JP2019137742A - Resin composition, method for producing resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition and a molded body having excellent impact resistance, low temperature impact resistance, chemical resistance and tracking resistance and having rigidity which can be applied to mechanical parts and structures. With the goal. SOLUTION: (a) a polyphenylene ether-based resin, (b) 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. Contains a first hydrogenated block polymer obtained by hydrogenating at least a part of the block polymer containing the above and / or a modified product of the hydrogenated block polymer, and has a vinyl fragrance in the component (b). The content of the group compound unit is 5% by mass or more and less than 20% by mass, and the 1,2-vinyl bond and the 3,4-vinyl bond with respect to the double bond in the conjugated diene compound unit contained in the component (b) A resin composition comprising a total ratio of more than 60% and (b) a hydrogenation rate of 60% or more for a double bond in the conjugated diene compound unit contained in the component. [Selection diagram] None

Description

  The present invention relates to a resin composition, a method for producing the resin composition, and a molded body.

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

  For this reason, in some applications, attempts have been made to improve the chemical resistance by alloying a crystalline resin with a PPE resin, but in a temperature region below the glass transition temperature of the crystalline resin, There was a problem that the impact property deteriorated rapidly.

  On the other hand, studies have been made to increase the low-temperature impact by adding a thermoplastic elastomer (for example, Patent Documents 1 to 4).

  Further, in order to improve chemical resistance and tracking resistance, it has been proposed to add a thermoplastic elastomer having a low styrene content (Patent Document 5).

International Publication No. 2015/550060 JP 2004-161929 A Japanese Patent No. 5422561 JP 2007-519882 A JP 2012-119087 A

  However, even with the composition disclosed in Patent Document 1, it is currently impossible to obtain a resin composition having tracking resistance in addition to low temperature impact resistance and chemical resistance. In addition, in the compositions disclosed in Patent Documents 2 to 4, since it is necessary to add a relatively large amount of thermoplastic elastomer, the resulting composition has low rigidity, and its use is limited. It was difficult to deploy to mechanical parts and structures. The thermoplastic elastomer with a low styrene content disclosed in Patent Document 5 is hardly compatible with the PPE resin, and it has been difficult to obtain a resin composition satisfying mechanical properties. Furthermore, if the amount of vinyl bonds is large, the glass transition temperature is increased, and it is considered that low temperature impact resistance is not exhibited.

  Therefore, the present invention provides a resin composition and a molded body that have excellent impact resistance, low temperature impact resistance, chemical resistance, and tracking resistance and have rigidity that can be applied to mechanical parts and structures. Objective.

As a result of intensive studies to solve the above problems, the present inventors have found that a polyphenylene ether-based resin and a hydrogenated block copolymer having a specific structure and / or a modified product of the hydrogen block copolymer are included. The present inventors have found that the composition can advantageously solve the above problems and have completed the present invention.
That is, the present invention is as follows.

[1]
(A) a polyphenylene ether resin;
(B) At least a 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 first hydrogenated block copolymer and / or a modified product of the hydrogenated block copolymer,
The content of the vinyl aromatic compound unit in the component (b) is 5% by mass or more and less than 20% by mass,
The total proportion of 1,2-vinyl bond and 3,4-vinyl bond to the double bond in the conjugated diene compound unit contained in the component (b) is more than 60%;
The hydrogenation rate with respect to the double bond in the conjugated diene compound unit contained in the component (b) is 60% or more.
The resin composition characterized by the above-mentioned.
[2]
The resin composition according to [1], further comprising (c) an admixture.
[3]
At least one block copolymer in which the component (c) 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 in which part is hydrogenated and / or a modified product of the hydrogenated block copolymer,
The content of the vinyl aromatic compound unit in the component (c) is 30 to 50% by mass,
The total ratio of 1,2-vinyl bond and 3,4-vinyl bond to the double bond in the conjugated diene compound unit contained in the component (c) is more than 50% and 90% or less,
[2] The resin composition according to [2], wherein a hydrogenation ratio to a double bond in the conjugated diene compound unit contained in the component (c) is 80 to 100%.
[4]
And (d) at least a 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. A hydrogenated second hydrogenated block copolymer and / or a modified product of the hydrogenated block copolymer,
The resin composition according to any one of [1] to [3], wherein a hydrogenation rate with respect to a double bond in the conjugated diene compound unit contained in the component (d) is 20% or more and less than 60%.
[5]
The resin composition according to [4], wherein the polymer block B in the component (d) has a glass transition temperature of −50 ° C. or lower.
[6]
The resin composition according to any one of [1] to [5], wherein the component (a) forms a continuous phase.
[7]
The resin composition in any one of [1]-[6] whose glass transition temperature of the said polymer block B in the said (b) component is 0 degrees C or less.
[8]
The resin composition according to any one of [1] to [7], wherein the component (b) forms a worm-like domain.
[9]
Resin composition in any one of [1]-[8] whose content of polypropylene resin is less than 10 mass%.
[10]
Furthermore, (e) The resin composition in any one of [1]-[9] containing a phosphate ester type compound.
[11]
The method for producing a resin composition according to any one of [2] or [3], comprising the following steps (1-1) and (1-2):
(1-1): A step of melt-kneading the component (a) and the component (c) to obtain a kneaded product.
(1-2): A step of adding the component (b) to the kneaded product obtained in the step (1-1) and melt-kneading.
[12]
[1] A molded article comprising the resin composition according to any one of [10].

  According to the present invention, it is possible to obtain a resin composition and a molded body having excellent impact resistance, low temperature impact resistance, chemical resistance, and tracking resistance and having rigidity that can be applied to mechanical parts and structures. .

It is a figure explaining the outline | summary of the barrel structure of the extruder used for manufacturing the resin composition of an Example and a comparative example. FIG. 2 is an image obtained by observing the resin composition in which the component (b) of Example 1 forms a worm-like domain with a TEM.

  Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

[Resin composition]
The resin composition of this embodiment includes (a) a polyphenylene ether 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 first hydrogenated block copolymer obtained by hydrogenating at least a part of a block copolymer containing at least one and / or a modified product of the hydrogenated block copolymer, 1) The content of the vinyl aromatic compound unit in the component is 5% by mass or more and less than 20% by mass, and the 1,2-vinyl bond with respect to the double bond in the conjugated diene compound unit contained in the component (b) And the total proportion of 3,4-vinyl bonds is more than 60%, and the hydrogenation rate with respect to double bonds in the conjugated diene compound unit contained in the component (b) is 60% or more. The features.

In the present specification, at least one block copolymer comprising 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 a part and / or a modified product of the hydrogenated block copolymer may be simply referred to as “hydrogenated block copolymer”. In addition, among the hydrogenated block copolymers, the unmodified hydrogenated block copolymer is referred to as “unmodified hydrogenated block copolymer”, and the modified product of the hydrogenated block copolymer is referred to as “modified hydrogenated block copolymer”. It may be referred to as “copolymer”.
Further, the 1,2-vinyl bond and 3,4-vinyl bond in the conjugated diene compound unit may be referred to as “all vinyl bonds”.

Hereinafter, it describes about the component of the resin composition of this embodiment.
The resin composition of this embodiment is excellent in impact resistance, low-temperature impact resistance, chemical resistance, and tracking resistance, and has rigidity that can be applied to mechanical parts and structures. Moreover, it is preferable that it is excellent also in a flame retardance. In addition, in this embodiment, being excellent in a flame retardance points out that it is the flame retardance level V-1 or more in the UL94 vertical combustion test as described in the below-mentioned Example.

((A) polyphenylene ether resin)
The (a) polyphenylene ether resin used in the present embodiment is not particularly limited, and examples thereof include polyphenylene ether, modified polyphenylene ether, and a mixture of both. (A) A component may be used individually by 1 type and may be used together in combination of 2 or more type.

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, It 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 the amount of catalyst.
The reduced viscosity can be measured with an Ubbelohde type viscosity tube using a chloroform solution of η _{sp /} c: 0.5 g / dL at a temperature of 30 ° C.

-Polyphenylene ether-
The polyphenylene ether is not particularly limited, and examples thereof include a homopolymer having a repeating unit structure represented by the following formula (1) and / or a copolymer having a repeating unit structure represented by the following formula (1). A polymer is mentioned.
[Wherein, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, or a carbon atom having 1 to 7 carbon atoms. 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 A monovalent group. ]

  Such polyphenylene ether is not particularly limited, and known ones can be used. Specific examples of the polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl- Homopolymers such as 6-phenyl-1,4-phenylene ether) and 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 the like, poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol And 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1,4-phenylene ether) is more preferable.

  A method for producing polyphenylene ether is not particularly limited, and a conventionally known method can be used. As a specific example of the method for producing polyphenylene ether, for example, US Pat. No. 3,306,874 produced by oxidative polymerization of 2,6-xylenol using, for example, a complex of cuprous salt and amine as a catalyst. US Pat. No. 3,306,875, US Pat. No. 3,257,357, US Pat. No. 3,257,358, Japanese Patent Publication No. 52-17880, Japanese Patent Laid-Open No. 50-51197, Examples include the method described in JP-A No. 63-152628.

-Modified polyphenylene ether-
The modified polyphenylene ether is not particularly limited, and examples thereof include those obtained by grafting and / or adding a styrene polymer and / or a derivative thereof to the 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. It is preferably 7% by mass or less, more preferably 5% by mass or less.

  The method for producing the modified polyphenylene ether is not particularly limited. For example, in the presence or absence of a radical generator, in the molten state, the solution state or the slurry state, under the conditions of 80 to 350 ° C. Examples include a method of reacting 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) First hydrogenated block copolymer)
The first hydrogenated block copolymer as the component (b) is at least one polymer block A mainly composed of a vinyl aromatic compound and at least 1 polymer block B mainly composed of a conjugated diene compound. A first hydrogenated block copolymer obtained by hydrogenating at least a part of a block copolymer containing a single component and / or a modified product of the hydrogenated block copolymer, The content is 5% by mass or more and less than 20% by mass, and the total ratio of 1,2-vinyl bond and 3,4-vinyl bond to the double bond in the conjugated diene compound unit is more than 60%, and the conjugated diene compound The hydrogenation rate with respect to the double bond in the unit is 60% or more.

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

Although it does not specifically limit as said vinyl aromatic compound, For example, styrene, (alpha) -methyl styrene, vinyl toluene, p-tert- butyl styrene, diphenylethylene etc. are mentioned. Of these, styrene is preferred.
Examples of the conjugated diene compound include the following conjugated diene compounds, and butadiene, isoprene and combinations thereof are preferable.
These may be used individually by 1 type and may be used in combination of 2 or more type.

  In polymer block A, the distribution of vinyl aromatic compound, conjugated diene compound, etc. in the molecular chain in the polymer block is random, tapered (in which the monomer component increases or decreases along the molecular chain), and partially in block form Or you may comprise by these arbitrary combinations.

  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, more preferably from the viewpoint of obtaining further excellent rigidity, chemical resistance, low temperature impact resistance, and tracking resistance. Is 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, a random copolymer block of a conjugated diene compound and a vinyl aromatic compound, and the like. Among these, a homopolymer block of a conjugated diene compound, 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 a conjugated diene compound unit are preferable.
Here, in the polymer block B, “consisting mainly of a conjugated diene compound” means that the polymer block B contains more than 50 mass% of the conjugated diene compound unit, and the conjugated diene compound unit is 70 mass% or more. It is preferable to contain.

The conjugated diene compound is not particularly limited, and examples thereof include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. Of these, butadiene, isoprene, and combinations thereof are preferable.
As said vinyl aromatic compound, the above-mentioned vinyl aromatic compound is mentioned, Styrene is preferable.
These may be used individually by 1 type and may be used in combination of 2 or more type.

  In polymer block B, the distribution of the conjugated diene compound, vinyl aromatic compound, etc. in the molecular chain in the polymer block is random, tapered (in which the monomer component increases or decreases along the molecular chain), partly in block form Or you may comprise by these arbitrary combinations.

  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 with respect to 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 further excellent rigidity, chemical resistance, low temperature impact resistance, and tracking resistance. % Is preferable, and more preferably 20% or more and less than 70%. It is preferable for the hydrogenation rate to be within the above range since the impact properties of the resin composition are improved.

The total ratio of 1,2-vinyl bond and 3,4-vinyl bond (total vinyl bond amount) to double bond (ethylenic double bond) in the conjugated diene compound unit in the polymer block B is one layer. From the viewpoint of obtaining excellent rigidity, chemical resistance, low temperature impact resistance, and tracking resistance, it is preferably 25% or more and less than 60%, more preferably 25 to 55%, and more preferably 25 to 50%. More preferably.
In this specification, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (total vinyl bond amount) is the conjugated diene compound unit in the conjugated diene compound-containing polymer block before hydrogenation. , The total of 1,2-vinyl bond amount and 3,4-vinyl bond amount, the sum of 1,2-vinyl bond amount, 3,4-vinyl bond amount, and 1,4-conjugated bond amount The ratio with respect to. The total amount of vinyl bonds was measured using an infrared spectrophotometer, and Analytical Chemistry, Volume 21, No. 8, calculated according to the method described in August 1949.

  The number average molecular weight (Mn) of the polymer block B is preferably 20,000 to 100,000, more preferably from the viewpoint of obtaining further excellent rigidity, chemical resistance, low temperature impact resistance, and tracking resistance. Is 20,000-80,000.

As the polymer block B, the ratio of the total of 1,2-vinyl bonds and 3,4-vinyl bonds to double bonds (ethylenic double bonds) in the conjugated diene compound unit contained in the polymer block B (total (Vinyl bond amount) may be a single polymer block exceeding 60%, for example, the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 25-45% A polymer block B1 mainly composed of a conjugated diene compound and a polymer block B2 mainly composed of a conjugated diene compound having a total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds of 45 to 70%. It may be a polymer block mainly composed of a conjugated diene compound.
The structure of the block copolymer having the polymer block B1 and the polymer block B2 is such that the polymer block A is “A”, the polymer block B1 is “B1”, and the polymer block B2 is “B2”. Then, for example, it can be obtained by a known polymerization method in which the total vinyl bond amount is controlled based on the feed sequence of each monomer unit represented by A-B2-B1-A and the like.

--Structure of first hydrogenated block copolymer--
The structure of the first hydrogenated block copolymer in the component (b) is, for example, when the polymer block A is "A" and the polymer block B is "B", for example, AB type, A- B-A type, B-A-B-A type, (A-B-) n-X type (where n is an integer of 1 or more, X is a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride) And a residue of an initiator such as a polyfunctional organolithium compound.), And a structure such as ABABABA type.
As for 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 a conjugated diene compound unit and a vinyl aromatic. A vinyl aromatic compound which is a copolymer block with a compound and the polymer block A contains a homopolymer block of a vinyl aromatic compound or a vinyl aromatic compound in an amount of more than 50% by mass (preferably 70% by mass or more) It is preferably a copolymer block of conjugated diene compound.
The component (b) may contain a block other than the polymer block A and the polymer block B.

  The molecular structure of the first 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 (the first hydrogenated block copolymer constituent unit derived from the vinyl aromatic compound) in the component (b) is not particularly limited, but the heat resistance and mechanical strength of the composition are not limited. From a viewpoint, it is 5 mass% or more and less than 20 mass%, More preferably, it is 10 mass% or more and less than 20 mass%, More preferably, it is 10-18 mass%. Moreover, not only the 1 type (b) component which has vinyl aromatic compound unit content of this range but the (b) component which has 2 or more types of different vinyl aromatic compound unit content can be used together.

-Total vinyl bond-
The total ratio of 1,2-vinyl bond and 3,4-vinyl bond (total vinyl bond amount) to ethylenic double bond in the conjugated diene compound unit contained in component (b) is:
From the viewpoint of affinity with polypropylene, it is more than 60% and more preferably 70% or more, but if it is too high, the low temperature impact property may be lowered.
The method for controlling the total ratio of 1,2-vinyl bond and 3,4-vinyl bond within the above range is not particularly limited. For example, in the production of component (b), the amount of 1,2-vinyl bond Examples thereof include a method of adding a regulator and a method of adjusting the polymerization temperature.
In the present specification, “the ratio of the total of 1,2-vinyl bonds and 3,4-vinyl bonds to double bonds in the conjugated diene compound unit” (total vinyl bond amount) means (b) first Of 1,2-vinyl bond and 3,4-vinyl bond to double bond (ethylenic double bond) in the conjugated diene compound unit in the block copolymer before hydrogenation of the hydrogenated block copolymer of Say. For example, a block copolymer before hydrogenation is measured with an infrared spectrophotometer, and Analytical Chemistry, Volume 21, No. 1 is used. 8, calculated according to the method described in August 1949. Moreover, it can also calculate using NMR from the block copolymer after hydrogenation.

--- Hydrogenation rate ---
In the component (b), the hydrogenation rate with respect to the ethylenic double bond (double bond in the conjugated diene compound unit) in the block copolymer is 60% or more from the viewpoint of chemical resistance, surface impact resistance, and dielectric breakdown strength. Preferably, it is 70% or more, more preferably 80% or more. Although an upper limit is not specifically limited, For example, it can be 100%.
The component (b) having such a hydrogenation rate can be easily obtained, for example, by controlling the amount of hydrogen consumption in a desired hydrogenation rate range in the hydrogenation reaction of the ethylenic double bond of the block copolymer. can get.
The hydrogenation rate can be determined, for example, by quantifying the amount of remaining double bonds in the polymer block B by NMR measurement.

--- Glass transition temperature--
The glass transition temperature of the polymer block B contained in the component (b) is preferably 0 ° C. or less, more preferably −10 from the viewpoint of obtaining further excellent rigidity, chemical resistance, low temperature impact resistance, and tracking resistance. ° C or lower, more preferably -15 ° 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, for example, a sample in a film state using a dynamic viscoelasticity measuring device. Used, tensile mode, temperature scan rate 3 ° C./min, frequency 1 Hz, nitrogen atmosphere.

-Number average molecular weight-
The number average molecular weight of the component (b) is determined in consideration of the melt viscosity of the component (b) from the viewpoint that the component (b) is appropriately dispersed in the melt-mixing system and easily exerts an effect as an impact resistance imparting agent. Thus, it is preferably 25,000 to 1,000,000, more preferably 25,000 to 200,000.
The method for controlling the number average molecular weight of the component (b) within the above range is not particularly limited, and examples thereof include a method of adjusting the amount of catalyst in the polymerization step of the component (b).
In addition, in this specification, a number average molecular weight can be measured on condition of the following using the gel permeation chromatography System21 by Showa Denko KK. In this measurement, a column in which Showa Denko Co., Ltd. KG, one K-800RL, and one K-800R were connected in series was used as the column, and the column temperature was 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 / liter of chloroform solution. Moreover, a calibration curve is prepared using standard polystyrene (the molecular weight of standard polystyrene is 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550). Further, the UV (ultraviolet) wavelength of the detection part is measured by setting both standard polystyrene and hydrogenated block copolymer to 254 nm.
The number average molecular weight (MnbA) of the polymer block A forming the component (b) is, for example, when the component (b) has an ABA type structure, the number average molecular weight (Mnb) of the component (b). Assuming that the molecular weight distribution of the component (b) is 1 and that two polymer blocks A mainly composed of vinyl aromatic compounds exist as the same molecular weight, (MnbA) = (Mnb) × bonded vinyl It can be obtained by the calculation formula of ratio of aromatic compound amount ÷ 2. Similarly, when the component (b) is a hydrogenated block copolymer of the ABABABA type, (MnbA) = (Mnb) × the proportion of the amount of bonded vinyl aromatic compounds ÷ 3 Can be obtained. In addition, when the sequence of the block structure A and the block structure B is clear at the step of synthesizing the vinyl aromatic compound-conjugated diene compound block copolymer, the measurement was performed without depending on the above formula ( You may calculate from the ratio of the block structure A based on the number average molecular weight (Mnb) of b) component.

-Manufacturing method-
The method for producing the first hydrogenated block copolymer in the component (b) is not particularly limited, and a known production method can be used. For example, JP-A-47-11486 and JP-A-49 JP-A-66743, JP-A-50-75651, JP-A-54-126255, JP-A-56-10542, JP-A-56-62847, JP-A-56-100840, JP-A-2-300218, British Patent No. 1130770, US Pat. No. 3,281,383, US Pat. No. 3,369,517, British Patent No. 1020720, US Pat. No. 3,330,024 and US Patent The method as described in the specification of 4501857 etc. is mentioned.

-Modified hydrogenated block copolymer-
As the modified product of the first hydrogenated block copolymer in the component (b), for example, the first hydrogenated block copolymer (particularly, the unmodified hydrogenated block copolymer) and α, β- Obtained by reacting an unsaturated carboxylic acid or a derivative thereof (ester compound or acid anhydride compound) at 80 to 350 ° C. in the molten state, in the solution state or in the slurry state in the presence or absence of a radical generator. And modified hydrogenated block copolymers. In this case, the α, β-unsaturated carboxylic acid or derivative thereof is preferably grafted or added at a ratio of 0.01 to 10% by mass with respect to the unmodified hydrogenated block copolymer.
As the component (b), when the unmodified hydrogenated block copolymer and the modified hydrogenated block copolymer are used in combination, the mixing ratio of the unmodified hydrogenated block copolymer and the modified hydrogenated block copolymer is It can be determined without particular limitation.

((C) Admixture)
The (c) admixture used as needed in the present embodiment is not particularly limited, but the segment chain having high compatibility with the component (a) and the segment chain having high compatibility with the component (b) It is preferable that the copolymer has Examples of the segment chain having high compatibility with the component (a) include a polystyrene chain and a polyphenylene ether chain. Examples of the segment chain having high compatibility with the component (b) include a polyolefin chain, a copolymer elastomer molecular chain of ethylene and α-olefin, and the like.

  Preferable specific examples of such a copolymer include, for example, a copolymer having a polystyrene chain-polyolefin chain, a copolymer having a polyphenylene ether chain-polyolefin chain, and a hydrogenated block copolymer thereof. . Among these, a hydrogenated block copolymer is 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 (c) 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. Examples thereof include a hydrogenated block copolymer in which at least a part of the block copolymer is hydrogenated and / or a modified product of the hydrogenated block copolymer. Among them, the hydrogenated block copolymer as the component (c) is at least a block copolymer composed of a polymer block I mainly composed of a vinyl aromatic compound and a polymer block II mainly composed of a conjugated diene compound. It is preferable that a part thereof is hydrogenated.
In addition, the above-mentioned (b) component shall not be contained in the hydrogenated block copolymer as (c) component.

Hereinafter, the matters relating to the unmodified and modified hydrogenated block copolymer in the component (c) will be described.
-Polymer block mainly composed of vinyl aromatic compounds I-
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 and a copolymer block of a vinyl aromatic compound and a conjugated diene compound. Can be mentioned.
In the polymer block I, “mainly composed of a vinyl aromatic compound” means that the polymer block I before hydrogenation contains more than 50% by mass of a vinyl aromatic compound unit. The compound unit is preferably contained in an amount of 70% by mass or more, more preferably 80% by mass or more, and may be 100% by mass or less.

The vinyl aromatic compound constituting the polymer block I is not particularly limited, and examples thereof include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, and the like, and styrene is preferable. .
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 are preferable. Butadiene is more preferred.
These may be used individually by 1 type and may be used in combination of 2 or more type.

  From the viewpoint of improving the dispersibility in the resin composition, the number average molecular weight (Mn) of the polymer block I is preferably 15,000 or more, more preferably 20,000 or more, 25, It is more preferable that it is 000 or more, and it is preferable that it is 100,000 or less.

-Polymer block II mainly composed of conjugated diene compounds-
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 and a copolymer block of a conjugated diene compound and a vinyl aromatic compound. .
In the polymer block II, “consisting mainly of a conjugated diene compound” means that the polymer block II before hydrogenation contains more than 50% by mass of the conjugated diene compound unit, and the flow of the resin composition From the viewpoint of enhancing the properties, the conjugated diene compound unit is preferably contained in an amount of 70% by mass or more, more preferably 80% by mass or more, and may be 100% by mass or less.

The conjugated diene compound constituting the polymer block II is not particularly limited, and examples thereof include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like. Isoprene and combinations thereof are preferred, and butadiene is more preferred.
The vinyl aromatic compound constituting the polymer block II is not particularly limited, and examples thereof include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, and the like, and styrene is preferable. .
These may be used individually by 1 type and may be used in combination of 2 or more type.

The hydrogenation rate with respect to 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 further excellent rigidity, chemical resistance, low temperature impact resistance, and tracking resistance. And more preferably 90% or more.
The hydrogenation rate can be measured using a nuclear magnetic resonance apparatus (NMR).

  In the microstructure of polymer block II (bonded form of conjugated diene compound), the amount of 1,2-vinyl bond and 3,4-vinyl bond with respect to the ethylenic double bond in the conjugated diene compound unit contained in polymer block II The total amount (total vinyl bond amount) is preferably 50% or more and 55% or more from the viewpoint of improving the compatibility with the component (b) of the polymer block II and improving the low-temperature impact property. More preferably, it is 65% or more, more preferably 90% or less.

  The number average molecular weight (Mn) of the polymer block II is preferably 30,000 to 100,000, more preferably from the viewpoint of obtaining further excellent rigidity, chemical resistance, low temperature impact resistance and tracking resistance. Is 40,000-100,000.

  The glass transition temperature after hydrogenation of the polymer block II is preferably more than −50 ° C., more preferably from the viewpoint of obtaining further excellent rigidity, chemical resistance, low temperature 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 in the polymer block I contained in the block copolymer as the component (c) and the conjugated diene compound in the molecular chain in the polymer block II are particularly limited. Without mentioning, for example, random, tapered (in which the monomer portion increases or decreases along the molecular chain), a partial block shape, or a combination thereof.

The block structure of the unmodified and modified hydrogenated block copolymer as the component (c) is not particularly limited. For example, the polymer block I is “I” and the polymer block When II is represented as “II”, (c) component includes I-II, I-II-I, II-I-II-I, (I-II-) ₄ M, I-II-I-II Examples of the structure include -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. Initiator residues, etc.
The component (c) may contain a block other than the polymer block I and the polymer block II.

  The molecular structure of the block copolymer of the unmodified and modified hydrogenated block copolymer as the component (c) is not particularly limited, and for example, linear, branched, radial, or a combination thereof Is mentioned.

  When the block copolymer as the component (c) includes a plurality of polymer blocks I or polymer blocks II, a plurality of polymer blocks I or a plurality of polymer blocks II are Each may have the same structure or a different structure.

(C) From the viewpoint of improving fluidity, impact resistance and appearance of the component and reducing weld generation, the content of the vinyl aromatic compound unit in the block copolymer before hydrogenation is 30% by mass or more. Preferably, it is 32% by mass or more, more preferably 50% by mass or less, and further preferably 48% by mass or less.
In addition, content of a vinyl aromatic compound can be measured using a ultraviolet spectrophotometer.

  The total ratio of the 1,2-vinyl bond amount and the 3,4-vinyl bond amount to the ethylenic double bond in the conjugated diene compound unit contained in the component (c) is more than 50% and 90% or less. Is more preferable, and 60 to 90% is more preferable.

  In the component (c), 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 component (c), 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 30,000 or more. Is particularly preferably 1,000,000 or less, more preferably 800,000 or less, and particularly preferably 500,000 or less.
The molecular weight distribution (Mw / Mn) of the block copolymer before hydrogenation is preferably 10 or less, more preferably 8 or less, and particularly preferably 5 or less.
The molecular weight distribution (Mw / Mn) is the weight average molecular weight (Mw) determined by a conventionally known method using GPC (moving layer: chloroform, standard material: polystyrene), and the aforementioned number average molecular weight (Mn). It can be calculated by dividing by.

  The method for adding hydrogen to the block copolymer is not particularly limited. For example, (1) a supported type in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. A heterogeneous hydrogenation catalyst, (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 and a reducing agent such as organic aluminum; ) 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 conditions of a reaction temperature of 0 to 200 ° C. and a hydrogen pressure of 0.1 to 15 MPa. And a method of hydrogenation.

The method for synthesizing the block copolymer including the polymer block I and the polymer block II is not particularly limited, and examples thereof include known methods such as anionic polymerization.
The production method of the unmodified and modified hydrogenated block copolymer is not particularly limited, and a known production method can be used. For example, JP-A-47-11486 and JP-A-49-66743. No. 50-75651, No. 54-126255, No. 56-10542, No. 56-62847, No. 56-100900, and No. 56-1000084. No. 2-300218, British Patent No. 1130770, US Pat. No. 3,281,383, US Pat. No. 3,639,517, British Patent No. 1020720, US Pat. No. 3,330,024, and US Pat. Examples include the method described in the specification of 4501857.

Hereinafter, the matter regarding the modified hydrogenated block copolymer in the component (c) will be described in particular.
-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 (for example, acid anhydride, ester, etc.) to the above-mentioned unmodified hydrogenated block copolymer. It is.

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

  The method for producing the modified hydrogenated block copolymer is not particularly limited, and for example, in the presence or absence of a radical generator, in a molten state, a solution state or a slurry state, at a temperature of 80 to 350 ° C. And a method of reacting the unmodified hydrogenated block copolymer with an α, β-unsaturated carboxylic acid or a derivative thereof.

((D) Second hydrogenated block copolymer)
The second hydrogenated block copolymer as component (d) is at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block mainly composed of a conjugated diene compound. A second hydrogenated block copolymer in which at least a part of the block copolymer containing B is hydrogenated, and a hydrogenation rate of a double bond in a conjugated diene compound unit is 20% or more and less than 60%, and / Or a modified product thereof.
The second hydrogenated block copolymer as the component (d) does not include the component (b).

--Polymer block A--
The polymer block A mainly composed of a vinyl aromatic compound may be the same as the component (b) described above.

--Polymer block B--
The polymer block B mainly composed of a conjugated diene compound may be the same as the component (b) described above.

--Structure of second hydrogenated block copolymer--
The structure of the 2nd hydrogenated block copolymer in (d) component may be the same as that of the above-mentioned (b) component.

-Content of vinyl aromatic compound unit-
The content of the vinyl aromatic compound unit (the second hydrogenated block copolymer constituent unit derived from the vinyl aromatic compound) in the component (d) is not particularly limited, but the heat resistance and mechanical strength of the composition are not limited. From a viewpoint, it is preferable that it is 20-70 mass%, More preferably, it is 20-60 mass%, More preferably, it is 30-50 mass%, Most preferably, it is 30-40 mass%. Moreover, not only the 1 type (d) component which has vinyl aromatic compound unit content of these ranges but the (d) component which has 2 or more types of different vinyl aromatic compound unit content can be used together. .

-Total vinyl bond-
The total ratio of 1,2-vinyl bond and 3,4-vinyl bond to ethylenic double bond in the conjugated diene compound unit contained in component (d) is more excellent in rigidity, chemical resistance, and low temperature impact. From the viewpoint of obtaining the property and tracking resistance, it is preferably 25% or more and less than 60%, more preferably 25% or more and 55% or less, and further preferably 25% or more and 50% or less.
When the total ratio of the 1,2-vinyl bond and the 3,4-vinyl bond is less than 60%, the impact resistance at low temperature of the resin composition is improved. When it is 50% or less, impact resistance at low temperatures is further improved. In addition, the component (d) having a total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds of 25% or more is preferable from the viewpoint of improving compatibility with the component (c).

--- Hydrogenation rate ---
In the component (d), the hydrogenation rate for the ethylenic double bond (double bond in the conjugated diene compound unit) in the block copolymer is more excellent in rigidity, chemical resistance, low temperature impact resistance, and tracking resistance. Is preferably 20% or more and less than 60%, more preferably 20% or more and less than 70%.

--- Glass transition temperature--
The glass transition temperature of the polymer block B as the component (d) is preferably −50 ° C. or less from the viewpoint of obtaining further excellent rigidity, chemical resistance, low-temperature impact resistance, and tracking resistance, and −60 ° C. Or less, more preferably −70 ° C. or less, and even more preferably −100 ° C. or more.

-Number average molecular weight-
The number average molecular weight of the component (d) is determined in consideration of the melt viscosity of the component (d) from the viewpoint that the component (d) is appropriately dispersed in the melt-mixing system and easily exerts an effect as an impact resistance imparting agent. It is preferably 25,000 to 1,000,000, and more preferably 25,000 to 100,000.
The molecular weight distribution (Mw / Mn) of the component (d) is preferably 1.01 to 1.50 from the viewpoint of obtaining further excellent rigidity, chemical resistance, low temperature impact resistance, and tracking resistance. More preferably, it is 0.03 to 1.40.

-Manufacturing method-
(D) It does not specifically limit as a manufacturing method of the 2nd hydrogenated block copolymer in a component, The same manufacturing method as (b) component can be used.

-Modified hydrogenated block copolymer-
Examples of the modified product of the second hydrogenated block copolymer in the component (d) include, for example, the second hydrogenated block copolymer (particularly, an unmodified hydrogenated block copolymer), α, β- Obtained by reacting an unsaturated carboxylic acid or a derivative thereof (ester compound or acid anhydride compound) at 80 to 350 ° C. in the molten state, in the solution state or in the slurry state in the presence or absence of a radical generator. And modified hydrogenated block copolymers. In this case, the α, β-unsaturated carboxylic acid or derivative thereof is preferably grafted or added at a ratio of 0.01 to 10% by mass with respect to the unmodified hydrogenated block copolymer.
As a component (d), when the unmodified hydrogenated block copolymer and the modified hydrogenated block copolymer are used in combination, the mixing ratio of the unmodified hydrogenated block copolymer and the modified hydrogenated block copolymer is It can be determined without particular limitation.

(Polypropylene resin)
In the composition of the present embodiment, the content of the polypropylene resin in the resin composition is preferably less than 10% by mass and more preferably less than 5% by mass from the viewpoint of low-temperature impact of the resin composition. Preferably it is less than 3% by weight, more preferably less than 1% by weight.
The polypropylene-based resin is not particularly limited, and examples thereof include polymers containing propylene units such as homopolypropylene, copolymers containing polypropylene blocks, modified polypropylene, and mixtures thereof.
The content of the polypropylene resin in the resin composition is, for example, by freeze-pulverizing the resin composition to form a powder, and then dissolving the powder in chloroform at 23 ° C., and 150 ° C. of the insoluble content. The fraction dissolved in o-dichlorobenzene can be further collected, and the fraction can be determined by measuring by NMR.

((E) Phosphate ester compound)
The resin composition of the present embodiment preferably further contains (e) a phosphate ester compound.

  The (e) phosphate ester compound optionally used in the present embodiment is not particularly limited, but is generally a phosphate ester compound having an effect of improving the flame retardancy of the resin composition (phosphate ester compound). For example, triphenyl phosphate, phenyl bisdodecyl phosphate, phenyl bisneopentyl 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, tolyl phosphate, bis- (2-ethylhexyl) phenyl phosphate, tri- (nonylphenyl) phosphate, di (dodecyl) -P-Torrho Fate, tricresyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolylbis (2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, bisphenol A bis (diphenyl phosphate), diphenyl -(3-hydroxyphenyl) phosphate, bisphenol A bis (dicresyl phosphate), resorcin bis (diphenyl phosphate), resorcin bis (dixylenyl phosphate), 2-naphthyl diphenyl phosphate, 1-naphthyl diphenyl phosphate, di (2-naphthyl) phenyl phosphate and the like.

In particular, (e) phosphate ester compounds include those represented by the following formula (2):
[In the formula (2), Q ²¹ , Q ²² , Q ²³ and Q ²⁴ are each independently an alkyl group having 1 to 6 carbon atoms; R ²¹ and R ²² are each independently methyl; Each of R ²³ and R ²⁴ is independently a hydrogen atom or a methyl group; x is an integer of 0 or more; and p ₁ , p ₂ , p ₃ , and p ₄ are each 0 to And q ₁ and q ₂ are each an integer of 0 to 2], and the following formula (3)
[In the formula (3), Q ³¹ , Q ³² , Q ³³ and Q ³⁴ are each independently an alkyl group having 1 to 6 carbon atoms; R ³¹ is a methyl group; y is 0 or more. R ₁ , r ₂ , r ₃ , r ₄ are each an integer from 0 to 3; s ₁ is an integer from 0 to 2, respectively]
The main component is at least one selected from the group consisting of aromatic condensed phosphate compounds represented by
In addition, the condensed phosphate ester compound represented by the above formula (2) and the above formula (3) may include a plurality of types of molecules, and for each molecule, n is an integer of 1 to 3. preferable.

  In a suitable (e) phosphate ester compound mainly comprising at least one selected from the group consisting of the condensed phosphate ester compounds represented by the above formula (2) and the above formula (3), x , Y is preferably 1 or more. Said suitable (e) phosphate ester-type compound can generally be obtained as a mixture containing 90% or more of compounds in which x and y are 1 to 3, and other than compounds in which x and y are 1 to 3 In addition, multimers and other by-products in which x and y are 4 or more are included.

((F) inorganic filler)
The resin composition of the present embodiment may further contain (f) an inorganic filler.

  (F) The inorganic filler is not particularly limited. For example, glass fiber, potassium titanate fiber, gypsum fiber, brass fiber, ceramic fiber, boron whisker fiber, mica, talc, silica, calcium carbonate, kaolin, Examples thereof include fibrous reinforcing materials such as calcined kaolin, wollastonite, zonotlite, apatite, glass beads, glass flakes, and titanium oxide, in the form of fibers, granules, plates, or needles. These inorganic fillers can be used in combination of two or more. Among these, more preferable inorganic fillers include glass fibers, carbon fibers, and glass beads. In addition, the inorganic filler may be a surface treated by a known method using a surface treating agent such as a silane coupling agent. However, since the natural ore filler often contains a small amount of iron element, it is preferable to use a refined material from which iron element has been removed.

((G) Other additives)
The additive (g) other than the components (a) to (f) that is optionally used in the present embodiment is not particularly limited, and for example, other than the components (a) to (d) Flame retardants such as thermoplastic resins, flame retardants other than component (e), plasticizers, antioxidants, metal deactivators, thermal stabilizers, fluoropolymers, antimony trioxide, weather resistance (light) improvement Agents, nucleating agents for polyolefins, slip agents, various colorants, release agents and the like.

  As thermoplastic resins other than the components (a) to (d), specifically, polystyrene, syndiotactic polystyrene, high impact polystyrene, vinyl aromatic compounds other than the components (b) to (d) -conjugated diene compounds Examples include block copolymers and olefin elastomers. Specific examples of flame retardants other than the component (e) include ammonium polyphosphate compounds, magnesium hydroxide, aromatic halogen flame retardants, silicone flame retardants, and zinc borate. Specific examples of the plasticizer other than the component (e) include low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, and fatty acid esters.

Hereinafter, it describes about the ratio of the component of the resin composition of this embodiment.
The content of each component in the resin composition of the present embodiment increases the low-temperature impact resistance, chemical resistance and dielectric breakdown strength of the resin composition, and imparts sufficient rigidity that can be applied to mechanical parts and structures. From a viewpoint, with respect to a total of 100 parts by mass of the component (a) and the component (b), the component (a) is 50 to 80 parts by mass, the component (c) is 1 to 20 parts by mass, and the component (d) is 5 to 5 parts by mass. It is preferably 30 parts by mass, more preferably 60 to 80 parts by mass of component (a), 5 to 20 parts by mass of component (c), and 10 to 30 parts by mass of component (d).
Moreover, content of (e) phosphate ester compound shall be 5-40 mass parts with respect to a total of 100 mass parts of (a) component and (b) component from a viewpoint of the mechanical characteristic balance of a composition. Is preferred. (F) Content of an inorganic filler will not be specifically limited unless the effect of this invention is impaired, For example, it is 0-400 with respect to a total of 100 mass parts of (a) component and (b) component. It may be a mass part. (G) The content of other additives is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, with respect to 100 parts by mass in total of the components (a) and (b). The amount is more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less.

(Flexural modulus)
The resin composition of the present embodiment has a flexural modulus measured according to ISO 178 of 1600 MPa or more, preferably 1700 to 3000 MPa. By being in this range, it is possible to have rigidity applicable to structural parts and structures.
In order to make the flexural modulus 1600 MPa or more, the specific components (a) and (b), and (c), (d), (e), (f), (G) It can adjust suitably by containing a specific amount of a component.

(Low temperature impact resistance)
The low temperature impact resistance of the resin composition of the present embodiment is evaluated by the falling weight impact strength measured according to JIS K 7211-1. The larger the drop weight impact strength value, the better the low-temperature impact resistance, preferably 20 J or more, more preferably 25 J.
In the present specification, the falling weight impact strength can be measured by the method described in Examples described later.

(Tracking resistance)
The resin composition of this embodiment is evaluated by a comparative tracking index measured in accordance with International Electrotechnical Commission standard IEC-60112: 2003. The larger the comparative tracking index, the better the tracking resistance, which is preferably 550 V or higher, and more preferably 575 V or higher.
In the present specification, the comparative tracking index can be measured by the method described in Examples described later.

(Morphology)
The morphology of the resin composition of the present embodiment is that (a) polyphenylene ether resin is a continuous phase from the viewpoint of mechanical strength and chemical resistance. Further, from the viewpoint of obtaining further excellent chemical resistance, it is preferable that at least a part of the component (b) forms a worm-like domain, and all the components (b) form a worm-like domain. More preferably.
The morphology of the resin composition can be measured by the method described in Examples below. For example, (b) the component part is stained with ruthenium tetroxide and then observed using a TEM (transmission electron microscope). be able to.

The earthworm-like domain here is also generally expressed as a worm-like shape, and “(b) component block co-polymers form earthworm-like domains” means that (b) component block The heavy body is a worm-like elongated structure, and is a domain formed by bending or branching. In the “worm-like” shape in the present embodiment, the domain may be bent or an arc may be drawn, or it may be divided into two or more branches, or the connection may be repeated.
Here, FIG. 2 is an image obtained by observing a resin composition having the continuous phase 2 and the earthworm-like domain 1 using a TEM. In FIG. 2, the stained part is a worm-like domain containing the component (b).
In addition, as a method for controlling the morphology of the component (b) in a worm shape, for example, the structure and molecular weight of each block part of the component (b) are adjusted, or the type of the admixture is appropriately selected. Can be achieved.

The length of the earthworm-like domain is preferably 0.1 to 10.0 μm, more preferably 0.1 to 5.0 μm, from the viewpoint of obtaining further excellent chemical resistance.
Moreover, as a width | variety of the said earthworm-like domain, 0.01-1.0 micrometer is preferable from a viewpoint from which the further outstanding chemical-resistance is acquired, More preferably, it is 0.02-0.5 micrometer.
Moreover, as an aspect-ratio of the said earthworm-like domain, 5-1000 are preferable from a viewpoint from which the further outstanding chemical-resistance is acquired, More preferably, it is 10-500.
The maximum distance between the earthworm-like domains is preferably 0.005 to 0.2 [mu] m, more preferably 0.01 to 0.15 [mu] m, from the viewpoint of obtaining further excellent chemical resistance. The maximum distance between worm-like domains was determined by observing arbitrary 100 worm-like domains in an image obtained by observing an arbitrary cross section of the resin composition with a TEM, and measuring the distance between each worm-like domain. The maximum distance.
In addition, the proportion of the worm-like domain in the resin composition is preferably 5 to 50%, more preferably 10 to 50% from the viewpoint of obtaining further excellent chemical resistance. In addition, the ratio of the said earthworm-like domain in a resin composition occupies the earthworm-like domain which occupies in the part of 100 micrometers ² or more arbitrarily selected in the image which observed the arbitrary cross sections of the resin composition with TEM. The area ratio.

In particular, the component (b) preferably has an average minor axis diameter of 2 μm or less and an average major axis diameter / average minor axis diameter of 1-10.
The morphology of the resin composition can be adjusted, for example, by adjusting the structure and molecular weight of each block portion of the component (b) or by appropriately selecting the type of the component (c).

(Production method of resin composition)
The resin composition of the present embodiment includes the components (a) and (b) described above, and, if necessary, the components (c), (d), (e), (f), (g) It can be produced by melt-kneading the components.

The preferable manufacturing method of the resin composition of this embodiment is a manufacturing method including the following processes (1-1) and (1-2).
(1-1): A step of melting and kneading the component (a) and, if necessary, the component (c) to obtain a kneaded product.
(1-2): A step of adding the component (b) to the kneaded product obtained in the step (1-1) and melt-kneading.
In the step (1-1), the component (a) may be added in whole or in part. Further, the component (c) may be added in whole or in part. Especially, it is preferable that the said process (1-1) is a process of melt-kneading the whole quantity of said (a) component, and the whole quantity or one part of said (c) component as needed, and obtaining a kneaded material.
In the step (1-2), the component (b) may be added in whole or in part. When part is added in the step (1-2), the component (b) may be added in the whole amount in the step (1-1) and the step (1-2). The step (1-2) is preferably a step in which the entire amount of the component (b) is added to the kneaded product obtained in the step (1-1) and melt kneaded.
As in this production method, at the time of melt-kneading, by adding the component (b) in the step (1-2) (particularly, by adding the total amount of the component (b) in the step (1-2)), The component (b) is efficiently dispersed in the component (a), and a resin composition having further excellent chemical resistance is obtained.

In the method for producing the resin composition of the present embodiment, the melt kneader suitably used for performing melt kneading of each component is not particularly limited, and examples thereof include a single screw extruder and a twin screw extruder. Among them, an extruder such as a multi-screw extruder, a heated melt kneader using a roll, a kneader, a Brabender plastograph, a Banbury mixer, and the like can be mentioned. A twin-screw extruder is particularly preferable from the viewpoint of kneadability. Specific examples of the twin screw extruder include a ZSK series manufactured by Coperion, a TEM series manufactured by Toshiba Machine Co., Ltd., and a TEX series manufactured by Nippon Steel Works.
The type and standard of the extruder are not particularly limited and may be known ones.

Hereinafter, it describes about suitable embodiment at the time of using extruders, such as multi-screw extruders, such as a single screw extruder and a twin screw extruder.
The L / D (barrel effective length / barrel inner diameter) of the extruder is preferably 20 or more, more preferably 30 or more, and preferably 75 or less, and more preferably 60 or less. preferable.

  The configuration of the extruder is not particularly limited. For example, the first raw material supply port on the upstream side in the flow direction of the raw material, the first vacuum vent downstream from the first raw material supply port, and the first vacuum vent. The second raw material supply port downstream, the first liquid supply pump downstream from the second raw material supply port, the second vacuum vent downstream from the first liquid supply pump, and the second vacuum vent downstream from the second vacuum vent. A two-liquid pump can be provided.

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

  When melt-kneading each component, 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 1200 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 pump or the like in the extruder cylinder portion. The liquid pump is not particularly limited, and examples thereof include a gear pump and a flange type pump, and a gear pump is preferable. At this time, from the viewpoint of reducing the load applied to the liquid pump and enhancing the operability of the raw material, the tank for storing the liquid raw material, the piping between the tank and the liquid pump, the pump and the extruder cylinder It is preferable to heat a portion that becomes a flow path of the liquid raw material such as a pipe between them using a heater or the like to reduce the viscosity of the liquid raw material.

[Molded body]
The molded body of the present embodiment is made of the resin composition of the present embodiment described above.

  The molded body of the present embodiment is not particularly limited, and examples thereof include automobile parts, interior / exterior parts of electrical equipment, and other parts. The automobile parts are not particularly limited, and include, for example, exterior parts such as bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, various aero parts, instrument panels, consoles, etc. Examples include interior parts such as boxes and trims; secondary battery battery case parts mounted on automobiles, electric cars, hybrid electric cars, etc .; lithium ion secondary battery parts. The interior and exterior parts of the electrical equipment are not particularly limited. For example, various computers and peripheral devices, junction boxes, various connectors, other OA equipment, televisions, videos, various disk player cabinets, chassis , Parts used for refrigerators, air conditioners, liquid crystal projectors, and the like. Other parts include electric 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 exterior cases, ink jet printer peripheral parts and components , Furniture (chairs, etc.), chassis, water piping, joints, etc.

(Method for producing molded body)
The molded body of the present embodiment can be produced by molding the resin composition of the present embodiment described above.

  The method for producing the molded body of the present embodiment is not particularly limited, and examples thereof include injection molding, extrusion molding, extrusion profile forming, hollow molding, compression molding, and the like, and the effects of the present invention are more effectively achieved. From the viewpoint of obtaining, injection molding is preferable.

  EXAMPLES Hereinafter, although an Example is given and embodiment of this invention is described, this invention is not limited to these Examples.

The raw materials used for the resin compositions and molded articles of Examples and Comparative Examples are shown below.
-(A) Polyphenylene ether resin-
(Ai): Reduced viscosity obtained by oxidative polymerization of 2,6-xylenol (η _sp / c: 0.5 g / dL chloroform solution) 0.51 dL / g polyphenylene ether (a-ii): 2,6-xylenol obtained by oxidative polymerization, polyphenylene ether Incidentally, reduced viscosity of 0.42 dl / g (chloroform solution of η _sp /c:0.5g/dL) reduced viscosity, η _sp / c: 0 It was measured with a Ubbelohde type viscosity tube under a condition of a temperature of 30 ° C. using a chloroform solution of 0.5 g / dL.

-(B) Hydrogenated block copolymer-
By a known method, an unmodified block copolymer having an ABA block structure was synthesized with the polymer block A made of polystyrene and the polymer block B made of polybutadiene. Hydrogenation was performed on the synthesized block copolymer by a known method. The polymer was not modified. The physical properties of the obtained hydrogenated block copolymer are shown below.
In addition, content of the vinyl aromatic compound was measured using the ultraviolet spectrophotometer. The number average molecular weight (Mn) was determined by a conventionally known method using GPC (moving layer: chloroform, standard material: polystyrene). The molecular weight distribution (Mw / Mn) is obtained by dividing the weight average molecular weight (Mw) obtained by a conventionally known method using GPC (moving layer: chloroform, standard material: polystyrene) by the above-mentioned number average molecular weight (Mn). Calculated by The total amount of vinyl bonds was measured using an infrared spectrophotometer, and Analytical Chemistry, Volume 21, No. 8, calculated according to the method described in August 1949. The hydrogenation rate was measured using a nuclear magnetic resonance apparatus (NMR).
(Bi)
Polystyrene content in block copolymer before hydrogenation: 12% by mass, 1,2-vinyl bond content (total vinyl bond content) in polybutadiene block before hydrogenation: 76%, block copolymer before hydrogenation Number average molecular weight (Mn): 189,300, hydrogenation rate with respect to the polybutadiene portion constituting the polybutadiene block: 61%, glass transition temperature of the polybutadiene block after hydrogenation: -21 ° C.
(B-ii)
Polystyrene content in block copolymer before hydrogenation: 6% by mass, 1,2-vinyl bond content (total vinyl bond content) in polybutadiene block before hydrogenation: 82%, block copolymer before hydrogenation Number average molecular weight (Mn): 7,700, hydrogenation rate with respect to the polybutadiene portion constituting the polybutadiene block: 99%, glass transition temperature of the polybutadiene block after hydrogenation: −3 ° C.
(B-iii)
Polystyrene content in block copolymer before hydrogenation: 17% by mass, 1,2-vinyl bond content (total vinyl bond content) in polybutadiene block before hydrogenation: 62%, block copolymer before hydrogenation Number average molecular weight (Mn): 112,300, hydrogenation rate with respect to the polybutadiene part constituting the polybutadiene block: 78%, glass transition temperature of the polybutadiene block after hydrogenation: −30 ° C.
(B-iv)
Polystyrene content in block copolymer before hydrogenation: 16% by mass, 1,2-vinyl bond content (total vinyl bond content) in polybutadiene block before hydrogenation: 79%, block copolymer before hydrogenation Number average molecular weight (Mn): 300,800, hydrogenation rate with respect to the polybutadiene portion constituting the polybutadiene block: 98%, glass transition temperature of the polybutadiene block after hydrogenation: −13 ° C.
(Bv)
Polystyrene content in block copolymer before hydrogenation: 12% by mass, 1,2-vinyl bond content in polybutadiene block before hydrogenation (total vinyl bond content): 72%, block copolymer before hydrogenation Number average molecular weight (Mn): 177,700, hydrogenation rate with respect to the polybutadiene part constituting the polybutadiene block: 61%, glass transition temperature of the polybutadiene block after hydrogenation: -38 ° C.
(B'-i)
Polystyrene content in block copolymer before hydrogenation: 80% by mass, 1,2-vinyl bond content (total vinyl bond content) in polybutadiene block before hydrogenation: 12%, block copolymer before hydrogenation Number average molecular weight (Mn): 4,900, hydrogenation rate with respect to the polybutadiene part constituting the polybutadiene block: 98%, glass transition temperature of the polybutadiene block after hydrogenation: 21 ° C.
(B'-ii)
Polystyrene content in block copolymer before hydrogenation: 4% by mass, 1,2-vinyl bond content (total vinyl bond content) in polybutadiene block before hydrogenation: 91%, block copolymer before hydrogenation Number average molecular weight (Mn): 13,800, hydrogenation rate with respect to the polybutadiene portion constituting the polybutadiene block: 99%, glass transition temperature of the polybutadiene block after hydrogenation: 10 ° C.

-(C) Admixture-
According to a known method, a block copolymer having a II-I-II-I block structure was synthesized with the polymer block I made of polystyrene and the polymer block II made of polybutadiene. Hydrogenation was performed on the synthesized block copolymer by a known method. The polymer was not modified. The physical properties of the resulting unmodified hydrogenated block copolymer are shown below.
Content of polystyrene in block copolymer before hydrogenation: 44 mass%, number average molecular weight (Mn) of block copolymer before hydrogenation: 95,000, number average molecular weight of polystyrene block (Mn): 41, 800, number average molecular weight (Mn) of polybutadiene block: 53,200, molecular weight distribution of block copolymer before hydrogenation (Mw / Mn): 1.06, 1,2-vinyl bond in polybutadiene block before hydrogenation Amount (total vinyl bond amount): 75%, hydrogenation rate with respect to the polybutadiene portion constituting the polybutadiene block: 99%, glass transition temperature of the polybutadiene block after hydrogenation: −15 ° C.

-(D) Hydrogenated block copolymer-
By a known method, an unmodified block copolymer having an ABA block structure was synthesized with the polymer block A made of polystyrene and the polymer block B made of polybutadiene. Hydrogenation was performed on the synthesized block copolymer by a known method. The polymer was not modified. The physical properties of the obtained block copolymer are shown below.
(Di)
Content of polystyrene in block copolymer before hydrogenation: 30% by mass, number average molecular weight of block copolymer before hydrogenation (Mn): 72,000, number average molecular weight of polystyrene block (Mn): 21, 600, number average molecular weight (Mn) of polybutadiene block: 50,400, molecular weight distribution of block copolymer before hydrogenation (Mw / Mn): 1.10, 1,2-vinyl bond in polybutadiene block before hydrogenation Amount (total vinyl bond amount): 40%, hydrogenation rate with respect to the polybutadiene portion constituting the polybutadiene block: 35%, glass transition temperature of the polybutadiene block after hydrogenation: −80 ° C.
(D-ii)
Polystyrene content in block copolymer before hydrogenation: 36% by mass, 1,2-vinyl bond content in polybutadiene block before hydrogenation (total vinyl bond content): 50%, block copolymer before hydrogenation Number average molecular weight (Mn): 129,300, hydrogenation rate with respect to the polybutadiene portion constituting the polybutadiene block: 50%, glass transition temperature of the polybutadiene block after hydrogenation: -70 ° C.

-(E) Phosphate ester compound-
(E): “E890” (condensed phosphate ester compound) manufactured by Daihachi Chemical Co., Ltd.

  Measuring methods (1) to (4) of physical properties in Examples and Comparative Examples are shown below.

(1) Chemical resistance 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. A flat plate of 150 mm × 150 mm × 3 mm was formed 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 × 12.7 mm × 3 mm was cut out from this flat plate, and the test piece was set on a bending foam designed so that the strain continuously changed. A phthalate ester compound (Bis (2-ethylhexyl) phthalate, manufactured by Tokyo Chemical Industry Co., Ltd.) was applied to the surface of the test piece, and left for 48 hours under the condition of 23 ° C. × 50 RH%. After 48 hours, the test piece was strained, and the stop position of the bending foam was measured when a crack occurred on the surface of the test piece, and the critical strain amount (%) indicating the limit strain amount at which no crack occurred was obtained. .
As an evaluation criterion, it was determined that the larger the numerical value of the critical strain amount, the better the chemical resistance.

(2) Low temperature impact resistance 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 a mold temperature of 70 ° C. A flat plate of 50 mm × 90 mm × 2 mm was formed under the conditions of an injection pressure of 70 MPa, an injection time of 20 seconds, and a cooling time of 10 seconds.
The obtained flat plate was subjected to a falling weight impact test using a striker with a tip diameter of 20 mmφ in accordance with JIS K 7211-1 in an environment of −40 ° C., and the total absorbed energy (J ) Was measured.
The larger the value, the better the low temperature impact resistance.

(3) Tracking resistance The obtained resin composition pellets 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. It was molded into a 120 mm × 80 mm × 3 mm flat plate under the condition of an injection pressure of 70 MPa. From the obtained flat plate, a 20 mm × 20 mm × 3 mm flat plate was cut out, and the maximum voltage (V) at which tracking breakdown did not occur was measured according to IEC60112: 2003 (used electrolyte: solution A, number of drops: 50 drops). The tracking resistance was evaluated.
It was determined that the larger the value, the better the tracking resistance.

(4) 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., injection pressure. Molding was performed under the conditions of 70 MPa, injection time of 20 seconds, and cooling time of 15 seconds to produce an evaluation ISO dumbbell. An ultrathin section was prepared from this evaluation ISO dumbbell using an ultramicrotome, and then component (b) was stained with ruthenium tetroxide. Using TEM (trade name “HT7700”, manufactured by Hitachi High-Technologies Corporation), the ultra-thin section after staining was observed to obtain an image with a magnification of 10,000 times. The obtained image was observed to determine whether the component (b) formed a worm-like domain. Then, “O” (good) indicates that an image in which a worm-like domain is observed is obtained over the entire image (for example, 70% or more of the entire image), and “X” indicates that an image is not obtained. Bad).
Here, the earthworm-like domain formed by the component (b) refers to the portion 1 in FIG. 2, and the continuous phase refers to the portion 2 in FIG.
In addition, in the image obtained above, whether or not (a) component forms a continuous phase, when (a) component forms a continuous phase ((a) component and other components are co-continuous) The case (including the case) was judged as “◯” (good), and the case where the component (a) was in the dispersed phase was judged as “x” (bad).
Determine whether component (b) is dispersed in the resin composition using the same image, measure the short axis diameter (μm) and the long axis diameter (μm) for 100 domains of component (b), The average minor axis diameter (μm) and the average major axis diameter (μm) were determined by taking the average of them. The case where the average minor axis diameter of the component (b) is 2 μm or less and the ratio of the average major axis diameter to the average minor axis diameter (average major axis diameter / average minor axis diameter) is 1 to 10 (good) Otherwise, it was determined as “x” (defective).

(Examples 1-18, Comparative Examples 1-8)
Hereinafter, each example and each comparative example will be described in detail.
A twin-screw extruder (manufactured by Coperion Co., Ltd., ZSK-25) was used as a melt-kneader used for the production of the resin compositions of Examples and Comparative Examples. The L / D of the extruder was 35.
The configuration of the twin-screw extruder includes a first raw material supply port on the upstream side in the flow direction of the raw material, a first vacuum vent downstream from the first raw material supply port, and a second raw material supply downstream from the first vacuum vent. And a second vacuum vent downstream from the liquid feed pump.
The barrel set temperature of the twin screw extruder is set to 320 ° C. from the first raw material supply port to the first vacuum vent, and 270 ° C. downstream from the second raw material supply port. The screw rotation speed is 300 rpm, and the extrusion rate is 15 kg / h. The pellet of the resin composition was manufactured on condition of this. The configuration of the twin screw extruder is shown in FIG.

Components (a) to (e) were supplied to the twin-screw extruder as shown in Table 1 to the twin-screw extruder set as described above to obtain resin composition pellets.
About each Example and each comparative example, the physical-property test was done by the above-mentioned measuring method (1)-(4). The results are shown in Table 1.

  As shown in Table 1, the resin compositions of the examples are superior in impact resistance, low temperature impact resistance, chemical resistance, and tracking resistance compared to the resin compositions of the comparative examples, and are suitable for mechanical parts and structures. It has been found that it has the rigidity that can be applied.

  According to the present invention, it is possible to obtain a resin composition and a molded body having excellent impact resistance, low temperature impact resistance, chemical resistance, and tracking resistance and having rigidity that can be applied to mechanical parts and structures. . The molded body containing the resin composition of the present invention is suitably used as an automobile part, an interior / exterior part of an electric device, other parts, and the like.

1: Worm-like domain 2: Continuous phase

Claims (12)

(A) a polyphenylene ether resin;
(B) At least a 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 first hydrogenated block copolymer and / or a modified product of the hydrogenated block copolymer,
The content of the vinyl aromatic compound unit in the component (b) is 5% by mass or more and less than 20% by mass,
The total proportion of 1,2-vinyl bond and 3,4-vinyl bond to the double bond in the conjugated diene compound unit contained in the component (b) is more than 60%;
The hydrogenation rate with respect to the double bond in the conjugated diene compound unit contained in the component (b) is 60% or more.
The resin composition characterized by the above-mentioned.   The resin composition according to claim 1, further comprising (c) an admixture. At least one block copolymer in which the component (c) 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 in which part is hydrogenated and / or a modified product of the hydrogenated block copolymer,
The content of the vinyl aromatic compound unit in the component (c) is 30 to 50% by mass,
The total ratio of 1,2-vinyl bond and 3,4-vinyl bond to the double bond in the conjugated diene compound unit contained in the component (c) is more than 50% and 90% or less,
The resin composition of Claim 2 whose hydrogenation rate with respect to the double bond in the conjugated diene compound unit contained in the said (c) component is 80 to 100%. And (d) at least a 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. A hydrogenated second hydrogenated block copolymer and / or a modified product of the hydrogenated block copolymer,
The resin composition as described in any one of Claims 1-3 whose hydrogenation rate with respect to the double bond in the conjugated diene compound unit contained in the said (d) component is 20% or more and less than 60%.   The resin composition of Claim 4 whose glass transition temperature of the said polymer block B in the said (d) component is -50 degrees C or less.   The resin composition according to claim 1, wherein the component (a) forms a continuous phase.   The resin composition as described in any one of Claims 1-6 whose glass transition temperature of the said polymer block B in the said (b) component is 0 degrees C or less.   The resin composition according to any one of claims 1 to 7, wherein the component (b) forms a worm-like domain.   The resin composition as described in any one of Claims 1-8 whose content of polypropylene resin is less than 10 mass%.   Furthermore, the resin composition as described in any one of Claims 1-9 containing (e) phosphate ester type compound. The manufacturing method of the resin composition as described in any one of Claim 2 or 3 characterized by including the following process (1-1) and (1-2).
(1-1): A step of melt-kneading the component (a) and the component (c) to obtain a kneaded product.
(1-2): A step of adding the component (b) to the kneaded product obtained in the step (1-1) and melt-kneading.   The molded object characterized by including the resin composition of any one of Claims 1-10.