JP5666160B2 - Resin composition and molded body thereof - Google Patents

Description

  The present invention relates to a resin composition comprising a polyphenylene ether having a specific molecular weight and a hydrogenated block copolymer, and a molded product thereof.

Conventionally, polyphenylene ether resins have been known as engineering plastics having excellent flame retardancy, heat resistance, dimensional stability, non-water absorption and electrical properties, but they have poor melt fluidity and are difficult to process. It has the disadvantage of being inferior in impact.
On the other hand, the hydrogenated styrene and conjugated diene block copolymer is excellent in thermal stability and weather resistance, but has insufficient rubber elasticity at high temperatures, large heat and pressure deformation, and compression set at high temperatures. It has the disadvantage of being large.
Polypropylene resins are low specific gravity and inexpensive plastics, and are excellent in chemical resistance, solvent resistance, moldability, etc., so they can be used in various fields such as automobile parts, electrical / electronic equipment parts, and household electrical appliances. It is used.
Various resin compositions have been proposed in order to combine the advantages of these polyphenylene ether resins, hydrogenated block copolymers, and polypropylene resins and to compensate for the disadvantages.
For example, Patent Documents 1 to 4 propose a polyphenylene ether resin / hydrogenated block copolymer composition, and Patent Documents 5 to 14 propose a polyphenylene ether / polypropylene resin composition. When high fluidity is required in a resin composition blended with a polyphenylene ether resin and a polypropylene resin as described above, the molecular weight of polyphenylene ether, which is a fluidity factor of polyphenylene ether, should be reduced. Thus, it is obvious that the processability of the resulting resin composition can be improved.
In addition, when obtaining a resin composition containing polyphenylene ether, (1) the processing temperature is high (eg, around 300 ° C.), and (2) the polyphenylene ether is a powder. At present, there are many restrictions on processing machines and processing conditions because of the necessity of introducing active gas). Then, the manufacturing method which can be processed with a general purpose processing machine and conditions is proposed, and patent documents 15-16 describe the resin composition containing polyphenylene ether and polystyrene, and its manufacturing method.

Japanese Patent Publication No.51-27256 JP-A-50-71742 JP 62-20551 A Japanese Examined Patent Publication No. 7-107126 Japanese Patent Laid-Open No. 02-113060 US Pat. No. 5,262,480 Japanese Patent Laid-Open No. 06-57130 Japanese Patent Laid-Open No. 06-192561 International Publication No. 97/01600 Pamphlet Japanese Patent Laid-Open No. 09-12799 JP 09-12804 A JP 09-87450 A Special table 2008-524379 Special Table 2008-52481 Special Table 2007-530774 JP-T-2002-541290

Patent Documents 1 to 4 disclose a resin composition comprising a polyphenylene ether / hydrogenated block copolymer having a molecular weight in a wide range of low molecular weight to high molecular weight. Since the properties and tensile elongation are insufficient, there is an inconvenience for applications requiring these characteristics. This is due to insufficient selection of the molecular weight of the polyphenylene ether used, the structure of the hydrogenated block copolymer, and the molecular weight.
Patent Documents 5 to 14 disclose a resin composition composed of polyphenylene ether / polyolefin, which is sufficient in terms of processability, heat resistance, mechanical properties, and morphological stability of the obtained resin composition. I can't say that. That is, the reason why the processability, heat resistance and mechanical properties of a polymer alloy in which an incompatible polyphenylene ether is emulsified and dispersed in polypropylene are insufficient is the selection of individual materials to be used for the polymer alloy. Due to that. In general, in order to emulsify and disperse polyphenylene ether in polypropylene, it is known that a hydrogenated block copolymer is essential as an emulsifying dispersant (admixture). However, the polymer alloy performance showing this emulsified dispersion structure is complemented by the structure of the polyphenylene ether emulsified in polypropylene to form the dispersed phase and the structure of the hydrogenated block copolymer of the emulsifying dispersant (admixture). Although it is dominated by the emulsification and dispersion technology, there are no technical suggestions or disclosures that clarify the interrelationship between the polyphenylene ether structure and the hydrogenated block copolymer structure, which are the control factors for emulsification and dispersion. is there.
In Patent Documents 15 to 16, although there is a description about pellets containing polyphenylene ether, there is no specific example of pellets containing polypropylene, and light resistance and delamination of the resulting resin composition, suppression of scumming during processing There is no description or suggestion regarding the relationship between the above point, the structure of the hydrogenated block copolymer as an admixture, and the molecular weight factor of polyphenylene ether.
In view of the above-mentioned problems of the prior art, the present invention optimizes the molecular weight of polyphenylene ether and optimizes the polymer structure factor of the hydrogenated block copolymer blended with the optimized polyphenylene ether. It is an object of the present invention to provide a resin composition of polyphenylene ether and hydrogenated block copolymer having excellent fluidity and mechanical properties.

  In view of the current situation, the present inventors, in designing a polymer alloy comprising a low molecular weight polyphenylene ether / hydrogenated block copolymer, in the first step, the compatibility in the polyphenylene ether / hydrogenated block copolymer. Compatibility, mechanical properties, fluidity, total light transmittance, and by comprehending the amount of components of specific molecular weight contained in polyphenylene ether and controlling the hydrogenated block copolymer to a specific structure They found that the mechanical properties, fluidity and total light transmittance were improved. In the second step, whether the polyphenylene ether found in the first step and / or the hydrogenated block copolymer controlled to a specific structure exhibits thermally stable emulsification dispersion in polypropylene, and the resulting polymer alloy As a result of intensive studies on processability, heat resistance, and mechanical properties exhibited by, the hydrogenated block copolymer as an emulsifying dispersant (admixture) is controlled to have a specific structure, so that the processability, heat resistance, It has been found that polyphenylene ether which is excellent in mechanical properties and forms a dispersed phase as a non-compatible polymer alloy results in a resin composition exhibiting a thermally stable dispersion form.

That is, the present invention is as follows.
[1]
(A) 1 to 99% by mass of polyphenylene ether,
(B) Hydrogenation obtained by hydrogenating a block copolymer comprising at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. 99 to 1% by mass of block copolymer,
A resin composition comprising:
The polyphenylene ether contains 5 to 20% by mass of a component having a molecular weight of 50,000 or more and 12 to 30% by mass of a component having a molecular weight of 8,000 or less, based on the whole polyphenylene ether,
The hydrogenated block copolymer has a number average molecular weight (Mnb) as a hydrogenated block copolymer of 100,000 or less, and the polymer block A has a number average molecular weight (MnbA) of 8,000 or more. A resin composition.
[2]
The resin composition according to the above [1], wherein the component (a) has a number average molecular weight (Mna) of 7,000 to 15,000.
[3]
The resin composition according to the above [1] or [2], wherein the content of the vinyl aromatic compound in the component (b) is 15 to 50% by mass with respect to the entire component (b).
[4]
In the bonding form of the conjugated diene compound in the polymer block B of the component (b), the total amount of the conjugated diene compound bonded by a 1,2-vinyl bond or a 3,4-vinyl bond is the above (b). Resin composition in any one of said [1]-[3] which is 30-90 mass% with respect to all the conjugated diene compounds of a component.
[5]
In the bonding form of the conjugated diene compound in the polymer block B of the component (b), the total amount of the conjugated diene compound bonded by a 1,2-vinyl bond or a 3,4-vinyl bond is the above (b). Resin composition in any one of said [1]-[4] which is 70-90 mass% with respect to all the conjugated diene compounds of a component.
[6]
(C) The resin composition according to any one of the above [1] to [5], further comprising a polypropylene resin in an amount of 1 to 95% by mass with respect to the total amount of the components (a) to (c).
[7]
The resin composition according to [6] above, wherein the melting point of the (c) polypropylene resin is 155 ° C. or higher.
[8]
The (c) polypropylene resin is homopolypropylene and / or block polypropylene, and its melt flow rate (measured in accordance with MFR: ASTM D1238 at 230 ° C. under a load of 2.16 Kg) is 0.1 to 100 g / 10 min. The resin composition as described in [6] or [7] above.
[9]
As component (d), it further comprises at least one hydrogenated block copolymer different from component (b),
The component (d) is a hydrogenated block copolymer comprising at least two polymer blocks A mainly composed of vinyl aromatic compounds and at least one polymer block B mainly composed of conjugated diene compounds. A hydrogenated block copolymer comprising:
The number average molecular weight (Mnd) as the hydrogenated block copolymer is 150,000 or less, the number average molecular weight (MndA) of the polymer block A is 8,000 or more,
The content of the polymer block A is more than 50% by mass and 70% by mass or less with respect to the total component (d),
In the bonding form of the conjugated diene compound in the polymer block B, the total amount of the conjugated diene compound bonded by a 1,2-vinyl bond or a 3,4-vinyl bond is 25 to 25 with respect to the whole conjugated diene compound. Resin composition in any one of said [1]-[8] which is 70 mass%.
[10]
The component (e) further includes at least one hydrogenated block copolymer different from the components (b) and (d),
The component (e) is a hydrogenated block copolymer comprising at least two polymer blocks A mainly composed of vinyl aromatic compounds and at least one polymer block B mainly composed of conjugated diene compounds. A hydrogenated block copolymer comprising:
The number average molecular weight (Mne) as the hydrogenated block copolymer is 100,000 or less, and the number average molecular weight (MneA) of the polymer block A is 8,000 or more,
The content of the polymer block A is 15% by mass or more and 50% by mass or less with respect to the total component (e),
In the bonding form of the conjugated diene compound in the polymer block B, the total amount of the conjugated diene compound bonded by 1,2-vinyl bond or 3,4-vinyl bond is 25 with respect to the whole conjugated diene compound. Resin composition in any one of said [1]-[9] which is -70 mass%.
[11]
Any one of said [1]-[10] whose total amount of said (b), (d), and (e) component is 20 mass% or less with respect to the said (a)-(e) whole component. Resin composition.
[12]
The resin composition according to any one of [1] to [11] above, wherein a quantitative ratio relationship between the component (a) and the component (b) is (a) <(b).
[13]
(F) The resin composition according to any one of [1] to [12], further including a filler in an amount of 2 to 60% by mass with respect to the total amount of the components (a) to (f).
[14]
A pellet obtained by melt-kneading the resin composition according to any one of [1] to [13].
[15]
The manufacturing method of a thermoplastic resin composition including the process of melt-kneading the pellet of said [14], and a thermoplastic resin.
[16]
The method according to [15], wherein the thermoplastic resin is (g) a polypropylene resin.
[17]
(G) A method in which a polypropylene resin is blended with the pellets described in [14] above and injection molded to obtain a molded body.
[18]
(G) A method in which a polypropylene resin is blended with the pellets described in [14] and extruded to obtain a molded body.
[19]
The molded object containing the resin composition in any one of said [1]-[13].
[20]
A sheet film or a stretched sheet film obtained by molding the resin composition according to any one of [1] to [13].

  According to the present invention, a polyphenylene ether / hydrogenated block copolymer resin composition excellent in fluidity, heat resistance, mechanical properties, light transmittance, and the like, and a molded article using the same can be obtained.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiment is an exemplification for explaining the present invention, and is not intended to limit the present invention only to this embodiment. And this invention can be deform | transformed suitably and implemented within the range of the summary.

The resin composition of the present embodiment is
(A) 1 to 99% by mass of polyphenylene ether,
(B) Hydrogenation obtained by hydrogenating a block copolymer comprising at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. 99 to 1% by mass of block copolymer,
A resin composition comprising:
The polyphenylene ether contains 5 to 20% by mass of a component having a molecular weight of 50,000 or more and 12 to 30% by mass of a component having a molecular weight of 8,000 or less, based on the whole polyphenylene ether,
The hydrogenated block copolymer has a number average molecular weight (Mnb) as a hydrogenated block copolymer of 100,000 or less, and the polymer block A has a number average molecular weight (MnbA) of 8,000 or more. is there.

[(A) component]
The (a) polyphenylene ether (hereinafter sometimes simply referred to as “PPE”) in the present embodiment is a homopolymer and / or copolymer having a repeating unit structure represented by the following formula (1). .

In the formula, R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 7 carbon atoms, a phenyl group, or a haloalkyl group. , An aminoalkyl group, a hydrocarbonoxy group or a group consisting of a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom.

  The polyphenylene ether is not particularly limited, and a known one may be used. For example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether) Phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol and 2 Polyphenylene ether copolymers such as (methyl-6-butylphenol) can also be used. Among these, preferably, poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, more preferably Poly (2,6-dimethyl-1,4-phenylene ether).

  The polyphenylene ether in the present embodiment is a polyphenylene ether having a low molecular weight and a small amount of oligomer. Further, by defining the amount of a component having a molecular weight of 8,000 or less and the amount of a component having a molecular weight of 50,000 or more, it has sufficiently high fluidity during melt processing and can maintain high mechanical properties. Specifically, from the viewpoint of fluidity, the component having a molecular weight of 50,000 or more is 5 to 20% by mass and preferably 5 to 18% by mass with respect to the whole polyphenylene ether. From the viewpoint of mechanical properties, the component having a molecular weight of 8,000 or less is 12 to 30% by mass, and more preferably 15 to 30% by mass with respect to the whole polyphenylene ether.

  Conventionally, the polyphenylene ether generally used has a molecular weight of about 50,000 or more of a normal molecular weight type and is about 40% by mass, and a low molecular weight type is about 25% by mass. The polyphenylene ether contained in the resin composition in the present embodiment is a low molecular weight type polyphenylene ether greatly lower than these.

In addition, the information regarding the molecular weight in this Embodiment is obtained by the measurement using a gel permeation chromatography measuring apparatus. Specifically, using a gel permeation chromatography measuring apparatus [GPC SYSTEM21: manufactured by Showa Denko KK], an ultraviolet spectroscopic detector [UV-41: manufactured by Showa Denko KK] is used to measure with standard polystyrene. It is the converted molecular weight. Specific conditions are as follows: solvent: chloroform, sample concentration: 0.1 g / 100 mL, temperature: 40 ° C., column: sample side (KG, K-800RL, K-800R), reference side (K-805L × 2) Main), flow rate of 10 mL / min, measurement wavelength: 283 nm, pressure of 15 to 17 kg / cm ² , measurement wavelength of UV detector when creating standard polystyrene calibration curve: 254 nm.

  The number average molecular weight (Mna) of the polyphenylene ether is preferably 7,000 or more and 15,000 or less. A more preferable lower limit is 8,000 or more, and a further preferable lower limit is 9,000 or more. Moreover, a more preferable upper limit is 14,000 or less, and a more preferable upper limit is 13,000 or less. From the viewpoint of suppressing deformation during heating of the resin composition, the lower limit of the number average molecular weight is preferably 7,000 or more. From the viewpoint of obtaining good fluidity during molding, the upper limit of the number average molecular weight is 15 1,000 or less.

  Polyphenylene ether can be produced by two types of production methods, precipitation precipitation polymerization and solution polymerization. The precipitation polymerization method is a polymerization form in which a precipitation of polyphenylene ether is deposited when a predetermined concentration range is reached. In the precipitation polymerization method, as the polymerization of polyphenylene ether proceeds, a sufficiently polymerized one is precipitated, and an insufficient one is dissolved. As the solvent, a mixed solvent of a good solvent of polyphenylene ether such as toluene, xylene or ethylbenzene and a poor solvent such as methanol or butanol is used. In the precipitated polyphenylene ether, the movement of the molecular chain is suppressed, and the catalyst is dissolved in the mixed solvent. Therefore, it is theoretically considered that the reaction rate becomes slow due to a solid-liquid reaction. On the other hand, polyphenylene ether, which has a molecular weight that is not yet high enough to precipitate in a dissolved state, maintains the reaction rate, and precipitates when the polymer reaches a high molecular weight sufficient for precipitation to proceed. To do. That is, theoretically, the molecular weight distribution becomes narrower. In addition, in the polymerization form as described above, when a particle having a small particle size is deposited, the surface area is increased in a solid-liquid reaction, so that the reaction is faster than when a particle having a large particle size is deposited. Furthermore, since polyphenylene ether precipitates during the polymerization, the viscosity in the system gradually decreases, the monomer concentration (phenol compound concentration) during polymerization can be increased, and further, the precipitated polyphenylene ether can be filtered. Polyphenylene ether can be obtained by an extremely simple process.

  On the other hand, the solution polymerization method is a polymerization method in which polymerization is performed in a good solvent of polyphenylene ether and no precipitate is deposited during the polymerization. All polyphenylene ether molecules are in a dissolved state, and the molecular weight distribution tends to be wide. In the solution polymerization method, a powdered polyphenylene ether is obtained by developing a polymerization solution in which polyphenylene ether is dissolved in a poor solvent of polyphenylene ether such as methanol.

  The reduced viscosity (0.5 dl / g chloroform solution, measured at 30 ° C.) of the polyphenylene ether in the present embodiment is preferably in the range of 0.20 to 0.40 dl / g, and 0.25 dl / g to 0.35 dl / g. The range of is more preferable.

  The polyphenylene ether may be a blend of two or more polyphenylene ethers having different reduced viscosities. For example, a mixture of a polyphenylene ether having a reduced viscosity of 0.40 dl / g or less and a polyphenylene ether having a reduced viscosity of 0.45 dl / g or more may be used, but the reduced viscosity of these mixtures is 0.20 to 0.40 dl. / G is preferable.

  In the present embodiment, various known stabilizers can be suitably used for stabilizing the polyphenylene ether. Examples of the stabilizer include metal stabilizers such as zinc oxide and zinc sulfide, organic stabilizers such as hindered phenol stabilizers, phosphate ester stabilizers, and hindered amine stabilizers. A preferable blending amount of the stabilizer is less than 5 parts by mass with respect to 100 parts by mass of the polyphenylene ether. Among the stabilizers, an antioxidant having both a sulfur element and a hydroxyl group in the molecule is particularly preferable. Specific product names include Irganox 1520 or Irganox 1726 available from Ciba Specialty Chemicals. These stabilizers are extremely effective from the viewpoint of preventing discoloration of pellets due to oxidation reaction.

  Further, modified polyphenylene ether may be used as the polyphenylene ether. Examples of the modified polyphenylene ether include polyphenylene ether grafted or added with 0.01 to 10% by mass of a styrene monomer or a derivative thereof. The mixing ratio of polyphenylene ether and modified polyphenylene ether is not particularly limited, and can be mixed at an arbitrary ratio.

  Content of (a) polyphenylene ether in the resin composition in this Embodiment is 1-99 mass%, Preferably it is 5-95 mass%, More preferably, it is 7-93 mass%.

[Component (b)]
The (b) hydrogenated block copolymer in the present embodiment comprises at least two polymer blocks A mainly composed of vinyl aromatic compounds and at least one polymer block B mainly composed of conjugated diene compounds. The block copolymer containing at least a part thereof is hydrogenated, and the number average molecular weight (Mnb) as the hydrogenated block copolymer is 100,000 or less, and the number average of the polymer block A The molecular weight (MnbA) is 8,000 or more.

(Polymer block A mainly composed of vinyl aromatic compounds)
The polymer block A mainly composed of a vinyl aromatic compound is a homopolymer block of a vinyl aromatic compound or a copolymer block of a vinyl aromatic compound and a conjugated diene compound. In the polymer block A, “mainly composed of a vinyl aromatic compound” means that the polymer block A contains a vinyl aromatic compound in an amount of more than 50% by mass, and the vinyl aromatic compound is 70% by mass or more. It is preferable to contain.

  Examples of the vinyl aromatic compound constituting the polymer block A include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, and the like. These may be used alone or in combination of two or more. Of the above, styrene is preferred.

  (B) The number average molecular weight (Mnb) of the component is measured by Showa Denko Co., Ltd. Gel Permeation Chromatography System 21 (Column: Showa Denko Co., Ltd., KG, one K-800RL) Standard polystyrene with K-800R connected in series in one column, column temperature: 40 ° C., solvent: chloroform, solvent flow rate: 10 ml / min, sample concentration: 1 g / liter of chloroform solution of hydrogenated block copolymer) (The molecular weight of standard polystyrene can be measured by preparing a calibration curve using 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550). The UV (ultraviolet) wavelength of the detection unit is measured by setting both standard polystyrene and hydrogenated block copolymer to 254 nm. In addition, the number average molecular weight (MnbA) of the polymer block A mainly composed of the vinyl aromatic compound of the hydrogenated block copolymer (MmbA) is, for example, the above-described hydrogenated block in the case of an ABA type structure. Based on the number average molecular weight (Mnb) of the copolymer, it is assumed that the molecular weight distribution of the hydrogenated block copolymer is 1, and that two polymer blocks A mainly composed of vinyl aromatic compounds exist as the same molecular weight. And (MnbA) = (Mnb) × the ratio of the amount of bonded vinyl aromatic compounds ÷ 2. Similarly, in the case of a hydrogenated block copolymer of the A-B-A-B-A type, it can be obtained by the following formula: (MnbA) = (Mnb) × the ratio of the amount of bonded vinyl aromatic compounds ÷ 3. it can. In addition, in the step of synthesizing the vinyl aromatic compound-conjugated diene block copolymer, when the sequence of the block structure A and the block structure B described above is clear, the measurement was performed without depending on the above calculation formula. You may calculate from the ratio of the block structure A based on the number average molecular weight (Mnb) of a hydrogenated block copolymer.

  The number average molecular weight (MnbA) of the polymer block A contained in the component (b) is 8,000 or more, preferably 9,000 or more. The hydrogenated block copolymer satisfying this condition is excellent in (a) polyphenylene ether in which the component amount having a molecular weight of 50,000 or more is 5 to 20% by mass and the component amount having a molecular weight of 8,000 or less is 12 to 30% by mass. So that the fluidity and mechanical properties of the resulting resin composition are greatly superior. The improvement of the total light transmittance, which is one of the effects of the present invention, is to increase the component weight of the molecular weight 8,000 or less in the component (a) and the number average molecular weight (MnbA) of the polymer block A in the component (b). By adjusting to a specific range, it is presumed that the compatibility of the component (a) and the component (b) is close to the molecular compatibility system. This total light transmittance can be measured using, for example, a turbidimeter (NDH2000: manufactured by Nippon Denshoku Industries Co., Ltd.) (based on JIS K7361). In addition, the reason why the impact resilience is improved is that the vinyl aromatic compound (hard segment) part in the component (b) and the component (a) are close to the molecular compatibility system, thereby increasing the cohesion of the hard segment, It is presumed that the conjugated diene compound (soft segment) efficiently contributes to the resilience.

  The number average molecular weight (Mnb) of the component (b) is adjusted to 100,000 or less. This is because in the melt mixing with the component (a), it is necessary to diffuse preferably in the system, and when the number average molecular weight (Mnb) of the component (b) is 100,000 or less, preferable diffusion is performed. A state can be achieved.

(Polymer block B mainly composed of conjugated diene compound)
The polymer block B mainly composed of a conjugated diene compound is a homopolymer block of a conjugated diene compound or a random copolymer block of a conjugated diene compound and a vinyl aromatic compound. In the polymer block B, “consisting mainly of a conjugated diene compound” means that the polymer block B contains more than 50% by mass of the conjugated diene compound, and contains 70% by mass or more of the conjugated diene compound. Is preferred.

  Examples of the conjugated diene compound constituting the polymer block B include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. These may be used alone or in combination of two or more. Among the above, butadiene, isoprene and combinations thereof are preferable.

  The microstructure of the polymer block B (bonded form of the conjugated diene compound) may be referred to as the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (hereinafter referred to as “total vinyl bond amount”). ) Is preferably 30 to 90% by mass, more preferably 35 to 90% by mass, and still more preferably 45 to 90% by mass with respect to all the conjugated diene compounds of the component (b). 70 to 90% by mass is particularly preferable. When the total vinyl bond amount exceeds 90% by mass, industrial production may be difficult.

  Assuming that the block polymer A is “A” and the block polymer B is “B”, the component (b) may be, for example, ABA type, ABAB type, BAB -A type, (A-B-) n-X type (where n is an integer of 1 or more, X is a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride, tin tetrachloride or polyfunctional organolithium) And a hydrogenated product of a vinyl aromatic-conjugated diene compound block copolymer having a structure in which block units such as ABABABA type are bonded. It is done. Among these, a hydrogenated block copolymer having an A-B-A-B type structure or a B-A-B-A type structure is more preferable because it has excellent fluidity as compared with an A-B-A type hydrogenated block copolymer. .

  Moreover, it is preferable that content of the vinyl aromatic compound couple | bonded in (b) component is 15-50 mass% with respect to the whole (b) component, More preferably, it is 25-45 mass%, More preferably, 30 to 45% by mass. If the vinyl aromatic compound amount is 15% by mass or more, the mechanical strength tends to be improved, and if it is 50% by mass or less, the balance between heat resistance and mechanical strength tends to be excellent. In the present embodiment, the content of the vinyl aromatic compound can be measured by NMR.

  The molecular structure of the block copolymer including the block polymer A and the block polymer B is not particularly limited and may be, for example, linear, branched, radial, or any combination thereof. In the polymer block A and the polymer block B, the distribution of vinyl aromatic compound or conjugated diene compound in the molecular chain in each polymer block is random and tapered (in which the monomer component increases or decreases along the molecular chain). , May be partly block-shaped or any combination thereof. When there are two or more polymer blocks A or polymer blocks B in the repeating unit, each polymer block may have the same structure or a different structure.

  Further, the hydrogenation rate with respect to the conjugated diene compound in the component (b) is not particularly limited, but is preferably 50% or more of the double bond derived from the conjugated diene compound, more preferably 80% or more, and further Preferably it is 90% or more. In the present embodiment, the hydrogenation rate can be measured by NMR.

  (B) It does not specifically limit as a manufacturing method of the hydrogenated block copolymer of a component, It can obtain by a well-known manufacturing method. Known production methods include, for example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-56- No. 10542, JP-A-56-62847, JP-A-56-1000084, JP-A-2-300218, British Patent 1130770, US Pat. No. 3,281,383, US Pat. No. 3639517 No. 1, British Patent No. 1020720, US Pat. No. 3,333,024 and US Pat. No. 4,501,857.

  The hydrogenated block copolymer of component (b) is a hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or derivative thereof (ester compound or acid anhydride compound) in the presence of a radical generator. The modified hydrogenated block copolymer obtained by making it react at 80-350 degreeC in a molten state, a solution state, or a slurry state in the bottom or absence. In this case, it is preferable that the α, β-unsaturated carboxylic acid or derivative thereof is grafted or added to the hydrogenated block copolymer at a ratio of 0.01 to 10% by mass. Further, it may be a mixture of the hydrogenated block copolymer and the modified hydrogenated block copolymer in an arbitrary ratio.

  When the resin composition further contains (c) a polypropylene resin described later, an emulsifying dispersant for compatibilizing the incompatible component (a) and the component (c) (hereinafter abbreviated as an admixture). Is essential, but in the present embodiment, a hydrogenated block copolymer (b) having a specific structure can be used as an admixture. When the component (b) is used as an admixture, the component (b) comprises at least two polymer blocks A mainly composed of styrene and butadiene having a 1,2-vinyl bond content of 70 to 90%. A hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising at least one polymer block B as a main component is preferable.

  The at least one polymer block B mainly composed of butadiene may be a single polymer block in which the 1,2-vinyl bond content of butadiene before hydrogenation is 70 to 90%, At least one polymer block B1 mainly composed of butadiene having a 1,2-vinyl bond content of 70 to 90% and at least 1 mainly composed of butadiene having a 1,2-vinyl bond content of less than 30 to 70%. It may be a polymer block B mainly composed of butadiene having both polymer blocks B2. A block copolymer showing such a block structure is, for example, a known A-B2-B1-A known in which 1,2-vinyl bond amount is controlled based on the adjusted feed sequence of each monomer unit. It can be obtained by a polymerization method. The bonding form of butadiene before hydrogenation can be known by an infrared spectrophotometer, NMR or the like.

  In the case where the component (c) described later is included, setting the number average molecular weight (Mnb) of the component (b) to 100,000 or less means that the role of the (b) hydrogenated block copolymer in the resin composition is only It is to serve as an emulsifying dispersant (admixture) between polymer (polypropylene) and polymer (polyphenylene ether). That is, during emulsification of a polymer (polypropylene) -polymer (polyphenylene ether) having a high viscosity in a melt bulk state, (b) the hydrogenated block copolymer as an emulsifying dispersant (admixture) is contained in the melt-mixing system. It is necessary to diffuse preferably. For this reason, the number average molecular weight (Mnb) of (b) component needs to be 100,000 or less in consideration of the melt viscosity of (b) hydrogenated block copolymer.

  In addition, when the number average molecular weight (MnbA) of the polymer block A mainly composed of styrene is 8,000 or more, the hydrogenated block copolymer satisfying this condition has a molecular weight of 50,000 or more. (A) Polyphenylene ether having a molecular weight of 8,000 mass% or less and a molecular weight of 8,000 or less can be satisfactorily solubilized, and in the emulsification dispersion between polymer- (polypropylene) -polymer (polyphenylene ether), polyphenylene This is a condition that must be satisfied in order to give a good emulsified dispersion of ether and to give a great advantage to the heat resistance, mechanical properties and processability of the resulting resin composition. The relationship between the molecular weight of this emulsified and dispersed (a) polyphenylene ether and the number average molecular weight of the polymer block A mainly composed of styrene of (b) hydrogenated block copolymer as an emulsifying dispersant (admixture) -(Polypropylene) -Polymer (polyphenylene ether) is an important polymer dispersion technology that is important for bringing about an emulsification dispersion. The present invention focuses on this previously unknown polymer emulsion dispersion technology. It is obtained.

  Content of (b) hydrogenated block copolymer in the resin composition in this Embodiment is 1-99 mass%, Preferably it is 5-95 mass%, More preferably, it is 7-93 mass%.

[Component (c)]
The resin composition in the present embodiment may further include (c) polypropylene resin in an amount of 1 to 95% by mass with respect to the total amount of components (a) to (c). The component (c) polypropylene resin is a crystalline propylene homopolymer, or a crystalline propylene homopolymer portion obtained in the first step of polymerization and propylene, ethylene and / or at least one other in the second and subsequent steps of polymerization. A crystalline propylene-ethylene block copolymer having a propylene-ethylene random copolymer portion obtained by copolymerizing an α-olefin (for example, butene-1, hexene-1 and the like), and further the crystalline propylene It may be a mixture of a homopolymer and a crystalline propylene-ethylene block copolymer.

  The polypropylene resin is usually a titanium trichloride catalyst or a titanium halide catalyst supported on a carrier such as magnesium chloride and the like in the presence of an alkylaluminum compound and a polymerization temperature in the range of 0 to 100 ° C. and a polymerization pressure of 3 to 100 atm. It can be obtained by polymerizing the monomer in the range. At this time, a chain transfer agent such as hydrogen can be added in order to adjust the molecular weight of the polymer. Also, the polymerization method can be either batch type or continuous type, and can be selected from methods such as solution polymerization in a solvent such as butane, pentane, hexane, heptane, and octane, and slurry polymerization. Below, bulk polymerization in monomers, gas phase polymerization methods in gaseous monomers, and the like can also be applied.

  Furthermore, in addition to the above polymerization catalyst, an electron donating compound can be used as an internal donor component or an external donor component as a third component in order to increase the isotacticity and polymerization activity of the resulting polypropylene. As these electron-donating compounds, known compounds can be used, for example, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate, methyl toluate, triphenyl phosphite, tributyl phosphite and the like. Phosphoric acid derivatives such as phosphoric acid esters and hexamethylphosphoric triamides, alkoxy ester compounds, aromatic monocarboxylic acid esters and / or aromatic alkyl alkoxy silanes, aliphatic hydrocarbon alkoxy silanes, various ether compounds, various alcohols And / or various phenols.

  The polypropylene resin is obtained by the above-described method, and the polymer is characterized in that the homo-polypropylene portion has a crystal melting point of preferably 155 ° C. or higher and a crystallization temperature of preferably 100 ° C. to 130 ° C. . The crystal melting point of this homo-polypropylene part is a melting point value measured at a temperature rising rate of 20 ° C./min and a temperature falling rate of 20 ° C./min with a differential scanning calorimeter (DSC: for example, DSC-2 type manufactured by Perkin Elmer). is there. More specifically, first, about 5 mg of a sample is kept at 20 ° C. for 2 minutes, then heated to 230 ° C. at 20 ° C./min, kept at 230 ° C. for 2 minutes, and then lowered to 20 ° C. at a rate of temperature drop of 20 ° C./min. After the temperature is lowered and kept at 20 ° C. for 2 minutes, the temperature of the top peak of the endothermic peak that appears when the temperature is raised at a rate of temperature rise of 20 ° C./min can be determined as the melting point. Polypropylene having a melting point of less than 155 ° C. tends to lower the rigidity and heat resistance (load deflection temperature: DTUL) of the resulting resin composition. More preferably, it is a polypropylene having a crystal melting point of the homo-polypropylene portion of 163 ° C. or higher, and gives a resin composition that is more excellent in rigidity and heat resistance (load deflection temperature: DTUL). In addition, at the time of measuring the crystal melting point by the differential scanning calorimeter (DSC), the crystallization temperature (solidification temperature) peak of the molten polypropylene can be known, and the crystallization temperature of the polypropylene can be confirmed in a temperature range of 100 ° C to 130 ° C. .

  The melt flow rate (measured in accordance with ASTM D1238 at 230 ° C. and a load of 2.16 Kg) of the polypropylene resin can be selected from the range of 0.1 to 100 g / 10 min, and the resulting resin composition has heat resistant creep resistance. From the viewpoint of expression, it is preferable to select a polypropylene resin having a melt flow rate in the range of 0.1 to 2 g / 10 minutes. When emphasizing the workability of the resulting resin composition, a polypropylene resin having a melt flow rate of 10 g / 10 min or more, and when emphasizing suppression of the resin may be selected from 0.2 to 100 g / 10 min. preferable.

  In addition to the polypropylene resin described above, the polypropylene resin can be obtained by mixing the polypropylene resin and an α, β-unsaturated carboxylic acid or derivative thereof in the molten state or in the solution state in the presence or absence of a radical generator. It may be a known modified polypropylene resin (obtained by grafting or adding 0.01 to 10% by mass of the α, β-unsaturated carboxylic acid or derivative thereof) obtained by reacting at a temperature of 350 ° C. It may be a mixture of the above-described polypropylene resin and the modified polypropylene resin in an arbitrary ratio.

  The resin composition comprising the components (a) to (c) is composed of the components having the characteristics described above, and is preferably a resin composition having the following two characteristics.

<Feature 1>
The resin composition has a morphology in which (a) polyphenylene ether and (b) hydrogenated block copolymer as a dispersed phase are dispersed in (c) polypropylene resin as a matrix phase.

<Feature 2>
(A) The equivalent circle average particle diameter (D1) of the polyphenylene ether dispersed in the resin composition (resin pellet or resin molded article) thermally relaxes the dispersed phase by a heat-melt test in which the resin composition is left still. (A) a resin composition that is smaller than the circle equivalent average particle diameter (D2) of the polyphenylene ether dispersed in the resin composition after the test, D2 / D1 ≦ 5, and exhibits a thermally stable dispersion form. is there.

This static heat melting test means that the mechanical dispersion factor between the polymer (polypropylene) and the polymer (polyphenylene ether) in the synthesis of a non-compatible polymer alloy (mechanical mixing factor by an extruder or injection molding machine) ) And the effect of emulsifying and dispersing by the emulsifying dispersant (admixture) is confirmed. In this static heat melting test, resin pellets or resin molded product pieces were molded using a heat compression molding machine in a mold frame of 54 mm long × 41 mm wide × 2 mm thick at a temperature of 260 ° C. and a pressure of 10 kg / cm ² . The plate is heat compression molded for 10 minutes and immediately cooled for 5 minutes with a cooling press at 10 ° C. to obtain a compression molded plate. Then, in order to confirm the dispersion state of (a) polyphenylene ether dispersed in the compression-molded plate, the central portion of the thickness of the central portion of the compression plate is cut parallel to the plate surface to confirm the dispersion form. This method of confirming the dispersion form can be easily confirmed and measured using a transmission electron microscope. For example, a sample is oxidized with a heavy metal compound such as ruthenium tetrachloride, an ultrathin section is cut out with an ultramicrotome, etc., and the section is observed with a transmission electron microscope (for example, observed at a magnification of 10,000 times) It can be obtained as an image. The dispersion diameter of the (a) polyphenylene ether obtained here can be usually obtained as an equivalent circle average particle diameter using an image processing apparatus.

  Here, the circle-equivalent average particle diameter is calculated as a circular particle diameter by measuring the entire circumference of the morphological dispersion particles obtained with a transmission electron microscope and regarding the value as the circumference. Specifically, as a method of knowing such a dispersion form, an ultrathin section is prepared by a microtome (Ultracut E manufactured by Reihert) from a resin pellet or a fragment of a resin molded product, and dyed with ruthenic acid, which is then transmitted to a transmission electron. Observe with a microscope (JEOL 1200EX). Based on the obtained transmission electron micrograph, the equivalent circle diameter is obtained from the circumference of the dispersed phase using an image analyzer (for example, IP1000 manufactured by Asahi Kasei Co., Ltd.), and the average particle diameter and the particle size distribution are obtained. be able to.

  Regarding the emulsion dispersion stability between the polymer (polypropylene) and the polymer (polyphenylene ether) that can be known by the above method, (a) When the emulsion dispersion stability of the polyphenylene ether is poor (D2 / D1> 5), the resin composition The physical properties of physical properties deteriorate or stable physical properties cannot be obtained. That is, (c) (a) polyphenylene ether resin having a molecular weight of 50,000 or more in the amount of 5 to 20% by mass and a molecular weight of 8,000 or less in the amount of 12 to 30% by mass is emulsified and dispersed in the polypropylene resin. The resulting polymer alloy in which (c) the polypropylene resin constitutes the matrix phase and (a) the polyphenylene ether resin forms the dispersed phase is the emulsion dispersion stability and the performance of the composition, such as heat resistance, mechanical properties and From the viewpoint of processability, the emulsifying dispersant (admixture) is mainly composed of at least two polymer blocks A mainly composed of styrene, and butadiene having a 1,2-vinyl bond content of 70 to 90%. A hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising at least one polymer block B and bonded. The number average molecular weight (MnbA) of the polymer block A mainly composed of 15 to 50% by mass of styrene, the number average molecular weight (Mnb) and styrene is Mnb ≦ 100,000 and MnbA ≧ 8,000 (b) It is preferable to contain a hydrogenated block copolymer.

  In this Embodiment, it is preferable that 1-95 mass% of (c) component is included with respect to the total amount of said (a)-(c) component, and it is more preferable that 5-90 mass% is included.

[Component (d)]
From the viewpoint of further improving the physical properties of the resin composition of the present embodiment,
As component (d), it further comprises at least one hydrogenated block copolymer different from component (b),
The component (d) is a hydrogenated block copolymer comprising at least two polymer blocks A mainly composed of vinyl aromatic compounds and at least one polymer block B mainly composed of conjugated diene compounds. A hydrogenated block copolymer comprising:
The number average molecular weight (Mnd) as the hydrogenated block copolymer is 150,000 or less, the number average molecular weight (MndA) of the polymer block A is 8,000 or more,
The content of the polymer block A is more than 50% by mass and 70% by mass or less with respect to the total component (d),
In the bonding form of the conjugated diene compound in the polymer block B, the total amount of the conjugated diene compound bonded by a 1,2-vinyl bond or a 3,4-vinyl bond is 25 to 25 with respect to the whole conjugated diene compound. It is preferable that it is 70 mass%.

  (D) The structure of the hydrogenated block copolymer is, for example, ABA type, ABAB type, (AB-) nX type (where n is 1 or more) An integer, X represents a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride or a residue of an initiator such as a polyfunctional organolithium compound.), A-B-A-B-A This is a hydrogenated vinyl aromatic compound-conjugated diene block copolymer having a structure in which block units such as molds are bonded. Among them, a hydrogenated block copolymer having a structure of ABAB type is used. Since it is excellent in fluidity | liquidity compared with an ABA type | mold hydrogenated block copolymer, it is more preferable.

  The content of the vinyl aromatic compound bonded in the (d) hydrogenated block copolymer having the above block structure is 50 to 70% by mass, preferably 53 to 68% by mass, more preferably based on the total component (d). Contains 58-67 mass%. When the amount of the vinyl aromatic compound is 50% by mass or more, heat resistance tends to be improved, and when it is 70% by mass or less, the balance between heat resistance and impact resistance tends to be excellent.

  Further, when referring to individual block structures, the polymer block A mainly composed of a vinyl aromatic compound is a homopolymer block of a vinyl aromatic compound or a vinyl aromatic compound in an amount exceeding 50% by mass, preferably 70% by mass. % Of a vinyl aromatic compound and a conjugated diene copolymer block structure. On the other hand, the polymer block B mainly composed of a conjugated diene is a homopolymer block of a conjugated diene or a conjugated diene containing more than 50 mass%, preferably 70 mass% or more of a conjugated diene and a vinyl aromatic compound. It has a copolymer block structure.

  The individual structures of the polymer block A mainly composed of these vinyl aromatic compounds and the polymer block B mainly composed of conjugated dienes are the vinyl aromatic compound or conjugated diene in the molecular chain in each polymer block. Distribution of random, tapered (in which the monomer component increases or decreases along the molecular chain), a block structure partially composed of 100% by weight of vinyl aromatic compound or a block structure partially composed of 100% by weight of conjugated diene It may consist of a combination. When there are two or more polymer blocks A mainly composed of vinyl aromatic compounds and two polymer blocks B mainly composed of conjugated dienes, the respective polymer blocks may have the same structure or different structures. There may be.

  Referring to polymer block B mainly composed of conjugated diene, at least one polymer block B mainly composed of conjugated diene in (d) hydrogenated block copolymer in the present embodiment is hydrogenated. It may be a single polymer block in which the amount of 1,2-vinyl bonds in the previous conjugated diene is 25 to 70%, and is mainly composed of the conjugated diene in which the amount of 1,2-vinyl bonds is 25 to 45%. And a conjugated diene mainly composed of at least one polymer block B1 and a conjugated diene mainly composed of a conjugated diene having a 1,2-vinyl bond content of more than 45 and less than 70%. The combined block B may be used. A block copolymer showing such a block structure is, for example, a known A-B2-B1-A known in which 1,2-vinyl bond amount is controlled based on the adjusted feed sequence of each monomer unit. It can be obtained by a polymerization method. The bond form of the conjugated diene before hydrogenation can be usually known by an infrared spectrophotometer, NMR or the like.

  Regarding the microstructure of polymer block B in component (d) (bonded form of conjugated diene compound), the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (hereinafter referred to as “total vinyl bond content”). Is sometimes 25 to 70% by mass, preferably 30 to 60% by mass, and preferably 40 to 55% by mass with respect to all the conjugated diene compounds of the component (d). More preferred.

  Hydrogenation reaction is performed on the aliphatic double bond of the polymer block B mainly composed of the conjugated diene of the block copolymer, and the hydrogenated block copolymer (hydrogenation of styrene-butadiene block copolymer) is performed. Can be used as component (d). The hydrogenation rate of such aliphatic double bonds is preferably 80% or more. The hydrogenation rate can be known by an infrared spectrophotometer, NMR or the like.

  (D) In addition to having the above structure, the hydrogenated block copolymer has a number average molecular weight (Mnd) of 150,000 or less, and the number average of the polymer block A mainly composed of a vinyl aromatic compound. The molecular weight (MndA) is 8,000 or more.

  The number average molecular weight (Mnd) of this (d) hydrogenated block copolymer is measured by using one gel permeation chromatography system 21 manufactured by Showa Denko KK (column: KG manufactured by Showa Denko KK). , One K-800RL and one K-800R in series in order, column temperature: 40 ° C., solvent: chloroform, solvent flow rate: 10 ml / min, sample concentration: 1 g /% of hydrogenated block copolymer A standard curve (the molecular weight of standard polystyrene is 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550) with a standard liter / chloroform solution). it can. The UV (ultraviolet) wavelength of the detection unit is measured by setting both standard polystyrene and hydrogenated block copolymer to 254 nm. (D) The number average molecular weight (MndA) of the polymer block A mainly composed of a vinyl aromatic compound of the hydrogenated block copolymer is, for example, the above-described hydrogenated block in the case of an ABA type structure. Based on the number average molecular weight (Mnd) of the copolymer, it is assumed that the molecular weight distribution of the hydrogenated block copolymer is 1, and that two polymer blocks A mainly composed of vinyl aromatic compounds exist as the same molecular weight. And (MndA) = (Mnd) × the proportion of the amount of bonded vinyl aromatic compounds ÷ 2. Similarly, in the case of the A-B-A-B-A type hydrogenated block copolymer (d), (MndA) = (Mnd) × the ratio of the amount of bonded vinyl aromatic compounds ÷ 3. Can. In addition, in the step of synthesizing the vinyl aromatic compound-conjugated diene block copolymer, when the sequence of the block structure A and the block structure B described above is clear, the measurement was performed without depending on the above calculation formula. You may calculate from the ratio of the block structure A based on the number average molecular weight (Mnd) of a hydrogenated block copolymer.

  The (d) hydrogenated block copolymer may be obtained by any production method as long as it has the structure described above. Examples of known production methods include, for example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-54-126255. No. 56-10542, JP-A-56-62847, JP-A-56-1000084, JP-A-2004-269665, British Patent No. 1130770, US Pat. Nos. 3,281,383 and 3,639,517. And the methods described in British Patent No. 1020720 and US Pat. Nos. 3,333,024 and 4,501,857.

  In addition to the above-mentioned hydrogenated block copolymer, the hydrogenated block copolymer of component (d) includes the hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or derivative thereof (ester compound or Modification obtained by reacting an acid anhydride compound, such as maleic anhydride, in the presence or absence of a radical generator, in the molten state, in the solution state, or in the slurry state at a temperature of 80 to 350 ° C. , Β-unsaturated carboxylic acid or a derivative thereof may be a hydrogenated block copolymer (0.01 to 10% by mass grafted or added), and the hydrogenated block copolymer and the modified hydrogenated block described above may be used. It may be a mixture of any proportion of the copolymer.

[(E) component]
From the viewpoint of further improving the physical properties of the resin composition of the present embodiment,
The component (e) further includes at least one hydrogenated block copolymer different from the components (b) and (d),
The component (e) is a hydrogenated block copolymer comprising at least two polymer blocks A mainly composed of vinyl aromatic compounds and at least one polymer block B mainly composed of conjugated diene compounds. A hydrogenated block copolymer comprising:
The number average molecular weight (Mne) as the hydrogenated block copolymer is 100,000 or less, and the number average molecular weight (MneA) of the polymer block A is 8,000 or more,
The content of the polymer block A is 15% by mass or more and 50% by mass or less with respect to the total component (e),
In the bonding form of the conjugated diene compound in the polymer block B, the total amount of the conjugated diene compound bonded by 1,2-vinyl bond or 3,4-vinyl bond is 25 with respect to the whole conjugated diene compound. It is preferable that it is -70 mass%.

  (E) The structure of the hydrogenated block copolymer is, for example, ABA type, ABBA type, (AB-) nX type (where n is an integer of 1 or more, X represents a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride or a residue of an initiator such as a polyfunctional organolithium compound.), ABABABA type, etc. Is a hydrogenated product of a styrene-butadiene block copolymer having a structure in which the block units are bonded. Among them, a hydrogenated block copolymer having an ABAB type structure is ABA. It is more preferable because it tends to be excellent in fluidity as compared with the type hydrogenated block copolymer.

  (E) Content of the vinyl aromatic compound couple | bonded in the hydrogenated block copolymer is 15-50 mass% with respect to the whole (e) component, Preferably it is 25-45 mass%, More preferably, it is 30-45. % By mass. If the vinyl aromatic compound amount is 15% by mass or more, the mechanical strength tends to be improved, and if it is 50% by mass or less, the balance between heat resistance and mechanical strength tends to be excellent.

  Further, when referring to individual block structures, the polymer block A mainly composed of a vinyl aromatic compound is more than 50% by mass, preferably 70% by mass of a homopolymer block of a vinyl aromatic compound or a vinyl aromatic compound. % Of a vinyl aromatic compound and a conjugated diene in the form of a copolymer block. The polymer block B mainly composed of a conjugated diene is a homopolymer block of conjugated diene or 50 conjugated dienes. It has a structure of a copolymer block of a conjugated diene and a vinyl aromatic compound that exceeds 70% by mass, and preferably 70% by mass or more.

  The individual structures of the polymer block A mainly composed of these vinyl aromatic compounds and the polymer block B mainly composed of conjugated dienes are the vinyl aromatic compound or conjugated diene in the molecular chain in each polymer block. Distribution of random, tapered (in which the monomer component increases or decreases along the molecular chain), a block structure partially composed of 100% by weight of vinyl aromatic compound or a block structure partially composed of 100% by weight of conjugated diene You may be comprised by the combination. When there are two or more polymer blocks A mainly composed of vinyl aromatic compounds and two polymer blocks B mainly composed of conjugated dienes, the respective polymer blocks may have the same structure or different structures. May be.

  Referring to polymer block B mainly composed of conjugated diene, at least one polymer block B mainly composed of conjugated diene in (e) hydrogenated block copolymer in the present embodiment is hydrogenated. It may be a single polymer block in which the amount of 1,2-vinyl bonds in the previous conjugated diene is 25 to 70%, and is mainly composed of the conjugated diene in which the amount of 1,2-vinyl bonds is 25 to 45%. A polymer mainly comprising a conjugated diene, which has at least one polymer block B1 and at least one polymer block B2 mainly comprising a conjugated diene having a 1,2-vinyl bond content of more than 45 to less than 70%. Block B may be used. A block copolymer showing such a block structure is, for example, a known A-B2-B1-A known in which 1,2-vinyl bond amount is controlled based on the adjusted feed sequence of each monomer unit. It can be obtained by a polymerization method. The bonding form of the conjugated diene before hydrogenation can be known by an infrared spectrophotometer, NMR or the like.

  Regarding the microstructure of the polymer block B in the component (e) (bonded form of the conjugated diene compound), the total amount of 1,2-vinyl bond and 3,4-vinyl bond (hereinafter referred to as “total vinyl bond amount”). ) Is 25 to 70% by mass, preferably 30 to 60% by mass, and preferably 40 to 55% by mass with respect to all the conjugated diene compounds of the component (e). More preferred.

  Hydrogenation reaction is performed on the aliphatic double bond of the polymer block B mainly composed of the conjugated diene of the block copolymer, and the hydrogenated block copolymer (hydrogenation of styrene-butadiene block copolymer) is performed. (E) as a component). The hydrogenation rate of the aliphatic double bond is preferably 80% or more. The hydrogenation rate can be known by an infrared spectrophotometer, NMR or the like.

  (E) The number of polymer blocks A whose number average molecular weight (Mne) is 100,000 or less and whose main component is a vinyl aromatic compound, in addition to the hydrogenated block copolymer having the above structure. Average molecular weight (MneA) is 8,000 or more.

  The measurement of the number average molecular weight (Mne) of this hydrogenated block copolymer was carried out using a gel permeation chromatography system 21 manufactured by Showa Denko K.K. (column: KG manufactured by Showa Denko K.K., one K-G). One 800RL and one K-800R are connected in series in order, column temperature: 40 ° C., solvent: chloroform, solvent flow rate: 10 ml / min, sample concentration: 1 g / liter of hydrogenated block copolymer / chloroform A calibration curve can be prepared and measured using standard polystyrene (solution) with standard polystyrene (the molecular weight of standard polystyrene is 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550). The UV (ultraviolet) wavelength of the detection unit is measured by setting both standard polystyrene and hydrogenated block copolymer to 254 nm. The number average molecular weight (MneA) of the polymer block A mainly composed of the vinyl aromatic compound of the hydrogenated block copolymer (e) is, for example, the above-described hydrogenated block in the case of an ABA type structure. Based on the number average molecular weight (Mne) of the copolymer, it is assumed that the molecular weight distribution of the hydrogenated block copolymer is 1, and that two polymer blocks A mainly composed of vinyl aromatic compounds exist as the same molecular weight. And (MneA) = (Mne) × bonded vinyl aromatic compound amount ratio ÷ 2. Similarly, in the case of the A-B-A-B-A type (e) hydrogenated block copolymer, (MneA) = (Mne) × the ratio of the amount of bonded vinyl aromatic compounds ÷ 3. Can. In addition, in the step of synthesizing the vinyl aromatic compound-conjugated diene block copolymer, when the sequence of the block structure A and the block structure B described above is clear, the measurement was performed without depending on the above calculation formula. You may calculate from the ratio of the block structure A based on the number average molecular weight (Mne) of a hydrogenated block copolymer.

  The hydrogenated block copolymer of the component (e) may be obtained by any production method as long as it has the structure described above. Known production methods include, for example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-56- No. 10542, JP-A-56-62847, JP-A-56-1000084, JP-A-2004-269665, British Patent No. 1130770 and US Pat. Nos. 3,281,383 and 3639517. And the methods described in British Patent No. 1020720 and US Pat. Nos. 3,333,024 and 4,501,857.

  In addition to the above-mentioned hydrogenated block copolymer, the hydrogenated block copolymer of component (e) includes the hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or derivative thereof (ester compound or Modification obtained by reacting an acid anhydride compound, such as maleic anhydride, in the presence or absence of a radical generator in the molten state, solution state or slurry state at a temperature of 80 to 350 ° C. The α, β-unsaturated carboxylic acid or derivative thereof may be a hydrogenated block copolymer grafted or added (0.01 to 10% by mass), and the above hydrogenated block copolymer and the modified water may be used. It may be a mixture in any proportion of the additive block copolymer.

  (B) The blending ratio of the above (d) hydrogenated block copolymer and / or (e) hydrogenated block copolymer that can be used in combination with the hydrogenated block copolymer is (b) / (d) = 1. -99 mass% / 99-1 mass%, (b) / (e) = 1-99 mass% / 99-1 mass%, and (b) / (d) / (e) = 1-98 mass% / It is preferable that it is 98-1 mass% / 1-98 mass%. Further, (a) polyphenylene ether having a molecular weight of 50,000 or more and a component weight of 5 to 20 mass and a molecular weight of 8,000 or less of 12 to 30 mass% was thermally stabilized in (c) a polypropylene resin matrix. From the viewpoint of obtaining a polymer alloy in an emulsified dispersion state, the proportion of (b) hydrogenated block copolymer contained in the total amount of hydrogenated block copolymers (b), (d), and (e) is 3 The content is preferably at least 5% by mass, more preferably at least 5% by mass.

  The total amount of the components (b), (d) and (e) with respect to the total components (a) to (e) is preferably 20% by mass or less, more preferably 18% by mass or less, Preferably it is 15 mass% or less.

  Furthermore, it is preferable that the quantity ratio relationship between the component (a) and the component (b) is (a) <(b) from the viewpoint of workability.

[Component (f)]
The resin composition in the present embodiment may further contain (f) filler in an amount of 2 to 60% by mass with respect to the total amount of components (a) to (f). The filler used as the component (f) is a component that gives a number of functions to the resin composition containing the components (a) to (e) described above. For example, imparting rigidity, imparting heat resistance, and heat conduction. It can be selected depending on the purpose such as imparting property, imparting conductivity, improving molding shrinkage, and improving linear expansion.

  Examples of the inorganic filler of component (f) include inorganic salts, glass fibers (glass long fibers, chopped strand glass fibers), cellulose, glass flakes, glass beads, carbon long fibers, chopped strand carbon fibers, whiskers, mica, clay. , Talc, kaolin, magnesium hydroxide, magnesium sulfate and its fibers, silica, carbon black, titanium oxide, calcium carbonate, fly ash (coal ash), potassium titanate, wollastonite, thermal conductive materials (graphite, aluminum nitride, Boron nitride, alumina, beryllium oxide, silicon dioxide, magnesium oxide, aluminum nitrate, barium sulfate, etc.), conductive metal fiber, conductive metal flake, carbon black indicating conductivity, carbon fiber indicating conductivity, car At least one selected from the group consisting of nanotubes may be selected. These fillers are further treated with surface treatment agents such as silane coupling agents, titanate coupling agents, aliphatic carboxylic acids, and aliphatic metal salts, and organic treatments such as ammonium salts by an intercalation method. It may also be a product obtained by treating a resin such as urethane resin or epoxy resin as a binder.

  Further, the blending amount of (f) filler is preferably 0.1 to 300 parts by weight, more preferably 1 to 250 parts by weight with respect to 100 parts by weight of the total of the components (a) and (b). Preferably it is 5-200 mass parts, Most preferably, it is 10-150 mass parts. When the blending amount is 10 parts by mass or more, in addition to improving the mechanical strength, the dimensional accuracy of a molded product obtained by molding using the obtained resin composition is improved, and the blending amount is 150 parts by weight. Molded products obtained by molding the resulting resin composition have less sink marks, a smaller linear expansion coefficient due to temperature changes (-30 ° C to 120 ° C), and superior dimensional accuracy and anisotropy thereof. It can be a molded product holding

  Furthermore, the resin composition in the present embodiment may contain a non-aromatic rubber softener. The non-aromatic rubber softener is a component blended to make the resin composition a flexible rubber-like composition, and non-aromatic mineral oil or a liquid or low molecular weight synthetic softener is suitable. Yes. Among them, mineral oil rubber softeners called process oil or extender oil, which are generally used for softening, increasing volume and improving processability of rubber, are a mixture of aromatic ring, naphthene ring and paraffin chain. A paraffin chain having 50% or more carbon atoms in the total carbon is called a paraffin type, a naphthenic ring carbon number of 30 to 45% is naphthenic, and an aromatic carbon number is more than 30%. Many are considered aromatic. As the mineral oil rubber softener, naphthenic and paraffinic ones are preferable in the above categories, and aromatic ones having an aromatic carbon number of 30% or more are not preferable in terms of dispersibility and solubility. These non-aromatic rubber softeners have a kinematic viscosity at 37.8 ° C. of 20 to 500 cst, a pour point of −10 to −15 ° C. and a flash point of 170 to 300 ° C. As the synthetic softening agent, polybutene, low molecular weight polybutadiene or the like can be used, but the mineral oil rubber softening agent gives better results. The compounding quantity of the non-aromatic rubber softening agent is 10 to 300 parts by mass, preferably 20 to 280 parts by mass with respect to 100 parts by mass of the component (b). When the blending amount of the softening agent exceeds 300 parts by mass, the softening agent tends to bleed out, and the final product may become sticky, and the mechanical properties may also be lowered. On the other hand, when the blending amount of the softening agent is less than 10 parts by mass, the hardness tends to increase and the flexibility tends to decrease.

  Other components that can be blended in the resin composition in the present embodiment include, for example, stabilizers, mold release agents, processing aids, flame retardants, anti-drip agents, nucleating agents, UV blockers, dyes, Examples thereof include additives such as pigments, antioxidants, antistatic agents, and foaming agents. These additives can be used as long as they are known in the art, and the lower limit of the blending amount is 0.1 parts by mass or more with respect to 100 parts by mass of all the resin mixtures, more preferably 0 .2 parts by mass or more, more preferably 0.3 parts by mass or more. As an upper limit, it is 10 mass parts or less, More preferably, it is 5 mass parts or less, More preferably, it is 3 mass parts or less. However, in the case of a flame retardant, the upper limit of the blending amount is 100 parts by mass or less, more preferably 70 parts by mass or less, and still more preferably 50 parts by mass or less with respect to 100 parts by mass of all the resin mixtures. Such flame retardants include organophosphate compounds, metal phosphinates, magnesium hydroxide, ammonium polyphosphate flame retardants, melamine flame retardants, triazine flame retardants, aromatic halogen flame retardants, and silicone flame retardants. , At least one selected from the group consisting of fluoropolymers can be selected and used.

  The resin composition of the present embodiment can be produced by various methods using the above-described components. For example, the above components may be heated and kneaded by a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, etc. A kneading method is preferred. In this case, the melting temperature is not particularly limited, but can be arbitrarily selected from the range of usually 150 to 350 ° C.

In the case where the resin composition contains the above components (a) to (c), a particularly preferred embodiment will be described below as a method for easily obtaining the resin composition (and its pellets).
(1) The above-mentioned melt kneader for melt kneading each component is a multi-screw extruder of two or more axes capable of incorporating a kneading block at an arbitrary position of the screw, and the entire kneading of the screw to be used The block portion is substantially (L / D) ≧ 1.5, more preferably (L / D) ≧ 5 [where L is the total length of the kneading block, and D is the maximum outer diameter of the kneading block. And (π · D · N / h) ≧ 50 (where π = 3.14, D = screw outer diameter corresponding to the metering zone, N = screw rotation speed (rev / sec)) H = groove depth of the metering zone].
(2) These extruders have at least a first raw material supply port on the upstream side with respect to the flow direction of the raw material, and at least a second raw material supply port on the downstream side, and downstream of the second raw material supply port as necessary. Further, one or more raw material supply ports may be provided, and a vacuum vent port may be provided between the raw material supply ports as necessary. In the method for producing a resin composition, the basic raw material supply method is such that (a) the total amount of polyphenylene ether or (a) the total amount of polyphenylene ether and (c) the total amount of polypropylene resin does not exceed 50% from the first raw material supply port. The total amount of the (c) component polypropylene resin and the (b) component hydrogenated block copolymer are supplied together, and from the second raw material supply port, (c) the total amount of the polypropylene resin or the first raw material supply port The extrusion method of supplying the remaining polypropylene resin of component (c) distributed to is usually set at an extruder barrel set temperature of 200 to 370 ° C, preferably 250 to 320 ° C, and a screw rotation speed of 100 to 1200 rpm, preferably 200 to Pellets are produced by melt-kneading at 500 rpm.
(3) The hydrogenated block copolymer of the components (d) and (e) is supplied to the first raw material supply port in whole quantity or dividedly supplied to the first raw material supply port and the second raw material supply port at an arbitrary ratio. be able to.
(4) The supply of the filler component (f) is basically a method in which all the resin components (a) to (e) are melt-kneaded and supplied from the third raw material supply port and melt-kneaded. Preferably, when the conveying ability of the side feed extruder that is supplied to the extruder, which tends to occur when the filler is fine powder or the like, decreases (f) component from the second raw material supply port, (c) polypropylene Melting and kneading is carried out by an extrusion method in which the entire amount of resin or the remaining (c) polypropylene resin distributed to the first raw material supply port is supplied together.
(5) Supply of additives such as stabilizers, mold release agents, processing aids, flame retardants, anti-drip agents, nucleating agents, UV blockers, dyes, pigments, antioxidants, antistatic agents, foaming agents, etc. It may be supplied together with other components from any one of the first raw material supply port and the second raw material supply port. In the case of a liquid additive, a liquid addition jig to the press-fitting zone provided in the extruder Is melt-kneaded by an extrusion method using a plunger pump and a gear pump.

  Also, a thermoplastic resin composition can be obtained by melt-kneading preferably 10 to 1000 parts by mass of a thermoplastic resin with respect to 100 parts by mass of pellets of the resin composition obtained by the above method.

  Examples of the thermoplastic resin include vinyl aromatic compound polymers, vinyl aromatic compound copolymers, polypropylene resins, polyethylene, polyamide 6, polyamide 66, polyamide 66/6, polycarbonate, polyacetal, polyethylene terephthalate, and polybutylene. At least one selected from the group consisting of terephthalate, polytrimethylene terephthalate, aromatic ring-containing polyamide, aliphatic ring-containing polyamide, polyphenylene sulfide, liquid crystal polymer, polyether ether ketone, polyarylate, polyether sulfone, and polysulfone. In particular, (g) polypropylene resin is preferred.

  The thermoplastic resin composition can be produced by various methods. For example, heating and kneading methods using a single screw extruder, twin screw extruder, roll, kneader, Brabender plastograph, Banbury mixer, etc. can be mentioned. Among them, melt kneading using a single screw extruder or twin screw extruder The method is preferred.

Furthermore, when obtaining a thermoplastic resin composition, you may knead | mix the said (f) filler component and another additive. When melt-kneading with a twin-screw extruder, and explaining the case of kneading pellets, thermoplastic resin, filler components as an example,
(1) A method of supplying pellets, thermoplastic resin and filler from the first raw material supply port,
(2) A method of supplying pellets from the first raw material supply port, a thermoplastic resin from the second raw material supply port, and (f) a filler component,
(3) A method of supplying pellets from the first raw material supply port, a thermoplastic resin from the second raw material supply port, and (f) a filler component from the third raw material supply port,
(4) A method of supplying a thermoplastic resin from the first raw material supply port, pellets from the second raw material supply port, and (f) a filler component from the third raw material supply port,
It can be selected appropriately according to the purpose, and it can be seen that the range of processing conditions is widened.
When the polypropylene resin is melt-kneaded using the pellets as a raw material, it is preferable to employ the method (3) from the viewpoint of preventing light resistance.

  For example, when the components (a), (b), and (c) are melt-kneaded all at once as is well known in the art, in order to plasticize polyphenylene ether, a processing machine represented by an extruder is used. The set temperature needs to be higher than 270 ° C. However, if the pellet of the present embodiment is used as a raw material, it can be melt kneaded (compounded) at a processing machine set temperature of 270 ° C. or lower. From the standpoint of light resistance and suppression of mains, the set temperature at the time of the second stage compound is preferably 260 ° C. or less, more preferably 250 ° C. or less. When the set temperature is within the above range, the occurrence of a scum is greatly suppressed at the interface between the resin extruded from the die of the extruder and the die.

  Further, a molded product can be obtained by dry blending (g) polypropylene resin, preferably 10 to 1000 parts by mass, and injection molding with respect to 100 parts by mass of pellets. In the case of this method, it is possible to greatly simplify the process and obtain a molded article of the resin composition having excellent light resistance.

  Furthermore, a molded body can be obtained by dry blending (g) polypropylene resin, preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the pellet, and extrusion molding. In the case of this method, it is possible to greatly simplify the process and to obtain a molded article having excellent light resistance, and it is possible to suppress the occurrence of scratches at the interface between the die and the molten resin during extrusion molding.

  The resin composition of the present embodiment can be molded as a molded body of various parts by various conventionally known methods such as injection molding, extrusion molding (sheet, film), and hollow molding. Examples of these various parts include automobile parts, specifically, bumper, fender, door panel, molding, emblem, engine hood, wheel cover, roof, spoiler and other exterior parts, instrument panel, and console box. Suitable for interior parts such as trims. Furthermore, it can also be used as various computers and peripheral devices, other OA devices, televisions, videos, various disk player cabinets, chassis, refrigerators, air conditioners, liquid crystal projectors, and the like.

The present embodiment will be described in more detail with reference to examples, but the present embodiment is not limited to these examples.
Each physical property was measured as follows.
(Polyphenylene ether / hydrogenated block copolymer composition)
[Number average molecular weight]
The number average molecular weight of each component was measured by GPC (mobile phase: chloroform, standard substance: polystyrene).
[Measurement of bound styrene content]
The amount of bound styrene was measured by NMR.
[Measurement of hydrogenation rate]
The hydrogenation rate was measured by NMR.
[Measurement of total vinyl bond content]
The total vinyl bond amount was measured with an infrared spectrophotometer.

[Production of resin composition]
(A) Component polyphenylene ether (a-1): 40 liters equipped with a sparger for introducing an oxygen-containing gas, a stirring turbine blade and a baffle at the bottom of the polymerization tank, and a reflux condenser in the vent gas line at the top of the polymerization tank 4.02 g of cupric oxide, 29.876 g of 47% hydrogen bromide aqueous solution, 9.684 g of di-t-butyl, while blowing nitrogen gas into the jacketed polymerization tank at a flow rate of 0.5 L / min. Ethylenediamine, 46.88 g of di-n-butylamine, 144.28 g of butyldimethylamine, 20.65 kg of toluene, 3.12 kg of 2,6-dimethylphenol were put into a homogeneous solution, and the internal temperature of the polymerization tank was Stir until 25 ° C.
Next, dry air was introduced into the polymerization tank at a rate of 32.8 NL / min from a sparger and polymerization was started. Aeration was performed for 86 minutes, and the internal temperature at the end of polymerization was controlled to 40 ° C. The polymerization solution at the end of the polymerization was in a solution state.
Stop the ventilation of dry air, add 10 kg of 2.5% aqueous solution of ethylenediaminetetraacetic acid tetrasodium salt (a reagent manufactured by Dojindo Laboratories) to the polymerization mixture, stir the polymerization mixture at 70 ° C. for 150 minutes, and And the organic and aqueous phases were separated by liquid-liquid separation.
After the obtained organic phase was brought to 50 ° C., methanol was added in excess to precipitate polyphenylene ether, followed by filtration. The remaining polyphenylene ether was dispersed in excess methanol, stirred at 50 ° C. for 30 minutes, and then filtered again. This operation was repeated twice to obtain wet polyphenylene ether. Furthermore, it was kept at 150 ° C. and 1 mmHg for 1.5 hours to obtain a dried polyphenylene ether powder.
The same operation as described above was repeated twice, followed by polymerization, filtration and drying to obtain about 6 kg of polyphenylene ether powder. Let this polyphenylene ether powder be (a-1). The molecular weight was as follows as a result of GPC measurement.
Amount of components having a molecular weight of 50,000 or more: 12% by mass
Component amount of molecular weight 8,000 or less: 22% by mass

(A-2): 500 ml / min in a 10 liter jacketed polymerization tank equipped with a sparger for introducing an oxygen-containing gas at the bottom of the polymerization tank, a stirring turbine blade and a baffle, and a vent gas line at the top of the polymerization tank with a reflux condenser. 1.1164 g of cupric chloride dihydrate, 4.9172 g of 35% hydrochloric acid, 42.642 g of N, N, N ′, N′-tetramethylpropanediamine, .082 g of di-n-butylamine, 2534.1 g of xylene, 2534.1 g of n-butanol, 1267.1 g of methanol, 1600.0 g of 2,6-dimethylphenol were put into a homogeneous solution, and the reactor The mixture was stirred until the internal temperature reached 30 ° C.
Subsequently, introduction of oxygen gas from the sparger was started at a rate of 1000 Nml / min into the vigorously stirred polymerization tank. Aeration was conducted for 420 minutes, and the internal temperature of the reactor was controlled to 40 ° C. Incidentally, after 135 minutes from the start of the supply of oxygen gas, polyphenylene ether was deposited to show a slurry form. The form of the polymerization solution at the end of the polymerization was precipitation polymerization.
Stop the ventilation of the oxygen-containing gas, add 12.0 g of 50% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) to the polymerization mixture, stir the polymerization mixture for 60 minutes, and then hydroquinone (Wako Pure Chemical Industries, Ltd.) And the stirring was continued until the slurry polyphenylene ether became white. The internal temperature of the reactor was controlled to 50 ° C. The slurry-like polyphenylene ether that became white was filtered, and the polyphenylene ether of the filtration residue was washed by sprinkling methanol and then held at 150 ° C. and 1 mmHg for 1.5 hours to obtain a dried polyphenylene ether powder.
The same operation as described above was repeated four times for polymerization, filtration, and drying to obtain about 6 kg of polyphenylene ether powder. Let this polyphenylene ether powder be (a-2). The molecular weight was as follows as a result of GPC measurement.
Amount of components having a molecular weight of 50,000 or more: 6% by mass
Component amount of molecular weight 8,000 or less: 12% by mass

(A-3): The same as (a-2) except that 4117.9 g of xylene, 950.3 g of n-butanol, and 1267.1 g of methanol were placed in the polymerization tank, and the polyphenylene ether powder was obtained. About 6 kg was obtained. This polyphenylene ether powder is defined as (a-3). The molecular weight was as follows as a result of GPC measurement.
Amount of components having a molecular weight of 50,000 or more: 42% by mass
Component amount of molecular weight 8,000 or less: 4% by mass

(A-4): A sparger for introducing an oxygen-containing gas, a stirring turbine blade and a baffle are provided at the bottom of the polymerization tank, a reflux condenser is provided in the vent gas line at the top of the polymerization tank, and the side of the polymerization tank is connected to the second polymerization tank. While blowing nitrogen gas at a flow rate of 500 mL / min into a 1.6 liter jacketed first polymerization tank equipped with an overflow line, 0.239 g of cupric chloride dihydrate, 1.122 g of 35% hydrochloric acid, Add 3.531 g di-n-butylamine, 18.154 g N, N, N ′, N′-tetramethylpropanediamine, 445.1 g xylene, 170.8 g n-butanol, 509.5 g methanol It was.
Similarly, a sparger for introducing an oxygen-containing gas, a stirring turbine blade and a baffle are provided at the bottom of the polymerization tank, a reflux condenser is provided in the vent gas line at the top of the polymerization tank, and an overflow line to the washing tank is provided on the side of the polymerization tank. 1007.8 g of xylene, 378.4 g of n-butanol, and 509.5 g of methanol were put into a 0.0 liter jacketed second polymerization tank while blowing nitrogen gas at a flow rate of 1000 mL / min.
Further, a 6.0 liter first raw material tank equipped with a reflux condenser in a line that can be fed to the first polymerization tank by a plunger pump, a stirring turbine blade and a vent gas line in the upper part of the tank, 0.642 g cupric chloride dihydrate, 2.827 g 35% hydrochloric acid, 9.247 di-n-butylamine, 24.519 g N, N, N while blowing nitrogen gas at a flow rate of minutes. ', N'-tetramethylpropanediamine, 1196.5 g of xylene, 457.5 g of n-butanol, 1369.2 g of methanol, 920.0 g of 2,6-dimethylphenol were added, and the liquid was mixed by stirring. . In addition, in order that the preparation liquid in a 1st raw material tank may reduce when it supplies to a superposition | polymerization tank, the thing of the said liquid composition was additionally added to the 1st raw material tank suitably.
Next, the polymerization solution is supplied from the first raw material tank to the vigorously stirred first polymerization tank at a flow rate of 19.42 g / min, and at the same time, oxygen is supplied from the sparger to the first polymerization tank at a rate of 329.42 mL / min. The introduction of. Furthermore, simultaneously with the start of overflow from the first polymerization tank to the second polymerization tank, oxygen was introduced from the sparger into the second polymerization tank at a rate of 32.4 mL / min. The polymerization temperature was adjusted by passing a heating medium through the jacket so as to maintain 40 ° C. in both the first polymerization tank and the second polymerization tank. The overflow from the second polymerization tank was collected in a collection container.
Thereafter, the overflowed slurry began to be collected after 40 hours, and then polymerization was continued for 23 hours to complete the polymerization. The obtained polyphenylene ether slurry was about 26.8 kg.
6.7 kg, which is a quarter of the polyphenylene ether slurry obtained as described above, is placed in a 10 liter jacketed tank equipped with a stirring turbine blade and baffle, a reflux gas cooler in the vent gas line at the top of the tank, 70 g of a 10% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) was added and warmed to 50 ° C.
Next, hydroquinone (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little, and the temperature was kept at 50 ° C. until the slurry polyphenylene ether became white. The slurry-like polyphenylene ether that became white was filtered, and methanol was sprinkled over the remaining polyphenylene ether, followed by washing treatment to obtain polyphenylene ether powder.
The same treatment was applied to the remaining polyphenylene ether slurry to obtain about 6 kg of polyphenylene ether powder. This polyphenylene ether powder is defined as (a-4). The molecular weight was as follows as a result of GPC measurement.
Component amount with molecular weight of 50,000 or more: 8% by mass
Amount of components having a molecular weight of 8,000 or less: 10% by mass

(B) Hydrogenated block copolymer of component (b-1) Hydrogenated polybutadiene-polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) hydrogenated block copolymer having a B-A-B-A type structure The polymer was synthesized by a conventional method. The physical properties of the obtained hydrogenated block copolymer are as follows.
Bonded styrene content: 32%
Total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in polybutadiene (total vinyl bond content): 36%
Number average molecular weight of hydrogenated block copolymer: 65000
Number average molecular weight of polystyrene (1): 9800
Number average molecular weight of polystyrene (2): 9800
Polybutadiene part hydrogenation rate: 99.9%

(B-2) Hydrogenated polybutadiene-polystyrene- (1) -hydrogenated polybutadiene-polystyrene (2) hydrogenated block copolymer having a B-A-B-A type structure was synthesized by a conventional method. The physical properties of the obtained hydrogenated block copolymer are as follows.
Bonded styrene content: 45%
Total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in polybutadiene (total vinyl bond content): 36%
Number average molecular weight of hydrogenated block copolymer: 49000
Number average molecular weight of polystyrene (1): 10300
Number average molecular weight of polystyrene (2): 10300
Polybutadiene part hydrogenation rate: 99.9%

(B-3) Hydrogenated polybutadiene-polystyrene- (1) -hydrogenated polybutadiene-polystyrene (2) hydrogenated block copolymer having a B-A-B-A type structure was synthesized by a conventional method. The physical properties of the obtained hydrogenated block copolymer are as follows.
Bonded styrene content: 40%
Total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in polybutadiene (total vinyl bond content): 35%
Number average molecular weight of hydrogenated block copolymer: 60000
Number average molecular weight of polystyrene (1): 12000
Number average molecular weight of polystyrene (2): 12000
Polybutadiene part hydrogenation rate: 99.9%

<Examples 1-5, Comparative Examples 1-5>
Using a twin-screw extruder (manufactured by Coperion, ZSK-25), a first raw material supply port was provided upstream with respect to the flow direction of the raw material, and a vacuum vent was provided downstream thereof. Using the extruder set in this way, the components (a) and (b) were blended in the composition shown in Table 1, and the conditions were an extrusion temperature of 230 to 280 ° C., a screw rotation speed of 250 rpm, and a discharge rate of 12 kg / hour. It was melt-kneaded and obtained as pellets. This pellet was formed into a test piece.
Each physical property of the resin composition containing the components (a) and (b) was measured as follows.
<Flowability MFR>
Based on JIS K7210, it measured by 230 degreeC and the load of 2.16Kg.
<Glass transition temperature Tg>
For the tan δ value and the peak temperature of tan δ, the sample cut to a size of 10 mm in width and 35 mm in length is set in the twist type geometry of the device “ARES” (trade name, manufactured by TI Instruments Inc.) The effective measurement length was 25 mm, the strain was 0.5%, the frequency was 1 Hz, and the temperature was increased from −70 ° C. to 50 ° C. at a temperature rising rate of 3 ° C./min. The tan δ peak temperature was determined from the peak detected by automatic detection of the peak of “RSI Orchestrator” (trade name, manufactured by TI Instrument Co., Ltd.).
<Tensile breaking elongation>
Measurement was performed at a test speed of 500 mm / min in accordance with JIS K6301.
<Rebound resilience>
In accordance with JIS K6255, it was determined by a trypso type rebound resilience test. Two samples were stacked and measured.
Sample shape: 10 mm x 10 mm, thickness 10 mm
<Transparency>
A sample with a thickness of 2 mm obtained by compression molding was placed on a paper on which characters were printed, and the transparency was classified as follows according to the appearance of the characters below.
○: Transparent (characters are clearly visible and can be read)
×: Opaque (characters are not visible)
<Total light transmittance>
Using a sample with a thickness of 2 mm obtained by compression molding, measurement was performed in accordance with JIS K7361.
The measurement results are shown in Table 1.

<Polypropylene / polyphenylene ether composition>
[Number average molecular weight]
The number average molecular weight of each component was measured by GPC (mobile phase: chloroform, standard substance: polystyrene).
[Measurement of bound styrene content]
The amount of bound styrene was measured by NMR.
[Measurement of hydrogenation rate]
The hydrogenation rate was measured by NMR.
[Measurement of total vinyl bond content]
The total vinyl bond amount was measured with an infrared spectrophotometer.
[Melting point]
The melting point was measured with a differential scanning calorimeter.
[MFR]
MFR was measured at 230 ° C. and a load of 2.16 kg according to ASTM D1238.

[Production of resin composition]
(A) Component polyphenylene ether (a-5): 40 liters equipped with a sparger for introducing an oxygen-containing gas, a stirring turbine blade and a baffle at the bottom of the polymerization tank, and a reflux condenser in the vent gas line at the top of the polymerization tank 4.02 g of cupric oxide, 29.876 g of 47% hydrogen bromide aqueous solution, 9.684 g of di-t-butyl, while blowing nitrogen gas into the jacketed polymerization tank at a flow rate of 0.5 L / min. Ethylenediamine, 46.88 g of di-n-butylamine, 144.28 g of butyldimethylamine, 20.65 kg of toluene, 3.12 kg of 2,6-dimethylphenol were put into a homogeneous solution, and the internal temperature of the polymerization tank was Stir until 25 ° C.
Next, dry air was introduced into the polymerization tank at a rate of 32.8 NL / min from a sparger and polymerization was started. Aeration was performed for 86 minutes, and the internal temperature at the end of polymerization was controlled to 40 ° C. The polymerization solution at the end of the polymerization was in a solution state.
Aeration of dry air was stopped, 10 kg of 2.5% aqueous solution of ethylenediaminetetraacetic acid tetrasodium salt (a reagent manufactured by Dojindo Laboratories) was added to the polymerization mixture, and the polymerization mixture was stirred at 70 ° C. for 150 minutes, and then allowed to stand. The organic phase and the aqueous phase were separated by liquid-liquid separation.
After the obtained organic phase was brought to 50 ° C., methanol was added in excess to precipitate polyphenylene ether, followed by filtration. The remaining polyphenylene ether was dispersed in excess methanol, stirred at 50 ° C. for 30 minutes, and then filtered again. This operation was repeated twice to obtain wet polyphenylene ether. Furthermore, it was kept at 150 ° C. and 1 mmHg for 1.5 hours to obtain a dried polyphenylene ether powder.
The same operation as described above was repeated twice, followed by polymerization, filtration and drying to obtain about 6 kg of polyphenylene ether powder. This polyphenylene ether powder is defined as (a-5). The molecular weight was as follows as a result of GPC measurement.
Amount of components having a molecular weight of 50,000 or more: 12% by mass
Component amount of molecular weight 8,000 or less: 22% by mass

(A-6): 500 ml / min in a 10 liter jacketed polymerization tank equipped with a sparger for introducing an oxygen-containing gas at the bottom of the polymerization tank, a stirring turbine blade and baffle, and a vent gas line at the top of the polymerization tank with a reflux condenser. 1.1164 g of cupric chloride dihydrate, 4.9172 g of 35% hydrochloric acid, 42.642 g of N, N, N ′, N′-tetramethylpropanediamine, .082 g of di-n-butylamine, 2534.1 g of xylene, 2534.1 g of n-butanol, 1267.1 g of methanol, 1600.0 g of 2,6-dimethylphenol were put into a homogeneous solution, and the reactor The mixture was stirred until the internal temperature reached 30 ° C.
Subsequently, introduction of oxygen gas from the sparger was started at a rate of 1000 Nml / min into the vigorously stirred polymerization tank. Aeration was conducted for 420 minutes, and the internal temperature of the reactor was controlled to 40 ° C. Incidentally, after 135 minutes from the start of the supply of oxygen gas, polyphenylene ether was deposited to show a slurry form. The form of the polymerization solution at the end of the polymerization was precipitation polymerization.
Stop the ventilation of the oxygen-containing gas, add 12.0 g of 50% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) to the polymerization mixture, stir the polymerization mixture for 60 minutes, and then hydroquinone (Wako Pure Chemical Industries, Ltd.) And the stirring was continued until the slurry polyphenylene ether became white. The internal temperature of the reactor was controlled to 50 ° C. The slurry-like polyphenylene ether that became white was filtered, and the polyphenylene ether of the filtration residue was washed by sprinkling methanol and then held at 150 ° C. and 1 mmHg for 1.5 hours to obtain a dried polyphenylene ether powder.
The same operation as described above was repeated four times for polymerization, filtration, and drying to obtain about 6 kg of polyphenylene ether powder. This polyphenylene ether powder is defined as (a-6). The molecular weight was as follows as a result of GPC measurement.
Amount of components having a molecular weight of 50,000 or more: 6% by mass
Component amount of molecular weight 8,000 or less: 12% by mass

(A-7): The same as (a-6) except that 3167.7 g of xylene, 1583.8 g of n-butanol, and 1583.8 g of methanol were placed in the polymerization tank, and the polyphenylene ether powder was obtained. About 6 kg was obtained. This polyphenylene ether powder is defined as (a-7). The molecular weight was as follows as a result of GPC measurement.
Amount of components having a molecular weight of 50,000 or more: 24% by mass
Component amount of molecular weight 8,000 or less: 5% by mass

(A-8): The same procedure as in (a-6) was carried out except that 4117.9 g of xylene, 950.3 g of n-butanol, and 1267.1 g of methanol were placed in the polymerization vessel, and polyphenylene ether powder was obtained. About 6 kg was obtained. This polyphenylene ether powder is defined as (a-8). The molecular weight was as follows as a result of GPC measurement.
Amount of components having a molecular weight of 50,000 or more: 42% by mass
Component amount of molecular weight 8,000 or less: 4% by mass

(B) Component hydrogenated block copolymer (b-4): Hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene structure (B-A-B-A), and amount of bound styrene 44%, number average molecular weight of the whole polymer 90,000, molecular weight distribution 1.06, number average molecular weight of polystyrene part (A) 19,800, 1,2-vinyl bond amount of polybutadiene before hydrogenation is 75%, polybutadiene A hydrogenated block copolymer having a hydrogenation ratio of 99.9% was synthesized, and this polymer was designated as (b-4).

(B-5): Polystyrene-hydrogenated polybutadiene-polystyrene structure (ABA), 44% bound styrene, number average molecular weight 87,000 of the whole polymer, molecular weight distribution 1.07, Synthesis of a hydrogenated block copolymer having a number average molecular weight of 19,000 in the polystyrene part (A), 85% of 1,2-vinyl bond in the polybutadiene before hydrogenation, and 99.9% in the hydrogenation ratio of the polybutadiene part. This polymer was designated as (b-5).

(B-6): Polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene structure (ABAB) having a bound styrene content of 32% and a number average molecular weight of the whole polymer of 52, 000, molecular weight distribution 1.07, number average molecular weight of polystyrene part (A) 8,300, 1,2-vinyl bond amount of polybutadiene before hydrogenation is 74%, hydrogenation rate of polybutadiene part is 99.9% A hydrogenated block copolymer was synthesized and this polymer was designated as (b-6).

(B-7): Polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene structure (ABAB) having a bonded styrene content of 44% and a number average molecular weight of the whole polymer of 34, 000, molecular weight distribution 1.07, number average molecular weight of polystyrene part (A) 7,500, 1,2-vinyl bond content of polybutadiene before hydrogenation is 73%, hydrogenation rate of polybutadiene part is 99.9% A hydrogenated block copolymer was synthesized and this polymer was designated as (b-7).

(B-8): Polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene structure (ABAB) having a bound styrene content of 44% and a number average molecular weight of the whole polymer of 120, 000, molecular weight distribution 1.07, number average molecular weight 26,400 of polystyrene part (A), 1,2-vinyl bond content of polybutadiene before hydrogenation is 75%, hydrogenation rate of polybutadiene part is 99.9% A hydrogenated block copolymer was synthesized, and this polymer was designated as (b-8).

(C) Component high crystalline polypropylene (c-1): Homo-polypropylene Melting point = 168 ° C., MFR = 0.45
(C-2): Homo-polypropylene Melting point = 166 ° C., MFR = 3.0
(C-3): Homo-polypropylene Melting point = 167 ° C., MFR = 5.5
(C-4): Homo-polypropylene Melting point = 160 ° C., MFR = 13.0
(C-5): Homo-polypropylene Melting point = 161 ° C., MFR = 70

(D) Component hydrogenated block copolymer (d-1): Polystyrene-hydrogenated polybutadiene-polystyrene structure (ABA), bound styrene content 60%, number average of the whole polymer Molecular weight 108,000, molecular weight distribution 1.08, number average molecular weight 32,000 of polystyrene part (A), 1,2-vinyl bond content of polybutadiene before hydrogenation is 35%, hydrogenation rate of polybutadiene part is 99.9% A hydrogenated block copolymer was synthesized, and this polymer was defined as (d-1).

(D-2): Polystyrene-hydrogenated polybutadiene-polystyrene structure (ABA), bound styrene content 65%, number average molecular weight 49,000 of the whole polymer, molecular weight distribution 1.04, A hydrogenated block copolymer having a number average molecular weight of 16,000 in the polystyrene part (A), a 1,2-vinyl bond amount of the polybutadiene before hydrogenation of 38%, and a hydrogenation rate of the polybutadiene part of 99.9% was synthesized. This polymer was designated as (d-2).

Component (e) Hydrogenated Block Copolymer (e-1): Polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene structure (A-B-A-B) and bound styrene content 30%, number average molecular weight of the whole polymer 75,000, molecular weight distribution 1.05, number average molecular weight 11,000 of polystyrene part (A), 1,2-vinyl bond amount of polybutadiene before hydrogenation is 33%, polybutadiene part A hydrogenated block copolymer having a hydrogenation rate of 99.9% was synthesized, and this polymer was designated as (e-1).

(F) Component filler (f-1): Talc with an average particle size of 7 microns (Hayashi Kasei Co., Ltd., trade name “PK-P”)

[ Reference Examples 1-14 and Comparative Examples 6-15]
Each component of polypropylene, polyphenylene ether, hydrogenated block copolymer and filler shown in Tables 2 and 3 is set to a temperature of 240 to 320 ° C. and a screw rotation speed of 300 rpm, and a first raw material supply port and a second raw material supply port The composition of the first raw material supply port and the second raw material supply port of the extruder shown in Tables 2 and 3 using a twin-screw extruder (ZSK-40 manufactured by Coperion Co., Ltd.) having (located approximately at the center of the extruder) The composition was supplied and melt-kneaded to obtain a resin composition as pellets.
Each physical property of the resin composition was evaluated as follows.

<MFR>
According to ISO1133, it measured with the load of 250 kg and 10 kg.
<Tensile test>
Using the resin composition pellets of the reference examples and comparative examples obtained as described above, the pellets were supplied to a screw in-line injection molding machine set at 240 to 280 ° C., and the tensile strength was 60 ° C. A test piece for measurement was injection-molded, and left in an environment of 80 ° C. for 24 hours using a gear oven to perform a heat history treatment.
The measurement was performed according to ISO527.
<Bending elastic modulus>
Using the pellets of the resin compositions of the reference examples and comparative examples obtained as described above, they are supplied to a screw in-line type injection molding machine set at 240 to 280 ° C. A test piece for rate measurement was injection-molded, and left in an environment of 80 ° C. for 24 hours using a gear oven to perform a heat history treatment.
The measurement was performed according to ISO178.
<Heat resistance (deflection temperature under load)>
Using the pellets of the resin compositions of Reference Examples and Comparative Examples obtained as described above, they are supplied to a screw in-line type injection molding machine set at 240 to 280 ° C., and the deflection of the load is performed at a mold temperature of 60 ° C. A temperature measurement test piece was injection-molded, and left in an environment of 80 ° C. for 24 hours using a gear oven to perform a heat history treatment.
The measurement was performed according to ISO75-2 (0.46 MPa load).
<Dispersed phase stability>
Resin pellets containing no filler and the pellets are compression-molded (molded 54 mm long x 41 mm wide x 2 mm thick, heat-compressed for 10 minutes at a temperature of 260 ° C and a pressure of 10 kg / cm ² and immediately cooled to 10 ° C. A plate obtained by cooling with a press machine for 5 minutes was used to obtain a dispersed phase of each sample as an image using a transmission electron microscope (TEM). From the morphology of this image, the dispersion diameter of polyphenylene ether was calculated as an equivalent circle average particle diameter using an image processing apparatus, and the equivalent circle average particle diameter (D2) of the compression-molded plate / the equivalent circle average particle diameter of the resin pellet ( The ratio of D1) was determined.
The measurement results are shown in Tables 2 and 3.

<Pellets>
[Number average molecular weight]
The number average molecular weight of each component was measured by GPC (mobile phase: chloroform, standard substance: polystyrene).
[Measurement of bound styrene content]
The amount of bound styrene was measured by NMR.
[Measurement of hydrogenation rate]
The hydrogenation rate was measured by NMR.
[Measurement of total vinyl bond content]
The total vinyl bond amount was measured with an infrared spectrophotometer.
[Melting point]
The melting point was measured with a differential scanning calorimeter.
[MFR]
MFR was measured at 230 ° C. and a load of 2.16 kg according to ASTM D1238.

(A) Component polyphenylene ether (a-9): 40 liters equipped with a sparger for introducing an oxygen-containing gas, a stirring turbine blade and a baffle at the bottom of the polymerization tank, and a reflux condenser in the vent gas line at the top of the polymerization tank 4.02 g of cupric oxide, 29.876 g of 47% hydrogen bromide aqueous solution, 9.684 g of di-t-butyl, while blowing nitrogen gas into the jacketed polymerization tank at a flow rate of 0.5 L / min. Ethylenediamine, 46.88 g of di-n-butylamine, 144.28 g of butyldimethylamine, 20.65 kg of toluene, 3.12 kg of 2,6-dimethylphenol were put into a homogeneous solution, and the internal temperature of the polymerization tank was Stir until 25 ° C.
Next, dry air was introduced into the polymerization tank at a rate of 32.8 NL / min from a sparger and polymerization was started. Aeration was performed for 86 minutes, and the internal temperature at the end of polymerization was controlled to 40 ° C. The polymerization solution at the end of the polymerization was in a solution state.
Aeration of dry air was stopped, 10 kg of 2.5% aqueous solution of ethylenediaminetetraacetic acid tetrasodium salt (a reagent manufactured by Dojindo Laboratories) was added to the polymerization mixture, and the polymerization mixture was stirred at 70 ° C. for 150 minutes, and then allowed to stand. The organic phase and the aqueous phase were separated by liquid-liquid separation.
After the obtained organic phase was brought to 50 ° C., methanol was added in excess to precipitate polyphenylene ether, followed by filtration. The remaining polyphenylene ether was dispersed in excess methanol, stirred at 50 ° C. for 30 minutes, and then filtered again. This operation was repeated twice to obtain wet polyphenylene ether. Furthermore, it was kept at 150 ° C. and 1 mmHg for 1.5 hours to obtain a dried polyphenylene ether powder.
The same operation as described above was repeated twice, followed by polymerization, filtration and drying to obtain about 6 kg of polyphenylene ether powder. This polyphenylene ether powder is defined as (a-9). The molecular weight was as follows as a result of GPC measurement.
Amount of components having a molecular weight of 50,000 or more: 12% by mass
Component amount of molecular weight 8,000 or less: 22% by mass

(A-10): 500 ml / min in a 10 liter jacketed polymerization tank equipped with a sparger for introducing an oxygen-containing gas at the bottom of the polymerization tank, a stirring turbine blade and baffle, and a vent gas line at the top of the polymerization tank with a reflux condenser. 1.1164 g of cupric chloride dihydrate, 4.9172 g of 35% hydrochloric acid, 42.642 g of N, N, N ′, N′-tetramethylpropanediamine, .082 g of di-n-butylamine, 2534.1 g of xylene, 2534.1 g of n-butanol, 1267.1 g of methanol, 1600.0 g of 2,6-dimethylphenol were put into a homogeneous solution, and the reactor The mixture was stirred until the internal temperature reached 30 ° C.
Subsequently, introduction of oxygen gas from the sparger was started at a rate of 1000 Nml / min into the vigorously stirred polymerization tank. Aeration was conducted for 420 minutes, and the internal temperature of the reactor was controlled to 40 ° C. Incidentally, after 135 minutes from the start of the supply of oxygen gas, polyphenylene ether was deposited to show a slurry form. The form of the polymerization solution at the end of the polymerization was precipitation polymerization.
Stop the ventilation of the oxygen-containing gas, add 12.0 g of 50% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) to the polymerization mixture, stir the polymerization mixture for 60 minutes, and then hydroquinone (Wako Pure Chemical Industries, Ltd.) And the stirring was continued until the slurry polyphenylene ether became white. The internal temperature of the reactor was controlled to 50 ° C. The slurry-like polyphenylene ether that became white was filtered, and the polyphenylene ether of the filtration residue was washed by sprinkling methanol and then held at 150 ° C. and 1 mmHg for 1.5 hours to obtain a dried polyphenylene ether powder.
The same operation as described above was repeated four times for polymerization, filtration, and drying to obtain about 6 kg of polyphenylene ether powder. This polyphenylene ether powder is defined as (a-10). The molecular weight was as follows as a result of GPC measurement.
Amount of components having a molecular weight of 50,000 or more: 6% by mass
Component amount of molecular weight 8,000 or less: 12% by mass

(A-11): The same as (a-10) except that 3167.7 g of xylene, 1583.8 g of n-butanol, and 1583.8 g of methanol were placed in the polymerization tank, and the polyphenylene ether powder was reduced to about 6 kg was obtained. This polyphenylene ether powder is defined as (a-11). The molecular weight was as follows as a result of GPC measurement.
Amount of components having a molecular weight of 50,000 or more: 24% by mass
Component amount of molecular weight 8,000 or less: 5% by mass

Component (b) Hydrogenated block copolymer (b-9): Hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene structure (B-A-B-A) and bound styrene content 42%, the number average molecular weight of the whole polymer 88,000, molecular weight distribution 1.06, number average molecular weight of polystyrene part (A) 19000, 1,2-vinyl bond content of polybutadiene before hydrogenation is 76%, polybutadiene part A hydrogenated block copolymer having a hydrogenation rate of 99.9% was synthesized, and this polymer was designated as (b-9).

(B-10): Polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene structure (ABAB) having a bound styrene content of 35% and a number average molecular weight of the whole polymer of 50, 000, molecular weight distribution 1.07, number average molecular weight 8800 of polystyrene part (A), 1,2-vinyl bond content of polybutadiene before hydrogenation is 74%, hydrogenation rate of polybutadiene part is 99.9% A block copolymer was synthesized, and this polymer was designated as (b-10).

(B-11): Polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene structure (ABAB), having a bound styrene content of 43%, a number average molecular weight of the whole polymer of 86, 000, molecular weight distribution 1.07, number average molecular weight 19000 of polystyrene part (A), 1,2-vinyl bond content of polybutadiene before hydrogenation is 36%, hydrogenation rate of polybutadiene part is 99.9% A block copolymer was synthesized, and this polymer was designated as (b-11).

(C) Component high crystalline polypropylene (c-6): Homo-polypropylene Melting point = 168 ° C., MFR = 0.6
(C-7): Homo-polypropylene Melting point = 167 ° C., MFR = 2.5
(C-8): Homo-polypropylene Melting point = 165 ° C., MFR = 75
(C-9): Homo-polypropylene Melting point = 164 ° C., MFR = 0.2

[ Reference Examples 15 to 27 and Comparative Examples 16 to 18]
Each component of polypropylene, polyphenylene ether, and hydrogenated block copolymer shown in Table 4 was set at a temperature of 270 to 320 ° C. and a screw rotation speed of 300 rpm, and the first raw material supply port and the second raw material supply port (of the extruder) Using a twin screw extruder (ZSK-40, manufactured by Coperion Co., Ltd.) having the composition of the first raw material supply port and the second raw material supply port of the extruder shown in Table 4. Melt kneading was performed to obtain pellets made of the resin composition.
Using this pellet, the polypropylene of (c-7) is set to a temperature of 150/250/250/250/250/250/250 ° C., set to a screw rotation speed of 150 rpm, and has a first raw material supply port. Using a twin screw extruder (PCM-30; Ikegai Machine Co., Ltd., Japan), the vent was open, the entire amount was fed to the first raw material feed port, and the polypropylene of (c-7) fed with pellets was (A) (b) (c) When the total resin component is 100% by mass, the amount of (c-7) component is adjusted so that (a) component is finally 30% by mass, Feeding, melt-kneading, and pellets were obtained. At that time, extrusion was continued for 30 minutes each, and the amount of mains generated at the die mouth was determined as the mains suppression amount according to the following criteria. The adjusted feed amount of (c-7) is shown in Table 4.
Evaluation of the resin composition was performed as follows.

<Meani suppression>
◯: There was no occurrence of any burrs for 30 minutes.
X: The occurrence of a bite in a little over 30 minutes.
In addition, about the reference example 22 , it implemented similarly to the reference example 18 except having used high impact polystyrene (the PS Japan company make, H9405) instead of the (c-7) component to dilute.

<Light resistance / tensile test>
Using this pellet, it is supplied to a screw in-line injection molding machine set at 240 to 280 ° C., and a test piece for tensile test under the condition of a mold temperature of 60 ° C. (external shape: full length × full width = 150 mm × 20 mm, test part: (Thickness × width × length = 4 mm × 10 mm × 80 mm) was injection molded. Using this test piece, an accelerated light resistance test was performed for 400 hours under the following conditions using an ATLAS xenon weatherometer. The test method was performed according to ASTM D4459.
Black panel temperature: 55 ° C., test chamber temperature: 45 ° C., relative humidity: 55%, irradiance (under 340 nm): 0.30 W / m ² , glass filter: inner Borosilicate / outer Soda Lim
The retention of tensile strength was calculated by the following formula, and light resistance was determined according to the following criteria.
(Tensile strength retention) (%) = (Tensile strength after irradiation for 400 hours) / (Tensile strength before irradiation) × 100
◯: Tensile strength retention ratio is 90% or more Δ: Tensile strength retention ratio is 80% or more and less than 90% X: Tensile strength retention ratio is less than 80% Measurement was performed according to ISO527.

<Presence or absence of delamination>
The constricted portion of the test piece for the tensile test was cut with pruning scissors, the fracture surface was visually observed, and judged according to the following criteria. (N number = 5)
○: No delamination was observed in all five samples.
Δ: 1 out of 5 layers was peeled off.
X: Two or more layers out of the five layers were peeled off.
From the above, it can be seen that using a hydrogenated block copolymer having a specific structure as an admixture as a pellet containing polyphenylene ether is important from the viewpoint of improving the performance of the final composition. Furthermore, it can be seen that the selection of polyphenylene ether having a specific structure can greatly improve the light resistance, delamination of the composition obtained, and suppression of sag during processing.
Table 4 shows the measurement results.

[ Reference Example 25 ]
Using the pellets of Reference Example 15 as a filler of (c-7) polypropylene and the component (f), talc (f-1) was added to 100% by mass of the components (a) to (c) and (f). The feed amount was adjusted so that the component (f) was 15% by mass and the component (a) was 30% by mass to obtain pellets. When evaluated in the same manner as described above, the light resistance was ◯, the suppression of the mean was: ◯, and the presence or absence of delamination was ◯.

[ Reference Example 26 ]
Using the pellets of Reference Example 17 , the amount of component (c-7) was dry blended so that the component (a) was finally 30% by mass, injection-molded in the same manner as in Reference Example 16, and then pulled. A test piece for testing was obtained. Light resistance: ○, presence or absence of delamination: ○.

[ Reference Example 27 ]
Using the pellets of Reference Example 17 , the amount of the component (c-7) was dry blended so that the component (a) was finally 30% by mass, and the cylinder temperature was set to 260 ° C. and the T die temperature was set to 260 ° C. Using a single-screw extruder with a vent with a screw diameter of 65 mm, the discharge amount is 60 kg / hr, the thickness of the T-die slit is 0.15 mm, the width of the die slit is 650 mm, the surface temperature of the rolling roller is 80 ° C., and the thickness is 50 μm. The take-off speed was controlled and extrusion film forming was performed. At the time of molding, no occurrence of a crack was observed at the interface between the T die and the molten resin for 30 minutes. Even when the film fracture surface was seen, there was no delamination at all and a film having a good appearance was obtained.

  The resin composition and molded product of the present invention have industrial applicability as automotive parts, heat-resistant parts, electronic device parts, industrial parts, and coating materials.

Claims (5)

(A) 1-20% by mass of polyphenylene ether,
(B) Hydrogenation obtained by hydrogenating a block copolymer comprising at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. 99 to 80% by mass of block copolymer,
A resin composition comprising:
The polyphenylene ether contains 5 to 20% by mass of a component having a molecular weight of 50,000 or more and 12 to 30% by mass of a component having a molecular weight of 8,000 or less, based on the whole polyphenylene ether,
The hydrogenated block copolymer has a number average molecular weight (Mnb) as a hydrogenated block copolymer of 100,000 or less, and the polymer block A has a number average molecular weight (MnbA) of 8,000 or more. A resin composition.   The resin composition according to claim 1, wherein the component (a) has a number average molecular weight (Mna) of 7,000 to 15,000.   The resin composition of Claim 1 or 2 whose content of the vinyl aromatic compound in the said (b) component is 15-50 mass% with respect to the whole (b) component.   In the bonding form of the conjugated diene compound in the polymer block B of the component (b), the total amount of the conjugated diene compound bonded by a 1,2-vinyl bond or a 3,4-vinyl bond is the above (b). The resin composition of any one of Claims 1-3 which is 30-90 mass% with respect to all the conjugated diene compounds of a component. The sheet | seat film or stretched sheet | seat film obtained by shape | molding the resin composition of any one of Claims 1-4.