less than 1,000,000, more preferably 120,000 from the viewpoint of moldability. ˜800,000, particularly preferably 140,000 to 500,000.

  In the present invention, the molecular weight distribution (Mw / Mn) of the component (c) hydrogenated copolymer (ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) is preferably 10 or less, more preferably 1. 01 to 8, particularly preferably 1.1 to 5. When emphasizing molding processability, it is preferably 1.3 to 5, more preferably 1.5 to 5, even more preferably 1.6 to 4.5, and particularly preferably 1.8 to 4. Since the weight average molecular weight of the component (c) hydrogenated copolymer is substantially equal to the weight average molecular weight of the base non-hydrogenated copolymer, the weight average molecular weight of the component (c) hydrogenated copolymer is the base non-hydrogenated copolymer. Calculated as the weight average molecular weight of the coalescence. The weight average molecular weight of the base non-hydrogenated copolymer is determined by gel permeation chromatography (GPC) using a calibration curve obtained for a commercially available standard monodisperse polystyrene having a known molecular weight. The number average molecular weight of the component (c) hydrogenated copolymer is determined in the same manner. The molecular weight distribution is obtained by calculation as a ratio of the weight average molecular weight to the number average molecular weight.

As described above, the component (c) hydrogenated copolymer of the present invention comprises a (non-hydrogenated) copolymer (that is, a base non-aqueous) containing a conjugated diene monomer unit and a vinyl aromatic compound monomer unit. (Added copolymer) is obtained by hydrogenation. The hydrogenation rate of the double bond of the conjugated diene monomer unit in the component (c) hydrogenated copolymer of the present invention is preferably 75 to 100%. From the viewpoint of thermal stability, the hydrogenation rate is more preferably 80 to 100%, still more preferably 85 to 100%, and particularly preferably 90 to 100%.
The hydrogenation rate of the double bond of the vinyl aromatic monomer unit in the component (c) hydrogenated copolymer is not particularly limited, but the hydrogenation rate is preferably 50% or less, more preferably 30%. Hereinafter, it is particularly preferably 20% or less. The hydrogenation rate in the component (c) hydrogenated copolymer can be measured using a nuclear magnetic resonance apparatus.

The component (c) hydrogenated copolymer of the present invention has a loss tangent (tan δ) peak in the dynamic viscoelastic spectrum obtained for the hydrogenated copolymer, preferably from −40 ° C. to less than 20 ° C. Preferably, at least one is present in the range of −35 to 15 ° C., more preferably −30 to 0 ° C. The loss tangent peak in the range of −40 ° C. or more and less than 20 ° C. is a hydrogenated random copolymer block (B) (consisting of a conjugated diene monomer unit, a vinyl aromatic compound, and a monomer unit (non- This is a peak due to hydrogenation) (hydrogenated polymer block obtained by hydrogenating random copolymer block). The presence of at least one loss tangent peak in the range of −40 ° C. or more and less than 20 ° C. means that the component (c) hydrogenated copolymer has flexibility, abrasion resistance, scratch resistance, tensile strength, etc. It is also preferable in terms of balance of characteristics. In the present invention, the loss tangent peak due to the polymer block (A) is not particularly limited, but the loss tangent peak due to the polymer block (A) usually exceeds 80 ° C. , Within a temperature range of 150 ° C. or less.
The loss tangent (tan δ) peak in the dynamic viscoelastic spectrum is measured at a frequency of 10 Hz using a viscoelasticity analyzer.

  As described above, the hydrogenated random copolymer block (B) is obtained by hydrogenating a non-hydrogenated random copolymer block composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit. The mass ratio of the conjugated diene monomer unit / vinyl aromatic monomer unit in the non-hydrogenated random copolymer is not particularly limited. However, considering that at least one loss tangent peak needs to be present in the range of −40 ° C. or higher and lower than 0 ° C. as described above, conjugated diene monomer unit / vinyl aromatic monomer unit. It is recommended that the mass ratio is preferably 50/50 to 90/10, more preferably 53/47 to 80/20, particularly preferably 56/44 to 75/25.

  As described above, the hydrogenated random copolymer block (B) is obtained by hydrogenating a (non-hydrogenated) random copolymer block composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit. It is done. The microstructure of the conjugated diene monomer unit in the above (non-hydrogenated) random copolymer (ratio of cis, trans, vinyl) can be arbitrarily changed according to the type and amount of the polar compound and the like described later, and the polymerization temperature. it can. The higher the polymerization temperature, the higher the vinyl bond ratio. In the present invention, the vinyl bond content of the conjugated diene monomer unit in the (non-hydrogenated) random copolymer block composed of a conjugated diene monomer unit and a vinyl aromatic monomer unit is less than 40%. It is preferable. {Hereafter, the total amount of 1,2-vinyl bond and 3,4-vinyl bond (however, when 1,3-butadiene is used as the conjugated diene, the amount of 1,2-vinyl bond) is simply vinyl bond. It is called quantity. }. From the viewpoint of handleability (blocking resistance) and mechanical properties (flexibility), the vinyl bond content is preferably 5 to 35%, more preferably 8 to 30%, and particularly preferably less than 10 to 20%.

As described above, the hydrogenated polymer block (C) is obtained by hydrogenating a (non-hydrogenated) polymer block having a vinyl bond content of less than 30% composed of conjugated diene monomer units. The vinyl bond amount of the above (non-hydrogenated) polymer block is preferably 8 to 25%, more preferably 10 to 25%, and particularly preferably less than 12 to 20% from the viewpoint of handleability (anti-blocking). .
The vinyl bond amount is measured using an infrared spectrophotometer using the base non-hydrogenated copolymer as a specimen.

The structure of the component (c) hydrogenated copolymer in the present invention is not particularly limited, and any structure can be used. In one embodiment of component (c) hydrogenated copolymer in the present invention, at least one polymer block (A), at least one hydrogenated random copolymer block (B), and optionally at least 1 Examples of such a hydrogenated copolymer include those having a structure represented by the following formula: a hydrogenated copolymer including one hydrogenated polymer block (C). .
AC- (BA) n, AC- (AB) n,
A-C- (B-A) n-B, [(A-B-C) n] m-X,
C- (BA) n, C- (AB) n,
C- (ABA) n, C- (BABB) n,
[A- (B-C) n] m-X, [(A-B) n-C] m-X,
[(A-B-A) n-C] m-X,
[(B-A-B) n-C] m-X, [(C-B-A) n] m-X,
[C- (BA) n] m-X,
[C- (ABA) n] m-X,
[C- (BAB) n] m-X

As another embodiment of the component (c) hydrogenated copolymer in the present invention, at least two polymer blocks (A) and at least one hydrogenated random copolymer block (B) Examples of such a hydrogenated copolymer include those having a structure represented by the following formula.
(A−B) n + 1, A− (B−A) n,
B- (AB) n + 1,
[(AB) n] mX, [(BA) nB] mX,
[(AB) n-A] m-X, [(B-A) n + 1] m-X

As a particularly preferred embodiment for further exhibiting the characteristics of the present invention, it contains at least two polymer blocks (A) and at least one hydrogenated random copolymer block (B), at the molecular end. A hydrogenated copolymer (c) having a structure represented by the following formula having a polymer block (A) is preferably used.
AC- (BA) n, AC- (AB) n,
A-C- (BA) n-B, [(ABBC) n] m-X,
[A- (B-C) n] m-X, [(AB) n-C] m-X,
[(ABA) n-C] m-X,
(A−B) n + 1, A− (B−A) n,
[(AB) n] m-X, [(AB) n-A] m-X

  In the above formula, each A independently represents a polymer block composed of vinyl aromatic monomer units. Each B independently represents a hydrogenated copolymer block obtained by hydrogenating a (non-hydrogenated) random copolymer consisting of a conjugated diene monomer unit and a vinyl aromatic monomer unit. Each C independently represents a hydrogenated polymer block obtained by hydrogenating a polymer block comprising a conjugated diene monomer unit and having a vinyl bond content of less than 30% (non-hydrogenated). The boundary of each block does not necessarily have to be clearly distinguished.

The vinyl aromatic monomer units in the hydrogenated copolymer block B obtained by hydrogenating the random copolymer may be distributed uniformly or in a tapered shape. Further, the hydrogenated copolymer block B may have a plurality of portions where the vinyl aromatic monomer units are uniformly distributed and / or a plurality of portions where the vinyl aromatic monomer units are distributed in a tapered shape. In the hydrogenated copolymer block B, a plurality of segments having different vinyl aromatic monomer unit contents may exist. Each n is independently an integer of 1 or more, preferably an integer of 1 to 5. Each m is independently an integer of 2 or more, preferably an integer of 2 to 11. Each X independently represents a residue of a coupling agent or a residue of a polyfunctional initiator.
As the coupling agent, a bifunctional or higher functional coupling agent described later can be used. As a polyfunctional initiator, a reaction product of diisopropenylbenzene and sec-butyllithium, a reaction product of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene, or the like can be used.

The component (c) hydrogenated copolymer in the present invention may be any mixture having the structure represented by the above formula. The hydrogenated copolymer includes a hydrogenated copolymer having a structure represented by the above formula, a polymer composed of vinyl aromatic monomer units, a copolymer having an AB structure, and B- It may be a mixture with at least one polymer selected from the group consisting of copolymers having an AB structure.
As described above, the component (c) hydrogenated copolymer of the present invention has a loss tangent (tan δ) peak of −40 ° C. or higher in the dynamic viscoelastic spectrum obtained for the hydrogenated copolymer, It is preferable that at least one peak is present in the range of less than 200 ° C., and the loss tangent peak in the above range is the hydrogenated random copolymer block (B) (conjugated diene monomer unit, vinyl aromatic compound, and single unit. This is a peak resulting from a hydrogenated copolymer block obtained by hydrogenating a random copolymer block (non-hydrogenated) composed of monomer units. Outside the above range, a loss tangent (tan δ) peak may or may not exist. For example, the component (c) hydrogenated copolymer of the present invention may contain a polymer block having a peak outside the above range. An example of such a polymer block is a (non-hydrogenated) copolymer block comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit (however, the content of the vinyl aromatic monomer unit is A hydrogenated copolymer block obtained by hydrogenating (over 50% by mass) and a (non-hydrogenated) polymer block comprising a conjugated diene monomer unit having a vinyl bond content of 30% or more. And a hydrogenated polymer block obtained as described above. However, when the hydrogenated copolymer contains these polymer blocks, in the differential scanning calorimetry (DSC) chart obtained for the hydrogenated copolymer, -20 to 80 ° C, preferably -50 to 100 It is recommended that there is substantially no crystallization peak in the range of ° C.

In addition, as the component (c) hydrogenated copolymer in the present invention, at least one peak of loss tangent (tan δ) exists in the range of −40 ° C. or higher and lower than 0 ° C., and the range of −10 to 80 ° C. The hydrogenated copolymer present in at least one of them is preferable in that the flexibility and low temperature characteristics, which are one of the characteristics of the present invention, are low in temperature. In such a hydrogenated copolymer, at least one peak of loss tangent (tan δ) exists in the range of −40 ° C. or more and less than −10 ° C., and the range of −10 to 15 ° C. and over 15 ° C. Particularly preferred are hydrogenated copolymers each present in the range of at most 1 ° C. or less.
In the present invention, a conjugated diene is a diolefin having a pair of conjugated double bonds. Examples of conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene (ie, isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1, Examples include 3-pentadiene and 1,3-hexadiene. Of these, 1,3-butadiene and isoprene are particularly preferred. These may be used alone or in combination of two or more.

Examples of vinyl aromatic compounds include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl- p-aminoethylstyrene may be mentioned. These may be used alone or in combination of two or more.
As described above, the component (c) hydrogenated copolymer in the present invention is obtained by hydrogenating a copolymer containing a conjugated diene monomer unit and a vinyl aromatic monomer unit (non-hydrogenated). can get. The method for producing the (non-hydrogenated) copolymer is not particularly limited, and a known method can be used. For example, it can be produced by anionic living polymerization using a polymerization initiator such as an organic alkali metal compound in a hydrocarbon solvent. Examples of hydrocarbon solvents include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic carbonization such as cyclohexane, cycloheptane, and methylcycloheptane Hydrogens; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

  Examples of the polymerization initiator include aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, and organic aminoalkali metal compounds having anionic polymerization activity with respect to conjugated dienes and vinyl aromatic compounds. Examples of the alkali metal include lithium, sodium, and potassium. Examples of suitable organic alkali metal compounds are aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, and compounds containing at least one lithium in one molecule (monolithium compounds, dilithium compounds, trilithium compounds, Lithium compounds, tetralithium compounds, etc.). Specifically, n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, diisopropenylbenzene and sec- A reaction product of butyllithium, a reaction product of divinylbenzene, sec-butyllithium, and a small amount of 1,3-butadiene can be used. Furthermore, organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent 2,241,239, US Pat. No. 5,527,753, etc. are also used. be able to.

In the present invention, when an organic alkali metal compound is used as a polymerization initiator and a conjugated diene monomer and a vinyl aromatic monomer are copolymerized, a vinyl bond resulting from a conjugated diene monomer unit incorporated in the polymer ( In order to adjust the amount of 1,2 vinyl bond or 3,4 vinyl bond) or the random copolymerization of conjugated diene and vinyl aromatic compound, a tertiary amine compound or ether compound is added as a regulator. be able to.
Examples of tertiary amine compounds are those of the formula R1R2R3N (wherein R1, R2 and R3 are each independently a hydrocarbon group having 1 to 20 carbon atoms or a tertiary amino group). And the compounds represented. Specifically, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N, N, N ′, N ″, N ″ -pentamethylethylenetriamine, N, N′-dioctyl-p-phenylenediamine Etc.

  Examples of ether compounds include linear ether compounds and cyclic ether compounds. Examples of linear ether compounds include dimethyl ether, diethyl ether, diphenyl ether; ethylene glycol dialkyl ether compounds such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether And dialkyl ether compounds of diethylene glycol. Examples of cyclic ether compounds include tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis (2-oxolanyl) propane, and furfuryl alcohol. Of these alkyl ethers.

  In the present invention, the method of copolymerizing a conjugated diene monomer and a vinyl aromatic monomer using an organic alkali metal compound as a polymerization initiator may be batch polymerization or continuous polymerization, and a combination thereof. There may be. In particular, continuous polymerization is recommended for adjusting the molecular weight distribution to a preferable range in terms of moldability. The polymerization temperature is usually 0 to 180 ° C, preferably 30 to 150 ° C. The time required for the polymerization varies depending on other conditions, but is usually within 48 hours, preferably 0.1 to 10 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is within a pressure range sufficient to maintain the monomer and solvent in a liquid phase within the above polymerization temperature range. Furthermore, care must be taken so that impurities (water, oxygen, carbon dioxide, etc.) that inactivate the catalyst and living polymer do not enter the polymerization system.

In the present invention, when the polymerization is completed, a coupling reaction may be performed using a bifunctional or higher functional coupling agent. There are no particular limitations on the bifunctional or higher functional coupling agent, and known coupling agents can be used. Examples of the bifunctional coupling agent include dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane; acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates. Examples of trifunctional or higher polyfunctional coupling agents include trihydric or higher polyalcohols; polyvalent epoxy compounds such as epoxidized soybean oil and diglycidyl bisphenol A; formula R4-n SiXn (where each R is independent) And a halogenated silicon compound such as methylsilyltrichloride, t, wherein each X independently represents a halogen atom, and n represents 3 or 4. - butylsilyl trichloride, silicon tetrachloride, and their bromides; formula R _{4-n SnX n (wherein} each R independently represents a hydrocarbon group having from 1 to 20 carbon atoms, each X is independently A halogen atom and n represents 3 or 4), for example, methyltin trichloride, t-butyltin trichloride, tin tetrachloride It includes polyvalent halogen compound. Moreover, dimethyl carbonate, diethyl carbonate, etc. can also be used as a polyfunctional coupling agent.

By hydrogenating the (non-hydrogenated) copolymer produced by the above method, the component (c) hydrogenated copolymer in the present invention is obtained. There is no limitation in particular in a hydrogenation catalyst, A well-known hydrogenation catalyst can be used. Examples of the hydrogenation catalyst include the following.
(1) A supported heterogeneous hydrogenation catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth,
(2) a so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt together with a reducing agent such as organoaluminum, and (3) Ti, Ru, Rh, Homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds such as Zr.

  Specific hydrogenation catalysts include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841 (corresponding to US Pat. No. 4,501,857), Japanese Patent Publication No. Hydrogenation catalysts described in Japanese Patent No. 37970 (corresponding to US Pat. No. 4,673,714), Japanese Patent Publication No. 1-53851 and Japanese Patent Publication No. 2-9041 can be used. Examples of preferred hydrogenation catalysts include titanocene compounds and mixtures of titanocene compounds and reducing organometallic compounds.

  As the titanocene compound, compounds described in JP-A-8-109219 can be used. Specifically, it has at least one ligand having a (substituted) cyclopentadienyl skeleton, indenyl skeleton or fluorenyl skeleton such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Compounds. Examples of the reducing organometallic compound include organoalkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

  The hydrogenation reaction for producing the component (c) hydrogenated copolymer in the present invention is usually carried out in a temperature range of 0 to 200 ° C, preferably 30 to 150 ° C. The pressure of hydrogen used for the hydrogenation reaction is usually 0.1 to 15 MPa, preferably 0.2 to 10 MPa, and more preferably 0.3 to 5 MPa. The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours. The hydrogenation reaction can be used in any of batch processes, continuous processes, and combinations thereof.

A hydrogenated copolymer solution is obtained by the above hydrogenation reaction. If necessary, catalyst residues are removed from the hydrogenated copolymer solution, and the hydrogenated copolymer is separated from the solution. An example of a method for separating the solvent is a method in which a polar solvent that is a poor solvent for the hydrogenated copolymer such as acetone or alcohol is added to the reaction solution after hydrogenation to precipitate and recover the polymer; Examples thereof include a method in which the solvent is removed by steam stripping and recovered by stirring in hot water under stirring; and a method in which the solvent is distilled off by directly heating the polymer solution.
In the present invention, the amount of the component (c) hydrogenated copolymer is 1 or more and less than 10 parts by mass, preferably 1 or more and less than 7 parts by mass, more preferably 1 or more and less than 5 parts by mass, and still more preferably. 2 to 5 parts by mass.

The (d) polyolefin of the present invention is an ethylene homopolymer or copolymer, and is an olefin polymer having a density (under 25 ° C.) of less than 0.94 g / ml. Specific examples include low-density polyethylene, linear low-density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-α-olefin copolymers such as ethylene-octene copolymer, and ethylene-ethyl acrylate. And ethylene- (meth) acrylic acid ester copolymers such as a copolymer, an ethylene-butyl acrylate copolymer, and an ethylene-ethyl acrylate-methyl methacrylate copolymer. Preferred are linear low density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer and ethylene-ethyl acrylate copolymer, and particularly preferred is ethylene-propylene copolymer. A polymer and an ethylene-octene copolymer. The polyolefin resin has a melt flow rate (MFR) in the range of 0.1 to 50 g / 10 min, preferably 0.2 to 20 g / 10 min.

  The ethylene-propylene copolymer and the ethylene-butene copolymer are generally amorphous or low-crystalline copolymers. In these copolymers, the third component may be copolymerized as long as the performance is not affected. The component ratio of ethylene and propylene or butene is not particularly specified, but the propylene or butene component is generally in the range of 5 to 50 mol%. These are generally commercially available, and are commercially available from Mitsui Chemicals, Inc. under the trade name Toughmer.

In this invention, the compounding quantity of (d) polyolefin is 0-10 mass parts, Preferably it is 0.5-5 mass parts, More preferably, it is 0.5-3 mass parts.
The blending amounts of the above (c) and (d) are less than 10 parts by mass, respectively, and excellent characteristics obtained by the combination of the polyphenylene ether resin and the condensed phosphate ester, such as tensile strength, bending strength, bending elastic modulus, etc. The mechanical properties are not impaired, and the influence on flame retardancy is small. Moreover, in 1 mass part or more, the improvement effect of impact resistance, mold release property, and chemical resistance is seen.
The combined ratio of component (c) hydrogenated copolymer and (d) polyolefin can be used in a mass ratio in the range of 100/0 to 20/80, but a significant impact resistance improvement effect can be expected. The (c) hydrogenated block copolymer and (d) the combined ratio of the polyolefin are 80/20 to 30/70, preferably 70/30 to 40/60, more preferably 60/40 in mass ratio. It is in the range of ~ 50/50.

In the present invention, it is possible to blend only the component (c) hydrogenated copolymer without using (d) polyolefin, but by using them together in the above ratio, impact resistance, mold release, Excellent chemical properties.
The composition of the present invention further contains a non-random copolymer portion basically obtained by hydrogenating a polymer block of vinyl aromatic monomer units and a polymer block of conjugated diene monomer units. A random hydrogenated block copolymer (e) can be blended. A preferred non-random hydrogenated block copolymer contains 40% by mass or more, more preferably 50 to 85% by mass of a polymer block of vinyl aromatic monomer units. In the composition of the present invention, (e) the non-random hydrogenated block copolymer has a mechanical strength and a moldability due to the polymer block content of the vinyl aromatic monomer unit being in the above range. Excellent balance. From the viewpoint of appearance and moldability, the content is more preferably 60 to 80% by mass.

(E) The weight average molecular weight of the non-random hydrogenated block copolymer is preferably 30,000 to 1,000,000. The component (e) non-random hydrogenated copolymer of the present invention has an excellent balance between mechanical strength and moldability because the weight average molecular weight is in the above range. From the viewpoint of the balance between mechanical strength, impact absorbability and moldability, the weight average molecular weight of the component (e) non-random hydrogenated copolymer of the present invention is more preferably 40,000 to 800,000, still more preferably. Is from 50,000 to 300,000, particularly preferably from 70,000 to 200,000.
In the resin composition of the present invention, an inorganic filler such as glass fiber, glass flake, kaolin clay, talc, and other fibrous reinforcing agents are blended to obtain a high strength composite excellent in fluidity and heat resistance. be able to.

To the resin composition of the present invention, other additives, for example, stabilizers such as plasticizers, antioxidants, and ultraviolet absorbers, in order to impart other characteristics or within the range not impairing the effects of the present invention, Antistatic agents, mold release agents, dyes and pigments, or other resins can be added. In addition, various conventionally known flame retardants and flame retardant aids, for example, alkali metal hydroxides or alkaline earth metal hydroxides such as magnesium hydroxide and aluminum hydroxide containing crystal water, zinc borate compounds, It is possible to further improve flame retardancy by adding a zinc stannate compound, and further inorganic silicon compounds such as silica, kaolin clay and talc.
The method for producing the resin composition of the present invention is not particularly specified, and can be kneaded and produced using a kneader such as an extruder, a heating roll, a kneader, or a Banbury mixer. Among these, kneading with an extruder is preferable in terms of productivity. The kneading temperature may be in accordance with the preferred processing temperature of the base resin, and is generally in the range of 200 to 360 ° C, preferably in the range of 240 to 320 ° C.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following examples.
Each component used in the examples and comparative examples is as follows.
(A) Polyphenylene ether (PPE), polystyrene (PS)
(PPE-1): Poly-2,6-dimethyl-1,4-phenylene ether having a ηsp / c of 0.51 and a weight average molecular weight / number average molecular weight of 2.8 measured with a chloroform solution at 30 ° C.
(PPE-2): Poly-2,6-dimethyl-1,4-phenylene ether having a ηsp / c of 0.53 and a weight average molecular weight / number average molecular weight of 2.1 measured with a chloroform solution at 30 ° C.

(PS-1); rubber-reinforced polystyrene having an average particle diameter of 1.5 to 2.0 μm (PSJ polystyrene H9302 manufactured by PS Japan Co., Ltd.) .
(PS-2); rubber reinforced polystyrene (PSJ polystyrene 403R, manufactured by PS Japan Co., Ltd.) having an average particle diameter of 0.5 to 1.0 μm of rubber particles observed with a transmission electron micrograph using an ultrathin slice. .
(PS-3); Styrene homopolymer (PSJ polystyrene 685, manufactured by PS Japan)

(B) Flame retardant (FR-1) A condensed phosphate ester having an acid value of 0.05, the main component of which is bisdiphenyl phosphate of bisphenol A. Product name CR-741, manufactured by Daihachi Chemical Co., Ltd.
(C) Random hydrogenated copolymer (c-1) Preparation of random hydrogenated copolymer;
Copolymerization was carried out by the following method using a stirrer having an internal volume of 10 liters and a tank reactor with a jacket.

  After 10 parts by weight of cyclohexane was charged into the reactor and adjusted to a temperature of 70 ° C., n-butyllithium was 0.076% by weight based on the weight of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor), 0.4 mol of N, N, N ′, N′-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added to 1 mol of n-butyllithium, and then a cyclohexane solution containing 8 parts by weight of styrene as a monomer (monomer A concentration of 22% by weight) was added over about 3 minutes, and the reaction was carried out for 30 minutes while adjusting the internal temperature of the reactor to about 70 ° C.

Next, a cyclohexane solution containing 48 parts by weight of butadiene and 36 parts by weight of styrene (
A monomer concentration of 22% by weight was continuously fed to the reactor at a constant rate over 60 minutes. During this time, the reactor internal temperature was adjusted to about 70 ° C.
Thereafter, a cyclohexane solution further containing 8 parts by weight of styrene (monomer concentration: 22% by weight) was added over 3 minutes and reacted for 30 minutes while adjusting the reaction temperature to about 70 ° C. to obtain a copolymer. The resulting copolymer had a styrene content of 52% by weight, a styrene polymer block content of 16% by weight, a vinyl bond content of the butadiene portion of 21% by weight, a weight average molecular weight of 16,000, and a molecular weight. The distribution was 1.2. Next, 100 weight ppm of the hydrogenation catalyst as titanium with respect to the weight of the copolymer was added to the obtained copolymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. After completion of the reaction, methanol is added, and then octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer is added in an amount of 0.3% by weight based on the weight of the polymer. A hydrogenated block copolymer was obtained. The results of the obtained polymer are shown in Table 1.

(C-2) Preparation of a random hydrogenated copolymer;
Copolymerization was carried out by the following method using a stirrer having an internal volume of 10 liters and a tank reactor with a jacket.
After charging 10 parts by weight of cyclohexane into the reactor and adjusting the temperature to 70 ° C., n-butyllithium was 0.076% by weight based on the weight of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor), A cyclohexane solution containing 0.4 mol of N, N, N ′, N′-tetramethylethylenediamine (hereinafter referred to as TMEDA) with respect to 1 mol of n-butyllithium, and then containing 15 parts by weight of styrene as a monomer. (Monomer concentration 22% by weight) was added over about 6 minutes, and the reaction was carried out for 30 minutes while adjusting the reactor internal temperature to about 70 ° C.

Next, a cyclohexane solution (monomer concentration of 22% by weight) containing 35 parts by weight of butadiene and 50 parts by weight of styrene was continuously fed to the reactor at a constant rate over 60 minutes. During this time, the reactor internal temperature was adjusted to about 75 ° C. to obtain a copolymer. Furthermore, 0.6 mol of dimethyldichlorosilane was added to 1 mol of n-butyllithium used, and a coupling reaction was performed for 10 minutes.
Thereafter, a hydrogenation reaction was carried out in the same manner as in (c-1) to obtain a hydrogenated copolymer (c-2) having a coupling structure. The results of the obtained polymer are shown in Table 1.
(C-3) Preparation of a random hydrogenated copolymer;
In the preparation of (c-1), the ratios of styrene and butadiene were adjusted, and (c-3) shown in Table 1 was obtained by the same operation.

(D) Polyolefin resin (d-1) Low density polyethylene having an MFR of 20 g / 10 min under a load of 2.16 kg at 190 ° C. according to ASTM D-1238.
(D-2) A linear low density polyethylene having an MFR of 1.2 g / 10 min under a load of 2.16 kg at 190 ° C. according to ASTM D-1238.
(D-3) An ethylene-propylene copolymer having an MFR of 190 ° C. of 2.9 g / 10 min according to ASTM D-1238 (Tafmer (registered trademark) P-0680 manufactured by Mitsui Chemicals, Inc.)

(D-4) An ethylene-butene copolymer having a MFR at 190 ° C. of 0.5 g / 10 min in accordance with ASTM D-1238 (Tafmer (registered trademark) TX610 from Mitsui Chemicals, Inc.)
(D-5) An ethylene-octene copolymer having an MFR at 190 ° C. of 1.0 g / 10 min according to ASTM D-1238 (Engage (registered trademark) 8003 manufactured by DuPont Dow Elastomer)
(D-6) An ethylene-butene copolymer having an MFR at 190 ° C. of 5 g / 10 min according to ASTM D-1238 (EVAFLEX-EEA (registered trademark) A-703, Mitsui DuPont Polychemical Co., Ltd.)

(E) a non-random hydrogenated block copolymer;
(E-1)
A (non-random) hydrogenated block copolymer of styrene / butadiene block copolymer having a styrene content of 60% by weight and a styrene block content of 60% by weight (Taftec (registered trademark) H1081 manufactured by Asahi Kasei Chemicals).
(E-2)
A (non-random) hydrogenated block copolymer of styrene / butadiene block copolymer having a styrene content of 29% by weight and a styrene block content of 29% by weight (Taftec (registered trademark) H1053, manufactured by Asahi Kasei Chemicals Corporation).

In the examples and comparative examples, the composition was evaluated by the following method.
(1) Surface impact strength (drop impact test)
A flat plate of 50 mm x 90 mm x thickness 2.5 mm is formed, and using a graphic impact tester manufactured by Toyo Seiki Co., Ltd., the total absorbed energy (J) under the conditions of a fixed surface diameter of 40 mmφ, a drop diameter of 13 mmφ, and 23 ° C Was measured.
(2) Flame retardance Based on UL-94 vertical combustion test, measured using a 1.6 mm-thickness injection-molded test piece, and evaluated the total combustion time at the 10th flame contact and the presence or absence of drops during combustion. .
(3) Releasability When a test piece was formed by injection molding, the degree of ease of releasing the test piece and the runner from the mold was visually determined. Those with good mold release were indicated with ○, those with slightly bad mold were indicated with Δ, and those with bad release were indicated with ×.

(4) Layer peeling The tensile test piece of 3.2 mm thickness according to ASTM-D-638 by injection molding was visually judged to determine the degree of surface peeling by repeating bending. The case where peeling was hardly observed was indicated by ○, the case where slight peeling was observed was indicated by Δ, and the case where peeling was severe was indicated by ×.
(5) Glossiness The minimum pressure required to form a tensile test piece (type I: total length 215 mm) according to ASTM-D-638, the same 50 mm × 90 mm × thickness as the test piece used for the surface impact strength test The glossiness (%) of the central part of the molded product was measured at a light incident (light receiving) angle of 60 degrees on a 2.5 mm flat plate according to JIS-Z-8741.

(6) Chemical resistance Based on ASTM-D-638, normal tensile strength (TSa) was measured using a 3.2 mm-thick test piece. On the other hand, after attaching the test piece to a bar having a circular arc shape with a surface strain of 1% and dipping in a chemical (mixed solution of 60/40 weight ratio of isopropyl alcohol and cyclohexane) and holding for 30 minutes, the same manner Tensile strength (TSb) was measured. The ratio of TSb to TSa (tensile strength retention) was expressed in%.
(7) Damping characteristics: loss factor η
Using a loss factor measuring device (manufactured by Matsushita Intertechno Co., Ltd.) at room temperature (23 ° C.), the test piece was subjected to electromagnetic excitation by the one-end fixed steady excitation method, and the response speed was read to obtain a transfer function. Next, the frequency at a point 3 dB lower than the absolute value of the secondary resonance peak was read, and the loss coefficient η was obtained from the half width method. The test piece used was a 127 × 12.7 × 3.2 mm strip test piece.

(8) Conspicuous weld line Minimum injection pressure + gauge pressure so that a weld line can be formed in the center of the bar by injection molding of a 127x1.6mm thick bar from both sides in the longitudinal direction by injection molding Molded with IMpa. The noticeability of the weld line was visually judged. A good sample in which a thin line was seen and the weld was not conspicuous was judged as “Good”, a weld part having haze (cloudiness) and a poorly conspicuous line was judged as “X”, and an intermediate product was judged as “△”.
(9) Colorability The black depth was visually evaluated using (5) gloss test pieces of the black-colored composition. Judgment was made by ○, Δ, and × in order from the deep and excellent colorability.

[Examples 1-5, Comparative Examples 1-5]
0.3 parts by weight of tris (2,4-di-t-butylphenyl) phosphite was added and mixed as a proportion and a stabilizer shown in Table 1. In Example 5, 0.05 part by mass of polytetrafluoroethylene was further added. They are supplied to a twin screw extruder with a screw diameter of 25 mm with the maximum temperature of the heating cylinder set to 300 ° C., melt kneaded while vacuum devolatilizing from a screw rotation speed of 300 rpm and the vent port, and the strand is cooled and cut. Resin composition pellets were obtained. Next, physical property test pieces were molded from the obtained resin composition pellets by injection molding at a maximum set temperature (injection cylinder) of 260 ° C. and a mold temperature of 70 ° C. Evaluation was made by the above test method, and the results shown in Table 2 were obtained.

[Examples 6 to 13, Comparative Examples 6 and 7]
The proportions shown in Table 2 for each component, and 0.3 parts by weight of tris (2,4-di-t-butylphenyl) phosphite as a stabilizer, and carbon black as a colorant (magnesium stearate as a dispersant) 0.5% by mass) was added and mixed. They are supplied to a twin screw extruder with a screw diameter of 25 mm with the maximum temperature of the heating cylinder set at 320 ° C., melt-kneaded while vacuum devolatilizing from the vent port with a screw speed of 300 rpm, and the strand is cooled and cut. Resin composition pellets were obtained. Next, test pieces were molded from the obtained resin composition pellets by injection molding at a maximum set temperature (injection cylinder) of 300 ° C. and a mold temperature of 85 ° C. Evaluation was performed by the above test method, and the results shown in Table 3 were obtained.

  The present invention does not contain a halogen compound, has excellent heat resistance, mechanical properties, and electrical properties, has good releasability during injection molding, has almost no problems such as smoke generation, flame retardant adhesion to the mold, and the like. A preferable polyphenylene ether-based flame retardant resin composition excellent in appearance of molded product and impact resistance is provided, and can be suitably used for various exterior materials and electrical parts.

Claims (14)

(A) 50 to 98 parts by mass of a polyphenylene ether resin or a combination of this with a styrene resin,
(B) Formula (I)

Or the following formula (II)

(Wherein Q1, Q2, Q3 and Q4 represent an alkyl group having 1 to 6 carbon atoms or hydrogen, R1, R2, R3 and R4 represent a methyl group or hydrogen. N represents an integer of 1 or more. , N1, and n2 represent integers from 0 to 2, and m1, m2, m3, and m4 represent integers from 1 to 3.)
1 to 40 parts by mass of a flame retardant mainly comprising a condensed phosphate ester represented by
(C) a hydrogenated copolymer obtained by hydrogenating a block copolymer comprising a conjugated diene monomer unit and a vinyl aromatic monomer unit, wherein the conjugated diene monomer unit and the vinyl aromatic 1 to less than 10 parts by mass of a random hydrogenated copolymer having a hydrogenated random copolymer block obtained by hydrogenating a (non-hydrogenated) random copolymer block consisting of a group monomer unit, and (d ) Polyphenylene ether composition comprising 0 to 10 parts by mass of polyolefin and 100 parts by mass in total of (a) + (b) + (c) + (d). (B) The flame retardant is
Formula (I)

(Wherein Q1, Q2, Q3 and Q4 represent an alkyl group having 1 to 6 carbon atoms or hydrogen, R1, R2, R3 and R4 represent a methyl group or hydrogen. N represents an integer of 1 or more. , N1, and n2 represent integers from 0 to 2, and m1, m2, m3, and m4 represent integers from 1 to 3.)
The polyphenylene ether composition of Claim 1 which has the condensed phosphate ester shown by these as a main component.   The polyphenylene ether composition according to claim 1 or 2, comprising (c) less than 1 to 7 parts by mass of a random hydrogenated copolymer and (d) 0.5 to 5 parts by mass of a polyolefin-based resin.   (C) The polyphenylene ether composition according to claim 1 or 2, comprising 1 to less than 5 parts by mass of a random hydrogenated copolymer.   (D) Polyphenylene ether composition in any one of Claims 1-3 which consists of 0.5-3 mass parts of polyolefin resin. (C) the random hydrogenated copolymer comprises at least one polymer block comprising a polymer block (A) comprising a vinyl aromatic monomer unit, a conjugated diene monomer unit and a vinyl aromatic monomer unit; A hydrogenated copolymer comprising at least one hydrogenated random copolymer block (B) obtained by hydrogenating a random copolymer block consisting of the following: (1) to (4) The polyphenylene ether composition according to any one of claims 1 to 5.
(1) The content of the vinyl aromatic monomer unit is more than 40% by mass and less than 95% by mass with respect to the mass of the (c) random hydrogenated copolymer,
(2) The content of the polymer block (A) is 10 to 50% by mass with respect to the mass of the (c) random hydrogenated copolymer,
(3) The weight average molecular weight is 30,000 to 1,000,000,
(4) The hydrogenation rate of the double bond of the conjugated diene monomer unit is 75% or more.   The polyphenylene ether composition according to any one of claims 1 to 6, wherein (d) the polyolefin comprises low density polyethylene.   The polyphenylene ether composition according to any one of claims 1 to 6, wherein (d) the polyolefin comprises a linear low density polyethylene.   The polyphenylene ether composition according to any one of claims 1 to 6, wherein (d) the polyolefin comprises an ethylene-propylene copolymer. (D) The polyolefin comprises an ethylene-butene copolymer.
The polyphenylene ether composition according to Item.   The polyphenylene ether composition according to any one of claims 1 to 6, wherein (d) the polyolefin comprises an ethylene-octene copolymer.   The polyphenylene ether composition according to any one of claims 1 to 11, which has a glossiness of 90% or more.   The polyphenylene ether composition according to claim 12, wherein the styrene resin used in combination with (a) the polyphenylene ether resin is polystyrene (styrene homopolymer).   A molded article obtained by injection molding the polyphenylene ether composition according to claim 12 or 13.