JP2022108192A - resin composition - Google Patents

Abstract

To provide a resin composition which is excellent in impact resistance, chemical resistance, and self-tapping strength and which has rigidity applicable to a mechanical component and a structural body.SOLUTION: A resin composition of this invention contains: a polyphenylene ether-based resin (a); a hydrogenated block copolymer and/or a modified substance of the hydrogenated block copolymer (b); an olefinic polymer composed of olefins except for propylene (c); a polypropylene-based resin (d); and an admixture (e), and is characterized as having: 50-80 pts.mass component (a); 5-30 pts.mass component (b); 1-20 pts.mass component (c); and 1-20 pts.mass component (e), and a mass ratio of the component (c) to the component (d) of 1-5, in which the component (a) forms a continuous phase, a glass-transition temperature of a polymer block B in the component (b) is -65°C or less, and a brittleness temperature of the component (c) is -50°C or less.SELECTED DRAWING: None

Description

The present invention relates to resin compositions.

Polyphenylene ether (hereinafter sometimes simply referred to as "PPE") has advantages such as heat resistance, low specific gravity, and flame retardancy, and is used in various applications such as OA and automobile applications. . However, since polyphenylene ether is an amorphous resin, it has insufficient resistance to oils and fats and organic solvents, and there is a problem that there are some restrictions on the usage and environment.

For this reason, in some applications, attempts have been made to improve the chemical resistance by alloying PPE resin with a crystalline resin. There is a problem that the impact resistance deteriorates rapidly.

On the other hand, studies have also been made on adding a thermoplastic elastomer having a low glass transition temperature to polyphenylene ether or an alloy of polypropylene and polyphenylene ether to increase the impact resistance (for example, Patent Documents 1 to 5).

WO2015/50060 JP 2004-161929 A Japanese Patent No. 5422561 JP 2007-519782 A WO2017/208945

However, even if the technique of Patent Document 1 is used, the current situation is that it has not been possible to obtain a composition having not only impact resistance and chemical resistance but also self-tapping strength that can withstand practical use. Even if the techniques of Patent Documents 2 to 4 are used, it is necessary to add a relatively large amount of thermoplastic elastomer in order to impart a certain level of impact resistance. Applications were limited, and it was difficult to develop mechanical parts and structures. Further, the technique of Patent Document 5 also has a further problem with the self-tapping strength.

Accordingly, an object of the present invention is to provide a resin composition which is excellent in impact resistance, chemical resistance, and self-tapping strength, and has rigidity which can be applied to mechanical parts and structures.

［式中、Ｒ^１１及びＲ^１２は、各々独立して、直鎖状若しくは分岐状の炭素原子数１～６のアルキル基及び／又は炭素原子数６～１０のアリール基であり；Ｍ^１は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ａは、１～３の整数であり；ｍは、１～３の整数であり；ａ＝ｍである］、及び
下記式（２）で表されるジホスフィン酸塩

［式中、Ｒ^２１及びＲ^２２は、各々独立して、直鎖状若しくは分岐状の炭素原子数１～６のアルキル基及び／又は炭素原子数６～１０のアリール基であり；Ｒ^２３は、直鎖状若しくは分岐状の炭素原子数１～１０のアルキレン基、炭素原子数６～１０のアリーレン基、炭素原子数６～１０のアルキルアリーレン基又は炭素原子数６～１０のアリールアルキレン基であり；Ｍ^２は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ｂは、１～３の整数であり；ｎは、１～３の整数であり；ｊは、１又は２の整数であり；ｂ・ｊ＝２ｎである］
からなる群より選ばれる少なくとも１種のホスフィン酸塩類を含有する、［１］又は［２］に記載の樹脂組成物。
［４］
前記（ｃ）成分が、エチレン－１－ブテン共重合体である、［１］～［３］のいずれかに記載の樹脂組成物。
［５］
前記（ｃ）成分の密度が、０．８７ｇ／ｃｍ^３以上である、［１］～［４］のいずれかに記載の樹脂組成物。
［６］
前記（ｃ）成分の密度が、０．９０ｇ／ｃｍ^３以上である、［１］～［５］のいずれかに記載の樹脂組成物。
［７］
前記（ｄ）成分が、プロピレンホモポリマーである、［１］～［６］のいずれかに記載の樹脂組成物。
［８］
前記（ｅ）成分が、ビニル芳香族化合物を主体とする少なくとも１個の重合体ブロックＩと、共役ジエン化合物を主体とする少なくとも１個の重合体ブロックＩＩとを含むブロック共重合体の少なくとも一部が水素添加されてなる水素添加ブロック共重合体及び／又は該水素添加ブロック共重合体の変性物であり、
前記（ｅ）成分中に含まれる共役ジエン化合物単位における二重結合に対する、１，２－ビニル結合及び３，４－ビニル結合の合計が５０％超９０％以下であり、
水素添加前の前記（ｅ）成分中の、ビニル芳香族化合物単位の含有量が３０～５０質量％であり、
前記（ｅ）成分中の、重合体ブロックＩＩのガラス転移温度が－５０℃超であり、
前記（ｅ）成分中に含まれる共役ジエン化合物単位における二重結合に対する水素添加率が８０～１００％である、［１］～［７］のいずれかに記載の樹脂組成物。
［９］
ＩＳＯ １７８に準じて測定した曲げ弾性率が、１６００ＭＰａ以上である、［１］～［８］のいずれかに記載の樹脂組成物。 That is, the present invention is as follows.
[1]
(a) a polyphenylene ether-based resin;
(b) At least part of a block copolymer containing at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound is hydrogenated a hydrogenated block copolymer and/or a modified product of the hydrogenated block copolymer,
(c) an olefin-based polymer composed of olefins other than propylene;
(d) a polypropylene-based resin;
(e) an admixture that is a compound different from the component (b);
contains
The mass ratio of the component (a) is 50 to 80 with respect to the total 100 parts by mass of the component (a), the component (b), the component (c), the component (d) and the component (e). Parts by mass, the mass ratio of the component (b) is 5 to 30 parts by mass, the mass ratio of the component (c) is 1 to 20 parts by mass, and the mass ratio of the component (e) is 1 to 20 parts by mass,
The mass ratio (c)/(d) of the component (c) and the component (d) is 1 to 5,
The component (a) forms a continuous phase,
The polymer block B in the component (b) has a glass transition temperature of −65° C. or lower,
The embrittlement temperature of the component (c) is −50° C. or lower,
A resin composition characterized by:
[2]
The resin composition according to [1], further comprising (f) a phosphate compound.
[3]
Furthermore, (g) containing phosphinates,
The component (g) is a phosphinate represented by the following general formula (1)

[wherein R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms and/or an aryl group having 6 to ¹⁰ carbon atoms; , calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions, and protonated nitrogen bases; is an integer; m is an integer of 1 to 3; a = m], and a diphosphinate represented by the following formula (2)

[wherein R ²¹ and R ²² are each independently a linear or branched alkyl group having ¹ to 6 carbon atoms and/or an aryl group having 6 to 10 carbon atoms; , a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 6 to 10 carbon atoms or an arylalkylene group having 6 to 10 carbon atoms. Yes; ^M2 is at least one selected from the group consisting of calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions and protonated nitrogen bases; b is , an integer from 1 to 3; n is an integer from 1 to 3; j is an integer from 1 or 2; b j = 2n]
The resin composition according to [1] or [2], containing at least one phosphinate salt selected from the group consisting of:
[4]
The resin composition according to any one of [1] to [3], wherein the component (c) is an ethylene-1-butene copolymer.
[5]
The resin composition according to any one of [1] to [4], wherein the component (c) has a density of 0.87 g/cm ³ or more.
[6]
The resin composition according to any one of [1] to [5], wherein the component (c) has a density of 0.90 g/cm ³ or more.
[7]
The resin composition according to any one of [1] to [6], wherein the component (d) is a propylene homopolymer.
[8]
The component (e) is at least one block copolymer containing at least one polymer block I mainly composed of a vinyl aromatic compound and at least one polymer block II mainly composed of a conjugated diene compound. A hydrogenated block copolymer and/or a modified product of the hydrogenated block copolymer, wherein
The total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is more than 50% and 90% or less with respect to the double bonds in the conjugated diene compound units contained in the component (e),
The content of the vinyl aromatic compound unit in the component (e) before hydrogenation is 30 to 50% by mass,
The glass transition temperature of the polymer block II in the component (e) is higher than -50°C,
The resin composition according to any one of [1] to [7], wherein the hydrogenation rate of the double bonds in the conjugated diene compound unit contained in the component (e) is 80 to 100%.
[9]
The resin composition according to any one of [1] to [8], which has a flexural modulus of 1600 MPa or more as measured according to ISO 178.

According to the present invention, it is possible to obtain a resin composition that is excellent in impact resistance, chemical resistance, and self-tapping strength, and has rigidity that can be applied to mechanical parts and structures.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

[Resin composition]
The resin composition of the present embodiment comprises (a) a polyphenylene ether-based resin, (b) at least one polymer block A mainly composed of a vinyl aromatic compound, and a polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating at least a portion of a block copolymer containing at least one and / or a modified product of the hydrogenated block copolymer;
(c) an olefin-based polymer composed of olefins other than propylene;
(d) a polypropylene-based resin;
(e) an admixture that is a compound different from the above component (b);
contains
The mass ratio of the component (a) is 50 to 100 parts by mass in total of the component (a), the component (b), the component (c), the component (d), and the component (e). 80 parts by mass, the mass ratio of component (b) is 5 to 30 parts by mass, the mass ratio of component (c) is 1 to 20 parts by mass, and the mass ratio of component (e) is 1 to 20 parts by mass. ,
The mass ratio (c)/(d) of the component (c) and the component (d) is 1 to 5,
The above component (a) forms a continuous phase,
The polymer block B in the component (b) has a glass transition temperature of −65° C. or lower,
The embrittlement temperature of the component (c) is -50°C or lower.
The resin composition of the present embodiment has excellent impact resistance, chemical resistance, and self-tapping properties, and has rigidity that allows application to mechanical parts and structures. Moreover, it is preferable to be excellent in flame retardancy. In the present embodiment, "excellent flame retardancy" refers to a flame retardancy level of V-1 or higher in the UL94 vertical combustion test described in Examples below.

In the present specification, at least a part of the block copolymer containing at least one polymer block mainly composed of a vinyl aromatic compound and at least one polymer block mainly composed of a conjugated diene compound is A hydrogenated block copolymer obtained by hydrogenation and/or a modified product of the hydrogenated block copolymer may be simply referred to as a "hydrogenated block copolymer". In addition, an unmodified hydrogenated block copolymer may be referred to as an "unmodified hydrogenated block copolymer", and a modified hydrogenated block copolymer may be referred to as a "modified hydrogenated block copolymer". .
Also, the total of 1,2-vinyl bonds and 3,4-vinyl bonds in the conjugated diene compound unit may be referred to as "all vinyl bonds".

The components of the resin composition of this embodiment are described below.

((a) polyphenylene ether resin)
The (a) polyphenylene ether-based resin is not particularly limited, and examples thereof include polyphenylene ether, modified polyphenylene ether, and mixtures thereof. Component (a) may be used singly or in combination of two or more.

From the viewpoint of further improving the flame retardancy of the resin composition, the reduced viscosity of the component (a) is preferably 0.25 dL/g or more, more preferably 0.28 dL/g or more, and , is preferably 0.60 dL/g or less, more preferably 0.57 dL/g or less, and particularly preferably 0.55 dL/g or less. The reduced viscosity can be controlled by the polymerization time and amount of catalyst.
The reduced viscosity can be measured with an Ubbelohde viscosity tube at a temperature of 30° C. using a chloroform solution of η _sp /c: 0.5 g/dL.

［式中、Ｒ^３１、Ｒ^３２、Ｒ^３３、及びＲ^３４は、各々独立して、水素原子、ハロゲン原子、炭素原子数１～７の第１級のアルキル基、炭素原子数１～７の第２級のアルキル基、フェニル基、ハロアルキル基、アミノアルキル基、炭化水素オキシ基、及び少なくとも２個の炭素原子がハロゲン原子と酸素原子とを隔てているハロ炭化水素オキシ基からなる群より選ばれる一価の基である。］ - Polyphenylene ether -
The polyphenylene ether is not particularly limited, for example, a homopolymer consisting of a repeating unit structure represented by the following formula (3), and / or having a repeating unit structure represented by the following formula (3) A copolymer is mentioned.

[wherein R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, a selected from the group consisting of secondary alkyl groups, phenyl groups, haloalkyl groups, aminoalkyl groups, hydrocarbonoxy groups, and halohydrocarbonoxy groups in which at least two carbon atoms separate the halogen and oxygen atoms; is a monovalent group that ]

As the polyphenylene ether, known ones can be used without any particular limitation. Specific examples of polyphenylene ether include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl- 6-phenyl-1,4-phenylene ether), homopolymers such as poly(2,6-dichloro-1,4-phenylene ether); 2,6-dimethylphenol and 2,3,6-trimethylphenol and 2 - copolymers such as copolymers with other phenols such as methyl-6-butylphenol; and 2,3,6-trimethylphenol are preferred, and poly(2,6-dimethyl-1,4-phenylene ether) is more preferred.

The method for producing the polyphenylene ether is not particularly limited, and conventionally known methods can be used. A specific example of the method for producing polyphenylene ether is US Pat. No. 3,306,874, in which polyphenylene ether is produced by oxidative polymerization of 2,6-xylenol, for example, using a complex of cuprous salt and amine as a catalyst. and the methods described in, US Pat. No. 3,306,875, US Pat. No. 3,257,357, US Pat. Methods such as those described in JP-A-63-152628 can be mentioned.

-Modified Polyphenylene Ether-
The modified polyphenylene ether is not particularly limited, and examples thereof include those obtained by grafting and/or adding a styrenic polymer and/or a derivative thereof to the above polyphenylene ether. The rate of mass increase due to grafting and/or addition is not particularly limited, and is preferably 0.01% by mass or more and 10% by mass or less with respect to 100% by mass of the modified polyphenylene ether. , more preferably 7% by mass or less, and particularly preferably 5% by mass or less.

The method for producing the modified polyphenylene ether is not particularly limited. Examples thereof include a method of reacting the above polyphenylene ether with a styrene polymer and/or a derivative thereof.

When the component (a) is a mixture of polyphenylene ether and modified polyphenylene ether, the mixing ratio of the polyphenylene ether and the modified polyphenylene ether is not particularly limited, and may be any ratio.

((b) hydrogenated block copolymer)
The hydrogenated block copolymer as the component (b) includes at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating at least a portion of a block copolymer containing and/or a modified product of the hydrogenated block copolymer.
The component (b) may contain blocks other than the polymer block A and the polymer block B, but preferably consists of the polymer block A and the polymer block B only. It is more preferable to consist of A and one type of polymer block B only.
The above component (b) may be used alone or in combination of multiple types.

--polymer block A--
Examples of the polymer block A mainly composed of a vinyl aromatic compound include a homopolymer block of a vinyl aromatic compound, a copolymer block of a vinyl aromatic compound and a conjugated diene compound, and the like. Among them, a homopolymer block of a vinyl aromatic compound and a copolymer block of a vinyl aromatic compound and a conjugated diene compound containing more than 50% by mass (preferably 70% by mass or more) of vinyl aromatic compound units are preferable.
Here, the phrase “mainly composed of a vinyl aromatic compound” in the polymer block A means that the polymer block A before hydrogenation contains more than 50% by mass of vinyl aromatic compound units, and the vinyl aromatic It is preferable to contain 70% by mass or more of compound units.

Examples of the vinyl aromatic compound include, but are not particularly limited to, styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, and the like. Among them, styrene is preferred.
Examples of the conjugated diene compound include conjugated diene compounds described later, and preferred are butadiene, isoprene, and combinations thereof.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

In the polymer block A, the distribution of the vinyl aromatic compound, the conjugated diene compound, etc. in the molecular chain of the polymer block may be random, tapered (monomer component increases or decreases along the molecular chain), or partial block. shape or any combination thereof.

When there are two or more polymer blocks A in the component (b), each polymer block A may have the same structure or a different structure.

The number average molecular weight (Mn) of the polymer block A is preferably 5,000 to 25,000 from the viewpoint of obtaining even better rigidity, impact resistance, chemical resistance, and self-tapping strength, and more It is preferably 10,000 to 25,000.

--polymer block B--
Examples of the polymer block B mainly composed of a conjugated diene compound include a homopolymer block of a conjugated diene compound and a random copolymer block of a conjugated diene compound and a vinyl aromatic compound. Among them, a homopolymer block of a conjugated diene compound and a copolymer block of a conjugated diene compound and a vinyl aromatic compound containing more than 50% by mass (preferably 70% by mass or more) of conjugated diene compound units are preferable.
Here, the phrase “mainly composed of a conjugated diene compound” in the polymer block B means that the polymer block B before hydrogenation contains more than 50% by mass of conjugated diene compound units. It is preferable to contain 70% by mass or more.

Examples of the conjugated diene compound include, but are not limited to, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like. Among them, butadiene, isoprene and combinations thereof are preferred.
Examples of the vinyl aromatic compound include the vinyl aromatic compounds described above, and styrene is preferred.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

In the polymer block B, the distribution of the conjugated diene compound, the vinyl aromatic compound, etc. in the molecular chain in the polymer block is random, tapered (monomer component increases or decreases along the molecular chain), partial block shape or any combination thereof.

When there are two or more polymer blocks B in the component (b), each polymer block B may have the same structure or a different structure.

The hydrogenation rate of the ethylenic double bond in the conjugated diene compound unit in the polymer block B is 20% or more and 80% from the viewpoint of obtaining even better rigidity, chemical resistance, impact resistance, and tracking resistance. %, more preferably 20% or more and less than 70%. When the hydrogenation rate is within the above range, the impact resistance of the resin composition is improved, which is preferable.

The total ratio of the 1,2-vinyl bond and the 3,4-vinyl bond to the ethylenic double bond in the conjugated diene compound unit in the polymer block B provides even better rigidity, impact resistance, and chemical resistance. , From the viewpoint of obtaining self-tapping strength, it is preferably 25% or more and less than 60%, more preferably 25 to 55%, still more preferably 25 to 50%, and particularly preferably 35 to 48%.
In this specification, the sum of the 1,2-vinyl bond amount and the 3,4-vinyl bond amount (total vinyl bond amount) means the conjugated diene compound unit in the conjugated diene compound-containing polymer block before hydrogenation. the total of the 1,2-vinyl bond amount, the 3,4-vinyl bond amount, and the 1,4-conjugated bond amount refers to the ratio of The total amount of vinyl bonds is measured using an infrared spectrophotometer, and is described in Analytical Chemistry, Volume 21, No. 8, August 1949.

The number average molecular weight (Mn) of the polymer block B is preferably 20,000 to 100,000 from the viewpoint of obtaining even better rigidity, impact resistance, chemical resistance, and self-tapping strength, and more It is preferably 20,000 to 80,000.

The glass transition temperature of the polymer block B after hydrogenation is −65° C. or less, and from the viewpoint of obtaining even better rigidity, impact resistance, chemical resistance, and self-tapping strength, it is −70° C. or less. is preferred, and more preferably -75°C or lower.
In the present specification, the glass transition temperature of the block copolymer and the glass transition temperature of the polymer block in the block copolymer are measured using, for example, a dynamic viscoelasticity measuring device, and a sample made into a film state. can be measured under a tensile mode, a temperature scan rate of 3° C./min, a frequency of 1 Hz, and a nitrogen atmosphere.

In the polymer block B, the total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds to the ethylenic double bonds in the conjugated diene compound units contained in the polymer block B is 25% or more and 60 %, or a polymer mainly composed of a conjugated diene compound in which the total proportion of 1,2-vinyl bonds and 3,4-vinyl bonds is 25 to 45% Mainly composed of a conjugated diene compound having both block B1 and polymer block B2 mainly composed of a conjugated diene compound in which the total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds is 45% or more and less than 70% It may be a polymer block that
In the structure of the block copolymer having the polymer block B1 and the polymer block B2, the polymer block A is "A", the polymer block B1 is "B1", and the polymer block B2 is "B2". Then, for example, it is represented by A-B2-B1-A, A-B2-B1, etc., and can be obtained by a known polymerization method in which the total amount of vinyl bonds is controlled based on the adjusted feed sequence of each monomer unit. can.

--Structure of hydrogenated block copolymer--
The structure of the hydrogenated block copolymer in the component (b) is such that the polymer block A is "A" and the polymer block B is "B". A type, BABA type, (AB-) _n -X type (where n is an integer of 1 or more, X is silicon tetrachloride, reaction of polyfunctional coupling agents such as tin tetrachloride or the residue of an initiator such as a polyfunctional organolithium compound.), structures such as ABABA type.
Further, referring to the block structure, the polymer block B is a homopolymer block of a conjugated diene compound, or a conjugated diene compound containing more than 50% by mass (preferably 70% by mass or more) of conjugated diene compound units and a vinyl aromatic is a copolymer block with a compound, and the polymer block A is a homopolymer block of a vinyl aromatic compound, or a vinyl aromatic compound containing more than 50% by mass (preferably 70% by mass or more) of the vinyl aromatic compound. and a conjugated diene compound.
The molecular structure of the hydrogenated block copolymer in component (b) is not particularly limited, and may be, for example, linear, branched, radial or any combination thereof.

-- Content of Vinyl Aromatic Compound Unit --
The content of the vinyl aromatic compound unit (hydrogenated block copolymer structural unit derived from the vinyl aromatic compound) in the component (b) before hydrogenation is not particularly limited, but the heat resistance and mechanical strength of the composition From the viewpoint of, it is preferably 10 to 70% by mass, more preferably 20 to 70% by mass, more preferably 20 to 60% by mass, still more preferably 30 to 50% by mass, particularly preferably 30 to 40% by mass. is. In addition, not only one type of component (b) having a vinyl aromatic compound unit content within these ranges, but also two or more types of (b) components having different vinyl aromatic compound unit contents can be used in combination. .

--Total amount of vinyl bonds--
The ratio of the total of 1,2-vinyl bonds and 3,4-vinyl bonds to the ethylenic double bonds in the conjugated diene compound units contained in the component (b) is 25% or more and less than 60%. It is preferably 25% or more and 55% or less, and still more preferably 25% or more and 50% or less. When the total proportion of 1,2-vinyl bonds and 3,4-vinyl bonds is less than 60%, the impact resistance of the resin composition is improved. When it is 50% or less, the impact resistance is further improved. Further, when the total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds is 25% or more, it is preferable from the viewpoint of improving compatibility with components (c) and (d).
The method for controlling the total proportion of 1,2-vinyl bonds and 3,4-vinyl bonds within the above range is not particularly limited. Examples include a method of adding a regulator and a method of adjusting the polymerization temperature.
"The sum of 1,2-vinyl bonds and 3,4-vinyl bonds with respect to the double bonds in the conjugated diene compound unit" means the conjugated diene compound in the block copolymer before hydrogenation of the hydrogenated block copolymer Refers to the sum of 1,2-vinyl bonds and 3,4-vinyl bonds for the double bonds (ethylenic double bonds) in the unit. For example, the block copolymer before hydrogenation can be measured with an infrared spectrophotometer and calculated by the Hampton method. It can also be calculated using NMR from the block copolymer after hydrogenation.

-- Hydrogenation rate --
In the above component (b), the hydrogenation rate for the ethylenic double bond (double bond in the conjugated diene compound unit) in the block copolymer is preferably more than 0% and less than 80%, more preferably 10% or more and less than 80%, more preferably 20% or more and less than 80%, still more preferably 20% to 70%, and particularly preferably 20% or more and less than 70%. When the hydrogenation rate is within the above range, the impact resistance of the resin composition is improved, which is preferable.
The (b) component having such a hydrogenation rate is, for example, in the hydrogenation reaction of the ethylenic double bond of the block copolymer, the amount of hydrogen consumed is set to the desired hydrogenation rate (for example, 10% or more and less than 80% ) can be easily obtained by controlling the range of
The hydrogenation rate can be obtained by, for example, quantifying the amount of remaining double bonds in the polymer block B by NMR measurement.
The total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds to the ethylenic double bonds in the conjugated diene compound units contained in component (b) is less than 60%, and When the hydrogenation rate of the ethylenic double bonds in the component (b) is less than 80%, the impact resistance of the resin composition is further improved, which is more preferable.

--molecular weight peak--
The molecular weight peak after hydrogenation in terms of standard polystyrene by GPC measurement of the component (b) is preferably 10,000 to 200,000 from the viewpoint of rigidity, impact resistance, chemical resistance, and self-tapping strength. More preferably, it is 30,000 to 150,000.
A method for controlling the molecular weight peak of the component (b) within the above range is not particularly limited, but an example thereof includes a method of adjusting the amount of catalyst in the polymerization step.
In addition, in this specification, a molecular weight peak can be measured under the following conditions using Showa Denko K.K. product gel permeation chromatography System21. In the measurement, a column in which one KG manufactured by Showa Denko Co., Ltd., one K-800RL, and one K-800R were connected in series in this order was used, and the column temperature was set to 40°C. , the solvent is chloroform, the solvent flow rate is 10 mL/min, and the sample concentration is 1 g of hydrogenated block copolymer/1 liter of chloroform solution. A calibration curve is also prepared using standard polystyrene (molecular weights of standard polystyrene are 3650000, 2170000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, and 550). Furthermore, the wavelength of UV (ultraviolet rays) in the detection section is set to 254 nm for both standard polystyrene and hydrogenated block copolymers.

The molecular weight distribution (Mw/Mn) of component (b) before hydrogenation is 1.01 to 1.50 from the viewpoint of obtaining even better rigidity, impact resistance, chemical resistance, and self-tapping strength. is preferred, and more preferably 1.03 to 1.40.

--Production method--
The method for producing the hydrogenated block copolymer in component (b) is not particularly limited, and known production methods can be used. Publications, JP-A-50-75651, JP-A-54-126255, JP-A-56-10542, JP-A-56-62847, JP-A-56-100840, JP-A 2-300218, GB 1130770, US 3281383, US 3639517, UK 1020720, US 3333024 and US 4501857 and the method described in the specification, etc.

-Modified hydrogenated block copolymer-
Modified products of the hydrogenated block copolymer in the component (b) include, for example, the hydrogenated block copolymer (particularly, an unmodified hydrogenated block copolymer), an α,β-unsaturated carboxylic acid or A modified hydrogenated block obtained by reacting it with a derivative thereof (ester compound or acid anhydride compound) in the presence or absence of a radical generator in a molten state, a solution state or a slurry state at 80 to 350°C. A copolymer etc. are mentioned. In this case, the α,β-unsaturated carboxylic acid or derivative thereof is preferably grafted or added in a proportion of 0.01 to 10% by mass relative to the unmodified hydrogenated block copolymer.
When an unmodified hydrogenated block copolymer and a modified hydrogenated block copolymer are used together as the component (b), the mixing ratio of the unmodified hydrogenated block copolymer and the modified hydrogenated block copolymer is can be determined without particular restrictions.

((c) olefin polymer)
The component (c) is not particularly limited, and examples thereof include homopolymers of olefinic monomers other than propylene and copolymers of two or more monomers containing olefinic monomers other than propylene. . Among them, a copolymer of ethylene and an α-olefin other than ethylene is preferable from the viewpoint of impact resistance. Here, from the viewpoint of impact resistance, chemical resistance, tracking resistance and rigidity of the resulting resin composition, propylene units are not included as monomer units constituting component (c).
The terms "olefin-based polymer composed of olefins other than propylene" and "contains no propylene units" also include cases where propylene is contained as a constituent unit to an extent that does not impair the effects of the invention. For example, component (c) It means that the content of propylene units in all structural units constituting component (c) is less than 0.1% by mass.

Examples of the component (c) include copolymers of ethylene and one or more C4 to C20 α-olefins. Among them, copolymers of ethylene and one or more C4 to C8 α-olefins are more preferable, and ethylene and 1-butene, 1-hexene, 4-methyl-1-pentene and A copolymer with one or two or more comonomers selected from the group consisting of 1-octene is more preferred, and a copolymer of ethylene and 1-butene is particularly preferred. By using such a copolymer as the component (c), there is a tendency to obtain a resin composition having higher impact resistance and higher chemical resistance.
The component (c) may be used singly or in combination of two or more. Also, two or more ethylene-α-olefin copolymers may be used as the component (c).

The content of structural units derived from ethylene in the component (c) is preferably 5 to 95% by mass with respect to the total amount of the olefin polymer from the viewpoint of low-temperature curability and flexibility of the resin composition. More preferably, it is 30 to 90% by mass.

The content of structural units derived from α-olefins other than ethylene in the component (c) is 5% by mass with respect to the total amount of the olefin polymer, from the viewpoint of low-temperature curability and flexibility of the resin composition. or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. From the viewpoint of the rigidity of the resin composition, the content is preferably 50% by mass or less, more preferably 48% by mass or less.

The embrittlement temperature of the component (c) is −50° C. or less, and from the viewpoint of obtaining even better impact resistance and chemical resistance, it is preferably −60° C. or less, more preferably −70° C. or less. is.
The embrittlement temperature can be measured according to ASTM D746.

The density of the component (c) measured according to JIS K7112 (the density at the raw material stage before kneading) is preferably 0.87 g/cm ³ or more from the viewpoint of the chemical resistance of the resin composition. More preferably, it is 0.90 g/cm ³ or more.
The method for controlling the density of the component (c) within the above range is not particularly limited, but an example thereof includes a method of adjusting by controlling the content of ethylene units.

The melt flow rate of the component (c) (MFR, measured under a load of 2.16 kgf at 190°C in accordance with ASTM D-1238, the density at the raw material stage before kneading) is the resin composition of the component (c). 0.1 to 5.0 g/10 min, more preferably 0.3 to 4.0 g/10 min, from the viewpoint of stabilization of morphology by dispersion in a substance and impact resistance of the resin composition, More preferably, it is 0.4 to 3.5 g/10 minutes.
The method for controlling the melt flow rate of component (c) within the above range is not particularly limited. , a method of adjusting the molar ratio of the concentration of monomer such as α-olefin and the concentration of hydrogen.

The component (c) may be, for example, an olefinic polymer rubber composed of olefins other than propylene.

The torsional rigidity of component (c) is preferably 1 to 30 MPa, more preferably 1 to 25 MPa, from the viewpoint of imparting sufficient impact resistance to the composition. The torsional stiffness of component (c) can be measured according to ASTM D 1043.

The Shore A of component (c) is preferably from 40 to 110, more preferably from 50 to 100, from the viewpoint of imparting sufficient impact resistance to the composition. In addition, the Shore A of the component (c) can be measured according to JIS K 6253.

The method for preparing component (c) is not particularly limited, and a catalyst (for example, titanium, metallocene, or vanadium) that can easily obtain a high-molecular-weight α-olefin polymer under ordinary processing conditions is used. and a method using a base catalyst, etc.). Among these, the method using a metallocene catalyst and a titanium chloride catalyst is preferable from the viewpoint of stability of structure control. As a method for producing the ethylene-α-olefin copolymer, known methods described in JP-A-6-306121 and JP-A-7-500622 can be used.

((d) polypropylene resin)
Examples of the component (d) include (d1) polypropylene resin, (d2) modified polypropylene resin, and mixtures thereof, which will be described later.

-(d1) polypropylene resin-
The (d1) polypropylene resin is a polymer in which 50 mol % or more of the constituent monomers is propylene, and is not particularly limited. (d1) The proportion of propylene in the monomers constituting the polypropylene resin is preferably 70 mol % or more, more preferably 90 mol % or more.

The (d1) polypropylene resin includes a crystalline propylene homopolymer; a crystalline propylene homopolymer portion obtained in the first step of polymerization, and propylene, ethylene and/or at least one other -crystalline propylene such as a crystalline propylene-ethylene block copolymer having a propylene-α-olefin random copolymer portion obtained by copolymerizing an olefin (e.g., butene-1, hexene-1, etc.)- α-olefin block copolymer;
These (d1) polypropylene resins may be used singly or in combination of two or more. Examples of the combined use of two or more types are not particularly limited, but for example, a crystalline propylene homopolymer and a crystalline propylene-ethylene block copolymer (excluding those having a Shore A hardness of 75 or less). mixtures. (d1) The polypropylene resin is preferably homopolypropylene and/or block polypropylene, more preferably homopolypropylene.

The method for producing the (d1) polypropylene resin is not particularly limited. A method of polymerizing a monomer containing propylene at a temperature in the range of 100° C. and a polymerization pressure in the range of 3 to 100 atm is exemplified. At this time, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the resulting polymer. The polymerization method is not particularly limited, and may be either a batch method or a continuous method. Moreover, solution polymerization in the presence of a solvent such as butane, pentane, hexane, heptane, octane, etc.; slurry polymerization; bulk polymerization in a monomer without a solvent; gas phase polymerization in a gaseous monomer, or the like can also be applied.

Furthermore, in order to increase the isotacticity and polymerization activity of the (d1) polypropylene resin to be obtained, an electron-donating compound can be used as a third component of the polymerization catalyst as an internal donor component or an external donor component. The type of the electron-donating compound is not particularly limited, and known compounds can be used. For example, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate and methyl toluate; phosphites such as triphenyl phosphite and tributyl phosphite; phosphoric acid derivatives such as hexamethylphosphoramide; Examples include alkoxy ester compounds, aromatic monocarboxylic acid esters, aromatic alkylalkoxysilanes, aliphatic hydrocarbon alkoxysilanes, various ether compounds, various alcohols and/or various phenols.

The melt flow rate (MFR) of the (d1) polypropylene resin (value measured at 230° C. under a load of 2.16 kg according to JIS K7210) is preferably 0.1 to 100 g/10 min, more preferably is 0.1 to 80 g/10 minutes. (d1) By setting the MFR of the polypropylene resin within the above range, the fluidity and rigidity of the resin composition tend to be well balanced.
(d1) A method for controlling the MFR of the polypropylene resin within the above range is not particularly limited, but an example thereof includes a method of controlling the supply amount ratio of hydrogen to the monomer.

-(d2) modified polypropylene resin-
The modified polypropylene resin (d2) is, for example, the polypropylene resin (d1) and an α,β-unsaturated carboxylic acid or derivative thereof in the presence or absence of a radical generator in a molten state or in a solution. and a resin obtained by reacting at 30 to 350° C. under these conditions. The (d2) modified polypropylene resin is not particularly limited, but for example, a modified polypropylene obtained by grafting or adding 0.01 to 10% by mass of an α,β-unsaturated carboxylic acid or a derivative thereof to the (d1) polypropylene resin. resin. Examples of the α,β-unsaturated carboxylic acid or derivative thereof include, but are not particularly limited to, maleic anhydride and N-phenylmaleimide.

When the (d1) polypropylene resin and the (d2) modified polypropylene resin are used in combination, the mixing ratio of the (d1) polypropylene resin and (d2) the modified polypropylene resin in the (d) polypropylene resin is not particularly limited and is arbitrary. can be determined to

The (d) polypropylene-based resin can be obtained by the above method or other known methods. Moreover, even when the (a) polypropylene-based resin has any crystallinity or melting point, it may be used alone, or two or more kinds thereof may be used in combination.

((e) admixture)
The (e) admixture is not particularly limited, but segment chains having high compatibility with components (a) and (b) and segment chains having high compatibility with components (c) and (d) and is preferably a copolymer having Examples of the segment chains having high compatibility with the components (a) and (b) include chains mainly composed of vinyl aromatic compounds such as polystyrene chains, polyphenylene ether chains, and the like. Examples of segment chains highly compatible with components (c) and (d) include polyolefin chains, elastomer molecular chains of copolymers of ethylene and α-olefin, chains mainly composed of conjugated diene compounds, and the like. .

Preferred specific examples of such copolymers include, for example, copolymers having a polystyrene chain-polyolefin chain, copolymers having a polyphenylene ether chain-polyolefin chain, copolymers having a polystyrene chain-conjugated diene chain, These hydrogenated block copolymers and the like are included. Among them, hydrogenated block copolymers are preferable from the viewpoint of thermal stability. These may be used individually by 1 type, and may use 2 or more types together.

The hydrogenated block copolymer as the component (e) includes at least one polymer block I mainly composed of a vinyl aromatic compound and at least one polymer block II mainly composed of a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating at least a part of a block copolymer containing, and a modified product of the hydrogenated block copolymer. Among them, the hydrogenated block copolymer as component (e) consists of one type of polymer block I mainly composed of a vinyl aromatic compound and one type of polymer block II mainly composed of a conjugated diene compound. At least part of the block copolymer is preferably hydrogenated.
The hydrogenated block copolymer as the component (e) does not contain the component (b).

Matters relating to the unmodified and modified hydrogenated block copolymers in component (e) are described below.

-Polymer block I mainly composed of vinyl aromatic compound-
The polymer block I mainly composed of a vinyl aromatic compound is not particularly limited, and examples thereof include a homopolymer block of a vinyl aromatic compound, a copolymer block of a vinyl aromatic compound and a conjugated diene compound, and the like. is mentioned.
In addition, in the polymer block I, "mainly composed of a vinyl aromatic compound" refers to containing more than 50% by mass of vinyl aromatic compound units in the polymer block I before hydrogenation. The compound unit content is preferably 70% by mass or more, more preferably 80% by mass or more, and may be 100% by mass or less.

Examples of the vinyl aromatic compound constituting the polymer block I include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene and the like, with styrene being preferred.
Examples of the conjugated diene compound constituting the polymer block I include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like, butadiene, isoprene, and combinations thereof. is preferred, and butadiene is more preferred.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

The number average molecular weight (Mn) of the polymer block I is preferably 15,000 or more, more preferably 20,000 or more, still more preferably 25, from the viewpoint of improving dispersibility in the resin composition. ,000 or more, particularly preferably 26,000 or more, and preferably 100,000 or less.

-Polymer Block II Mainly Conjugated Diene Compound-
The polymer block II mainly composed of a conjugated diene compound is not particularly limited, and examples thereof include a homopolymer block of a conjugated diene compound, a copolymer block of a conjugated diene compound and a vinyl aromatic compound, and the like. be done.
In addition, in the polymer block II, "mainly composed of a conjugated diene compound" means that more than 50% by mass of conjugated diene compound units are contained in the polymer block II before hydrogenation. From the viewpoint of enhancing the properties, the content of the conjugated diene compound unit is preferably 70% by mass or more, more preferably 80% by mass or more, and may be 100% by mass or less.

Examples of the conjugated diene compound constituting the polymer block II include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like, butadiene, isoprene, and combinations thereof. is preferred, and butadiene is more preferred.
Examples of the vinyl aromatic compound constituting polymer block II include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene and the like, with styrene being preferred.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

The hydrogenation rate of the ethylenic double bond in the conjugated diene compound unit contained in the polymer block II is 80% or more from the viewpoint of obtaining even better rigidity, chemical resistance, impact resistance, and tracking resistance. is preferably 90% or more.
The hydrogenation rate can be measured using a nuclear magnetic resonance spectrometer (NMR).

In the microstructure (bonding form of the conjugated diene compound) of the polymer block II, the amount of 1,2-vinyl bonds and 3,4-vinyl The total amount of vinyl bonds (total vinyl bond amount) is preferably 50% or more from the viewpoint of enhancing the compatibility of polymer block II with components (c) and (d) and improving impact resistance. , more preferably 55% or more, still more preferably 65% or more, and preferably 90% or less.

The number average molecular weight (Mn) of the polymer block II is preferably 30,000 to 100,000 from the viewpoint of obtaining even better rigidity, chemical resistance, impact resistance, and tracking resistance, and more It is preferably 40,000 to 100,000.

The glass transition temperature of the polymer block II after hydrogenation is preferably higher than −50° C., more preferably higher than −50° C., from the viewpoint of obtaining even better rigidity, chemical resistance, impact resistance, and tracking resistance. It is more than -50°C and 0°C or less, more preferably -40 to -10°C.

The distribution of the vinyl aromatic compound in the molecular chain of the polymer block I and the conjugated diene compound in the molecular chain of the polymer block II contained in the block copolymer as the component (e) is not particularly limited. random, tapered (increasing or decreasing monomeric moieties along the molecular chain), partially blocky, or combinations thereof.

The block structure of the block copolymer of the unmodified and modified hydrogenated block copolymers as the component (e) is not particularly limited. When block II is represented as "II", the component (c) includes I-II, I-II-I, II-I-II-I, (I-II-) ₄ M, I-II-I- Examples include structures such as II-I. Here, (I-II-) ₄ M is a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride (M=Si), tin tetrachloride (M=Sn), or a polyfunctional organolithium compound. and the residue of the initiator of
The component (e) may contain blocks other than polymer block I and polymer block II.

The molecular structure of the block copolymer of the unmodified and modified hydrogenated block copolymers as the component (e) is not particularly limited. A combination is mentioned.

When a plurality of polymer blocks I or polymer blocks II are included in the block copolymer as the component (e), the polymer blocks I or the polymer blocks II are , may have the same structure or may have different structures.

From the viewpoint of improving the fluidity, impact resistance, and appearance of the component (e) and reducing the occurrence of welds, the content of the vinyl aromatic compound unit in the block copolymer before hydrogenation is 30% by mass or more. is preferably 32% by mass or more, more preferably more than 40% by mass, and preferably 50% by mass or less, more preferably 48% by mass or less.
The content of the vinyl aromatic compound can be measured using an ultraviolet spectrophotometer.

The ratio of the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds to the ethylenic double bonds in the conjugated diene compound units contained in the component (e) is more than 50% and 90% or less. is preferred, and more preferably 60 to 90%.

In the above component (e), the hydrogenation rate with respect to the ethylenic double bond (double bond in the conjugated diene compound unit) in the block copolymer is preferably 80 to 100%, more preferably 90 to 100%.

In the above component (e), the number average molecular weight (Mn) of the block copolymer before hydrogenation is preferably 5,000 or more, more preferably 10,000 or more, and still more preferably 30,000 or more. It is preferably 1,000,000 or less, more preferably 800,000 or less, still more preferably 500,000 or less.
In component (e), the block copolymer after hydrogenation preferably has a molecular weight peak of 5,000 or more, more preferably 10,000 or more, and still more preferably 30,000 or more. Also, it is preferably 1,000,000 or less, more preferably 800,000 or less, still more preferably 500,000 or less, and particularly preferably 100,000 or less.

In component (e) above, the molecular weight distribution (Mw/Mn) of the block copolymer before hydrogenation is preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less.
The molecular weight distribution (Mw/Mn) is obtained by dividing the weight average molecular weight (Mw) obtained using GPC (moving layer: chloroform, standard substance: polystyrene) by the above number average molecular weight (Mn). can be calculated.

The method of hydrogenating the block copolymer is not particularly limited, and for example, (1) Support type in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc. Heterogeneous hydrogenation catalyst, (2) So-called Ziegler type hydrogenation catalyst using organic acid salt such as Ni, Co, Fe, Cr or transition metal salt such as acetylacetone salt and reducing agent such as organic aluminum, (3 ) Using a homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Ti, Ru, Rh, Zr, etc., for example, under the conditions of a reaction temperature of 0 to 200 ° C. and a hydrogen pressure of 0.1 to 15 MPa. , a method of hydrogenating.

The method for synthesizing the block copolymer containing polymer block I and polymer block II is not particularly limited, and examples thereof include known methods such as anionic polymerization.

Methods for producing the unmodified and modified hydrogenated block copolymers are not particularly limited, and known production methods can be used. Publications, JP-A-50-75651, JP-A-54-126255, JP-A-56-10542, JP-A-56-62847, JP-A-56-100840, JP-A 2-300218, GB 1130770, US 3281383, US 3639517, GB 1020720, US 3333024 and US The method described in 4501857 and the like can be mentioned.

In the following, particulars regarding the modified hydrogenated block copolymer in component (e) will be described.

-Modified hydrogenated block copolymer-
The modified hydrogenated block copolymer is obtained by grafting or adding an α,β-unsaturated carboxylic acid or a derivative thereof (e.g., acid anhydride, ester, etc.) to the unmodified hydrogenated block copolymer. It is.

The rate of increase in mass due to grafting or addition is not particularly limited, but is preferably 0.01% by mass or more with respect to 100% by mass of the unmodified hydrogenated block copolymer, and 10% by mass. or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less.

The method for producing the modified hydrogenated block copolymer is not particularly limited. and a method of reacting the above unmodified hydrogenated block copolymer with an α,β-unsaturated carboxylic acid or a derivative thereof.

((f) phosphate ester compound)
The resin composition of the present embodiment preferably further contains (f) a phosphate compound.
The (f) phosphate ester compound optionally used in the present embodiment is not particularly limited, and general phosphate ester compounds having the effect of improving the flame retardancy of the resin composition (phosphate ester compounds , condensed phosphate compounds, etc.), for example, triphenyl phosphate, phenyl bis dodecyl phosphate, phenyl bis neopentyl phosphate, phenyl-bis (3,5,5'-trimethyl-hexyl phosphate), ethyl diphenyl phosphate, 2-ethyl-hexyl di(p-tolyl) phosphate, bis-(2-ethylhexyl)-p-tolyl phosphate, tritolyl phosphate, bis-(2-ethylhexyl) phenyl phosphate, tri-(nonylphenyl) phosphate, di(dodecyl) )-p-tolyl phosphate, tricresyl phosphate, dibutylphenyl phosphate, 2-chloroethyldiphenyl phosphate, p-tolylbis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyldiphenyl phosphate, bisphenol A bis( diphenyl phosphate), diphenyl-(3-hydroxyphenyl) phosphate, bisphenol A bis(dicresyl phosphate), resorcin bis(diphenyl phosphate), resorcin bis(dixylenyl phosphate), 2-naphthyldiphenyl phosphate, 1- naphthyldiphenyl phosphate, di(2-naphthyl)phenyl phosphate and the like. Among them, a condensed phosphate compound is preferable.

［式（４）中、Ｑ^４１、Ｑ^４２、Ｑ^４３、Ｑ^４４は、各々独立して、炭素原子数１～６のアルキル基であり；Ｒ^４１、Ｒ^４２は、各々独立して、メチル基であり；Ｒ^４３、Ｒ^４４は、各々独立して、水素原子又はメチル基であり；ｘは０以上の整数であり；ｐ_１、ｐ_２、ｐ_３、ｐ_４は、それぞれ、０～３の整数であり；ｑ_１、ｑ_２は、それぞれ、０～２の整数である］、及び
下記式（５）

［式（５）中、Ｑ^５１、Ｑ^５２、Ｑ^５３、Ｑ^５４は、各々独立して、炭素原子数１～６のアルキル基であり；Ｒ^５１は、メチル基であり；ｙは０以上の整数であり；ｒ_１、ｒ_２、ｒ_３、ｒ_４は、それぞれ、０～３の整数であり；ｓ_１は、それぞれ、０～２の整数である］
で表される芳香族縮合リン酸エステル化合物よりなる群から選ばれる少なくとも１種を主成分とするもの好ましい。
なお、上記式（４）及び上記式（５）で表される縮合リン酸エステル化合物は、それぞれ複数種の分子を含んでよく、各分子について、ｘ及びｙは、１～３の整数であることが好ましい。 In particular, as the (f) phosphate ester compound, the following formula (4)

[ ^In formula (4), Q ⁴¹ , Q ⁴² , Q ⁴³ and Q ⁴⁴ are each independently an alkyl group having 1 to 6 carbon atoms ^; R ⁴³ and R ⁴⁴ are each independently a hydrogen atom or a methyl group; x is an integer of 0 or more; p ₁ , p ₂ , p ₃ and p ₄ are each 0 to is an integer of 3; q ₁ and q ₂ are each an integer of 0 to 2], and the following formula (5)

[In formula (5), Q ⁵¹ , Q ⁵² , Q ⁵³ and Q ⁵⁴ are each independently an alkyl group having 1 to 6 carbon atoms; R ⁵¹ is a methyl group; r ₁ , r ₂ , r ₃ , r ₄ are each integers from 0 to 3; s ₁ is each an integer from 0 to 2]
Preferably, the main component is at least one selected from the group consisting of aromatic condensed phosphate ester compounds represented by:
The condensed phosphate compounds represented by the above formulas (4) and (5) may each contain a plurality of types of molecules, and x and y are integers of 1 to 3 for each molecule. is preferred.

As a suitable (e) phosphate-based compound containing at least one selected from the group consisting of the condensed phosphate ester compounds represented by the above formulas (4) and (5) as a main component, as a whole, Compounds in which the average values of x and y are 1 or more are preferred. The above-mentioned suitable (e) phosphate ester compound is generally available as a mixture containing 90% or more of compounds in which x and y are 1 to 3, and compounds other than compounds in which x and y are 1 to 3 contains multimers where x and y are 4 or more and other by-products.

［式（１）中、Ｒ^１１及びＲ^１２は、各々独立して、直鎖状若しくは分岐状の炭素原子数１～６のアルキル基及び／又は炭素原子数６～１０のアリール基であり；Ｍ^１は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ａは、１～３の整数であり；ｍは、１～３の整数であり；ａ＝ｍである］、及び下記式（２）で表されるジホスフィン酸塩

［式（２）中、Ｒ^２１及びＲ^２２は、各々独立して、直鎖状若しくは分岐状の炭素原子数１～６のアルキル基及び／又は炭素原子数６～１０のアリール基であり；Ｒ^２３は、直鎖状若しくは分岐状の炭素原子数１～１０のアルキレン基、炭素原子数６～１０のアリーレン基、炭素原子数６～１０のアルキルアリーレン基又は炭素原子数６～１０のアリールアルキレン基であり；Ｍ^２は、カルシウムイオン、マグネシウムイオン、アルミニウムイオン、亜鉛イオン、ビスマスイオン、マンガンイオン、ナトリウムイオン、カリウムイオン及びプロトン化された窒素塩基からなる群より選ばれる少なくとも１種であり；ｂは、１～３の整数であり；ｎは、１～３の整数であり；ｊは、１又は２の整数であり；ｂ・ｊ＝２ｎである］
からなる群より選ばれる少なくとも１種が挙げられる。
また、上記（ｇ）ホスフィン酸塩類は、上記式（１）で表されるホスフィン酸塩と上記式（２）で表されるジホスフィン酸塩との混合物としてもよい。 ((g) phosphinates)
In this embodiment, (g) phosphinates can be used as needed. As the above (g) phosphinates, phosphinates represented by the following formula (1)

[In formula (1), R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms and/or an aryl group having 6 to 10 carbon atoms; M ¹ is at least one selected from the group consisting of calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions and protonated nitrogen bases; is an integer of ~3; m is an integer of 1 to 3; a = m], and a diphosphinate represented by the following formula (2)

[In formula (2), R ²¹ and R ²² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms and/or an aryl group having 6 to 10 carbon atoms; R ²³ is a linear or branched alkylene group having 1 to 10 carbon atoms, arylene group having 6 to 10 carbon atoms, alkylarylene group having 6 to 10 carbon atoms or aryl having 6 to 10 carbon atoms. is an alkylene group; ^M2 is at least one selected from the group consisting of calcium ion, magnesium ion, aluminum ion, zinc ion, bismuth ion, manganese ion, sodium ion, potassium ion and protonated nitrogen base; b is an integer of 1 to 3; n is an integer of 1 to 3; j is an integer of 1 or 2;
At least one selected from the group consisting of
The (g) phosphinate may be a mixture of the phosphinate represented by the formula (1) and the diphosphinate represented by the formula (2).

Examples of the (g) phosphinates include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, methyl-n-propylphosphine aluminum acid, zinc methyl-n-propylphosphinate, calcium methanedi(methylphosphinate), magnesium methanedi(methylphosphinate), aluminum methanedi(methylphosphinate), zinc methanedi(methylphosphinate), benzene-1,4- Calcium (dimethylphosphinate), magnesium benzene-1,4-(dimethylphosphinate), aluminum benzene-1,4-(dimethylphosphinate), zinc benzene-1,4-(dimethylphosphinate), methylphenylphosphinate Calcium, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, zinc diphenylphosphinate, calcium dimethylphosphinate, dimethylphosphine aluminum acid, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, and aluminum diethylphosphinate. is more preferable.
(g) Commercially available phosphinic acid salts are not particularly limited, and examples include Exolit (registered trademark) OP1230, OP1240, OP1311, OP1312, OP930, OP935 manufactured by Clariant Japan.

((h) thermoplastic resin)
The resin composition of the present embodiment may further contain (h) a thermoplastic resin.
The (h) thermoplastic resin is a thermoplastic resin other than the components (a) to (g) described above, and examples thereof include polystyrene, syndiotactic polystyrene, and high impact polystyrene.

((i) other additives)
The resin composition of the present embodiment may further contain (i) other additives.
The above (i) other additive is a compound other than the above components (a) to (h), for example, a vinyl aromatic compound-conjugated diene compound block copolymer other than the component (b)(e) , (c) Olefin-based elastomers other than component (d), antioxidants, metal deactivators, heat stabilizers, flame retardants other than components (f) and (g) (ammonium polyphosphate compounds, hydroxylated magnesium, aromatic halogen flame retardants, silicone flame retardants, zinc borate, etc.), fluoropolymers, plasticizers (low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), antimony trioxide, etc. Flame retardant aids, weather (light) resistance modifiers, polyolefin nucleating agents, slip agents, various colorants, release agents, and the like.

Hereinafter, the proportions of the components of the resin composition of this embodiment will be described.

The content of each component in the resin composition of the present embodiment increases the impact resistance, chemical resistance, and self-tapping strength of the resin composition, and imparts sufficient rigidity that can be applied to mechanical parts and structures. From the point of view, the mass ratio of the component (a) to a total of 100 parts by mass of the component (a), the component (b), the component (c), the component (d), and the component (e) is 50 to 80 parts by mass, the mass ratio of component (b) is 5 to 30 parts by mass, the mass ratio of component (c) is 1 to 20 parts by mass, and the mass ratio of component (e) is 1 to 20 parts by mass. is. 55 to 75 parts by mass of component (a), 5 to 20 parts by mass of component (b), 1 to 10 parts by mass of component (c), and 1 to 15 parts by mass of component (e) is preferred. Component (a) is preferably 55 to 75 parts by mass, more preferably 60 to 75 parts by mass. Component (b) is preferably 5 to 30 parts by mass, more preferably 7 to 25 parts by mass.
In addition, the total mass of the above component (a), the above component (b), the above component (c), the above component (d) and the above component (e) is It may be 80 to 100 parts by mass, 85 to 100 parts by mass, or 100 parts by mass.

The mass ratio of the component (d) to 100 parts by mass of the total mass of the component (a), the component (b), the component (c), the component (d) and the component (e) is the impact resistance , From the viewpoint of increasing chemical resistance and self-tapping strength and imparting sufficient rigidity that can be applied to mechanical parts and structures, it is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass. is.
From the viewpoint of increasing the impact resistance, chemical resistance, and self-tapping strength of the resin composition and imparting sufficient rigidity that can be applied to mechanical parts and structures, the combination of the above component (c) and the above component (d) The mass ratio (c)/(d) is 1-5, preferably 1-3.

The content of the above (f) phosphate ester compound is 5 to 30 parts by mass with respect to the total of 100 parts by mass of components (a) to (e) from the viewpoint of the mechanical property balance of the composition. preferable.

The content of the above (g) phosphinate is 100 parts by mass in total of the components (a) to (e) from the viewpoint of the balance between the mechanical properties and flame retardancy of the resin composition and the improvement of the self-tapping strength. On the other hand, it is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass.

The content of the thermoplastic resin (h) is not particularly limited as long as it does not impair the effects of the present invention. It may be 400 parts by mass.

(flexural modulus)
The resin composition of the present embodiment preferably has a flexural modulus of 1600 MPa or more, more preferably 1700 to 3000 MPa, as measured according to ISO 178. By being within this range, it is possible to have rigidity applicable to structural parts and structures.
In order to increase the flexural modulus to 1600 MPa or more, specific components (a) to (e) and, if necessary, components (f), (g), and (h) are contained in specific amounts. It can be adjusted as appropriate.

(morphology)
From the viewpoint of mechanical strength and chemical resistance, the morphology of the resin composition of the present embodiment is such that (a) the polyphenylene ether-based resin forms a continuous phase. These morphologies can be observed, for example, using a TEM (transmission electron microscope). Specifically, it can be observed by the method described in Examples below.

(Method for producing resin composition)
The resin composition of the present embodiment is prepared by melt-kneading the above-described components (a) to (e) and, if necessary, components (f), (g), (h), and (i). It can be manufactured by

A preferred method for producing the resin composition of the present embodiment is a production method including the following steps (1-1) and (1-2).
(1-1): A step of melt-kneading the components (a) and (e) to obtain a kneaded product.
(1-2): A step of adding the components (b), (c) and (d) to the kneaded product obtained in the step (1-1) and melt-kneading them.
In the above step (1-1), the above component (a) may be added in whole or in part. Moreover, the above component (e) may be added in whole or in part. Above all, the above step (1-1) is preferably a step of melt-kneading the whole amount of the above component (a) and, if necessary, the whole amount or part of the above component (e) to obtain a kneaded product.
In the step (1-2) above, the components (b), (c) and (d) may be added entirely or partially. When a part is added in step (1-2), the entire amount of components (b), (c), and (d) may be added in steps (1-1) and (1-2). . In the step (1-2), the total amount of the components (b), (c), and (d) is added to the kneaded product obtained in the step (1-1), and melt-kneaded. It is preferable that it is a step of performing.
As in this production method, by adding components (b), (c), and (d) in step (1-2) during melt-kneading (especially, components (b) and (c) , (d) by adding the entire amount of component (d) in step (1-2)), (b) component, (c) component, and (d) component are efficiently dispersed in (a) component, chemical resistance and A resin composition having even better self-tapping strength can be obtained.

The melt-kneader suitably used for melt-kneading each component in the method for producing the resin composition of the present embodiment is not particularly limited, and examples include a single-screw extruder and a twin-screw extruder. Extruders such as multi-screw extruders, rolls, kneaders, Brabender plastographs, Banbury mixers, and the like can be mentioned, but twin-screw extruders are particularly preferred from the viewpoint of kneadability. Specific examples of twin-screw extruders include the ZSK series manufactured by Coperion, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by The Japan Steel Works, Ltd.
The type, standard, etc. of the extruder are not particularly limited, and may be known ones.

Preferred embodiments in the case of using an extruder such as a single-screw extruder or a multi-screw extruder such as a twin-screw extruder are described below.

L/D (effective barrel length/barrel inner diameter) of the extruder is preferably 20 or more, more preferably 30 or more, and preferably 75 or less, more preferably 60 or less.

The configuration of the extruder is not particularly limited, for example, the first raw material supply port on the upstream side with respect to the direction of raw material flow, the first vacuum vent downstream from the first raw material supply port, and the first vacuum vent a second raw material supply port downstream of the second raw material supply port, a first liquid addition pump downstream of the second raw material supply port, a second vacuum vent downstream of the first liquid addition pump, a second vacuum vent downstream of the second vacuum vent A two-liquid pump may be provided.

In addition, the method of supplying the raw material in the second raw material supply port is not particularly limited, and the method of simply adding from the upper opening of the raw material supply port or the method of adding from the side opening using a forced side feeder. In particular, from the viewpoint of stable supply, a method of adding from a side opening using a forced side feeder is preferable.

When the components are melt-kneaded, the melt-kneading temperature is not particularly limited, and may be 200 to 370° C., and the screw rotation speed is not particularly limited, and may be 100 to 1,200 rpm.

When a liquid raw material is added, it can be added by directly feeding the liquid raw material into the cylinder system using a liquid addition pump or the like in the cylinder portion of the extruder. Examples of the liquid-added pump include, but are not limited to, gear pumps and flange-type pumps, with gear pumps being preferred. At this time, from the viewpoint of reducing the load on the liquid addition pump and improving the operability of the raw material, It is preferable to reduce the viscosity of the liquid raw material by heating the portion, such as the pipe between them, which will be the flow path of the liquid raw material, using a heater or the like.

[Molded body]
A molded article can be obtained from the resin composition of the present embodiment.
Examples of the molded article include, but are not particularly limited to, automotive parts, interior and exterior parts of electrical equipment, and other parts. Exterior parts such as bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, and various aero parts; instrument panels, consoles, etc. Interior parts such as boxes and trims; secondary battery container parts mounted on automobiles, electric vehicles, hybrid electric vehicles, power-assisted bicycles and wheelchairs; and lithium ion secondary battery parts. In addition, the interior and exterior parts of electrical equipment are not particularly limited. , refrigerators, air conditioners, parts used in liquid crystal projectors, and the like. Other parts include wires and cables obtained by coating metal conductors or optical fibers, fuel cases for solid methanol batteries, fuel cell water pipes, water cooling tanks, boiler outer cases, ink peripheral parts and parts for inkjet printers. , furniture (such as chairs), chassis, water pipes, joints, and the like.

(Manufacturing method of compact)
The molded article can be produced by molding the resin composition of the present embodiment described above.
The method for producing the molded article is not particularly limited, and examples thereof include injection molding, extrusion molding, extrusion molding, blow molding, compression molding, and the like, from the viewpoint of obtaining the effects of the present invention more effectively. , injection molding is preferred.

EXAMPLES Hereinafter, embodiments of the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

Raw materials used for the resin compositions and molded articles of Examples and Comparative Examples are shown below.

-(a) polyphenylene ether resin-
(ai): Polyphenylene ether having a reduced viscosity (η _sp /c: chloroform solution of 0.5 g/dL) of 0.51 dL/g obtained by oxidative polymerization of 2,6-xylenol (a-ii): Polyphenylene ether with a reduced viscosity of 0.42 dL/g (η _sp /c: 0.5 g/dL chloroform solution) obtained by oxidative polymerization of 2,6-xylenol Note that the reduced viscosity is η _sp /c: 0 Using a chloroform solution of 0.5 g/dL, the measurement was performed with an Ubbelohde-type viscosity tube at a temperature of 30°C.

-(b) hydrogenated block copolymer-
An unmodified block copolymer was synthesized by using polystyrene as the polymer block A and polybutadiene as the polymer block B. The physical properties of the obtained block copolymer are shown below.
(bi):
Polystyrene content in block copolymer before hydrogenation: 30% by mass Molecular weight peak of block copolymer after hydrogenation: 125,000 Number average molecular weight (Mn) of polystyrene block: 18,750 Polybutadiene block number average molecular weight (Mn): 87,500, molecular weight distribution (Mw/Mn) of block copolymer before hydrogenation: 1.10, 1,2-vinyl bond amount in polybutadiene block before hydrogenation (total vinyl Bonding amount): 40%, Hydrogenation rate of polybutadiene portion constituting polybutadiene block: 35%, Glass transition temperature of polybutadiene block after hydrogenation: -80°C.
The content of the vinyl aromatic compound was measured using an ultraviolet spectrophotometer. The number average molecular weight (Mn) and molecular weight peak were determined using GPC (moving phase: chloroform, standard: polystyrene). The molecular weight distribution (Mw/Mn) is obtained by dividing the weight average molecular weight (Mw) determined by a conventionally known method using GPC (moving layer: chloroform, standard material: polystyrene) by the above number average molecular weight (Mn). It was calculated by The total amount of vinyl bonds is measured using an infrared spectrophotometer, and is described in Analytical Chemistry, Volume 21, No. 8, August 1949. The hydrogenation rate was measured using a nuclear magnetic resonance spectrometer (NMR). The mixing ratio was obtained from the peak area ratio during GPC measurement.
(b-ii):
Polystyrene content in block copolymer before hydrogenation: 30% by mass Molecular weight peak of block copolymer after hydrogenation: 53,000 Number average molecular weight (Mn) of polystyrene block: 8,000 Polybutadiene block number average molecular weight (Mn): 37,000, molecular weight distribution (Mw/Mn) of block copolymer before hydrogenation: 1.10, 1,2-vinyl bond amount in polybutadiene block before hydrogenation (total vinyl Bonding amount): 40%, Hydrogenation rate of polybutadiene portion constituting polybutadiene block: 35%, Glass transition temperature of polybutadiene block after hydrogenation: -80°C.
(b-iii):
Polystyrene content in block copolymer before hydrogenation: 20% by mass Molecular weight peak of block copolymer after hydrogenation: 100,000 Number average molecular weight (Mn) of polystyrene block: 10,000 Polybutadiene block number average molecular weight (Mn): 80,000, molecular weight distribution (Mw/Mn) of block copolymer before hydrogenation: 1.10, 1,2-vinyl bond amount in polybutadiene block before hydrogenation (total vinyl bonding amount): 45%, hydrogenation rate of polybutadiene portion constituting polybutadiene block: 70%, glass transition temperature of polybutadiene block after hydrogenation: -73°C.
(b-iv):
Polystyrene content in block copolymer before hydrogenation: 30% by mass Molecular weight peak of block copolymer after hydrogenation: 200,000 Number average molecular weight (Mn) of polystyrene block: 30,000 Polybutadiene block number average molecular weight (Mn): 140,000, molecular weight distribution (Mw/Mn) of block copolymer before hydrogenation: 1.10, 1,2-vinyl bond amount in polybutadiene block before hydrogenation (total vinyl Bonding amount): 33%, Hydrogenation rate of the polybutadiene portion constituting the polybutadiene block: 99%, Glass transition temperature of the polybutadiene block after hydrogenation: -55°C.

-(c) Olefin polymer-
(ci): Ethylene-butene copolymer, trade name "Tafmer DF610", manufactured by Mitsui Chemicals, Inc., MFR: 1.2 g/10 min (190°C, 2.16 kgf conditions), embrittlement temperature: < -70°C, density: 0.862g/ ^cm3
(c-ii): Ethylene-butene copolymer, trade name “Tafmer DF810”, manufactured by Mitsui Chemicals, Inc., MFR: 1.2 g/10 min (190° C., 2.16 kgf conditions), embrittlement temperature: < −70° C., density: 0.885 g/cm ³
(c-iii): Ethylene-butene copolymer, trade name “Tafmer DF110”, manufactured by Mitsui Chemicals, Inc., MFR: 1.2 g/10 min (190° C., 2.16 kgf conditions), embrittlement temperature: < -70°C, density: 0.905g/ ^cm3
(c-iv): low-density polyethylene, MFR = 2.0 g/10 min (190°C, 2.16 kgf conditions), embrittlement temperature: -80°C, density: 0.918 g/cm ³
(cv): Trade name “Tafmer BL3450M”, manufactured by Mitsui Chemicals, Inc., MFR: 4.0 g/10 min (190°C, 2.16 kgf conditions), embrittlement temperature: -32°C

-(d) polypropylene resin-
Propylene homopolymer (melting point: 165°C, MFR: 0.4 g/10 min (230°C, 2.16 kgf conditions))

-(e) admixture-
A block copolymer having a block structure of II-I-II-I was synthesized by a known method, with polymer block I consisting of polystyrene and polymer block II consisting of polybutadiene. The synthesized block copolymer was hydrogenated by a known method. No modification of the polymer was performed. The physical properties of the obtained unmodified hydrogenated block copolymer are shown below.
Polystyrene content in block copolymer before hydrogenation: 44% by mass Molecular weight peak of block copolymer after hydrogenation: 95,000 Number average molecular weight (Mn) of polystyrene block: 41,800 Polybutadiene block number average molecular weight (Mn): 53,200, molecular weight distribution (Mw/Mn) of block copolymer before hydrogenation: 1.06, 1,2-vinyl bond amount in polybutadiene block before hydrogenation (total vinyl Bonding amount): 75%, Hydrogenation ratio of the polybutadiene portion constituting the polybutadiene block: 99%, Glass transition temperature of the polybutadiene block after hydrogenation: -15°C.

-(f) phosphate ester compound-
(f): Daihachi Chemical Co., Ltd. "E890" (condensed phosphate ester compound)

-(g) phosphinates-
(g): "Exolit OP930" manufactured by Clariant Japan (corresponding to formula (1))

Methods (1) to (5) for measuring physical properties in Examples and Comparative Examples are shown below.

(1) Morphology The obtained resin composition pellets are supplied to a small injection molding machine (trade name: IS-100GN, manufactured by Toshiba Machine Co., Ltd.) set at a cylinder temperature of 280 ° C., and the mold temperature is 70 ° C. and the injection pressure is 70 MPa. , an injection time of 20 seconds and a cooling time of 15 seconds to prepare an ISO dumbbell for evaluation.
An ultra-thin section was prepared from this ISO dumbbell using an ultramicrotome, and then the component (b) was stained with osmium tetroxide. Using a TEM (trade name “HT7700”, manufactured by Hitachi High-Technologies Corporation), the ultra-thin sections after staining were observed to obtain images at a magnification of 10,000. The resulting image was observed to determine whether the component (a) formed a continuous phase. If the component (a) forms a continuous phase (including the case where the component (a) and other components are co-continuous), "O", and if the component (a) is a dispersed phase, "X" I judged.

(2) Flexural modulus (1) The flexural modulus (MPa) of an ISO dumbbell injection-molded under the same conditions as those used for evaluating morphology was measured according to ISO 178.
It was judged that the higher the bending elastic modulus value, the better the rigidity. In particular, when it was 1600 MPa or more, it was determined that it had a rigidity that could be applied to mechanical parts and structures.

(3) Charpy impact strength (1) Notched Charpy impact strength was measured according to ISO179 1eA in a 23° C. environment using an ISO dumbbell injection-molded under the same conditions as used for morphology evaluation.

(4) Chemical resistance The pellets of the obtained resin composition were supplied to a small injection molding machine (trade name: IS-100GN, manufactured by Toshiba Machine Co., Ltd.) set at a cylinder temperature of 280 ° C., and the mold temperature was 70 ° C. A flat plate of 150 mm×150 mm×3 mm was molded under the conditions of an injection pressure of 75 MPa, an injection time of 20 seconds, and a cooling time of 15 seconds.
A test piece of 75 mm x 12.7 mm x 3 mm was cut from this flat plate, and the test piece was set in a bending form designed to continuously change strain. CRC 5-56 (manufactured by CRC Industries, Inc., USA) was applied to the surface of the test piece and left for 48 hours under conditions of 23° C. and 50 RH%. After 48 hours, strain was applied to the test piece, and the stopping position of the bending foam when cracks occurred on the surface of the test piece was measured to obtain the critical strain amount (%) that indicates the limit amount of strain at which cracks do not occur. .
As an evaluation criterion, it was determined that the larger the numerical value of the critical strain amount, the better the chemical resistance.

(5) Self-tapping strength The pellets of the obtained resin composition were supplied to a small injection molding machine (trade name: IS-100GN, manufactured by Toshiba Machine Co., Ltd.) set at a cylinder temperature of 280 ° C., and the mold temperature was 70 ° C. A molded product having a boss with an inner diameter of 2.55 mm and an outer diameter of 5.75 mm was molded at an injection pressure of 70 MPa.
A P-tight screw (size M3×10) was screwed into the boss of the obtained molded product, and the maximum screw-in torque (N·m) when breaking or damaging the resin inside the boss was measured.
It was judged that the higher the torque value, the better the self-tapping strength, and the higher the degree of freedom in designing and assembling the actual product.

(6) Flame retardancy The obtained resin composition pellets are supplied to a small injection molding machine (trade name: IS-100GN, manufactured by Toshiba Machine Co., Ltd.) set at a cylinder temperature of 280 ° C., and the mold temperature is 70 ° C. Molding was performed at a pressure of 60 MPa to prepare five test pieces (1.6 mm thick) for UL94 vertical burning test measurement. The flame retardancy of these five specimens was evaluated based on the UL94 vertical burning test method. After 10 seconds of flame contact, the combustion time from when the flame is removed until the flame goes out is t1 (seconds). ), and the average of t1 and t2 was obtained as the average burning time for each of the five tubes. On the other hand, the maximum burning time was determined as the maximum burning time among the 10 burning times including t1 and t2. Then, based on the UL94 standard, V-0, V-1, V-2, and HB were determined.
In particular, when the flame retardancy level was V-1 or higher, it was determined that the flame retardancy was excellent.

(Examples 1 to 16, Comparative Examples 1 to 11)
Hereinafter, each example and each comparative example will be described in detail.
A twin-screw extruder (ZSK-25 manufactured by Coperion Co., Ltd.) was used as a melt-kneader used for producing the resin compositions of each example and each comparative example. The L/D of the extruder was set at 35.
The configuration of the twin-screw extruder includes a first raw material supply port on the upstream side with respect to the direction of raw material flow, a first vacuum vent downstream of the first raw material supply port, and a second raw material supply downstream of the first vacuum vent. A port, a liquid addition pump downstream of the second raw material supply port, and a second vacuum vent downstream of the liquid addition pump.
The barrel setting temperature of the twin-screw extruder is set to 320 ° C. from the first raw material supply port to the first vacuum vent, and 280 ° C. downstream from the second raw material supply port, screw rotation speed 300 rpm, extrusion rate 15 kg / h. Pellets of the resin composition were produced under the conditions. Table 1 shows the configuration of the twin-screw extruder.

Components (a) to (g) were supplied to the twin-screw extruder set up as described above as shown in Tables 2 and 3 to obtain pellets of the resin composition.
For each example and each comparative example, physical property tests were conducted by the above-described measurement methods (1) to (6). Tables 2 and 3 show the results.

As shown in Tables 2 and 3, the resin compositions of Examples have excellent impact resistance, chemical resistance, and tracking resistance as compared with the resin compositions of Comparative Examples, and can be applied to mechanical parts and structures. was also found to have a possible stiffness.

According to the present invention, it is possible to obtain a resin composition and a molded article which are excellent in impact resistance, chemical resistance, and tracking resistance, and which have rigidity that can be applied to mechanical parts and structures. Molded articles containing the resin composition of the present invention are suitably used as automobile parts, interior and exterior parts of electrical equipment, other parts, and the like.

Claims (9)

(a) a polyphenylene ether-based resin;
(b) At least part of a block copolymer containing at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound is hydrogenated a hydrogenated block copolymer and/or a modified product of the hydrogenated block copolymer,
(c) an olefin-based polymer composed of olefins other than propylene;
(d) a polypropylene-based resin;
(e) an admixture that is a compound different from the component (b);
contains
The mass ratio of the component (a) is 50 to 80 with respect to the total 100 parts by mass of the component (a), the component (b), the component (c), the component (d) and the component (e). Parts by mass, the mass ratio of the component (b) is 5 to 30 parts by mass, the mass ratio of the component (c) is 1 to 20 parts by mass, and the mass ratio of the component (e) is 1 to 20 parts by mass,
The mass ratio (c)/(d) of the component (c) and the component (d) is 1 to 5,
The component (a) forms a continuous phase,
The polymer block B in the component (b) has a glass transition temperature of −65° C. or lower,
The embrittlement temperature of the component (c) is −50° C. or lower,
A resin composition characterized by: 2. The resin composition according to claim 1, further comprising (f) a phosphate compound. Furthermore, (g) containing phosphinates,
The component (g) is a phosphinate represented by the following general formula (1)

[wherein R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms and/or an aryl group having 6 to ¹⁰ carbon atoms; , calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions, and protonated nitrogen bases; is an integer; m is an integer of 1 to 3; a = m], and a diphosphinate represented by the following formula (2)

[wherein R ²¹ and R ²² are each independently a linear or branched alkyl group having ¹ to 6 carbon atoms and/or an aryl group having 6 to 10 carbon atoms; , a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 6 to 10 carbon atoms or an arylalkylene group having 6 to 10 carbon atoms. Yes; ^M2 is at least one selected from the group consisting of calcium ions, magnesium ions, aluminum ions, zinc ions, bismuth ions, manganese ions, sodium ions, potassium ions and protonated nitrogen bases; b is , an integer from 1 to 3; n is an integer from 1 to 3; j is an integer from 1 or 2; b j = 2n]
The resin composition according to claim 1 or 2, containing at least one phosphinate selected from the group consisting of. The resin composition according to any one of claims 1 to 3, wherein the component (c) is an ethylene-1-butene copolymer. The resin composition according to any one of claims 1 to 4, wherein the component (c) has a density of 0.87 g/cm ³ or more. The resin composition according to any one of claims 1 to 5, wherein the component (c) has a density of 0.90 g/cm ³ or more. The resin composition according to any one of claims 1 to 6, wherein the component (d) is a propylene homopolymer. The component (e) is at least one block copolymer containing at least one polymer block I mainly composed of a vinyl aromatic compound and at least one polymer block II mainly composed of a conjugated diene compound. A hydrogenated block copolymer and/or a modified product of the hydrogenated block copolymer, wherein
The total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is more than 50% and 90% or less with respect to the double bonds in the conjugated diene compound units contained in the component (e),
The content of the vinyl aromatic compound unit in the component (e) before hydrogenation is 30 to 50% by mass,
The glass transition temperature of the polymer block II in the component (e) is higher than -50°C,
8. The resin composition according to any one of claims 1 to 7, wherein the hydrogenation rate of double bonds in the conjugated diene compound unit contained in the component (e) is 80 to 100%. The resin composition according to any one of claims 1 to 8, which has a flexural modulus of 1600 MPa or more as measured according to ISO 178.