JPH0912804A - Resin composition - Google Patents

Abstract

PURPOSE: To obtain a resin composition having an excellent heat resistance after a heat history by mixing a mixture comprising a PP resin and a polyphenylene ether in a specified ratio with a hydrogenated block copolymer having a specified structure. CONSTITUTION: A block copolymer composed of at least two polymer blocks A containing about 50wt.% or above aromatic vinyl compound (e.g. styrene) and at least two polymer blocks B containing a conjugated diene compound (e.g. butadiene) and having a 1,2-vinyl or 3,4-vinyl bond content of 65-80% is hydrogepated to obtain a hydrogenated block copolymer (e.g. PS/hydrogenated polybutadiene/PS/PS/hydrogenated polybutadiene) of a molecular weight of about 5,000-1,000,000. 1-30 pts.wt. obtained copolymer is added to 100 pts.wt. molten mixture comprising 30-90wt.% PP resin mixture having a highly crystalline PP/intermediately crystalline PP ratio of 90/10 to 10/90 by weight and 70-10wt.% polyphenylene ether (e.g. poly(2,6-dimethyl-1,4-poly-phenylene ether), and the resultant mixture is melt-kneaded to obtain a resin composition which can give a cured product of excellent durability.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention relates to oil resistance, which can be used in electric / electronic fields, automobile fields, and various other industrial material fields.
The present invention relates to a resin composition having excellent chemical resistance, heat resistance, impact resistance, rigidity, particularly toughness (elongation) after heat history and excellent durability as a heat resistant material.

[0002]

2. Description of the Related Art Polyphenylene ether has a mechanical property, an electrical property, a heat resistance, a low temperature property, a low water absorption property and excellent dimensional stability, but has a drawback that it is inferior in moldability and impact resistance. By blending with high-impact polystyrene, these problems are improved, and it is widely used as a resin composition for, for example, electric / electronic parts, office equipment housings, automobile parts, precision parts, and various industrial parts. However, the classical polyphenylene ether resin composition (US Pat. No. 3,383,435) consisting of this polyphenylene ether and high-impact polystyrene has the drawback of being poor in chemical resistance, although the impact resistance is improved. .

For this reason, for example, US Pat.
In the specification of Japanese Laid-Open Patent Publication No. 51, it has been proposed to blend polyphenylene ether with polyolefin to improve solvent resistance and impact resistance, and US Pat. No. 3,994,485.
No. 6 describes improvement in impact resistance and solvent resistance by blending polyphenylene ether or polyphenylene ether and styrene resin with a hydrogenated block copolymer, and US Pat. No. 4,145,377.
In the specification, a polyphenylene ether or a polyphenylene ether and a styrene resin are used as a polyolefin / hydrogenated block copolymer = 20 to 80 parts by weight / 80 to 2
There is a description on improvement of impact resistance and solvent resistance by blending with 0 parts by weight of a premixture and a hydrogenated block copolymer.

Further, US Pat. No. 4,166,055 and US Pat. No. 4,239,673 describe improving impact resistance by blending polyphenylene ether with hydrogenated block copolymers and polyolefins. U.S. Pat. No. 4,383,082 and EP-A-115712 describe that polyphenylene ether is blended with a polyolefin and a hydrogenated block copolymer to improve impact resistance.

Further, Japanese Patent Laid-Open No. 63-113058,
JP-A-63-225642, US Pat. No. 4,863.
Japanese Patent Application Laid-Open No. 997, JP-A-2-305814, JP-A-3-72512, JP-A-4-183748 and JP-A-5-320471 disclose resin compositions comprising a polyolefin resin and a polyphenylene ether resin. A resin composition has been proposed in which a specific hydrogenated block copolymer is blended for modification and which is excellent in chemical resistance and processability.

[0006] The applicant of the present invention is also disclosed in JP-A-62-2055.
1, JP-A-62-25149, JP-A-62-62
-48757, JP-A-62-48758,
JP-A-62-199637 and US Pat. No. 47.
No. 72,256 proposes a rubber composition comprising a polyphenylene ether, a polyolefin and a hydrogenated block copolymer, which is excellent in rubber elasticity.
No. 3, JP-A-3-185058, JP-A-5-205
70679, JP-A-5-295184, JP-A-6-9828, JP-A-6-16924, JP-A-6-57130 and JP-A-6-13
In JP 6202, a resin composition comprising polyphenylene ether, polyolefin and a specific hydrogenated block copolymer, which is excellent in compatibility, rigidity and heat resistance, and solvent resistance is proposed.

[0007]

These prior arts are:
Compared with the classical polyphenylene ether resin composition, it provides a resin composition having dramatically improved solvent resistance and an elastomer composition having excellent heat resistance. Such inventive step of the prior art certainly brings about a great improvement in terms of compatibility (whether or not the composition is delaminated when the both components are mixed) when mixing the polyolefin resin and the polyphenylene ether. However, it has been revealed that they do not necessarily have sufficient compatibility when used in complicated molding processes accompanying recent advances in molding technology.

That is, in the resin composition obtained by the above-mentioned conventional technique, the orientation of the disperse phase is extremely observed at the time of injection molding, and in the case of various molded articles, the proof stress against external pressure and internal pressure is lowered and the orientation direction is changed. At present, the delamination phenomenon is observed along the line. However, a resin composition in which a polyphenylene ether added for heat resistance imparting a polypropylene component as a matrix forms a dispersed phase, and although having these problems, a marked improvement in heat resistance is achieved as compared with a single polypropylene resin. It is one of the attractive industrial materials.

For this reason, polypropylene-polyphenylene ether-based polymer alloys having improved heat resistance have a potential for delamination, but substantially improved heat resistance has been proposed, and therefore various improvements have been proposed. Above all, since the rigidity of the resin composition obtained is affected by the admixture used, a high crystalline polypropylene tends to be used in recent years as the polypropylene constituting the matrix.

However, the polypropylene-polyphenylene ether-based polymer alloy using this high crystalline polypropylene has a reduced toughness (especially a reduced elongation) after thermal history.
However, the current situation is that they have practical defects such as poor durability as a heat resistant material.

[0011]

In view of such a situation, the present inventors have made a composition containing polypropylene and polyphenylene ether have a high level of compatibility, heat resistance, rigidity and thermal history. In order to impart the toughness (especially elongation) of the polymer, a result of extensive studies on a hydrogenated block copolymer that can be an admixture and a polypropylene resin that can be a matrix material. As a result, a hydrogenated block copolymer having a specific structure is a polypropylene. And a polyphenylene ether as an admixture of a composition containing less dispersed phase orientation at the time of injection molding, and resulting in a resin composition with improved delamination. In addition to that, the polypropylene resin used has different properties By controlling the two types of polypropylene resins within a specific range, polypropylene and Heat resistance of the composition containing the ether, and completed the present invention found that improved toughness after rigidity and thermal history (especially elongation) results in a resin composition which is excellent in durability as a heat resistant material.

That is, the present invention is based on 100 parts by weight of (a) 30 to 90% by weight of polypropylene resin, (b) 70 to 10% by weight of polyphenylene ether, and (a) and (b) above. And (c) a polymer block A mainly composed of at least two vinyl aromatic compounds
And a polymer block B mainly composed of at least two conjugated diene compounds having a 1,2-vinyl bond content or a 3,4-vinyl bond content of the conjugated diene compound of 65% to 80%. The present invention provides a resin composition comprising 1 to 30 parts by weight of a hydrogenated block copolymer obtained by hydrogenating a block copolymer having at least one polymer block B.

The polypropylene resin used as the component (a) in the present invention is a crystalline propylene homopolymer and a crystalline propylene homopolymer portion obtained in the first step of polymerization and propylene, ethylene and And / or a crystalline propylene-ethylene block copolymer having a propylene-ethylene random copolymer moiety obtained by copolymerizing at least one other α-olefin (eg, butene-1, hexene-1 etc.). Further, it may be a mixture of these crystalline propylene homopolymers and crystalline propylene-ethylene block copolymers.

The polypropylene resin is usually used in the presence of a titanium trichloride catalyst or a titanium halide catalyst supported on a carrier such as magnesium chloride and an alkylaluminum compound at a polymerization temperature of 0 to 100 ° C. It is obtained by polymerizing in the range of 3 to 100 atm. On this occasion,
It is also possible to add a chain transfer agent such as hydrogen to adjust the molecular weight of the polymer, and the polymerization method can be a batch method or a continuous method, butane, pentane, hexane, heptane, octane, etc. A method such as solution polymerization in a solvent, slurry polymerization or the like can also be selected, and further, a bulk polymerization in a monomer without a solvent, a gas phase polymerization method in a gaseous monomer or the like can be applied.

In addition to the above-mentioned polymerization catalyst, an electron donating compound can be used as an internal donor component or an external donor component as the third component in order to increase the isotacticity and the polymerization activity of the polypropylene obtained. As these electron donating compounds, known compounds can be used, for example, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate, and methyl toluate; and triphenyl phosphite and tributyl phosphite. Phosphoric acid derivatives such as phosphoric acid esters and hexamethylphosphoric triamide, 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 used in the present invention can be used alone as long as it has the crystallinity and melting point as long as it can be obtained by the above method. When durability is required due to history, it is optimal to use a polypropylene resin in which two polypropylene resins having different properties are blended in a specific range.

That is, in the present invention, (a-1) homo-determined from free induction decay (FID) by pulse NMR.
The proportion of the crystalline phase in the polypropylene portion is 96% or more and the melting point is 163 ° C. or more, and the high crystalline polypropylene resin and (a-2) the homo-polypropylene portion obtained by free induction decay (FID) by pulse NMR. The proportion of crystalline phase is 93 to less than 96% and the melting point is 155 to 1
A polypropylene resin in which a medium crystal polypropylene resin having a temperature of less than 63 ° C. is blended in a specific range is more preferably used. (Hereinafter, (a-1) is a highly crystalline polypropylene,
(A-2) is a medium crystalline polypropylene, and these blends are abbreviated as polypropylene resins).

The proportion of the crystal phase of the homo-polypropylene portion in the present invention is determined by the well-known pulse NMR method by utilizing the different motility of the crystalline portion and the amorphous portion, and the magnetization change after the 90-degree pulse based on the spin-spin relaxation. It can be determined from some free induction damping (FID). Specifically, solid-state polypropylene is converted to pulsed NMR (Bruker).
PC-120) manufactured by K.K. at a temperature of 40 ° C., a proton resonance frequency of 20 MHZ, a pulse time of 4 μsec, and an integration of 3 times. Attributing, the crystalline phase was regressed with a Gaussian curve, the amorphous part was regressed with a Lorentzian curve, and the respective peak heights were set to SA1 and SA2, and R ₁₂ = {100 ×
(SA1-SA2) × F｝ ÷ ｛(SA1-SA2) × F
The ratio of the crystal phase can be calculated from + SA2}. Here, R ₁₂ is the ratio of the measured crystalline phase of the homo-polypropylene portion, and F is the correction coefficient obtained from the strength ratio when using salad oil and polymethyl methacrylate of the standard sample.

The composition containing polypropylene having a crystal phase ratio of less than 93% gives a resin composition excellent in toughness (elongation) after heat history, but has low rigidity and poor heat resistance. Further, a resin composition containing polypropylene having a crystal phase ratio of 96% or more has high rigidity and good heat resistance, but the toughness (elongation) after thermal history is extremely deteriorated and the durability as a heat resistant material is lowered. Not preferable.

The melting point of the homo-polypropylene portion in the present invention is measured with a differential scanning calorimeter (DSC: Perkin Elmer DSC-2 type) at a heating rate of 20 ° C./min and a cooling rate of 20 ° C./min. Is the value of.
More specifically, first, about 5 mg of the sample was stored at 20 ° C. for 2 hours.
After holding the temperature for 20 minutes, the temperature was raised to 230 ° C at 20 ° C / min and kept at 230 ° C for 2 minutes, then the temperature was lowered to 20 ° C at 20 ° C / min and further 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 20 ° C./min can be obtained as the melting point.

When polypropylene having a melting point of less than 155 ° C. is used, the obtained resin composition is excellent in toughness (elongation) after heat history, but the rigidity and heat resistance are remarkably poor, which is not preferable. Further, polypropylene having a melting point of 163 ° C. or higher gives a resin composition having excellent rigidity and heat resistance after heat history, but the toughness (elongation) after heat history remarkably deteriorates and durability as a heat resistant material decreases, which is preferable. Absent.

The polypropylene-based resin used in the present invention contains, in addition to the above-mentioned polypropylene-based resin, the polyolefin-based resin and α, β-unsaturated carboxylic acid or its derivative in the absence of a radical generator. Known modification (0.01 to 10% by weight of the α, β-unsaturated carboxylic acid or its derivative is grafted or added) obtained by reacting in a molten state or a solution state at a temperature of 30 to 350 ° C. It may be a polypropylene resin, or may be a mixture of the above-mentioned polypropylene resin and the modified polypropylene resin in an arbitrary ratio.

Next, the component (b), polyphenylene ether (hereinafter abbreviated as PPE) used in the present invention, is an essential component for imparting heat resistance and flame retardancy to the polymer composition of the present invention. The PPE is a bonding unit represented by the following general formula (Formula 1).

[0024]

Embedded image

(Where R ₁ , R ₂ , R ₃ , and R ₄
Are hydrogen, halogen, a primary or secondary lower alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, or at least two carbon atoms each being a halogen atom. Selected from the group consisting of halohydrocarbonoxy groups separating an oxygen atom, which may be the same or different.
A homopolymer having a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) of 0.15 to 0.70, more preferably 0.20 to 0.60. Alternatively, it is a copolymer.

Specific examples of this PPE include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly ( 2-methyl-6-phenyl-
1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), and the like, and further 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethyl). Also included are polyphenylene ether copolymers such as copolymers with phenol and 2-methyl-6-butylphenol). Especially poly (2,6-dimethyl-1,4-phenylene ether),
A copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable, and poly (2,6-diphenylphenol)
6-dimethyl-1,4-phenylene ether) is preferred.

The method for producing PPE is not particularly limited as long as it can be obtained by a known method, and for example, a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 is used as a catalyst. , And can be easily produced by oxidative polymerization of 2,6-xylenol, for example, and US Pat. No. 3,306,873
No. 5, No. 3257357 and No. 3257358.
Each specification, JP-B-52-17880, JP-A-5
0-51197 and JP-A-63-152628.
It can be easily manufactured by the method described in Japanese Patent Publication.

The PPE used in the present invention contains, in addition to the above-mentioned PPE, the PPE and a styrene-based monomer and / or an α, β-unsaturated carboxylic acid or a derivative thereof in the absence of a radical generator. A known modification (the styrene-based monomer and / or the α, β-unsaturated carboxylic acid or its derivative is obtained by reacting in a molten state, a solution state, or a slurry state at a temperature of 80 to 350 ° C.). (01 to 10 wt% graft or addition) PPE, or a mixture of the above PPE and the modified PPE in any proportion.

Further, phosphorus compound-treated PPE prepared by adding 0.2 to 5 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene to 100 parts by weight of PPE and melt-kneading was also excellent in color tone and fluidity. It can be used as a PPE. As the PPE used in the present invention, in addition to the above PPE, polystyrene or high-impact polystyrene added to 100 parts by weight of these PPE in an amount not exceeding 400 parts by weight can be preferably used.

Next, the hydrogenated product of the vinyl aromatic compound-conjugated diene compound (hereinafter abbreviated as hydrogenated block copolymer) used as the component (c) in the present invention is the polypropylene resin as the component (a). It is a hydrogenated block copolymer having an ability to suitably finely disperse the polyphenylene ether of the component (b) in the polypropylene resin of the component (a) when the polyphenylene ether of the component (b) is melt-mixed.

That is, in the present invention, a polymer block A mainly containing at least two vinyl aromatic compounds,
1,2-vinyl bond or 3,4 of conjugated diene compound
-A block copolymer comprising a polymer block B mainly composed of at least two conjugated diene compounds having a vinyl bond content of 65% to 80%, and at least one of the polymer chain ends is the polymer block B. It is a hydrogenated block copolymer obtained by hydrogenation. This vinyl bond amount is 6
If it is less than 5%, the miscibility of the polypropylene resin and the polyphenylene ether decreases, and the impact resistance and toughness (elongation)
Unfavorably deteriorates. Further, when the vinyl bond amount exceeds 80%, the miscibility of the polypropylene resin and the polyphenylene ether is not significantly improved. These vinyl bond amounts can usually be known by an infrared spectrophotometer or NMR.

Further, when a hydrogenated block copolymer consisting of a polymer block containing one vinyl aromatic compound as a main component and / or a polymer block containing one conjugated diene compound as a main component is used, a polypropylene-based copolymer is used. Although it has excellent miscibility when the resin and polyphenylene ether are melt-kneaded, rigidity, heat resistance, impact resistance, and toughness (elongation) are deteriorated, which is not preferable. Further, by making at least one of the polymer chain terminals of the hydrogenated block copolymer a block copolymer composed of the polymer block B, the miscibility of the polypropylene resin and the polyphenylene ether is improved more efficiently and the heat resistance is improved. A resin composition having excellent rigidity can be obtained.

The hydrogenated block copolymer as the component (C) contains 30 to 95% by weight, preferably 3% by weight, of the vinyl aromatic compound bonded to the block copolymer before hydrogenation.
5 to 70% by weight, more preferably 35 to 45% by weight, and referring to the block structure, 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. A polymer having a structure of a copolymer block of a vinyl aromatic compound and a conjugated diene compound containing a group compound in an amount of more than 50% by weight, preferably 70% by weight or more, and further comprising a conjugated diene compound as a main component The block is a homopolymer block of a conjugated diene compound or a conjugated diene compound 50
It has a structure of a copolymer block of a conjugated diene compound and a vinyl aromatic compound which is contained in an amount of more than 70% by weight and preferably 70% by weight or more.

Further, the polymer block A mainly containing these vinyl aromatic compounds and the polymer block B mainly containing these conjugated diene compounds are the conjugated diene compound or vinyl aromatic compound in the molecular chain of each polymer block. The distribution of the compound may be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-like or any combination thereof, and the polymer block mainly containing the vinyl aromatic compound and Each of the polymer blocks mainly containing the conjugated diene compound is 2
Each polymer block may have the same structure or different structures.

The vinyl aromatic compound constituting this block copolymer is, for example, one or more of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene and the like. It can be selected, and styrene is particularly preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethyl-1,3.
One or more selected from butadiene and the like, with butadiene, isoprene and combinations thereof being particularly preferred.

The number average molecular weight of the block copolymer having the above structure is in the range of 5,000 to 1,000,000, preferably 10,000 to 800,000, and more preferably 30,000 to 500,000. And the molecular weight distribution [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography] is 10 or less. Further, the molecular structure of this block copolymer may be linear, branched, radial, or any combination thereof.

The block copolymer having such a structure is a hydrogenated block copolymer obtained by hydrogenating the aliphatic double bond of the polymer block B mainly composed of the conjugated diene compound of the above block copolymer. (Vinyl aromatic compound-conjugated diene compound block copolymer hydrogenated product) can be used as the component (c) of the present invention. The hydrogenation rate of such an aliphatic double bond is at least over 80%, preferably at least 95%. This hydrogenation rate can usually be known by an infrared spectrophotometer or NMR.

The hydrogenated block copolymer as the component (c) may be obtained by any production method as long as it has the above-mentioned structure. Known manufacturing methods include, for example, JP-A-47-11486, JP-A-49-66743, and JP-A-50-75.
651, JP-A-54-126255, JP-A-56-10542, JP-A-56-62847, JP-A-56-100840, British Patent No. 1
130770, U.S. Pat. Nos. 3,281,383 and 3639517, and British Patent No. 1020720, U.S. Pat. Nos. 3,333,024 and 4,501,857.

The hydrogenated block copolymer of the component (c) used in the present invention is, in addition to the above-mentioned hydrogenated block copolymer, the hydrogenated block copolymer and an α, β-unsaturated carboxylic acid. Or a derivative thereof in the presence or absence of a radical generator in a molten state, a solution state, or a slurry state at 80 to 3
Known modified hydrogenated block copolymers obtained by reacting at a temperature of 50 ° C. (the α, β-unsaturated carboxylic acid or its derivative is grafted or added in an amount of 0.01 to 10% by weight) Further, a mixture of the above-mentioned hydrogenated block copolymer and the modified hydrogenated block copolymer in any ratio may be used.

The resin composition of the present invention comprises the above-mentioned (a) to
The component (c) is used as a basic component. When the polypropylene resin as the component (a) is a combination of high crystal polypropylene and medium crystal polypropylene, the ratio of high crystal polypropylene / medium crystal polypropylene is 95 each.
/ 5 to 10/90 (weight ratio), preferably 90/10 to
50/50, more preferably 90/10 to 70/30
Used in the ratio of. In such a ratio, when the high crystalline polypropylene exceeds 95%, the heat resistance (80 ° C x 4
It is not preferable because the toughness (elongation) after 8 hours is significantly deteriorated and the durability as a heat resistant material is deteriorated. On the other hand, when the content of the medium crystalline polypropylene exceeds 90%, the toughness (elongation) of the resulting resin composition after the heat history (80 ° C. × 48 hours) is not significantly decreased, but the heat resistance and the rigidity are decreased, which is not preferable. .

The compounding amount of the polypropylene resin as the component (a) of the present invention is 30 to 90% by weight, preferably 45 to 65% by weight, and the high crystalline polypropylene and the medium crystalline polypropylene are within the above specified range. Even when it contains, the total amount is 30 to 90% by weight, preferably 45 to 65% by weight. If the blending amount is less than 30% by weight, the heat resistance of the obtained resin composition is excellent, but the moldability and solvent resistance are poor, which is not preferable. If it exceeds 90% by weight, the moldability and solvent resistance are good, but the heat resistance is poor and the material cannot be used as a heat resistant material.

The content of the polyphenylene ether as the component (b) is 70 to 10% by weight, preferably 55 to 35% by weight.
It is. When the blending amount exceeds 70% by weight, the heat resistance of the obtained resin composition is extremely excellent, but the molding processability,
Solvent resistance is inferior, which is not preferable. If it is less than 10% by weight, the moldability and solvent resistance are excellent, but the heat resistance is poor and it cannot be used as a heat resistant material.

The amount of the high vinyl hydrogenated block copolymer as the component (c) is 1 to 30 parts by weight based on 100 parts by weight of the total of the components (a) and (b). If the compounding amount is less than 1 part by weight, the effect as an admixture is not observed and it is not preferable. If the amount exceeds 30 parts by weight, (a), (b)
The heat and solvent resistance, the rigidity and the mechanical strength of the components are remarkably lowered, which is not preferable.

In the present invention, in addition to the above-mentioned components, if necessary, other additional components such as a styrene-butadiene block copolymer having a bound styrene content of 10 to 90% are used as long as the characteristics and effects of the present invention are not impaired. Polymer, bound styrene content 1
0-90% of styrene-isoprene block copolymers and hydrogenated block copolymers obtained by hydrogenating 80% or more of aliphatic double bonds resulting from conjugated diene compounds of these block copolymers, antioxidants, Metal deactivators, flame retardants (organic phosphate compounds, inorganic phosphorus compounds,
Aromatic halogen flame retardants, silicone flame retardants, etc.),
Fluorine-based polymers, plasticizers (oil, low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retardant aids such as antimony trioxide,
Weather (light) resistance improver, nucleating agent for polyolefin, slip agent, inorganic or organic filler or reinforcing material (glass fiber,
Carbon fiber, polyacrylonitrile fiber, whiskers, mica, talc, carbon black, titanium oxide,
Calcium carbonate, potassium titanate, wollastonite,
Conductive metal fibers, conductive carbon black, etc.), various coloring agents, release agents, etc. may be added.

The resin composition of the present invention is a method in which the components (b) and (c) are melt-kneaded in advance using the above-mentioned components, and then the mixture is melt-kneaded together with the component (a).
A method in which a part of the component (c) is pre-kneaded with the components (a) and (b) in advance, and these pre-kneaded products are melt-kneaded together again, and the components (b) and ( It can be produced by various methods such as a method in which the component (c) is supplied and the component (a) is supplied to the composition in a molten state from the intermediate port of the extruder and melt-kneaded. These methods include, for example, a single-screw extruder, a twin-screw extruder, a roll, a kneader, a Brabender plastograph, a heating melt-kneading method using a Banbury mixer, and the like, and particularly a melt-kneading method using a twin-screw extruder. Most preferred. The melt-kneading temperature at this time is not particularly limited, but can be arbitrarily selected from the range of usually 200 to 350 ° C.

The resin composition of the present invention thus obtained is subjected to various conventionally known methods such as injection molding,
It can be molded as a molded body of various parts by extrusion molding or hollow molding. These various parts include, for example, automobile parts.Specifically, exterior parts such as bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, various aero parts, etc. Suitable for interior parts such as instrument panel, console box, trim etc. Further, it can be suitably used as an interior / exterior component of electric equipment, and is specifically suitable for various computer and its peripheral equipment, other office automation equipment, cabinets such as televisions, videos, various disc players, and parts such as refrigerators. There is.

[0047]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting.

Reference Example 1: Preparation of highly crystalline polypropylene of component (a-1) PP-1: homo-polypropylene Proportion of crystalline phase in homo-polypropylene portion = 97.3% Melting point = 169 ° C., MFR = 15.4 MFR (melt flow rate) of polypropylene is AS
Based on TM D1238, it measured at 230 degreeC and the load of 2.16 kg.

Reference Example 2: Preparation of medium crystalline polypropylene of component (a-2) PP-2: homo-polypropylene Ratio of crystalline phase of homo-polypropylene portion = 93.5% Melting point = 160 ° C., MFR = 0.5 MFR (melt flow rate) of polypropylene is AS
Based on TM D1238, it measured at 230 degreeC and the load of 2.16 kg.

Reference Example 3: Preparation of PPE as component (b) Polyphenylene ether b-2: 2,6-xylenol having a reduced viscosity of 0.54 obtained by oxidative polymerization of b-1: 2,6-xylenol. Polyphenylene ether having a reduced viscosity of 0.31 obtained by oxidative polymerization

Reference Example 4: Preparation of Hydrogenated Block Copolymer of Component (c) Having a structure of polystyrene-hydrogenated polybutadiene, bound styrene content 44%, number average molecular weight 137,0.
00, molecular weight distribution 1.08, 1,2-vinyl bond amount of polybutadiene before hydrogenation is 73%, hydrogenation rate of polybutadiene part is 99.9% to synthesize a hydrogenated block copolymer, (C-1).

Similarly, it has a structure of polystyrene-hydrogenated polybutadiene-polystyrene and has a bound styrene content of 42%, a number average molecular weight of 119,000, a molecular weight distribution of 1.06, and a polybutadiene of 1,2- The vinyl bond content is 74%, and the hydrogenation rate of the polybutadiene part is 9
A 9.9% hydrogenated block copolymer was synthesized, and this polymer was designated as (c-2).

Similarly, having a structure of polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene, the bound styrene content is 43%, the number average molecular weight is 133,000, the molecular weight distribution is 1.10, and the polybutadiene before hydrogenation is The hydrogenated block copolymer having a 1,2-vinyl bond content of 57% and a hydrogenation rate of the polybutadiene portion of 99.9% was synthesized, and this polymer was designated as (c-3).

Similarly, it has a structure of polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene, with a bound styrene content of 42%, a number average molecular weight of 122,000, a molecular weight distribution of 1.05, and before hydrogenation. A hydrogenated block copolymer having a 1,2-vinyl bond content of polybutadiene of 74% and a hydrogenation rate of the polybutadiene portion of 99.9% was synthesized, and this polymer was designated as (c-4).

Similarly, having the structure of hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene,
Bound styrene amount 44%, number average molecular weight 135,000,
A hydrogenated block copolymer having a molecular weight distribution of 1.08, a 1,2-vinyl bond content of polybutadiene before hydrogenation of 73%, and a hydrogenation rate of the polybutadiene portion of 99.9% was synthesized. -5).

Examples 1 to 3 and Comparative Examples 1 to 6 High crystal polypropylene, medium crystal polypropylene, polyphenylene ether and an admixture were blended in the composition shown in Table 1, and the biaxial shaft with a vent port was set to 260 to 280 ° C. Extruder (ZSK-25; WERNER & PFLEIDE
Melted and kneaded by using RER (Germany) to obtain pellets. The pellets are supplied to a screw in-line type injection molding machine set at 240 to 280 ° C, and a tensile test piece, a bending elastic modulus measurement test piece, and an Izod impact test test are performed at a mold temperature of 60 ° C. A piece and a test piece for measuring heat distortion temperature were injection molded.

A tensile strength test (ASTM D-638: 23 ° C.) was carried out using these test pieces to measure tensile strength and elongation at break, and further flexural modulus (AST
MD-790: 23 ° C), Izod (notched) impact strength (ASTM D-256: 23 ° C) and heat distortion temperature (ASTM D-648) were measured. Also, some of these test pieces assume a predicted thermal history,
A tensile strength test (ASTM D) was performed in the same manner after passing through a heat history environment (80 ° C x 48 hours) using a gear oven.
-638: 23 ° C) to measure tensile strength and elongation at break, and further flexural modulus (ASTM D-790:
23 ° C, Izod (notched) impact strength (AST
MD-256: 23 ° C) and heat distortion temperature (ASTM
D-648: 18.6 Kg / cm2 load) was measured. The results are also shown in Table 1.

From these results, the polymer block A mainly composed of at least two vinyl aromatic compounds and the 1,2-vinyl bond or 3,4-vinyl bond amount of the conjugated diene compound were 65% to 80%. By using a hydrogenated block copolymer composed of at least two conjugated diene compounds as a main component and a polymer block B in which at least one of the polymer chain ends is the polymer block B, Since the miscibility with polyphenylene ether is improved, a resin composition having excellent impact resistance, toughness (elongation), heat resistance, and rigidity can be obtained.

Further, the resin composition containing only high crystalline polypropylene and medium crystalline polypropylene is inferior in the physical property balance of heat resistance, rigidity and toughness (elongation) after thermal history. On the other hand, the resin composition of the present invention contains the high crystalline polypropylene and the medium crystalline polypropylene specified in the present invention in a specific range, so that the heat resistance after thermal history, the physical property balance of rigidity and toughness is maintained at a high level. To be done.

[0060]

[Table 1]

[0061]

The resin composition of the present invention comprises a polypropylene resin, polyphenylene ether and an admixture, and controls the amount of vinyl bond within a specific range as the admixture.
By using a hydrogenated block copolymer having a further specified structure, delamination phenomenon and oil resistance of a resin composition containing a polypropylene resin and polyphenylene ether, which was difficult in the prior art and oil resistance, chemical resistance, heat resistance, A resin composition having excellent impact resistance and toughness (elongation), improved toughness after heat history, and excellent in durability as a heat resistant material was obtained.

[Procedure amendment]

[Submission date] August 2, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction contents]

[0060]

[Table 1]

Claims (1)

[Claims] 1. A resin composition comprising 30 to 90% by weight of (a) a polypropylene resin, 70 to 10% by weight of (b) polyphenylene ether, and 100 parts by weight of the above components (a) and (b). On the other hand, (c) a polymer block A mainly composed of at least two vinyl aromatic compounds
And a polymer block B mainly composed of at least two conjugated diene compounds having a 1,2-vinyl bond content or a 3,4-vinyl bond content of the conjugated diene compound of 65% to 80%. A resin composition comprising 1 to 30 parts by weight of a hydrogenated block copolymer obtained by hydrogenating a block copolymer at least one of which is a polymer block B.