JP6763698B2 - Resin composition and molded product - Google Patents

Description

The present invention relates to a resin composition and a molded product.

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

For this reason, in some applications, attempts have been made to alloy the PPE resin with a crystalline resin to improve chemical resistance, but in the temperature range below the glass transition temperature of the crystalline resin, resistance is achieved. There was a problem that the impact property deteriorated sharply.

On the other hand, studies have been made to improve the low temperature impact resistance by adding a thermoplastic elastomer having a low glass transition temperature (for example, Patent Document 1), but the compatibility between the low temperature impact resistance and the chemical resistance is considered. Not disclosed.

Further, in order to impart a certain degree of impact resistance, it is necessary to add a relatively large amount of thermoplastic elastomer, so that the rigidity of the obtained composition is lowered, and its use is limited, and mechanical parts are used. (For example, Patent Documents 2 to 4).

International Publication No. 2015/5060 Japanese Unexamined Patent Publication No. 2004-161929 Japanese Patent No. 5422561 Japanese Unexamined Patent Publication No. 2007-591782

Therefore, an object of the present invention is to provide a resin composition and a molded product having excellent low temperature impact resistance and chemical resistance and having rigidity that can be applied to mechanical parts and structures.

As a result of diligent studies to solve the above problems, the present inventors have conducted a polyphenylene ether-based resin, a first hydrogenated block copolymer having a specific structure and / or an olefin-based polymer, and a first having a specific structure. It can be said that a resin composition containing the second hydrogenated block copolymer, talc, and containing no polypropylene-based resin and having a bending elasticity measured according to ISO 178 of a specific value or more can advantageously solve the above problems. We have found and completed the present invention.
That is, the present invention is as follows.

[1]
(A) Polyphenylene ether-based resin, (b) First hydrogenated block copolymer, (c) Olefin-based polymer composed of olefins excluding propylene, and (d) Second hydrogenated block copolymer. And (e) talkene,
The total of (a) component to (d) component is 100 parts by mass, the total of (a) component is 50 to 80 parts by mass, and the total of (b) component and (c) component is 5 to 30 parts by mass, (d). ) Component is 1 to 20 parts by mass, (e) component is 1 to 15 parts by mass,
The block (b) and the component (d) contain 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. It is a hydrogenated block copolymer obtained by hydrogenating at least a part of the copolymer and / or a modified product of the hydrogenated block copolymer.
The glass transition temperature of the polymer block B in the component (b) is −50 ° C. or lower.
The total ratio of 1,2-vinyl bond and 3,4-vinyl bond to the ethylenic double bond in the conjugated diene compound unit contained in the component (b) is 25% or more and 50% or less.
The embrittlement temperature of the component (c) is −50 ° C. or lower.
In the component (d), the hydrogenation rate for the double bond in the conjugated diene compound unit contained in the component (d) is 80 to 100%.
The total ratio of 1,2-vinyl bond and 3,4-vinyl bond to the ethylenic double bond in the conjugated diene compound unit contained in the component (d) is more than 50% and 90% or less.
Substantially, (h) polypropylene-based resin is not contained,
The flexural modulus measured according to ISO 178 is 2000 MPa or more.
A resin composition characterized by that.
[2]
The resin composition according to [1], wherein in the component (b), the hydrogenation rate with respect to the double bond in the conjugated diene compound unit contained in the component (b) is more than 0% and less than 80%.
[3]
The resin composition of [1] or [2] in which the glass transition temperature of the polymer block B in the component (b) is −70 ° C. or lower.

[4]
Further, it contains (f) a phosphoric acid ester compound ,
The component (f) is 5 to 30 parts by mass with respect to a total of 100 parts by mass of the components (a) to (d) .
The resin compositions of [1] to [3].

[5]
In addition, it contains (g) phosphinates and
The component (g) is a phosphinate represented by the following general formula (1).
[In the formula, 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 , Calcium ion, magnesium ion, aluminum ion, zinc ion, bismus ion, manganese ion, sodium ion, potassium ion and protonated nitrogen base; a is 1 to 3 It is an integer; m is an integer of 1 to 3; a = m], and the diphosphinate represented by the following formula (2).
[In the formula, 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, an arylene group having 6 to 10 carbon atoms, an alkyl arylene group having 6 to 10 carbon atoms, or an arylalkylene group having 6 to 10 carbon atoms. Yes; M ² 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 , 1-3; n is an integer of 1-3; j is an integer of 1 or 2; b · j = 2n]
At least one phosphinic acid salts selected from the group consisting of saw including a
The component (g) is 3 to 30 parts by mass with respect to a total of 100 parts by mass of the components (a) to (d) .
The resin compositions of [1] to [4].

[6]
The resin composition according to any one of [1] to [5] , wherein the component (b) contains 30 to 50% by mass of a vinyl aromatic compound unit.

[7]
The resin composition according to any one of [1] to [6] , wherein the component (c) is an ethylene-1-butene copolymer.

[8]
The resin composition according to any one of [1] to [7] , wherein the density of the component (c) is 0.87 g / cm ³ or more.

[9]
The resin composition according to any one of [1] to [8] , wherein the density of the component (c) is 0.90 g / cm ³ or more.

[10]
The resin composition according to any one of [1] to [9] , wherein the average particle size (D50) of the component (e) measured by a laser diffraction method is 5 μm or less.

[11]
The resin composition according to any one of [1] to [10] , wherein the bulk specific gravity of the component (e) is 0.4 g / cm ³ or more.

[12]
The resin composition according to any one of [1] to [11] , wherein the bulk specific gravity of the component (e) is 0.5 g / cm ³ or more.

[13]
The method for producing a resin composition according to any one of [1] to [12] , which comprises the following steps (1-1), (1-2), and (1-3);
(1-1): Step of melt-kneading the component (a) and the component (d) to obtain a kneaded product 1 (1-2): In the kneaded product 1 obtained in the step (1-1). in contrast, the (b) was added component及beauty before SL component (c), step (1-3) to obtain a kneaded product 2 was melt-kneaded: the kneaded product obtained in the step (1-2) Step of adding the component (e) to 2 and melt-kneading

[14]
A molded product containing the resin composition according to any one of [1] to [12] .

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

Hereinafter, a mode for carrying out the present invention (hereinafter, also referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

[Resin composition]
The resin composition of the present embodiment comprises (a) a polyphenylene ether-based resin, (b) an olefin-based polymer composed of (b) a first hydrogenated block copolymer and / or (c) an olefin excluding propylene, and (d). ) Containing a second hydrogenated block copolymer and (e) talc,
A block in which the component (b) and the component (d) include 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. It is a hydrogenated block copolymer obtained by hydrogenating at least a part of the copolymer and / or a modified product of the hydrogenated block copolymer.
The glass transition temperature of the polymer block B in the component (b) is −50 ° C. or lower.
The embrittlement temperature of the component (c) is −50 ° C. or lower.
In the component (d), the hydrogenation rate for the double bond in the conjugated diene compound unit contained in the component (d) is 80 to 100%.
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 (d) is more than 50% and 90% or less.
Substantially, (h) polypropylene-based resin is not contained,
The flexural modulus measured according to ISO 178 is 2000 MPa or more.
In the present specification, at least one 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 block copolymer and / or a modified product of the hydrogenated block copolymer having a portion hydrogenated may be simply referred to as a "hydrogenated block copolymer". 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". It may be referred to as "block-polymer".
Further, the 1,2-vinyl bond and the 3,4-vinyl bond in the conjugated diene compound unit may be referred to as "total vinyl bond".
Further, (d) the polymer block A in the second hydrogenated block copolymer is referred to as "polymer block Ad", and (d) the polymer block B in the second hydrogenated block copolymer is referred to as "polymer". It may be referred to as "block Bd".

Hereinafter, the components of the resin composition of the present embodiment will be described.
The resin composition of the present embodiment has excellent low-temperature impact resistance and chemical resistance, and has rigidity that can be applied to mechanical parts and structures. It is also preferable that the flame retardancy is excellent. In this embodiment, excellent flame retardancy means that the flame retardancy level is V-1 or higher in the UL94 vertical combustion test described in Examples described later.

((A) Polyphenylene ether-based resin)
The (a) polyphenylene ether-based resin used in the present embodiment is not particularly limited, and examples thereof include polyphenylene ether, modified polyphenylene ether, and a mixture of both. The component (a) may be used alone or in combination of two or more.

The reduced viscosity of the component (a) is preferably 0.25 dL / g or more, more preferably 0.28 dL / g or more, and more preferably 0.28 dL / g or more, from the viewpoint of further improving the flame retardancy of the resin composition. 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 viscous tube under the condition of a temperature of 30 ° C. using a chloroform solution having η _{sp /} c: 0.5 g / dL.

-Polyphenylene ether-
The polyphenylene ether is not particularly limited, and for example, a copolymer having a repeating unit structure represented by the following formula (3) and / or a copolymer having a repeating unit structure represented by the following formula (3). Examples include polymers.
[In the formula, R ³¹ , R ³² , R ³³ , and R ³⁴ each independently have a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, and 1 to 7 carbon atoms. Selected from the group consisting of a secondary alkyl group, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbon oxy group, and a halo hydrocarbon oxy group in which at least two carbon atoms separate the halogen atom and the oxygen atom. Is the basis of the monovalent value]

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

The method for producing the polyphenylene ether is not particularly limited, and a conventionally known method can be used. Specific examples of the method for producing polyphenylene ether include US Pat. No. 3,306,874, which is produced, for example, by oxidatively polymerizing 2,6-xylenol using a complex of ferrous salt and amine as a catalyst. Methods described in such documents, US Pat. No. 3,306,875, US Pat. No. 3,257,357, US Pat. No. 3,257,358, Japanese Patent Application Laid-Open No. 52-17880, Japanese Patent Application Laid-Open No. 50-51197, Examples thereof include the methods described in JP-A-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 above-mentioned 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 preferable, it is 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, and is, for example, in the presence or absence of a radical generator, in a molten state, a solution state, or a slurry state under the conditions of 80 to 350 ° C. Examples thereof include a method of reacting a polyphenylene ether with a styrene-based polymer and / or a derivative thereof.

When the component (a) is a mixture of the polyphenylene ether and the 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 hydrogenated block copolymer as a 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. At least a part of the block copolymer containing the polymer is hydrogenated, and the glass transition temperature of the polymer block B is −50 ° C. or lower, which is a hydrogenated block copolymer or a modified product thereof.

-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.
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 vinyl aromatic compound units, and is vinyl aromatic. It is preferable to contain 70% by mass or more of the compound unit.

The vinyl aromatic compound is not particularly limited, and examples thereof include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, and diphenylethylene. Of these, styrene is preferable.
Examples of the conjugated diene compound include the conjugated diene compound described later, and butadiene, isoprene and a combination thereof are preferable.
These may be used individually by 1 type, or may be used in combination of 2 or more type.

In the polymer block A, the distribution of vinyl aromatic compounds, conjugated diene compounds, etc. in the molecular chain in the polymer block is random, tapered (monomer component increases or decreases along the molecular chain), and partially blocked. Alternatively, it may be composed of 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 may have a different structure.

The number average molecular weight (Mn) of the polymer block A is preferably 5,000 to 25,000, more preferably 5, from the viewpoint of obtaining more excellent rigidity, chemical resistance, and low temperature impact resistance. It is 000 to 14,000.
In the present specification, the number average molecular weight of can be measured under the following conditions using Gel Permeation Chromatography System 21 manufactured by Showa Denko KK. In the measurement, as a column, a column in which one KG manufactured by Showa Denko KK, 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 the hydrogenated block copolymer / 1 liter of the chloroform solution. In addition, a calibration curve is prepared using standard polystyrene (the molecular weight of standard polystyrene is 3650000, 2100000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550). Further, the wavelength of UV (ultraviolet rays) in the detection unit is set to 254 nm for both the standard polystyrene and the hydrogenated block copolymer for measurement.
The number average molecular weight (MnbA) of the polymer block A forming the component (b) is, for example, the number average molecular weight (Mnb) of the component (b) when the component (b) has an ABA type structure. Based on the above, it is assumed that the molecular weight distribution of the component (b) is 1, and that two polymer blocks A mainly composed of vinyl aromatic compounds have the same molecular weight, and (MnbA) = (Mnb) × bonded vinyl. It can be calculated by the formula of the ratio of the amount of aromatic compound ÷ 2. Similarly, when the component (b) is an ABBA type hydrogenated block copolymer, the calculation formula is (MnbA) = (Mnb) × ratio of the amount of bonded vinyl aromatic compound ÷ 3. Can be obtained at. When the sequences of the block structure A and the block structure B were clarified at the stage of synthesizing the vinyl aromatic compound-conjugated diene compound block copolymer, the measurement was performed without depending on the above formula (). b) It may be calculated from the ratio of the block structure A based on the number average molecular weight (Mnb) of the components.

-Polymer block B-
Examples of the polymer block B mainly composed of the conjugated diene compound include a homopolymer block of the conjugated diene compound, a random copolymer block of the conjugated diene compound and a vinyl aromatic compound, and the like.
Here, in the polymer block B, "mainly composed of a conjugated diene compound" means that the polymer block B contains more than 50% by mass of the conjugated diene compound unit, and 70% by mass or more of the conjugated diene compound unit. It is preferable to contain it.

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.
Examples of the vinyl aromatic compound include the vinyl aromatic compound described above, and styrene is preferable.
These may be used individually by 1 type, or 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), and partially block-like. Alternatively, it may be composed of 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 may have a different structure.

The hydrogenation rate for the ethylenic double bond in the conjugated diene compound unit in the polymer block B is 20% or more and less than 80% from the viewpoint of obtaining more excellent rigidity, chemical resistance, and low temperature impact resistance. It is preferable, and more preferably 20% or more and less than 70%.
In the present specification, the hydrogenation rate can be measured by using a nuclear magnetic resonance apparatus (NMR).

The total ratio of 1,2-vinyl bond and 3,4-vinyl bond to the ethylenic double bond in the conjugated diene compound unit in the polymer block B has more excellent rigidity, chemical resistance, and low temperature impact resistance. From the viewpoint of obtaining the above, it is preferably 25% or more and less than 60%, more preferably 25 to 55%, still more preferably 25 to 50%.
In the present specification, the total of the 1,2-vinyl bond amount and the 3,4-vinyl bond amount (total vinyl bond amount) is the conjugated diene compound unit in the polymer block containing the conjugated diene compound before hydrogenation. 1,2-vinyl bond amount, 3,4-vinyl bond amount, 1,2-vinyl bond amount, 3,4-vinyl bond amount, and 1,4-conjugate bond amount. Refers to the ratio to. The total vinyl bond amount was measured using an infrared spectrophotometer, and Analytical Chemistry, Volume21, No. 8. It can be 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 40,000, from the viewpoint of obtaining more excellent rigidity, chemical resistance, and low temperature impact resistance. ~ 80,000.

The glass transition temperature of the polymer block B is −50 ° C. or lower, preferably −60 ° C. or lower, preferably −70 ° C. or lower, from the viewpoint of obtaining more excellent rigidity, chemical resistance, and low temperature impact resistance. It is more preferable that the temperature is -100 ° C. or higher.
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 determined by, for example, using a dynamic viscoelasticity measuring device to obtain a film-like sample. It can be measured in a tensile mode, a temperature scan speed of 3 ° C./min, a frequency of 1 Hz, and a nitrogen atmosphere.

The polymer block B is a single polymer block in which the ratio of the total vinyl bond amount to the ethylenic double bond in the conjugated diene compound unit contained in the polymer block B is 25% or more and less than 60%. Alternatively, a polymer block B1 mainly composed of a conjugated diene compound having a total vinyl bond amount ratio of 25 to 45% and a conjugated diene compound having a total vinyl bond amount ratio of 45% or more and less than 70% may be used. It may be a polymer block mainly composed of a conjugated diene compound having both a polymer block B2 as a main component.
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 represented by A-B2-B1-A or the like and in which the total vinyl bond amount is controlled based on the adjusted feed sequence of each monomer unit.

-Structure of hydrogenated block copolymer-
Regarding the structure of the hydrogenated block copolymer in the component (b), assuming that the polymer block A is "A" and the polymer block B is "B", for example, AB type and ABA. Type, B-ABA type, (AB-) n-X type (where n is an integer of 1 or more, X is the reaction residue of a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride. Residues of initiators such as groups or polyfunctional organic lithium compounds), structures such as ABABBA type can be mentioned. Further, referring to the block structure, the polymer block B is a homopolymer block of the conjugated diene compound, or a conjugated diene compound and a vinyl fragrance containing more than 50% by mass (preferably 70% by mass or more) of the conjugated diene compound unit. It is a copolymer block with a group 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 a group compound and a conjugated diene compound.
The component (b) may contain blocks other than the polymer block A and the polymer block B.

The molecular structure of the hydrogenated block copolymer in the 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 constituent unit derived from the vinyl aromatic compound) in the component (b) is not particularly limited, but from the viewpoint of heat resistance and mechanical strength of the resin composition. Therefore, it is preferably 20 to 70% by mass, more preferably 20 to 60% by mass, still more preferably 30 to 50% by mass, and particularly preferably 30 to 40% by mass. Further, not only one kind of component (b) having a vinyl aromatic compound unit content in these ranges but also two or more kinds of components having different vinyl aromatic compound unit contents (b) can be used in combination. ..
The content of the vinyl aromatic compound unit can be measured using an ultraviolet spectrophotometer.

--Total vinyl bond amount ---
(B) The total ratio of 1,2-vinyl bond and 3,4-vinyl bond to the ethylenic double bond in the conjugated diene compound unit contained in the component is preferably 25% or more and less than 60%. , 25% or more and 55% or less, and more 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 of the resin composition at low temperature is improved. When it is 50% or less, the impact resistance at low temperature is further improved. Further, the component (b) in which the total ratio of the 1,2-vinyl bond and the 3,4-vinyl bond is 25% or more is preferable from the viewpoint of improving the compatibility with the component (d).
The method for controlling the total ratio of the 1,2-vinyl bond and the 3,4-vinyl bond within the above range is not particularly limited, but for example, in the production of the component (b), the 1,2-vinyl bond amount. Examples thereof include a method of adding an adjusting agent and a method of adjusting the polymerization temperature.
“The total of 1,2-vinyl bond and 3,4-vinyl bond with respect to the double bond in the conjugated diene compound unit” means (b) in the block copolymer of the hydrogenated block copolymer before hydrogenation. It refers to the total of 1,2-vinyl bond and 3,4-vinyl bond with respect to the double bond (ethylene double bond) in the conjugated diene compound unit. For example, the block copolymer before hydrogenation can be measured by 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 component (b), the hydrogenation rate of the block copolymer with respect to the ethylenic double bond (double bond in the conjugated diene compound unit) is preferably more than 0% and less than 80%, more preferably 10%. It is more than 80%, more preferably 20% or more and less than 80%, further 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 component (b) having such a hydrogenation rate can be used to reduce the amount of hydrogen consumed to a desired hydrogenation rate (for example, 10% or more and less than 80%) in the hydrogenation reaction of an ethylenic double bond of a block copolymer. ) Is easily obtained by controlling the range.

The total ratio of 1,2-vinyl bond and 3,4-vinyl bond to the ethylenic double bond in the conjugated diene compound unit contained in the component (b) is less than 60%, and / Alternatively, when the hydrogenation rate for the ethylenic double bond in the component (b) is less than 80%, the impact resistance of the resin composition at low temperature is further improved, which is more preferable.

-Number average molecular weight-
The number average molecular weight of the component (b) takes into consideration the melt viscosity of the component (b) from the viewpoint that the component (b) is appropriately dispersed in the melt-mixed system and the effect as an impact-resistant imparting agent is easily exerted. It is preferably 5,000 to 1,000,000, and more preferably 100,000 or less.
The method of 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 catalytic amount in the polymerization step of the component (b).

The molecular weight distribution (Mw / Mn) of the component (b) is preferably 1.01 to 1.50 from the viewpoint of obtaining more excellent rigidity, chemical resistance, low temperature impact resistance, and tracking resistance. More preferably, it is .03 to 1.40.
The molecular weight distribution (Mw / Mn) is the weight average molecular weight (Mw) obtained by a conventionally known method using GPC (moving layer: chloroform, standard substance: polystyrene), and the above-mentioned number average molecular weight (Mn). It can be calculated by dividing by.

-Manufacturing method-
The method for producing the 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-49-66743. Japanese Patent Application Laid-Open No. 50-75651, Japanese Patent Application Laid-Open No. 54-126255, Japanese Patent Application Laid-Open No. 56-10542, Japanese Patent Application Laid-Open No. 56-62847, Japanese Patent Application Laid-Open No. 56-160840, Japanese Patent Application Laid-Open No. 2 -300218, UK Patent No. 1130770, US Pat. No. 3,281,383, US Pat. No. 3,369,517, UK Pat. No. 102,720, US Pat. No. 3,333,024 and US Pat. No. 4,501,857. Examples thereof include the methods described in the specification.

-Modified hydrogenated block copolymer-
Examples of the modified product of the hydrogenated block copolymer in the component (b) include the above hydrogenated block copolymer (particularly, an unmodified hydrogenated block copolymer), α, β-unsaturated carboxylic acid or the like. A modified hydrogenated block obtained by reacting a derivative (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. Examples include block polymers. In this case, the α, β-unsaturated carboxylic acid or a 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.

When the unmodified hydrogenated block copolymer and the modified hydrogenated block copolymer are used in combination as the component (b), the mixing ratio of the unmodified hydrogenated block copolymer and the modified hydrogenated block copolymer is It can be decided without any particular limitation.

((C) Olefin-based polymer)
The olefin-based polymer of the component (c) is not particularly limited, and for example, a homopolymer of an olefin-based monomer excluding propylene, a copolymer of two or more types of monomers including an olefin-based monomer excluding propylene, and the like. Can be mentioned. Of these, a copolymer of ethylene and an α-olefin other than ethylene is preferable from the viewpoint of low temperature impact resistance. Here, from the viewpoint of low temperature impact resistance, chemical resistance, tracking resistance, and rigidity of the obtained resin composition, the propylene unit is not included as the monomer unit constituting the component (c).
The "olefin-based polymer composed of an olefin excluding propylene" and "not including a propylene unit" include a case where propylene is contained as a constituent unit to the extent that the effect of the invention is not impaired. For example, the component (c) It means that the content of the propylene unit in all the constituent units constituting the component (c) in the component (c) is less than 0.1% by mass.

Examples of the component (c) include a copolymer of ethylene and one or more C4 to C20 α-olefins. Among them, it is more preferable that it is a copolymer of ethylene and one or more kinds of C4 to C8 α-olefins, and ethylene and 1-butene, 1-hexene, 4-methyl-1-pentene and It is more preferably a copolymer with one or more comonomer selected from the group consisting of 1-octene, and particularly preferably a copolymer of ethylene and 1-butene. 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 alone or in combination of two or more. Further, as the component (c), two or more kinds of ethylene-α-olefin copolymers may be used.

The content of ethylene in the component (c) is preferably 5 to 95% by mass, more preferably 30 to 90% by mass, based on the total amount of the olefin polymer, from the viewpoint of low temperature curability and flexibility of the resin composition. It is mass%.
The content of the α-olefin other than ethylene in the component (c) is not particularly limited, and is 5% by mass or more based on the total amount of the olefin polymer from the viewpoint of low temperature curability and flexibility of the resin composition. It is preferably 20% by mass or more, and from the viewpoint of the rigidity of the resin composition, it is preferably 50% by mass or less, and more preferably 48% by mass or less.

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

The density of the component (c) measured in accordance with JIS K7112 (density at the raw material stage before kneading) is preferably 0.87 g / cm ³ or more, preferably 0, from the viewpoint of chemical resistance of the resin composition. .90 g / cm ³ or more is more preferable.
The method of controlling the density of the component (c) within the above range is not particularly limited, and examples thereof include a method of adjusting by controlling the content ratio of ethylene units.

The melt flow rate of the component (c) (measured at 190 ° C. under a load of 2.16 kgf according to MFR, ASTM D-1238, density at the raw material stage before kneading) is determined by the resin composition of the component (c). From the viewpoint of stabilizing morphology by dispersion in the resin and impact resistance of the resin composition, 0.1 to 5.0 g / 10 minutes is preferable, and 0.3 to 4.0 g / 10 minutes is more preferable.
The method for controlling the melt flow rate of the component (c) within the above range is not particularly limited, but for example, a method for adjusting the polymerization temperature and the polymerization pressure when producing the component (c), ethylene in the polymerization system. , A method of adjusting the molar ratio between the monomer concentration of α-olefin or the like and the hydrogen concentration and the like.

The component (c) may be, for example, an olefin polymer rubber composed of an olefin excluding propylene.
The torsional rigidity of the 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 rigidity of the component (c) can be measured according to ASTM D 1043.
Further, the shore A of the component (c) is preferably 40 to 110, more preferably 50 to 100, from the viewpoint of imparting sufficient impact resistance to the composition. The shore A of the component (c) can be measured in accordance with JIS K 6253.

The method for preparing the component (c) is not particularly limited, and is based on a catalyst (for example, titanium, metallocene, or vanadium) capable of easily obtaining a high molecular weight α-olefin polymer under usual processing conditions. A method using a catalyst or the like) can be mentioned. Among these, a method using a metallocene catalyst and a titanium chloride catalyst is preferable from the viewpoint of stability of structural control. As a method for producing the ethylene-α-olefin copolymer, a known method described in JP-A-6-306121 and JP-A-7-500122 can be used.

((D) Second hydrogenated block copolymer)
The (d) second hydrogenated block copolymer used in the present embodiment is not particularly limited, but includes a segment chain having high compatibility with the component (a), the component (b) and / or (. c) A hydrogenated block copolymer having a segment chain having high compatibility with the component is preferable. 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) and / or the component (c) include a polyolefin chain and a copolymer elastomer molecular chain of ethylene and α-olefin.

Examples of such hydrogenated block copolymers include hydrogenated block copolymers having a polystyrene chain-polyolefin chain and hydrogenated block copolymers having a polyphenylene ether chain-polyolefin chain from the viewpoint of thermal stability. Be done. These may be used alone or in combination of two or more.
In the resin composition of the present embodiment, the polymer block Ad and the polymer block Bd in the component (d) may be the same as the polymer block A and the polymer block B in the component (b). It may be different.
It is preferable that the polymer block A in the component (b) and the polymer block Ad in the component (d), the polymer block B in the component (b) and the polymer block Bd in the component (d) are different.

The matters concerning the unmodified and modified hydrogenated block copolymers in the component (d) will be described below.
-Polymer block Ad-
The polymer block Ad 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. Can be mentioned.
In the polymer block Ad, "mainly composed of a vinyl aromatic compound" means that the polymer block Ad before hydrogenation contains more than 50% by mass of a vinyl aromatic compound unit, which means that the vinyl aromatic compound is contained. 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 Ad is not particularly limited, and examples thereof include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, and diphenylethylene, and styrene is preferable. ..
Examples of the conjugated diene compound constituting the polymer block Ad include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and butadiene, isoprene, and combinations thereof are preferable. Butadiene is more preferred.
These may be used individually by 1 type, or may be used in combination of 2 or more type.

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

-Polymer block Bd-
The polymer block Bd 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 Bd, "mainly a conjugated diene compound" means that the polymer block Bd 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 further preferably 100% by mass or less.

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

The hydrogenation rate for the ethylenic double bond in the conjugated diene compound unit contained in the polymer block Bd is preferably 80% or more from the viewpoint of obtaining more excellent rigidity, chemical resistance, and low temperature impact resistance. , More preferably 90% or more.

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

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

The glass transition temperature of the polymer block Bd is preferably more than -50 ° C, more preferably more than -50 ° C and 0 ° C or less, and further, from the viewpoint of obtaining more excellent rigidity, chemical resistance, and low temperature impact resistance. It is preferably -40 to -10 ° C.

The distribution of the vinyl aromatic compound in the molecular chain in the polymer block Ad and the conjugated diene compound in the molecular chain in the polymer block Bd is not particularly limited, and is, for example, random or tapered (along the molecular chain). The monomer portion increases or decreases), a partial block shape, or a combination thereof.

(D) Block structure of unmodified and modified hydrogenated block copolymer as a component The block structure of the copolymer is not particularly limited, and for example, the polymer block Ad is referred to as "A" and the polymer block. expressed as "B" bd, as the component (d), a-B, a-B -a, B-a-B-a, (a-B-) 4 M, a-B-a-B Examples include structures such as −A. Here, (AB-) ₄ M is a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride (M = Si) or tin tetrachloride (M = Sn), or a polyfunctional organolithium compound or the like. It is a residue of the initiator of.
The component (d) may contain blocks other than the polymer block Ad and the polymer block Bd.

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

(D) When a plurality of polymer block Ad or polymer block Bd are contained in the block copolymer as a component, the plurality of polymer block Ad or the plurality of polymer block Bd may be mixed with each other. , Each may have the same structure or may have a different structure.

(D) The content of the vinyl aromatic compound in the block copolymer before hydrogenation is 30% by mass or more from the viewpoint of improving the fluidity, impact resistance and appearance of the component and reducing the generation of welds. It is preferably 32% by mass or more, more preferably 50% by mass or less, and further preferably 48% by mass or less.

(D) 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 is more than 50% and 90% or less. It is preferably 60% to 90%.

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 80 to 100%, preferably 90 to 100%.

In the component (d), 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 further preferably 30,000 or more. It is particularly preferable, and it is preferably 1,000,000 or less, more preferably 800,000 or less, and particularly preferably 500,000 or less.

In the component (d), 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) obtained by a conventionally known method using GPC (moving layer: chloroform, standard substance: polystyrene), and the above-mentioned number average molecular weight (Mn). It can be calculated by dividing by.

In the component (d), the method of hydrogenating the block copolymer is not particularly limited, and for example, (1) a metal such as Ni, Pt, Pd, Ru is added to carbon, silica, alumina, silica soil, etc. A so-called Cheegler type that uses a carrying-type non-uniform hydrogenation catalyst carried on the ground, (2) a transition metal salt such as an organic acid salt such as Ni, Co, Fe, Cr, or an acetylacetone salt, and a reducing agent such as organic aluminum. Using a hydrogenation catalyst, (3) a uniform hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Ti, Ru, Rh, or Zr, for example, a reaction temperature of 0 to 200 ° C. and a hydrogen pressure of 0.1. Examples thereof include a method of hydrogenating under the condition of ~ 15 MPa.

The method for synthesizing the block copolymer containing the polymer block Ad and the polymer block Bd is not particularly limited, and examples thereof include known methods such as anionic polymerization.
The method for producing 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. Japanese Patent Application Laid-Open No. 50-75651, Japanese Patent Application Laid-Open No. 54-126255, Japanese Patent Application Laid-Open No. 56-10542, Japanese Patent Application Laid-Open No. 56-62847, Japanese Patent Application Laid-Open No. 56-160840, Japanese Patent Application Laid-Open No. 2-3018, UK Patent No. 1130770, US Pat. No. 3,281,383, US Pat. No. 3,639,517, UK Pat. No. 102,720, US Pat. No. 3,333,024, and US Pat. Examples thereof include the method described in the specification of No. 4501857.

In particular, the matters concerning the modified hydrogenated block copolymer in the component (d) will be described below.
-Modified hydrogenated block copolymer-
The modified hydrogenated block copolymer is obtained by grafting or adding α, β-unsaturated carboxylic acid or a derivative thereof (for example, acid anhydride, ester, etc.) to the above-mentioned unmodified hydrogenated block copolymer. 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 10% by mass or less with respect to 100% by mass of the unmodified hydrogenated block copolymer. It is preferably 7% by mass or less, and particularly preferably 5% by mass or less.

The method for producing the modified hydrogenated block copolymer is not particularly limited, and is, for example, in the presence or absence of a radical generator, in a molten state, a solution state, or a slurry state under the conditions of 80 to 350 ° C. Then, a method of reacting the above-mentioned unmodified hydrogenated block copolymer with α, β-unsaturated carboxylic acid or a derivative thereof and the like can be mentioned.

((E) Talc)
(E) Talc as a component is a mineral containing magnesium hydroxide and a silicate, and has a chemical name of hydrous magnesium silicate. The talc is generally, SiO ₂ about 60% MgO 30%, mainly composed of 4.8% crystal water.

The average particle size (D50) measured by the laser diffraction method of talc is preferably 5 μm or less, more preferably 4 μm or less, and 3 μm or less from the viewpoint of enhancing the low temperature impact resistance of the resin composition. Is even more preferable.

The talc bulk specific gravity, in view of enhancing the rigidity of the resin composition, is preferably 0.40 g / cm ³ or more, more preferably 0.50 g / cm ³ or more, 0.60 g / cm ³ The above is more preferable, and the amount is preferably 1.00 g / cm ³ or less.
The bulk specific gravity of talc can be measured in accordance with JIS K 5101.

The talc may be treated with a surface treatment agent from the viewpoint of improving the affinity with the resin. The surface treatment agent is not particularly limited, and is, for example, a silane coupling agent such as aminosilane or epoxysilane; a titanate-based coupling agent; fatty acids (saturated fatty acids, unsaturated fatty acids); alicyclic carboxylic acids; resins. Acids; metal soaps; etc. The amount of the surface treatment agent added is not particularly limited, and is preferably 3% by mass or less, more preferably 2% by mass or less, and substantially not added, based on 100% by mass of talc. Is most preferable.

The commercially available talc product is not particularly limited, and examples thereof include talc MS and MS-KY manufactured by Nippon Talc, and Hytron A manufactured by Takehara Chemical Industry Co., Ltd.

((F) Phosphate ester compound)
The resin composition of the present embodiment preferably further contains (f) a phosphoric acid ester compound.
The (f) phosphoric acid ester-based compound used arbitrarily in the present embodiment is not particularly limited, and is a general phosphoric acid ester compound having an effect of improving the flame retardancy of the resin composition (phosphate ester compound). , Condensed phosphate compound, etc.), for example, triphenyl phosphate, phenylbisdodecyl phosphate, phenylbisneopentyl phosphate, phenyl-bis (3,5,5'-trimethyl-hexyl phosphate), ethyldiphenyl phosphate, 2, -Ethyl-hexyl di (p-tolyl) phosphate, bis- (2-ethylhexyl) -p-tolyl phosphate, tritryl phosphate, bis- (2-ethylhexyl) phenyl phosphate, tri- (nonylphenyl) phosphate, di (dodecyl) -P-trilphosphate, tricresyl phosphate, dibutylphenyl phosphate, 2-chloroethyldiphenyl phosphate, p-tolylbis (2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyldiphenyl phosphate, bisphenol A-bis (diphenyl) Phenyl phosphate), diphenyl- (3-hydroxyphenyl) phosphate, bisphenol A bis (dicrezyl phosphate), resorcin bis (diphenyl phosphate), resorcin bis (dixylenyl phosphate), 2-naphthyldiphenyl phosphate, 1- Examples thereof include naphthyldiphenyl phosphate and di (2-naphthyl) phenyl phosphate.

In particular, as the (f) phosphoric acid 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 ⁴¹ and R ⁴² are each independently methyl. Groups; R ⁴³ and R ⁴⁴ are independent hydrogen atoms or methyl groups; x is an integer greater than or equal to 0; p ₁ , p ₂ , p ₃ , and p ₄ are 0 to 0, respectively. It is an integer of 3; q ₁ and q ₂ are integers of 0 to ₂ , respectively], and the following equation (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; y is 0 or more. R ₁ , r ₂ , r ₃ , and r ₄ are integers 0 to 3, respectively; s ₁ is an integer from 0 to 2, respectively]
It is preferable that the main component is at least one selected from the group consisting of aromatic condensed phosphoric acid ester compounds represented by.
The condensed phosphoric acid ester compound represented by the above formula (4) and the above formula (5) may each contain a plurality of types of molecules, and for each molecule, n may be an integer of 1 to 3. preferable.

In a suitable (f) phosphoric acid ester compound containing at least one selected from the group consisting of condensed phosphoric acid ester compounds represented by the above formula (4) and the above formula (5) as a main component, x as a whole. , Y preferably have an average value of 1 or more. The above-mentioned suitable (f) phosphate ester-based compound can be generally obtained as a mixture containing 90% or more of a compound having x and y of 1 to 3 and other than a compound having x and y of 1 to 3. Includes multimers and other by-products with x, y of 4 or greater.

-(G) Phosphates-
In this embodiment, (g) phosphinates can be used, if necessary. (E) The phosphinates are represented by the following formula (1).
[In formula (1), R ¹¹ and R ¹² are linear or branched alkyl groups having 1 to 6 carbon atoms and / or aryl groups having 6 to 10 carbon atoms, respectively; M ¹ is at least one selected from the group consisting of calcium ion, magnesium ion, aluminum ion, zinc ion, bismus ion, manganese ion, sodium ion, potassium ion and protonated nitrogen base; a is 1 It 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 linear or branched alkyl groups having 1 to 6 carbon atoms and / or aryl groups having 6 to 10 carbon atoms, respectively; R ²³ is a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkyl arylene group having 6 to 10 carbon atoms, or an aryl having 6 to 10 carbon atoms. It is an alkylene group; M ² 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 1-3; n is an integer of 1-3; j is an integer of 1 or 2; b · j = 2n]
At least one selected from the group consisting of.
Further, the (g) phosphinates may be a mixture of the phosphinate represented by the above formula (1) and the diphosphinate represented by the above formula (2).

Such (g) phosphinates are not particularly limited, and for example, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, ethylmethylphosphine. Magnesium acid, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphine, methyl-n-propylphosphine Magnesium acid, aluminum methyl-n-propylphosphinate, zinc methyl-n-propylphosphinate, calcium methanedi (methylphosphinic acid), magnesium methanedi (methylphosphinic acid), aluminum methanedi (methylphosphinic acid), methanedi (methylphosphinic acid) ) Zinc, benzene-1,4- (dimethylphosphinic acid) calcium, benzene-1,4- (dimethylphosphinic acid) magnesium, benzene-1,4- (dimethylphosphinic acid) aluminum, benzene-1,4- (dimethyl) Zinc (phosphinic acid), calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, zinc diphenylphosphite. With calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate. It is preferably present, and more preferably aluminum diethylphosphinate.

(G) Commercially available products of phosphinates are not particularly limited, and examples thereof include Exolit (registered trademark) OP1230, OP1240, OP1311, OP1312, OP930, OP935 manufactured by Clariant Japan.

((H) Polypropylene resin)
From the viewpoint of the low temperature impact resistance of the resin composition, the composition of the present embodiment preferably contains substantially (h) polypropylene-based resin. Here, substantially not contained means that the content of the (h) polypropylene-based resin in the resin composition is less than 0.1%. The polypropylene-based resin (h) is not particularly limited, and examples thereof include homopolypropylene, copolymers containing polypropylene blocks, modified polypropylene, and mixtures thereof.
The content of the polypropylene-based resin in the resin composition is, for example, the resin composition is freeze-crushed into a powder, and then the powder is dissolved in chloroform at 23 ° C., and the insoluble content thereof is 150 ° C. The fraction dissolved in o-dichlorobenzene is further recovered, and the fraction can be determined by measuring the fraction by NMR.

((I) Thermoplastic resin)
The thermoplastic resin (i) other than the components (a) to (d) used arbitrarily in the present embodiment is not particularly limited, and is, for example, polystyrene, syndiotactic polystyrene, high impact polystyrene, or the like. Can be mentioned.

((J) Other additives)
The other additive (j) other than the components (a) to (i) used arbitrarily in the present embodiment is not particularly limited, and for example, vinyl other than the components (b) and (d). A block copolymer of aromatic compound-conjugated diene compound, olefin elastomer, antioxidant, metal inactivating agent, heat stabilizer, flame retardant other than component (f) and component (g) (ammonium polyphosphate compound) , Magnesium hydroxide, 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.), trioxide Examples thereof include flame retardant aids such as antimony, weather resistance (light) improving agents, nucleating agents for polyolefins, slip agents, various colorants, and mold release agents.

Hereinafter, the proportions of the components of the resin composition of the present embodiment will be described.
The content of each component in the resin composition of the present embodiment is (from the viewpoint of enhancing the low temperature impact resistance and chemical resistance of the resin composition and imparting sufficient rigidity that can be applied to mechanical parts and structures. The total of the components (a) to (d) is 100 parts by mass, the total of the components (a) is 50 to 80 parts by mass, the total of the components (b) and (c) is 5 to 30 parts by mass, and (d). The component is preferably 1 to 20 parts by mass, the component (e) is preferably 1 to 15 parts by mass, and more preferably the component (a) is 60 to 80 parts by mass, and the total of the component (b) and the component (c). Is 10 to 30 parts by mass, the component (d) is 5 to 20 parts by mass, and the component (e) is 3 to 15 parts by mass.
Further, the content of the (f) phosphoric acid ester compound is 5 to 30 parts by mass with respect to 100 parts by mass in total of the components (a) to (d) from the viewpoint of the balance of mechanical properties of the composition. preferable.
Further, the content of (g) phosphinate is 3 to 3 to 100 parts by mass in total of the components (a) to (d) from the viewpoint of the balance between the mechanical properties of the resin composition and the flame retardancy. It is preferably 30 parts by mass, and more preferably 4 to 27 parts by mass.
Further, the content of (i) the thermoplastic resin is not particularly limited as long as the effect of the present invention is not impaired, and is, for example, 0 with respect to a total of 100 parts by mass of the components (a) to (d). It may be ~ 400 parts by mass.

(Flexural modulus)
The resin composition of the present embodiment has a flexural modulus of 2000 MPa or more, preferably 2000 to 3000 MPa, measured according to ISO 178. Within this range, it is possible to have rigidity applicable to structural parts and structures.
In order for the flexural modulus to be 2000 MPa or more, the components (a) to (e) and, if necessary, the components (f), (g), (i), and (j) are contained in specific amounts. It can be adjusted as appropriate.

(Manufacturing method of resin composition)
In the resin composition of the present embodiment, the above-mentioned components (a) to (e) and, if necessary, the components (f), (g), (i), and (j) are melt-kneaded. 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) to (1-3).
(1-1): A step of melt-kneading the above-mentioned component (a) and the above-mentioned component (d) to obtain a kneaded product 1.
(1-2): The component (b) and / or the component (c) is added to the kneaded product 1 obtained in the step (1-1), melt-kneaded, and the kneaded product 2 is kneaded. The process of obtaining.
(1-3): A step of adding the component (e) to the kneaded product 2 obtained in the above step (1-2) and melt-kneading.
In the above step (1-1), the whole amount or a part of the component (a) may be added. In addition, the above component (d) may be added in whole amount or in part. Above all, the step (1-1) is preferably a step of melt-kneading the whole amount of the component (a) and the whole amount or a part of the component (d) to obtain a kneaded product.
In the above step (1-2), the whole amount or a part of the component (b) may be added. In addition, the above component (c) may be added in whole amount or in part. When a part is added in the step (1-2), the whole amount of the component (b) and / or the component (c) may be added in the steps (1-1) and (1-2). The step (1-2) is a step of adding the entire amount of the component (b) and / or the component (c) to the kneaded product obtained in the step (1-1) and melt-kneading. It is preferable to have.
By adding the component (b) and / or the component (c) in the step (1-2) at the time of melt-kneading as in this production method (in particular, the total amount of the component (b) and / or the component (c)). (By adding in step (1-2)), the component (b) and / or the component (c) is efficiently dispersed in the component (a), and a resin composition having further excellent chemical resistance can be obtained. .. Further, by further adding the component (e) after that (by adding the component (b) and / or the component (c) after adding the entire amount), the pulverization of the component (e) during melt-kneading is suppressed. , The resin composition can be efficiently imparted with rigidity.

The melt-kneading machine preferably used for melt-kneading each component in the method for producing a resin composition of the present embodiment is not particularly limited, and is, for example, a single-screw extruder, a twin-screw extruder, or the like. Examples thereof include an extruder such as a multi-screw extruder, a heat-melt kneader using a roll, a kneader, a brabender plastic, a Banbury mixer, and the like, and a twin-screw extruder is particularly preferable from the viewpoint of kneadability. Specific examples of the twin-screw extruder include the ZSK series manufactured by Coperion, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by Japan Steel Works, Ltd.
The type and standard of the extruder are not particularly limited and may be known.

Hereinafter, preferred embodiments when an extruder such as a multi-screw extruder such as a single-screw extruder or a twin-screw extruder is used will be described.
The L / D (barrel effective length / barrel inner diameter) of the extruder is preferably 20 or more, more preferably 30 or more, more preferably 75 or less, and further preferably 60 or less. preferable.

The configuration of the extruder is not particularly limited, and for example, the first raw material supply port is upstream in the direction in which the raw material flows, the first vacuum vent is downstream from the first raw material supply port, and the first vacuum vent is used. From the second raw material supply port downstream, the first liquid addition pump (described later) downstream from the second raw material supply port, the third raw material supply port downstream from the first liquid addition pump, and the third raw material supply port. A second vacuum vent may be provided downstream, and a second liquid addition pump (described later) may be provided downstream of the second vacuum vent.

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

When each component is melt-kneaded, the melt-kneading temperature is not particularly limited and may be 200 to 370 ° C., and the screw rotation speed may be 100 to 1200 rpm without particular limitation.

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. The liquid addition 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 addition pump and improving the operability of the raw material, the tank for storing the liquid raw material, the piping between the tank and the liquid addition pump, and the pump and the extruder cylinder It is preferable to reduce the viscosity of the liquid raw material by heating the portion serving as the flow path of the liquid raw material such as the piping between them using a heater or the like.

(Molded body)
The molded product of the present embodiment comprises 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 electric devices, and other parts. The automobile parts are not particularly limited, and are, for example, 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 battery parts mounted on automobiles, electric vehicles, hybrid electric vehicles and the like; lithium ion secondary battery parts and the like. The interior / exterior parts of electrical equipment are not particularly limited, and are, for example, various computers and their peripherals, junction boxes, various connectors, other OA equipment, televisions, videos, cabinets of various disc players, and chassis. , Refrigerators, air conditioners, parts used in liquid crystal projectors, etc. Other parts include electric wires / cables obtained by coating metal conductors or optical fibers, fuel cases for solid methanol batteries, fuel cell water distribution pipes, water cooling tanks, boiler exterior cases, and ink peripheral parts / members for inkjet printers. , Furniture (chairs, etc.), chassis, water pipes, joints, etc.

(Manufacturing method of molded product)
The molded product of the present embodiment can be produced by molding the resin composition of the present embodiment described above.
The method for producing the molded product of the present embodiment is not particularly limited, and examples thereof include injection molding, extrusion molding, extrusion malformed molding, hollow molding, compression molding, and the like, and the effects of the present invention can be more effectively achieved. From the viewpoint of obtaining, injection molding is preferable.

Hereinafter, embodiments of the present invention will be described with reference to examples, but the present invention is not limited to these examples.
In addition, Examples 8-12, 16 , 17, 24-28 , 33-34 are described as reference examples.

The resin compositions of Examples and Comparative Examples and the raw materials used for the molded product are shown below.
-(A) Polyphenylene ether resin-
(Ai): Polyphenylene ether (a-ii) having a reduced viscosity (η _{sp /} c: 0.5 g / dL chloroform solution) of 0.51 obtained by oxidative polymerization of 2,6-xylenol (a-ii): 2, Polyphenylene ether having a reduced viscosity (η _{sp /} c: 0.5 g / dL chloroform solution) obtained by oxidative polymerization of 6-xylenol. The reduced viscosity is η _{sp /} c: 0.5 g / dL. It was measured with a Uberode type viscosity tube under the condition of a temperature of 30 ° C. using the chloroform solution of.

-(B) First hydrogenated block copolymer-
An unmodified block copolymer having a block structure of ABA was synthesized by using polymer block A as polystyrene and polymer block B as polybutadiene. The physical properties of the obtained block copolymer are shown below.
(Bi) A-BA type Polystyrene content in the block copolymer before hydrogenation: 30% by mass, number average molecular weight (Mn) of block copolymer before hydrogenation: 72,000, polystyrene Number average molecular weight of blocks (Mn): 21,600, number average molecular weight of polybutadiene blocks (Mn): 50,400, molecular weight distribution of block copolymer before hydrogenation (Mw / Mn): 1.10, hydrogenation 1,2-Vinyl bond amount (total vinyl bond amount) in the previous polybutadiene block: 40%, hydrogenation rate to the polybutadiene part constituting the polybutadiene block: 35%, glass transition temperature of the polybutadiene block after hydrogenation: -80 ℃.
The content of the vinyl aromatic compound was measured using an ultraviolet spectrophotometer. The number average molecular weight (Mn) was determined by a conventionally known method using GPC (moving layer: chloroform, standard substance: polystyrene). For the molecular weight distribution (Mw / Mn), the weight average molecular weight (Mw) obtained by a conventionally known method is divided by the above-mentioned number average molecular weight (Mn) using GPC (moving layer: chloroform, standard substance: polystyrene). It was calculated by doing. The total vinyl bond amount was measured using an infrared spectrophotometer, and Analytical Chemistry, Volume21, No. 8. Calculated according to the method described in August 1949. The hydrogenation rate was measured using a nuclear magnetic resonance apparatus (NMR).
(B-iii-x) A-BA type Polystyrene content in the block copolymer before hydrogenation: 20% by mass, number average molecular weight (Mn) of the block copolymer before hydrogenation: 100,000 , Polystyrene block number average molecular weight (Mn): 20,000, Polybutadiene block number average molecular weight (Mn): 80,000, Block copolymer molecular weight distribution before hydrogenation (Mw / Mn): 1.10, 1,2-Vinyl bond amount (total vinyl bond amount) in the polybutadiene block before hydrogenation: 50%, hydrogenation rate with respect to the polybutadiene part constituting the polybutadiene block: 99%, glass transition temperature of the polybutadiene block after hydrogenation: -48 ° C.
(B-iii) A-BA type Polystyrene content in the block copolymer before hydrogenation: 50% by mass, number average molecular weight (Mn) of the block copolymer before hydrogenation: 70,000, polystyrene Number average molecular weight of blocks (Mn): 35,000, number average molecular weight of polybutadiene blocks (Mn): 35,000, molecular weight distribution of block copolymer before hydrogenation (Mw / Mn): 1.09, hydrogenation 1,2-Vinyl bond amount (total vinyl bond amount) in the previous polybutadiene block: 40%, hydrogenation rate to the polybutadiene part constituting the polybutadiene block: 35%, glass transition temperature of the polybutadiene block after hydrogenation: -80 ℃.
(B-iv) A-BA type Polystyrene content in the block copolymer before hydrogenation: 15% by mass, number average molecular weight (Mn) of the block copolymer before hydrogenation: 130,000, polystyrene Number average molecular weight of blocks (Mn): 19,500, number average molecular weight of polybutadiene blocks (Mn): 110,500, molecular weight distribution of block copolymer before hydrogenation (Mw / Mn): 1.10, hydrogenation 1,2-Vinyl bond amount (total vinyl bond amount) in the previous polybutadiene block: 41%, hydrogenation rate to the polybutadiene part constituting the polybutadiene block: 98%, glass transition temperature of the polybutadiene block after hydrogenation: -55 ℃.

-(C) Olefin copolymer-
(Ci) Ethylene-butene copolymer, trade name "Toughmer DF610", manufactured by Mitsui Kagaku Co., Ltd., MFR: 1.2 g / 10 minutes (190 ° C., 2.16 kgf condition), embrittlement temperature: <- 70 ° C, density: 0.862 g / cm ³
(C-ii) Ethylene-butene copolymer, trade name "Toughmer DF810", manufactured by Mitsui Kagaku Co., Ltd., MFR: 1.2 g / 10 minutes (190 ° C, 2.16 kgf condition), embrittlement temperature: <- 70 ° C, density: 0.885 g / cm ³
(C-iii) Ethylene-butene copolymer, trade name "Toughmer DF110", manufactured by Mitsui Kagaku Co., Ltd., MFR: 1.2 g / 10 minutes (190 ° C., 2.16 kgf condition), embrittlement temperature: <- 70 ° C, density: 0.905 g / cm ³
(C-iv-x) Product name "Toughmer BL3450M", manufactured by Mitsui Chemicals, Inc., MFR: 4.0 g / 10 minutes (190 ° C, 2.16 kgf condition), embrittlement temperature: -32 ° C
(Cv) Ethylene-1-octene copolymer, MFR: 1.0 g / 10 minutes (190 ° C., 2.16 kgf condition), embrittlement temperature: <-70 ° C., density: 0.857 g / cm ³

-(D) Second hydrogenated block copolymer-
A block copolymer having a block structure of BABA was synthesized by using a known method as a polymer block A made of polystyrene and a polymer block B made of polybutadiene. Hydrogenation was performed on the synthesized block copolymer by a known method. No modification of the polymer was performed. The physical properties of the obtained unmodified hydrogenated block copolymer are shown below.
(Di)
Polystyrene content in block copolymer before hydrogenation: 44% by mass, number average molecular weight (Mn) of block copolymer before hydrogenation: 95,000, number average molecular weight (Mn) of polystyrene block: 41, 800, number average molecular weight (Mn) of polybutadiene block: 53,200, molecular weight distribution (Mw / Mn) of block copolymer before hydrogenation: 1.06, 1,2-vinyl bond in polybutadiene block before hydrogenation Amount (total vinyl bond amount): 75%, hydrogenation rate for the polybutadiene portion constituting the polybutadiene block: 99%, glass transition temperature of the polybutadiene block after hydrogenation: -15 ° C.
(D-iii-x)
Polystyrene content in block copolymer before hydrogenation: 60% by mass, number average molecular weight (Mn) of block copolymer before hydrogenation: 84,800, number average molecular weight (Mn) of polystyrene block: 46, 800, number average molecular weight (Mn) of polybutadiene block: 38,000, molecular weight distribution (Mw / Mn) of block copolymer before hydrogenation: 1.09, 1,2-vinyl bond in polybutadiene block before hydrogenation Amount (total vinyl bond amount): 36%, hydrogenation rate for the polybutadiene portion constituting the polybutadiene block: 99%, glass transition temperature of the polybutadiene block after hydrogenation: -30 ° C.

-(E) Talc-
(Ei): Average particle size (D50) measured by laser diffraction method = 2 μm, bulk specific gravity = 0.65 g / cm ³ talc (ei): Average particle size measured by laser diffraction method (D50) = 3 μm, bulk specific gravity = 0.17 g / cm ³ talc (e-iii): average particle size (D50) measured by laser diffraction method = 15 μm, bulk specific gravity = 0.35 g / cm ³ talc (e-iv) ): Tarku with average particle size (D50) = 20 μm and bulk specific gravity = 0.57 g / cm ³ measured by laser diffraction method.

-(F) Phosphate ester compound-
(F): "E890" manufactured by Daihachi Chemical Co., Ltd. (condensed phosphoric acid ester compound)

-(G) Phosphates-
(G): "Exolit OP1230" manufactured by Clariant Japan (corresponding to formula (1))

-(H) Polypropylene resin-
(H-1) Propylene homopolymer (melting point: 165 ° C., MFR: 6.0 g / 10 minutes (190 ° C., 2.16 kgf condition))
(H-2) Ethylene-propylene copolymer having an ethylene content of 30% by mass, MFR: 6.0 g / 10 minutes (190 ° C., 2.16 kgf condition), embrittlement temperature: −48 ° C., density: 0.890 g / Cm ³

Methods (1) to (4) for measuring physical properties in Examples and Comparative Examples are shown below.
(1) Bending elasticity The obtained resin composition pellets are supplied to a small injection molding machine (trade name: IS-100GN, manufactured by Toshiba Machine Co., Ltd.) set to a cylinder temperature of 280 ° C., and injected at a mold temperature of 70 ° C. Molding was performed under the conditions of a pressure of 70 MPa, an injection time of 20 seconds, and a cooling time of 15 seconds to prepare an ISO dumbbell for evaluation. Using this ISO dumbbell, the flexural modulus (MPa) was measured according to ISO 178.
It was determined that the larger the flexural modulus, the better the rigidity. In particular, when it is 2000 MPa or more, it has rigidity that can be applied to mechanical parts and structures.

(2) Chemical resistance The pellets of the obtained resin composition are supplied to a small injection molding machine (trade name: IS-100GN, manufactured by Toshiba Machine Co., Ltd.) whose cylinder temperature is set to 280 ° C., and the mold temperature is 70 ° C. It was molded into a flat plate of 150 mm × 150 mm × 3 mm under the conditions of an injection pressure of 75 MPa, an injection time of 20 seconds, and a cooling time of 15 seconds.
A 75 mm × 12.7 mm × 3 mm test piece was cut out from this flat plate, and the test piece was set in a bending foam designed so that the strain was continuously changed. A phthalate compound (manufactured by Tokyo Kasei Kogyo Co., Ltd., bis (2-ethylhexyl) phthalate) was applied to the surface of the test piece, and the mixture was allowed to stand for 48 hours under the conditions of 23 ° C. × 50 RH%. After 48 hours, the test piece was strained, and the stop position of the bending foam when cracks were generated on the surface of the test piece was measured to determine the critical strain amount (%) indicating the limit strain amount at which cracks did not occur. ..
As an evaluation standard, it was judged that the larger the value of the critical strain amount, the better the chemical resistance.

(3) Charpy Impact Strength The obtained resin composition pellets are supplied to a small injection molding machine (trade name: IS-100GN, manufactured by Toshiba Machine Co., Ltd.) set to a cylinder temperature of 280 ° C., and injected at a mold temperature of 70 ° C. Molding was performed under the conditions of a pressure of 70 MPa, an injection time of 20 seconds, and a cooling time of 15 seconds to prepare an ISO dumbbell for evaluation. Using this ISO dumbbell, the Charpy impact strength (kJ / m ² ) was measured at −40 ° C. according to ISO 179.

(4) 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 to a cylinder temperature of 280 ° C., and injected at a mold temperature of 70 ° C. Molding was performed under the condition of a pressure of 60 MPa, and five UL94 vertical combustion test measurement test pieces (1.6 mm thickness) were prepared. The flame retardancy of these five test pieces was evaluated based on the UL94 vertical combustion test method. After 10 seconds of contact with the flame, the burning time from when the flame is released until the flame is extinguished is t1 (seconds), and after 10 seconds of contact with the flame again, the burning time from when the flame is released until the flame is extinguished is t2 (seconds). ), The average of t1 and t2 was calculated as the average burning time for each of the five pieces. On the other hand, the maximum burning time of 10 points including t1 and t2 was determined as the maximum burning time. Then, V-0, V-1, V-2, and HB were determined based on the UL94 standard.
In particular, when it was determined that the flame retardancy level was V-1 or higher, it was determined that the flame retardancy was excellent.

(Examples 1 to 35, Comparative Examples 1 to 24)
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 35.
The configuration of the twin-screw extruder consists of a first raw material supply port on the upstream side in the direction of raw material flow, a first vacuum vent downstream of the first raw material supply port, and a second raw material supply port downstream of the first vacuum vent. A liquid addition pump is provided downstream of the second raw material supply port, a third raw material supply port is provided downstream of the liquid addition pump, and a second vacuum vent is provided downstream of the third raw material supply port.
The barrel set temperature of the 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, and the conditions are a screw rotation speed of 300 rpm and an extrusion rate of 15 kg / h. The pellet of the resin composition was produced in. The configuration of the twin-screw extruder is shown in Table 1.

The components (a) to (h) were supplied to the twin-screw extruder set as described above as shown in Table 2 to obtain pellets of the resin composition.
Physical property tests were carried out for each Example and each Comparative Example by the above-mentioned measurement methods (1) to (4). The results are shown in Table 2.

As shown in Table 2, the resin composition of the example has excellent low temperature impact resistance and chemical resistance as compared with the resin composition of the comparative example, and has rigidity that can be applied to mechanical parts and structures. I understood.

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

Claims (14)

(A) Polyphenylene ether-based resin and
(B) With the first hydrogenated block copolymer,
(C) An olefin polymer composed of olefins excluding propylene, and
(D) With the second hydrogenated block copolymer,
(E) Containing with talc,
The total of the components (a) to (d) is 100 parts by mass, the total of the components (a) is 50 to 80 parts by mass, and the total of the components (b) and (c) is 5 to 30 parts by mass, (d). ) Component is 1 to 20 parts by mass, (e) component is 1 to 15 parts by mass,
The block (b) and the component (d) contain 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. It is a hydrogenated block copolymer obtained by hydrogenating at least a part of the copolymer and / or a modified product of the hydrogenated block copolymer.
The glass transition temperature of the polymer block B in the component (b) is −50 ° C. or lower.
The total ratio of 1,2-vinyl bond and 3,4-vinyl bond to the ethylenic double bond in the conjugated diene compound unit contained in the component (b) is 25% or more and 50% or less.
The embrittlement temperature of the component (c) is −50 ° C. or lower.
In the component (d), the hydrogenation rate for the double bond in the conjugated diene compound unit contained in the component (d) is 80 to 100%.
The total ratio of 1,2-vinyl bond and 3,4-vinyl bond to the ethylenic double bond in the conjugated diene compound unit contained in the component (d) is more than 50% and 90% or less.
Substantially, (h) polypropylene-based resin is not contained,
The flexural modulus measured according to ISO 178 is 2000 MPa or more.
A resin composition characterized by that. The resin composition according to claim 1, wherein in the component (b), the hydrogenation rate for the double bond in the conjugated diene compound unit contained in the component (b) is more than 0% and less than 80%. The resin composition according to claim 1 or 2, wherein the glass transition temperature of the polymer block B in the component (b) is −70 ° C. or lower. Further, it contains (f) a phosphoric acid ester compound ,
The component (f) is 5 to 30 parts by mass with respect to a total of 100 parts by mass of the components (a) to (d) .
The resin composition according to any one of claims 1 to 3. In addition, it contains (g) phosphinates and
The component (g) is a phosphinate represented by the following general formula (1).
[In the formula, 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 , Calcium ion, magnesium ion, aluminum ion, zinc ion, bismus ion, manganese ion, sodium ion, potassium ion and protonated nitrogen base; a is 1 to 3 It is an integer; m is an integer of 1 to 3; a = m], and the diphosphinate represented by the following formula (2).
[In the formula, 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, an arylene group having 6 to 10 carbon atoms, an alkyl arylene group having 6 to 10 carbon atoms, or an arylalkylene group having 6 to 10 carbon atoms. Yes; M ² 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 , 1-3; n is an integer of 1-3; j is an integer of 1 or 2; b · j = 2n]
At least one phosphinic acid salts selected from the group consisting of saw including a
The component (g) is 3 to 30 parts by mass with respect to a total of 100 parts by mass of the components (a) to (d) .
The resin composition according to any one of claims 1 to 4. The resin composition according to any one of claims 1 to 5, wherein the component (b) contains 30 to 50% by mass of a vinyl aromatic compound unit. The resin composition according to any one of claims 1 to 6, wherein the component (c) is an ethylene-1-butene copolymer. The resin composition according to any one of claims 1 to 7, wherein the density of the component (c) is 0.87 g / cm ³ or more. The resin composition according to any one of claims 1 to 8, wherein the density of the component (c) is 0.90 g / cm ³ or more. The resin composition according to any one of claims 1 to 9, wherein the average particle size (D50) of the component (e) measured by a laser diffraction method is 5 μm or less. The resin composition according to any one of claims 1 to 10, wherein the component (e) has a bulk specific gravity of 0.4 g / cm ³ or more. The resin composition according to any one of claims 1 to 11, wherein the component (e) has a bulk specific gravity of 0.5 g / cm ³ or more. The method for producing a resin composition according to any one of claims 1 to 12, which comprises the following steps (1-1), (1-2), and (1-3);
(1-1): Step of melt-kneading the component (a) and the component (d) to obtain a kneaded product 1 (1-2): In the kneaded product 1 obtained in the step (1-1). On the other hand, a step (1-3) of adding the component (b) and the component (c) and melt-kneading to obtain the kneaded product 2: The kneaded product 2 obtained in the step (1-2). On the other hand, the step of adding the component (e) and melt-kneading. A molded product comprising the resin composition according to any one of claims 1 to 12.