JPH1143561A - Resin composition with suppressed morphology change and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition essentially comprising a polypropylene- based resin and a polyphenylene ether-based resin, and suppressed in deformation and morphology change in its molding processing. SOLUTION: This composition is obtained by compounding a total of 100 pts.wt. of (a) 45-95 wt.% of a polypropylene-based resin and (b) 55-5 wt.% of a polyphenylene ether-based resin with (c) 1-30 pts.wt. of a hydrogenated block copolymer having a specific structure and (d) 1-30 pts.wt. of a polymer made from a conjugated diene compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition comprising a polypropylene resin and a polyphenylene ether resin. More specifically, the present invention relates to a resin composition which can be suitably used as a molding material for various molded articles and has a suppressed morphological change, and a method for producing the same.

[0002]

2. Description of the Related Art Many attempts have been made to improve solvent resistance, heat resistance and impact resistance by blending polyphenylene ether with polyolefin. For example, US Pat. No. 3,361,851 discloses polyphenylene ether. Proposals have been made to improve solvent resistance and impact resistance by blending ether with polyolefin.
U.S. Pat. No. 3,994,856 describes improvement of impact resistance and solvent resistance by blending polyphenylene ether or polyphenylene ether and a styrene resin with a hydrogenated block copolymer. In the specification, polyphenylene ether or polyphenylene ether and a styrene resin are mixed with a polyolefin / hydrogenated block copolymer = 20.
A description is given of improvement in impact resistance and solvent resistance by blending with a pre-mixture of from 80 to 80 parts by weight / 80 to 20 parts by weight and a hydrogenated block copolymer, and further describes in US Pat. No. 4,166,055 and US Pat. Patent No. 42
39673 describes an improvement in impact resistance by blending a polyphenylene ether with a hydrogenated block copolymer and a polyolefin. In U.S. Pat. No. 4,383,082 and EP-A-115,712, it is described that polyphenylene ether is blended with polyolefin and hydrogenated block copolymer to improve impact resistance.

[0003] Also, JP-A-63-113050,
JP-A-63-113058 and JP-A-63-2
No. 25642, U.S. Pat. No. 4,863,997, JP-A-2-247240, JP-A-2-248847, and JP-A-2-3058.
No. 14, JP-A-3-72512, JP-A-4-183748, and JP-A-5-3204.
No. 71 and JP-A-7-165998,
A resin composition having excellent compatibility, chemical resistance, and processability by mixing a specific hydrogenated block copolymer for modifying a resin composition comprising a polyolefin resin and a polyphenylene ether resin has been proposed.

[0004]

A resin composition in which polyphenylene ether and polyolefin are blended has provided a resin composition having dramatically improved solvent resistance.

However, when a molding machine provided with a hot runner is used, or when a resin is retained in the molding machine, the morphology changes, and the morphology of a large molded product or an ultra-thin molded part causes deformation of the morphology. This can be a major factor in lowering the properties of the material. Therefore,
It has been an issue to provide a resin composition in which the morphological change is suppressed.

[0006]

SUMMARY OF THE INVENTION In view of such circumstances, the inventors of the present invention have proposed a hydrogenated block copolymer which can be an admixture and a polyphenylene which can be a dispersed phase in order to impart excellent morphological stability during molding. As a result of intensive studies on the structure of the ether-based resin and further on the production method of the resin composition, a resin comprising a hydrogenated block copolymer having a specific structure and a polymer composed of a conjugated diene compound was produced under a specific production method. It has been found that by emulsifying and kneading the composition, the emulsifying and dispersing properties are improved, and furthermore, by controlling the structure of the dispersed phase component, an excellent resin composition is obtained in which the morphological change and deformation during molding are suppressed.

That is, the present invention relates to (1) 45 to 95% by weight of a polypropylene resin (a), 55 to 5% by weight of a polyphenylene ether resin (b), and a total of 100% of the above components (a) and (b). For parts by weight,
(C) at least one polymer block A mainly composed of a vinyl aromatic compound and a conjugated diene compound having a vinyl bond amount (total amount of 1,2- and 3,4-vinyl bond amounts) of 45% or more; A hydrogenated block copolymer comprising at least one polymer block B mainly comprising a conjugated diene compound, wherein the hydrogenated block copolymer has an iodine value of 40 or less. 30 parts by weight (d) A polymer composition comprising a conjugated diene compound in an amount of 1 to 30 parts by weight, and a resin composition in which morphological change is suppressed, and (2) (a) 0 to 30 parts by weight of a polypropylene resin %, (B) 55 to 5% by weight of the polyphenylene ether-based resin and 100 parts by weight of the total of the components (a) and (b) (including the component (a) below)
(A) a polypropylene resin is added to a melt-kneaded product of (c) 0 to 30 parts by weight of a hydrogenated block copolymer and (d) 1 to 30 parts by weight of a polymer comprising a conjugated diene compound; 15 to 95% by weight corresponding to the balance of 95% by weight and (c) the hydrogenated block copolymer in its total amount of 1 to
A method for producing a resin composition according to the above (1), wherein 0 to 30 parts by weight corresponding to the remaining 30 parts by weight is added, and the mixture is further melt-kneaded.

Hereinafter, the present invention will be described in detail. The (a) polypropylene-based resin used in the present invention comprises a crystalline propylene homopolymer and a crystalline propylene homopolymer portion obtained in the first step of polymerization and propylene, ethylene and / or at least one of A crystalline propylene-ethylene block copolymer having a propylene-ethylene random copolymer portion obtained by copolymerizing other α-olefins (eg, butene-1, hexene-1 and the like); It may be a mixture of a propylene homopolymer and a crystalline propylene-ethylene block copolymer.

[0009] Such a polypropylene-based resin is usually subjected to polymerization at a polymerization temperature of 0 to 100 ° C in the presence of an alkylaluminum compound and a titanium halide catalyst or the like supported on a carrier such as titanium trichloride catalyst or magnesium chloride. It is obtained by polymerization in the range of 3 to 100 atm. At this time, it is also possible to add a chain transfer agent such as hydrogen to adjust the molecular weight of the polymer, and it is also possible to use a batch method or a continuous method as a polymerization method, butane, pentane, hexane, heptane A method such as solution polymerization or slurry polymerization in a solvent such as octane or octane can also be selected, and a bulk polymerization in a monomer without a solvent, a gas phase polymerization in a gaseous monomer, and the like can be applied.

Furthermore, in order to increase the isotacticity and polymerization activity of the polypropylene obtained 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 a third component. .

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. Such as phosphites, phosphoric acid derivatives such as hexamethylphosphoric triamide, alkoxyester compounds, aromatic monocarboxylic acid esters and / or aromatic alkylalkoxysilanes, aliphatic hydrocarbonalkoxysilanes, and various ether compounds And various alcohols and / or various phenols.

As the polypropylene resin used in the present invention, any resin having any crystallinity, melting point and molecular weight can be used as long as it can be obtained by the above-mentioned method. Can also be used in combination. Next, the polyphenylene ether-based resin (b) used in the present invention is a polyphenylene ether having the following structure. Polyphenylene ether is a compound known per se. Binding unit:

[0013]

Embedded image

(Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each 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 a group selected from the group consisting of a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom, which may be the same or different from each other ), Reduced viscosity (0.5 g / dl, chloroform solution,
(Measured at 30 ° C.) is in the range of 0.15 to 2.50, preferably 0.30 to 2.00, more preferably 0.35 to 2.
Homopolymers and / or copolymers in the range of 00.

Specific examples of the polyphenylene ether include, for example, poly (2,6-dimethyl-1,4-phenylene ether) and 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. Further, 2,6-dimethylphenol and other phenols (for example, 2,3 Polyphenylene ether copolymers such as copolymers with 6-trimethylphenol and 2-methyl-6-butylphenol) are also included. Among them, poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3
A copolymer with 6-trimethylphenol is preferred, and poly (2,6-dimethyl-1,4-phenylene ether) is more preferred.

The method for producing the polyphenylene ether is not particularly limited as long as it can be obtained by a known method. For example, a complex of a cuprous salt and an amine by Hay described in US Pat. It can be easily produced by oxidative polymerization of 2,6-xylenol, for example, as a catalyst. In addition, U.S. Pat. Nos. 3,306,875 and 3,257,357.
No. 3,257,358, Japanese Patent Publication No. Sho 5
It can be easily produced by the methods described in JP-A-2-17880, JP-A-50-51197 and JP-A-63-152628.

The polyphenylene ether resin used in the present invention, in addition to the above-mentioned polyphenylene ether, exceeds 400 parts by weight of polystyrene (including syndiotactic polystyrene) or high impact polystyrene with respect to 100 parts by weight of the polyphenylene ether. Those added to the extent that they do not exist can also be suitably used.

Next, (c) water obtained by hydrogenating a block copolymer composed of a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound used in the present invention. The hydrogenated block copolymer (hereinafter abbreviated as hydrogenated block copolymer) includes (a)
A hydrogenated block copolymer having the ability to suitably disperse (b) the polyphenylene ether resin in (a) the polypropylene resin when the polypropylene resin and (b) the polyphenylene ether resin are melted and mixed. That is, in the present invention, a polymer block A mainly composed of at least one vinyl aromatic compound and a block B mainly composed of at least one conjugated diene compound having a vinyl bond content of 45% or more of the conjugated diene compound. And wherein the iodine value of the hydrogenated block copolymer is 40 or less. The structure of these hydrogenated block copolymers is, for example,
AB, ABA, ABAB, (AB-) 4
It is a hydrogenated block copolymer having a structure such as -Si, ABABA or the like.

The vinyl aromatic compound constituting the 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 among them, styrene is preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethyl-1,3.
-One or more of butadiene and the like are selected, and among them, butadiene, isoprene and a combination thereof are preferable. The total amount of 1,2- and 3,4-vinyl bonds (hereinafter abbreviated as vinyl bond amount) of the polymer block mainly composed of a conjugated diene compound is 45%.
As described above, preferably, in the polymer block mainly composed of butadiene, the vinyl bond content is 65 to 90%,
More preferably, it is 70 to 85%. In the polymer block mainly composed of isoprene, the vinyl bond amount is preferably 48% or more, more preferably 48 to 90%.
It is. In a polymer block composed of a conjugated diene compound such as a random, tapered (a monomer component increases or decreases along a molecular chain) composed of a combination of butadiene and isoprene, or a block copolymer, a vinyl bond amount is preferably used. Is 48% or more, more preferably 48 to 90%. If the vinyl bond content is less than 45% by weight, the miscibility of the polypropylene-based resin and the modified polyphenylene ether-based resin is reduced, and the impact resistance and tensile elongation are undesirably reduced. Further, even if the vinyl bond amount exceeds 90%, the effect of improving the miscibility is not remarkable.
The amount of these vinyl bonds can usually be known by an infrared spectrophotometer or NMR.

The hydrogenated block copolymer has an iodine value of 40 or less, preferably 37 or less, more preferably 35 or less. If the iodine value of this hydrogenated block copolymer exceeds 40, the thermal degradation of the hydrogenated block copolymer occurs when the resin composition is produced by heat-melt kneading and when the resin composition is placed at a high temperature. Is large, and the impact strength and tensile elongation are undesirably reduced. The iodine value of this hydrogenated block copolymer is usually determined by an iodine titration method, and is a numerical value in which the amount of consumed iodine is expressed as a percentage based on the weight of the hydrogenated block copolymer.

The hydrogenated block copolymer having the above structure has a number average molecular weight of 40,000 to 500,000, preferably 50,000 to 300,000, more preferably 60,000 to 200,000, and has a molecular weight distribution (gel permeation chromatography). Ratio of weight average molecular weight (Mw) to number average molecular weight (Mn)
Is 10 or less. Further, the molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.

These (c) hydrogenated block copolymers may be obtained by any production method as long as they have the above-mentioned structure. Examples of known production methods include, for example, JP-A-47-1148.
No. 6, JP-A-49-66743, JP-A-50-67743
-75651, JP-A-54-126255, JP-A-56-10542, JP-A-56-62
847, JP-A-56-100840, JP-A-2-300218, and British Patent No. 1130770.
And U.S. Pat. Nos. 3,281,383 and 3,693,517; and British Patent No. 1,020,720 and U.S. Pat.
There is a method described in U.S. Pat. No. 3,024, and U.S. Pat. No. 4,501,857.

The (c) hydrogenated block copolymer 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 are heated to 80 to 350 ° C. in a molten state, a solution state, or a slurry state in the presence or absence of a radical generator.
A known modification (the α, β-unsaturated carboxylic acid or a derivative thereof is 0.1%) obtained by reacting at a temperature of 0.1%.
(Graft or addition of 0 to 10% by weight) may be a hydrogenated block copolymer, or a mixture of the above-mentioned hydrogenated block copolymer and the modified hydrogenated block copolymer in any ratio. Absent.

Next, the polymer comprising the conjugated diene compound (d) used in the present invention is an essential component for suppressing a morphological change, and it is necessary that the polymer is present at least in polyphenylene ether forming a dispersed phase. is there.

Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-
One or more of dimethyl-1,3-butadiene and the like are selected, and among them, butadiene, isoprene and a combination thereof are preferable. Examples of the polymer comprising a conjugated diene compound include a block polymer of butadiene or isoprene, a random or tapered (combination of butadiene and isoprene, in which a monomer component increases or decreases along a molecular chain) or a block copolymer. A polymer comprising a conjugated diene compound, and
It is a copolymer comprising a conjugated diene compound and a vinyl aromatic compound and having a binding mode such as block, random, tapered, or graft. As the vinyl aromatic compound as a copolymer component constituting the polymer comprising the conjugated diene compound, for example, one or more of styrene, vinyl toluene, α-methylstyrene, and the like can be selected. Is preferred. Further, the polymer comprising the conjugated diene compound may have a double bond derived from a conjugated diene and partially include a crosslinked structure.

The polymer comprising the conjugated diene compound is
The microstructure (bonding form of the conjugated diene compound) can be arbitrarily selected, and the amount of vinyl bonds (1, 2- and 3,
(Total amount of 4-vinyl bonds) is 1 to 90%, preferably 5 to 85%, more preferably 10 to 60%, and still more preferably 10 to 50%. The bonding form of these conjugated diene compounds can usually be known by an infrared spectrophotometer, NMR or the like. The content of the vinyl aromatic compound in the polymer composed of the conjugated diene compound is from 0 to 8
0% by weight, preferably 0 to 70% by weight, more preferably 15 to 65% by weight. The number average molecular weight of the polymer comprising the conjugated diene compound having the above structure is 5,
000 to 1,000,000, preferably 10,000
~ 800,000, more preferably 30,000 ~ 5
It is in the range of 00,000.

The polymer comprising the conjugated diene compound (d) described above may be obtained by any production method as long as it has the above structure. Examples of known production methods include, for example,
No. 23798, U.S. Pat. No. 3,595,942, and U.S. Pat. No. 4,090,996.

The polymer comprising the conjugated diene compound (d) used in the present invention may be, in addition to the above-mentioned polymer, the polymer and an α, β-unsaturated carboxylic acid or a derivative thereof as a radical generator. A known modification (the α, β-unsaturated carboxylic acid or a derivative thereof is 0.01%) obtained by reacting in the presence, absence or presence of a molten state, a solution state, or a slurry state at a temperature of 80 to 350 ° C. (Graft or addition) polymer of 10 to 10% by weight, or a mixture of the above-mentioned polymer and the modified polymer in any ratio.

The polymers comprising these conjugated diene compounds may be used alone or in combination of two or more.

The resin composition of the present invention has the above (a) to
The component (d) is configured as a basic component.

In the present invention, the blending amount of (a) the polypropylene resin is 45 to 95% by weight, preferably 45 to 85% by weight. When the amount is less than 45% by weight, the obtained resin composition has excellent heat resistance,
Molding processability and solvent resistance are poor, which is not preferable. Also, 95
When the content is more than 10% by weight, the moldability and solvent resistance are good, but the heat resistance is inferior and cannot be used as a heat resistant material.

In the present invention, the blending amount of the (b) polyphenylene ether resin is 55 to 5% by weight, preferably 5 to 5% by weight.
5 to 15% by weight. When the amount is more than 55% by weight, the heat resistance of the obtained resin composition is extremely excellent, but the molding processability and the solvent resistance are inferior. If the content is less than 5% by weight, the moldability and solvent resistance are excellent, but the heat resistance is inferior and cannot be used as a heat-resistant material.

In the present invention, the blending amount of the (c) hydrogenated block copolymer is 100% of the total of the components (a) and (b).
It is 1 to 30 parts by weight with respect to parts by weight. If the amount is less than 1 part by weight, the effect as an admixture cannot be obtained, which is not preferable. If the amount exceeds 30 parts by weight, the effects of the components (a) and (b) are remarkably reduced in heat resistance, solvent resistance, rigidity and mechanical strength, which is not preferable.

In the present invention, the compounding amount of the polymer comprising the conjugated diene compound (d) is 1 to 30 parts by weight based on 100 parts by weight of the total of the components (a) and (b). If the amount is less than 1 part by weight, the effect of suppressing the change in morphology is not seen, which is not preferable. On the other hand, when the amount is more than 30 parts by weight, the effect of the component (b), heat resistance and rigidity are remarkably reduced, which is not preferable.

In the present invention, in addition to the above-mentioned components, other additional components such as an antioxidant, a metal deactivator, and a flame retardant (if necessary) as long as the characteristics and effects of the present invention are not impaired. Organic phosphate compounds, inorganic phosphorus compounds,
Aromatic halogen-based flame retardants, silicone-based flame retardants, etc.),
Fluoropolymers, 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,
Glass flake, carbon fiber, polyacrylonitrile fiber, whisker, mica, talc, carbon black, titanium oxide, calcium carbonate, potassium titanate,
Wollastonite, conductive metal fibers, conductive carbon black, etc.), various coloring agents, release agents, and the like.

In the present invention, an excellent emulsified dispersion form can be easily obtained by employing a specific heat-melt kneading method. That is, (c) a hydrogenated block copolymer and (a) a polypropylene resin are additionally added to a melt-kneaded state of (b) a polymer composed of a polyphenylene ether-based resin and (d) a conjugated diene compound, and melt-kneaded together. How and
A method in which (a) a polypropylene-based resin is additionally added to a melt-kneaded state of (b) a polymer comprising a polyphenylene ether-based resin and (d) a conjugated diene compound and (c) a hydrogenated block copolymer, and melt-kneading together; , (C) a part of a hydrogenated block copolymer, (b) a polymer comprising a polyphenylene ether-based resin and (d) a conjugated diene compound in a melt-kneaded state, (a) a polypropylene-based resin and (c) a hydrogenated block. A method of additionally adding a copolymer and melt-kneading together,
(A) a hydrogenated block copolymer and (a) a polypropylene-based resin in a melt-kneaded state of a polymer composed of (a) a part of a polypropylene-based resin, (b) a polyphenylene ether-based resin and (d) a conjugated diene compound. A method of additionally adding and melt-kneading together, or a method of (a) a polymer composed of a part of a polypropylene resin, (b) a polyphenylene ether resin and (d) a conjugated diene compound, and (c) a hydrogenated block copolymer. (A) a method of additionally adding a polypropylene-based resin to the melt-kneaded state and melt-kneading together, or (a) a part of the polypropylene-based resin and (c) a part of the hydrogenated block copolymer and (b) a polyphenylene ether (A) in a melt-kneaded state of a polymer comprising a base resin and (d) a conjugated diene compound
A preferred method is to additionally add a polypropylene resin and (c) a hydrogenated block copolymer and melt-knead them together.

On the other hand, kneading is performed by additionally supplying (a) a polypropylene resin, (c) a hydrogenated block copolymer, and (d) a polymer comprising a conjugated diene compound to a melt of the (b) polyphenylene ether resin. The method is insufficient in suppressing the morphological change of the obtained resin composition. Examples of the melt kneader for performing these methods include a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, and a heat melt kneading method using a Banbury mixer, among which a twin screw extruder is used. The melt kneading method used is most preferred. Specifically, WERNER
& PFLEIDERER ZSK series, Toshiba Machine Co., Ltd. TEM series, Japan Steel Works Co., Ltd.
EX series and the like. A preferred embodiment of the present invention using an extruder will be described below. The L / D (barrel effective length / barrel inner diameter) of the extruder is in the range of 20 to 60, preferably 30 to 50. The extruder is provided with a first raw material supply port on the upstream side with respect to the flow direction of the raw material, a first vacuum vent downstream of the first raw material supply port, a second raw material supply port on the downstream side thereof, and a second vacuum vent further downstream thereof. Is preferred. In particular, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the first vacuum vent and the second material supply port, and
More preferably, a kneading section is provided between the raw material supply port and the second vacuum vent. The method of supplying the raw material to the second supply port is not particularly limited, but the raw material is supplied from the extruder side open port using a forced side feeder, rather than simply added and supplied from the extruder second supply port open port. Is more stable and preferable. In particular, when powders, fillers, etc. are contained, the forced side feeder supplied from the extruder side is more preferable, and the upper opening of the second supply port of the extruder should be opened to remove the air to be conveyed. Can also. The melt-kneading temperature and the screw rotation speed at this time are not particularly limited, but usually the melt-kneading temperature is 200 to 3
It can be arbitrarily selected from 70 ° C. and a screw rotation speed of 100 to 1200 rpm.

In the present invention, (a) 0 to 30% by weight, preferably 1 to 3
0% by weight and (b) 55-polyphenylene ether resin
5% by weight, 100 parts by weight of the total of the components (a) and (b) (including the component (a) below), and 0 to 30 parts by weight of the (c) hydrogenated block copolymer and (d) the conjugated diene 1-30 parts by weight of a polymer composed of a compound is supplied and melt-kneaded,
From the second raw material supply port, (c) 0 to 30 parts by weight corresponding to the remaining of 1 to 30 parts by weight of the hydrogenated block copolymer and (a) 45 to 45 parts by weight of the polypropylene resin
15 to 95% by weight corresponding to the remaining 95% by weight was supplied, and a polymer comprising (a) a polypropylene resin and (b) a polyphenylene ether resin, (c) a hydrogenated block copolymer, and (d) a conjugated diene compound. The polymer comprising (b) a polyphenylene ether-based resin, (c) a hydrogenated block copolymer and (d) a conjugated diene compound, (A) A dispersed phase is formed in a polypropylene resin matrix and an excellent emulsified dispersion form is easily provided. Taking such a manufacturing method is an important method for improving the emulsifying and dispersing ability, the impact strength, and the tensile elongation.

The resin composition of the present invention thus obtained can be prepared by various known methods, for example, injection molding,
It can be molded as various parts by extrusion molding and hollow molding, and when using a molding machine equipped with a hot runner, or when resin is retained in the molding machine, large molded products and ultra thin molded products Can be used. 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. Furthermore, it can be suitably used as an interior / exterior component of an electric device, and specifically, is suitable for various computer and its peripheral devices, other OA devices, televisions, videos, cabinets for various disc players, refrigerators and the like. I have.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to examples, but the present invention is not limited to these examples.

(A) Polypropylene resin used in Examples (a-1): Homo-polypropylene MFR = 6.5 g / 10 min The MFR (melt flow rate) of polypropylene is AS
It was measured at 230 ° C. under a load of 2.16 kg according to TM D1238.

(B) Polyphenylene ether-based resin (b-1) used in Examples: Polyphenylene ether having a reduced viscosity of 0.35 obtained by oxidative polymerization of 2,6-xylenol (b-2): 2,6 -Polyphenylene ether having reduced viscosity of 0.90 obtained by oxidative polymerization of xylenol (c) hydrogenated block copolymer (c-1): polystyrene (1) -hydrogenated polyisoprene-polystyrene (2 ) Having an iodine value of 33.
9, number average molecular weight 86,300, molecular weight distribution 1.10,
54% of vinyl bond amount of polyisoprene before hydrogenation,
A hydrogenated block copolymer of polystyrene (1) having a number average molecular weight of 20,200 and polystyrene (2) having a number average molecular weight of 20,000 was synthesized, and this polymer was designated as (c-1).

(C-2): Polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) structure, iodine value 3.9, number average molecular weight 82,000, molecular weight distribution 1.10, before hydrogenation Polybutadiene having a vinyl bond content of 75% and a polystyrene (1) having a number average molecular weight of 19,8
00, number average molecular weight of polystyrene (2) 19,800
To obtain a hydrogenated block copolymer of
-2).

(C-3): Polystyrene (1) -hydrogenated polybutadiene having a vinyl bond amount of 69% -vinyl bond amount 51
% Hydrogenated polyisoprene-polystyrene (2), hydrogenated polybutadiene / hydrogenated polyisoprene = 50
/ 50 (weight ratio), iodine value 12.9, number average molecular weight 8
3,000, molecular weight distribution 1.10, polystyrene (1)
A hydrogenated block copolymer having a number average molecular weight of 20,100 and polystyrene (2) having a number average molecular weight of 20,100 was synthesized, and this polymer was designated as (c-3).

(C-4): Polystyrene (1) -hydrogenated polyisoprene-polystyrene (2) structure, iodine value 29.9, number average molecular weight 83,000, molecular weight distribution 1.10, hydrogenation The previous polyisoprene had a vinyl bond content of 42%, and the polystyrene (1) had a number average molecular weight of 20,1.
00, number average molecular weight of polystyrene (2) 20,100
To obtain a hydrogenated block copolymer of
-4).

(C-5): Polystyrene (1) -hydrogenated polyisoprene-polystyrene (2) structure, iodine value 43.3, number average molecular weight 89,000, molecular weight distribution 1.10, hydrogenation The vinyl bond content of the previous polyisoprene was 48%, and the number average molecular weight of polystyrene (1) was 18.9
00, number average molecular weight of polystyrene (2) 18,900
To obtain a hydrogenated block copolymer of
-5).

Polymer (d) comprising a conjugated diene compound used in Examples (d-1): having a structure of polystyrene (1) -polybutadiene-polystyrene (2), and having a styrene content of 48
%, Block styrene content 40%, number average molecular weight 95.0
A copolymer having a polybutadiene vinyl bond content of 12% was synthesized, and this polymer was designated as (d-1).

(D-2): Polystyrene (1) -polyisoprene-polystyrene (2) structure, bound styrene content 30%, block styrene content 30%, number average molecular weight 82,000, polyisoprene vinyl 35 binding
% Of a copolymer was synthesized, and this polymer was designated as (d-2).

(D-3): Polystyrene (1) -polybutadiene-polystyrene (2) structure, bound styrene content 25%, block styrene content 18%, number average molecular weight 170,000, vinyl bond content of polybutadiene Is 1
A 6% copolymer was synthesized, and this polymer was designated as (d-3).

Melt kneading method of resin composition (A): Using a twin screw extruder, (b) from the first raw material supply port
A melt kneading method in which a polymer comprising a polyphenylene ether-based resin, (c) a hydrogenated block copolymer, and (d) a conjugated diene compound is supplied, and (a) a polypropylene-based resin is supplied from a second raw material supply port, (A ).

(B): Using a twin-screw extruder, a polymer comprising (b) a polyphenylene ether-based resin and (d) a conjugated diene compound is supplied from a first raw material supply port, and (a) is supplied from a second raw material supply port. (B) The melt kneading method for supplying the polypropylene resin and (c) the hydrogenated block copolymer was defined as (B).

(C): Using a twin-screw extruder, (b) a polymer comprising a polyphenylene ether-based resin and (d) a conjugated diene compound and (a) a part of a polypropylene-based resin from the first raw material supply port. The melt kneading method of supplying and supplying the (c) hydrogenated block copolymer and the remaining (a) polypropylene resin from the second raw material supply port was defined as (C).

The melt kneading temperature was 330 ° C. for the barrel from the first raw material supply port to the second raw material supply port in all of (A), (B) and (C), and the barrel set temperature was downstream of the second raw material supply port. Is set to 290 ° C. and the screw rotation speed is set to 350 rpm
m and melt kneading was performed.

The physical properties were evaluated as follows.

(1) Heat hysteresis treatment The product was left in an environment of 80 ° C. for 48 hours using a gear oven.

(2) Tensile Elongation Test The elongation at break was measured at 23 ° C. according to ASTM D-638.

(3) Izod (notched) impact strength Measured at 23 ° C. according to ASTM D-256.

(4) Confirmation of Morphological Stability of Resin Composition Using a Capillograph 1C (manufactured by Toyo Seiki Co., Ltd.), a constant extrusion speed was applied to the resin composition, and the degree of morphology deformation by the extrusion speed was confirmed. Capillograph 1
The barrel temperature of C was set to 280 ° C, the diameter was 2.0 mm,
Using a capillary with a length of 20 mm, set the extrusion speed to 1
The sample was extruded at mm / sec and 100 mm / sec, and the molten resin flowing out of the capillary was immersed in liquid nitrogen to obtain a sample. A plane parallel to the flow direction of the obtained sample was formed into an ultrathin section using an ultramicrotome (Ultracut E manufactured by Reichert), stained with ruthenic acid, and then transmitted through a transmission electron microscope (manufactured by JEOL Ltd.). 12
00EX) and photographed. Based on this photograph, the major axis (L) and minor axis (D) of the dispersed phase were determined using an image analyzer (IP1000, manufactured by Asahi Kasei Corporation), and the average L / D was determined.

Further, the resin composition was supplied to a screw in-line type injection molding machine set at 240 to 280 ° C.
After the resin has been retained in the molding machine for a minute, a box-shaped molded product (15 cm (width) x 15 cm (depth)) at a mold temperature of 60 ° C
× 8cm (height), thickness 2mm, 2mmΦ pin gate)
Was injection molded. A plane parallel to the flow direction at the center of the side surface (8 cm × 15 cm) of this molded product is formed into an ultra-thin section using an ultramicrotome (Ultracut E manufactured by Reichert), and stained with ruthenic acid. Observation and photography were performed using a microscope (1200 EX manufactured by JEOL Ltd.). Based on this photograph, the major axis (L) and minor axis (D) of the dispersed phase were determined using an image analyzer (IP1000, manufactured by Asahi Kasei Corporation), and the average L / D was determined.

[0060]

EXAMPLE 1 A polypropylene resin, a polyphenylene ether resin,
A hydrogenated block copolymer and a polymer comprising a conjugated diene compound were blended and melt-kneaded to obtain pellets. Melt kneading is performed with a twin-screw extruder (ZSK-25; WERNER & PFLEIDERE) with a vent port set at 290 to 330 ° C.
R, Germany).

The dispersion form of the resin composition was confirmed using the pellets, and further supplied to a screw in-line type injection molding machine set at 240 to 280 ° C., and the mold temperature was set to 60 ° C.
A test piece for a tensile test, a test piece for an Izod impact test, and a test piece for measuring a heat distortion temperature were injection-molded under the following conditions. Measure the physical properties of these test pieces,
The results are also shown in Table 1.

Example 1 within the scope of the present invention is Comparative Example 1 in which a polymer comprising a conjugated diene is not used, Comparative Examples 2 and 3 in which a hydrogenated block copolymer is out of the scope of the present invention, and a conjugated diene compound. It is clear that, compared to Comparative Example 4 in which the amount of the polymer consisting of was out of the range of the present invention, the elongation at break, the Izod impact strength and the dispersion form were excellent.

[0063]

Example 2 Example 2 was obtained in the same manner as in Example 1 except for the composition and the melt kneading method according to Table 1.

It is understood that Example 2 by the melt kneading method B in which the addition of the polypropylene-based resin was divided into two stages was excellent in physical properties and dispersion form.

[0065]

Example 3 Example 3 was obtained in the same manner as in Example 1 except for the composition and the melt kneading method according to Table 1. This is an example in which the type and amount of the polymer comprising the conjugated diene compound are different.

[0066]

Example 4 Example 4 was obtained in the same manner as in Example 1 except for the composition and the melt kneading method according to Table 1. This is an example using a high-viscosity polyphenylene ether-based resin.

[0067]

Example 5 The composition and the melt-kneading method were as shown in Table 1. Other than that, Example 5 was obtained in the same manner as in Example 1.

In Example 5 of the present invention in which a high-viscosity polyphenylene ether-based resin was used and a hydrogenated block copolymer was added from the first supply port, the method of melt-kneading a polymer comprising a conjugated diene compound was used. It can be seen that within the scope of the present invention, the desired physical properties and dispersion form are exhibited.

From these results, it is found that at least one polymer block A mainly containing a vinyl aromatic compound and at least one conjugated diene compound mainly containing at least 45% of vinyl bonds of the conjugated diene compound are used. A polyphenylene ether-based resin and a conjugated diene are obtained by using a hydrogenated block copolymer comprising a polymer block B, wherein the hydrogenated block copolymer has an iodine value of 40 or less, and further controlling the heating and melting and kneading means. By forming a dispersed phase in which a polymer comprising a compound is finely dispersed in a polypropylene resin matrix, an excellent resin composition having improved morphological stability between the polypropylene resin and the polyphenylene ether resin can be obtained.

[0070]

[Table 1]

[0071]

The resin composition of the present invention comprises a polymer comprising a polypropylene resin, a polyphenylene ether resin, a hydrogenated block copolymer and a conjugated diene compound, and has a specific structure as a hydrogenated block copolymer. Because of the use of a hydrogenated block copolymer and a specific heat-melt kneading means, the resin composition containing a polypropylene-based resin and a polyphenylene ether-based resin, which was difficult in the prior art, has excellent morphological stability and chemical resistance A resin composition having excellent heat resistance, heat resistance, impact resistance, and tensile elongation is provided.

Claims (2)

[Claims] 1. A resin composition comprising: (a) 45 to 95% by weight of a polypropylene resin; (b) 55 to 5% by weight of a polyphenylene ether resin;
(C) At least one polymer block A mainly composed of a vinyl aromatic compound and the vinyl bond amount of the conjugated diene compound (1,2-
And a polymer block B mainly composed of at least one conjugated diene compound having a total content of 3,4-vinyl bonds of not less than 45% in the hydrogenated block copolymer. A hydrogenated block copolymer having a combined iodine value of 40 or less 1 to 30 parts by weight (d) A polymer comprising a conjugated diene compound 1 to 30 parts by weight is blended, and a resin composition having a suppressed morphological change Stuff. 2. A total of (a) 0 to 30% by weight of a polypropylene resin, (b) 55 to 5% by weight of a polyphenylene ether resin and (a) and (b) components (including the following (a) component) 100 (A) a polypropylene resin is added to a melt-kneaded product of (c) 0 to 30 parts by weight of a hydrogenated block copolymer and (d) 1 to 30 parts by weight of a polymer comprising a conjugated diene compound, based on parts by weight. 15 to 95% by weight corresponding to the balance of 45 to 95% by weight of the total amount thereof, and (c) 0 to 30 parts by weight of the hydrogenated block copolymer corresponding to the balance of 1 to 30% by weight of the hydrogenated block copolymer. The method for producing a resin composition according to claim 1, further comprising adding and kneading the mixture.