JP2683825B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a resin composition exhibiting a particularly excellent balance of mechanical properties centering on rigidity and having good moldability, oil resistance and chemical resistance.

Specifically, polyolefin, particularly crystalline polyolefin, polyphenylene ether resin and partially hydrogenated alkenyl aromatic compound-isoprene block copolymer,
It also consists of a specific ethylene elastomer and has an excellent balance of mechanical properties centering on rigidity and heat resistance, and has good moldability, organic solvent resistance, and chemical resistance for injection molding, extrusion molding, or hollow molding. It relates to a resin composition.

[Prior art and its problems] Polyolefin has been widely used in various molded products, sheets, etc. since it is excellent in molding processability, toughness, water resistance, organic solvent resistance, chemical resistance, etc., and has low specific gravity. Although it is used, it has a point to be improved in heat resistance, which is an obstacle to the development of new applications.

On the other hand, polyphenylene ether resin has excellent heat resistance, but since it has drawbacks in moldability and solvent resistance,
Its range of use is limited. For the purpose of improving moldability and impact strength, for example, it is blended with styrene resin,
Although it is used, it has a problem in solvent resistance and therefore has a limited range of use, and is not suitable for fields requiring resistance to oily solvents such as gasoline.

Combined with the respective advantages of these polyolefins and polyphenylene ether, various blend compositions have been proposed for the purpose of compensating for the drawbacks, for example, compositions intended to improve processability and tensile strength (Japanese Patent Publication No. 47-7079). However, the relatively high mechanical strength level required in the industrial field cannot always be satisfied. In addition, further improving the compatibility of polyolefin and polyphenylene ether resin,
A composition comprising, for example, a block copolymer of styrene and butadiene or a hydrogenated product thereof for the purpose of improving the mechanical strength (JP-A-53-71158).
JP-A-54-88960, JP-A-59-100159, etc.), and a composition (JP-A-58-103556) in which an inorganic filler is added to these components has been proposed. Moldability and mechanical strength can be improved, but the amount of polyolefin is small, or matrix (continuous phase)
Since it is composed of a polyphenylene ether resin or a combination thereof with a styrene resin, the organic solvent resistance of polyolefin is not sufficiently exhibited. In addition, a polyphenylene ether resin is blended with a large amount of polyolefin of more than 20% by weight, and a diblock copolymer or radial tereblock copolymer composed of an alkenyl aromatic compound and a conjugated diene as a compatibilizer and their hydrogenated weights are further added. A composition obtained by adding coalescence (JP-A-58
No. 103557, JP-A-60-76547), low density polyethylene is used as an example of a polyolefin, and a blended product thereof with a polyphenylene ether resin is an alkenyl aromatic compound-conjugated diene diblock copolymer. It is said that the compatibility can be improved and the tensile properties, brittleness, etc. can be improved by blending a hydrogenated substance. However, the improvement in compatibility alone is not sufficient to satisfy the properties generally required for resins. For example, the composition disclosed in JP-A-60-76547, that is, polyphenylene ether, low density polyethylene as a polyolefin as a major component, alkenyl aromatic-conjugated diene diblock copolymer as a compatibilizing component of both components. The resin composition comprising the three components of the combined hydrogenated product has a significantly poor rigidity level,
There are limits to its use. Among the above combinations, the resin composition using polypropylene as the polyolefin has a slight improvement in rigidity and heat resistance, but there is a case in which it is still insufficient in practical use, and there is room for improvement.

[Means for Solving the Problems] In view of the above problems, the present inventors have made further improvements to provide various applications such as a relatively high level of mechanical strength required in the field of industrial parts. Balance and solvent resistance,
An intensive search was conducted for the purpose of providing a resin composition that can be used for molding processability.

Therefore, as a result of studying polyphenylene ether resin, polyolefin, and various compounding agents, it was found that a combination of polyphenylene ether resin and polyolefin, preferably crystalline polyolefin, had an alkenyl aromatic compound of specific structure-conjugated diene diene. By blending a hydrogenated product of a block copolymer and an ethylene elastomer having a specific structure, a resin composition exhibiting excellent mechanical property balance and good solvent resistance and moldability can be obtained. It was found that the present invention has been completed.

That is, the present invention relates to (a) 20 to 95% by weight of a polyolefin resin, (b) 80 to 5% by weight of a polyphenylene ether resin, and 100 parts by weight of the total amount of the (a) component and the (b) component. , (C) 3-45 parts by weight of partially hydrogenated alkenyl aromatic compound-isoprene block copolymer and (d) styrene-based compound modified ethylene-α-olefin copolymer elastomer 3
The resin composition is characterized by containing ˜45 parts by weight.

[Structure of the Invention] (a) Component: Polyolefin Resin The polyolefin used in the present invention is propylene,
Butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, heptene-1,
Homopolymers of α-olefins having 3 or more carbon atoms such as octene-1, interpolymers in the form of random, block, etc. of α-olefins containing ethylene and α-olefins, and their copolymers. A mixture, a copolymer such as a random or block of a predominant amount of α-olefin having 3 or more carbon atoms and another unsaturated monomer, or a graft, or a product obtained by oxidizing, halogenating or sulfonated these polymers. Those at least partially showing crystallinity are preferable.

Other unsaturated monomers include acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, maleic anhydride,
Unsaturated organic acids such as aryl maleic acid imides and alkyl maleic acid imides or derivatives thereof; vinyl esters such as vinyl acetate and vinyl butyrate; aromatic vinyl compounds such as styrene and methyl styrene; vinyltrimethylmethoxysilane, γ-methacryloyloxypropyl Vinylsilane such as trimethoxysilane, dicyclopentadiene, 4-
Non-conjugated dienes such as ethylidene-2-norbornene, 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene are used.

In the case of a copolymer, the α-olefin and other monomers are not limited to two types, but may be a plurality of types.

These copolymers are obtained by polymerization or modification by a known method, and commercially available products may be appropriately selected and used. Of course, they can be used together.

Of these, copolymers or homopolymers containing propylene, butene-1,3-methylbutene-1,4-methylpentene-1 in a majority weight ratio are preferable, and among them, crystalline propylene-based polymers, that is, crystalline propylene homopolymers are particularly preferable. A polymer, a crystalline propylene-ethylene block or random copolymer, a crystalline propylene-based polymer and an α-olefin rubber, that is, a rubbery copolymer composed of a plurality of α-olefins or a plurality of α-olefins. A mixture of a conjugated diene and a rubbery copolymer is preferable in terms of mechanical property balance.

These crystalline propylene-based polymers and these and α
The melt flow rate (MFR) (230 ° C., load 2.16 kg) of the mixture containing an olefin rubber is preferably in the range of 0.01 to 400, more preferably 0.15 to 60. MFR value is 0.0
If it is less than 1, molding processability tends to be difficult and 400
In the larger range, the mechanical strength level is low, which is not preferable.

As a polyolefin, one with a smaller MFR value,
That is, a polymer having a high molecular weight is subjected to a known method, for example, heat treatment in the presence or absence of a radical generator (organic and inorganic peroxides, organic tin compounds, organic azo compounds, etc.), or during melt kneading. Including those within the MFR range due to changes in molecular weight due to heating and mechanical shearing.

Component (b): polyphenylene ether resin The polyphenylene ether resin used in the present invention is
General formula Wherein the ether oxygen atom of one unit is connected to the benzene nucleus of the next adjacent unit, n is at least 30, and a plurality of R are each independently Hydrogen, halogen, a hydrocarbon group not containing a tertiary α-carbon atom, a halohydrocarbon group having at least two carbon atoms between a halogen atom and a phenyl nucleus, a hydrocarbonoxy group, and a halogen atom and a phenyl nucleus And a monovalent substituent selected from the group consisting of hydrocarbon oxy groups having at least two carbon atoms between and.

Typical examples of polyphenylene ethers include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6- Ethyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene)
Ether, poly (26-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene)
Ether, poly (2,6-dibutyl-1,4-phenylene) ether, poly (2,6-dipropenyl-1,4-phenylene) ether, poly (2,6-dilauryl-1,4-phenylene) ether, Poly (2,6-diphenyl 1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-diethoxy-1,4-phenylene) ether, poly (2 -Methoxy-6-ethoxy-1,4-phenylene) ether, poly (2-ethyl-6-stearyloxy-1,4-phenylene) ether, poly (2,6-dichloro-1,4-phenylene) ether, Poly (2-methyl-6-phenyl-1,4-phenylene)
Ether, poly (2,6-dibenzyl-1,4-phenylene) ether, poly (2-ethoxy, 1,4-phenylene) ether, poly (2-chloro-1,4-phenylene) ether, poly (2, There is 5-dibromo-1,4-phenylene) ether and the like.

Also, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and 2,3,5,6-tetramethylphenol, 2,6-diethylphenol Copolymers such as a copolymer of phenol and 2,3,6-trimethylphenol can also be mentioned.

Further, the polyphenylene ether used in the present invention is a modified polyphenylene ether obtained by grafting a styrene-based monomer (for example, styrene, p-methylstyrene, α-methylstyrene, etc.) onto the polyphenylene ether defined by the above general formula. Also includes ether.

Methods for producing polyphenylene ethers corresponding to the above are known, for example, US Pat. Nos. 3,306,874 and 33068.
Nos. 75, 3257357 and 3257358, and Japanese Patent Publication No. 52-17880 and Japanese Patent Laid-Open No. 50-51197.

Preferred polyphenylene ethers for the purposes of the present invention are those having alkyl substituents at the two ortho positions relative to the ether oxygen atom and copolymers of 2,6-dialkylphenol and 2,3,6-trialkylphenol. .

Of these, a polymer of 2,6-dimethylphenol is particularly preferable. In addition, the range of the preferable molecular weight is, as a measure, in terms of the value of the intrinsic viscosity in 25 ° C. chloroform, the range is 0.2 to 0.7 dl / g, and more preferably the range is 0.25 to 0.6 dl / g. And more preferably 0.3 to 0.55 dl / g. When the intrinsic viscosity is less than 0.2 dl / g, the mechanical strength of the composition becomes unsatisfactory, and when it is more than 0.7 dl / g, the moldability of the composition decreases, which is not preferable.

Further, it may be one in which half or less by weight of the polyphenylene ether is substituted with a styrene resin, for example, polystyrene, high impact polystyrene reinforced with various rubbers, ABS resin or the like.

Component (c): partially hydrogenated alkenyl aromatic compound-isoprene copolymer The partially hydrogenated alkenyl aromatic compound-isoprene block copolymer used in the present invention is a chain block "A derived from an alkenyl aromatic compound. And a chain block "B" derived from isoprene, respectively, is a block copolymer in which the aliphatic unsaturated group of block B of the alkenyl aromatic compound-isoprene block copolymer is reduced by hydrogenation. . The arrangement of blocks A and B includes those having a linear structure or those having a branched structure, that is, a so-called radial teleblock structure.

The distribution of the monomer component is not particularly limited, and may be uniform, non-uniform, or tapered such that the amount of the monomer component increases or decreases along the molecular chain. Therefore, a plurality of A blocks or B
The respective molecular weights of the blocks may be the same or different. Further, a part of these structures may include a random chain derived from a random copolymerization part of the alkenyl aromatic compound and isoprene. Among these, a diblock (AB block) having a linear structure,
Triblock (ABAA block, BABB block), Tetrablock (ABBAB block), Pentablock (ABBABA block, BAA-
(B-A-B blocks) or those having a linear structure containing a total of 6 or more blocks of A and B are more preferable, and among these, diblock, triblock and tetrablock structures are more preferable, and Those having an AB diblock structure are preferable.

The alkenyl aromatic compound forming the block A has a chemical structure represented by the following general formula.

In the formula, R ¹ and R ² are selected from the group consisting of hydrogen and a lower alkyl group or alkenyl group having 1 to 6 carbon atoms, and R ³ and
R ⁴ is selected from the group consisting of hydrogen, a lower alkyl group having 1 to 6 carbon atoms, chlorine and bromine, and R ⁵ , R ⁶ and R ⁷ are hydrogen, a lower alkyl group having 1 to 6 carbon atoms and an alkenyl group. It may be selected from the group, or R ⁶ and R ⁷ may have a naphthyl group linked together with a hydrocarbyl group.

Specific examples of the alkenyl aromatic compound include styrene, paramethylstyrene, α-methylstyrene, vinylxylene, vinyltoluene, vinylnaphthalene, civinylbenzene, bromostyrene and chlorostyrene, and they can be used in combination. Among these, styrene, α-methylstyrene, paramethylstyrene, vinyltoluene and vinylxylene are preferable, and styrene is more preferable.

The proportion of repeating units derived from the alkenyl aromatic compound in the partially hydrogenated alkenyl aromatic compound-isoprene block copolymer (c) is 20% by weight.
Over 80% by weight is good, especially above 25% by weight 65
A range of less than or equal to wt% is preferred.

When the proportion of the repeating units derived from the alkenyl aromatic compound in the partially hydrogenated alkenyl aromatic compound-isoprene block polymer (c) exceeds 80% by weight, the impact strength of the resin composition is unsatisfactory. In the range of 20% by weight or less, the rigidity level and heat resistance of the resin composition become unsatisfactory and the object of the present invention cannot be achieved, which is not preferable.

Among the aliphatic chain moieties in these block copolymers (c), the proportion of unsaturated bonds derived from isoprene and remaining without being hydrogenated is preferably 50% or less, and 20% or less.
The following is more preferable, and 10% or less is further preferable. Also, about 25% or less of the aromatic unsaturated bond derived from the alkenyl aromatic compound may be hydrogenated.

These hydrogenated block copolymers (c) have a number average molecular weight measured by gel permeation chromatography of 5,000 g / mol or more and 500,000 g / mol or less as a measure of their molecular weight. Those of 10,000 g / mol or more and 300,000 g / mol or less are more preferable. More preferably 30,000 g / mol
Above 200,000 g / mol, particularly preferably 45,000 g / mo
It is in the range of l or more and 150,000 g / mol or less. Measured by gel permeation chromatography,
The value of the average molecular weight by the polystyrene conversion method is 500,000 g / m
ol and the number average molecular weight by the same method is 5,
Those less than 000 g / mol tend to be expensive in terms of manufacturing cost.

In the measurement by gel permeation chromatography, monodisperse polystyrene was used as a standard substance when determining the relationship between the elution time and the molecular weight. Each average molecular weight was a polystyrene-equivalent molecular weight.

The molecular weight distribution of these hydrogenated block copolymers (c) can be measured by the above gel permeation chromatography, but the preferable molecular weight distribution is not particularly limited, and the weight average molecular weight value is the number average molecular weight value. The so-called Q value obtained by the division may be in any range. Further, the molecular weight distribution has not only one mountainous dispersion but also a plurality of mountainous dispersions, or a small amount of a component having a higher molecular weight or a lower molecular weight than the main dispersion in addition to the mountainous main dispersion. In addition to the mountain-shaped main dispersion, a shape that draws a skirt can be used.

The molecular weight of the alkenyl aromatic chain block (block A) and the hydrogenated isoprene chain block (block B) in these hydrogenated block copolymers (c) should be in the range satisfying the above number average molecular weight. For example, various types and various combinations can be used.

Some of these hydrogenated block copolymers (c) have a hydrogenated isoprene polymerization chain portion and show crystallinity derived from this chain. It is presumed that this is because the hydrogenated isoprene polymerization chain has a molecular structure similar to polyolefin. The crystallinity of the hydrogenated block copolymer (c) is a differential scanning calorimeter (abbreviated as DSC).
Can be measured by

As the hydrogenated block copolymer (c) in the present invention, those having any crystallinity can be used.

Any glass transition temperature based on the hydrogenated isoprene polymerization chain portion of the hydrogenated block copolymer (c) can be used.

The glass transition temperature can be measured by the above-mentioned DSC method or the temperature change behavior of viscoelasticity using a mechanical spectrometer or the like.

Many methods have been proposed as a method for producing an alkenyl aromatic compound-isoprene block copolymer. As an alternative method, for example, Japanese Patent Publication No. 40-23798
No. 3595942 and US Pat. No. 4,090,996, etc., and block copolymerization is carried out in an inert solvent such as cyclohexane using a lithium catalyst or a Ziegler type catalyst. As one of such block copolymers, "TR24
Some of them are sold under the brand name such as "00". The hydrogenation treatment of these block copolymers is carried out, for example, in Japanese Patent Publication
42-8704, 43-6636 or 46-20814, etc. by the method described in the specification, for example, by hydrogenating in the presence of a hydrogenation catalyst in an inert solvent such as cyclohexane. .

Also, Journal of Polymer Science Part B Polymer
It is also possible to carry out hydrogenation using paratoluenesulfonyl hydrazide and the like in an inert solvent by the method shown in Letters Volume 11, pp. 427-434 (1973).

Component (d): Modified ethylene-based elastomer The modified ethylene-α-olefin copolymer used in the present invention is obtained by graft-copolymerizing a styrene-based compound on the ethylene-α-olefin copolymer.

The ethylene-α-olefin copolymer used for the graft modification needs to have an ethylene content of 30 to 93 mol%, and more preferably 35 to 90 mol%. Even if the ethylene content of the ethylene-α-olefin copolymer is more than 93 mol% or less than 30 mol%, the ethylene-α-olefin copolymer becomes highly crystalline, and the impact resistance of the composition is high. The effect of improving sex is not sufficient. Also, the ethylene-α-
Melt flow rate of olefin copolymer at 190 ℃ [MFR, value measured at 190 ℃ with a load of 2160 g (ASTM D-1
238 E condition)] is preferably in the range of 0.1 to 50 g / 10 minutes, and particularly preferably in the range of 0.2 to 20 g / 10 minutes. MF of the ethylene-α-olefin copolymer
When R is smaller than 0.1 g / 10 minutes or larger than 50 g / 10 minutes, the effect of improving impact resistance tends to be small.

The density of the ethylene-α-olefin copolymer is
It is preferably in the range of 0.90 g / cm ³ or less, and more preferably in the range of 0.85 to 0.89 g / cm ³ . Further, the ethylene-α-olefin copolymer is preferably low crystalline or amorphous, and its crystallinity is usually in the range of 0 to 50%, preferably in the range of 0 to 40%. .

Α-constituting the ethylene-α-olefin copolymer
The olefin component unit is an α-olefin having 3 to 18 carbon atoms, and propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-decene and the like can be exemplified. One kind or a mixture of two or more kinds is used. The ethylene-α-olefin copolymer is usually a copolymer of an ethylene component and an α-olefin, but a diene component may be contained in the range of 5 mol% or less.

Typical examples of the diene component are dicyclopentadiene and ethylidene norbornene.

The styrene compound that is graft-copolymerized with the ethylene-α-olefin copolymer is the alkenyl aromatic compound described above. Further, it is also possible to use it together with another monomer which can be copolymerized with a majority weight of the styrene compound.
Specific examples of such a monomer include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, methyl acrylate, ethyl acrylate, methyl methacrylate, glycidyl methacrylate, glycidyl acrylate, and maleide.

The graft ratio of the graft monomer is such that the ethylene-α
The amount is preferably 0.3 to 50 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the olefin copolymer. When the graft ratio of the styrene-based hydrocarbon is less than 0.3 parts by weight, the compatibility with the polyphenylene ether-based resin becomes poor, the layered peeling easily occurs, and the impact resistance improving effect becomes small. In addition, the graft ratio of styrene hydrocarbon is
When the amount is more than 50 parts by weight, the graft deformed product does not exhibit the properties of a rubber-like elastic body, and the effect of improving the impact resistance of the polyphenylene ether resin decreases. Furthermore, the melt flow rate of the styrene-based hydrocarbon graft ethylene-α-olefin copolymer [MFR, load 2160 g, 190
The value measured at ° C] is 0.1 to 50/10 minutes, preferably 0.2 to 20 g / 10 minutes.

In the modified ethylene-α-olefin copolymer used in the present invention, the ethylene-α-olefin copolymer is directly melted or dissolved in a solvent, and a radical initiator and the graft monomer are added to carry out a graft reaction. It is desirable to prepare it. A reactor, an extractor, a kneader or the like is used for the graft reaction. Radical initiators include organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne 3,1 , 4-bis (tert-butylperoxoisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne 3,
2,5-Dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-
Butyl perpivalate, cumyl perpivalate and te
There are rt-butyl perdiethyl acetate and other azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5 di (tert-butylperoxy) hexyne 3,
Dialkyl peroxides such as 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

[Composition ratio of constituent components] The proportion of the polyolefin component (a) in the resin composition according to the present invention is 20 with the total amount of the polyolefin (a) and the polyphenylene ether resin (b) being 100% by weight.
〜95wt% is recommended, among which the range of 30-95wt% is preferable, and the range of 40-90wt% is especially preferable.

If it is less than 20% by weight, the organic solvent resistance is insufficient, and if it exceeds 95% by weight, the heat resistance becomes unsatisfactory.
It is not preferable because the object of the present invention cannot be achieved.

Similarly, the proportion of the polyphenylene ether resin as the component (b) is such that the total amount of the resin components (a) and (b) is 10
80 to 5% by weight is recommended as 0% by weight, among which 7
A range of 0-5% by weight is preferred, especially 60-10% by weight
Is preferable. If it is less than 5% by weight, the rigidity level becomes unsatisfactory, and if it exceeds 80% by weight, the organic solvent resistance becomes insufficient, which is not preferable.

Partly hydrogenated alkenyl aromatic compound of component (c)-
The amount of isoprene block copolymer is preferably in the range of 3 to 45 parts by weight, particularly preferably in the range of 5 to 40 parts by weight, particularly preferably 5 parts by weight, based on 100 parts by weight of the total amount of the components (a) and (b). A range of up to 30 parts by weight is preferred. If it is less than 3 parts by weight, the impact strength level will be insufficient, and if it exceeds 45 parts by weight, the rigidity level will be unsatisfactory and the object of the present invention cannot be achieved, which is not preferable.

The proportion of the modified ethylene-α-olefin copolymer as the component (d) is preferably in the range of 3 to 45 parts by weight, and particularly 5 to 5 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b).
30 parts by weight is preferred. If it is less than 3 parts by weight, the impact strength level becomes insufficient, and if it exceeds 45 parts by weight, the rigidity level becomes unsatisfactory, and the object of the present invention cannot be achieved, which is not preferable.

In the present invention, in addition to the above components, other additional components, if necessary, within a range that does not impair the effects of the present invention, for example,
Antioxidant, weather resistance improver, nucleating agent for polyolefin,
Slip agents, inorganic or organic fillers and reinforcing agents, flame retardants,
Various colorants, antistatic agents, release agents, small amounts of radical generators (organic peroxides, etc.) for controlling the molecular weight of polyolefins
Etc. may be added.

Further, a plasticizer such as triphenyl phosphate used for polyphenylene ether resin, further, glass fiber, wollastonite, potassium titanate, whiskers,
Fillers such as mica, talc, and calcium carbonate are effective for improving the balance of physical properties such as rigidity, moldability, dimensional accuracy, and dimensional stability.

[Blending Method] As a blending method for obtaining the resin composition according to the present invention, generally, various methods of blending resins or resins with a stabilizer or colorant, and further blending a resin with a filler can be applied. . For example, a powdery or granular component is uniformly dispersed in a Henschel mixer, a super mixer, a ribbon blender, a V blender, etc., and then a biaxial kneading extruder, a uniaxial kneading extruder, a roll, a Banbury. A mixer, blast mill, Brabender Blastograph melt kneader can be used. The melt-kneading temperature is usually in the range of 200 ° C to 350 ° C. The resin composition obtained as described above can be extruded into pellets after melt-kneading.

[Application of Resin Composition According to the Present Invention] The resin composition according to the present invention can be easily molded by the moldability generally applied to thermoplastic resins, that is, injection molding, extrusion molding, blow molding, and the like. Injection molding is most preferred. Since it has good mechanical properties, it is used for automobile parts, specifically, for van bars, doors, door panels, fenders, moldings, emblems, wheel covers, engine hoods, roof parts, exterior parts such as spoilers, instrument panels, and consoles. Interior parts such as boxes and trims, as well as exterior parts for electrical equipment,
Specifically, it is suitable for parts such as televisions, refrigerators, and so-called office automation equipment.

[Examples] Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but these are merely examples and the present invention is not limited thereto.

Measurement and Evaluation Methods In the following Examples and Comparative Examples, each physical property value and various properties were measured and evaluated under the following conditions.

1) MFR (standard of flowability) MFR of polyolefin was measured according to JIS K 7210-1975.

2) Flexural modulus (standard for rigidity) Measured using an Instron tester according to ISO R178-1974 Procedure 12 (JIS K 7203).

3) Izod impact value Measured using an Izod impact tester manufactured by Toyo Seiki Seisakusho according to ISO R 180-1969 (JIS K 7110) (notched Izod impact strength).

4) Heat distortion temperature (standard for heat resistance) ISO R 75-1958 Method A (JIS K 7207-1974 A method)
It measured according to. An injection-molded test piece that was annealed at 100 ° C for 30 minutes was used.

Reference Example 1 Production of styrene-grafted modified ethylene-propylene copolymer Ethylene-propylene copolymer rubber (Sumitomo Chemical Co., Ltd.,
Esplen E-120: trade name) 100 parts by weight, styrene 40
Parts by weight, 500 parts by weight of water, 1.5 parts by weight of baizoyl peroxide, 3 parts by weight of calcium phosphate and 3 parts by weight of polyethylene glycol were charged into a polymerization kettle and the inside of the tank was sufficiently replaced with nitrogen while stirring. Then 90 ° C for 1 hour, then 110 ° C
For 1 hour. As a result of extracting polystyrene in the obtained graft copolymer with methyl ethyl ketone, it was confirmed that about 20% by weight of styrene was graft-copolymerized in the copolymer.

Example 1 Propylene homopolymer (Sumitomo Chemical Co., Ltd., Sumitomo Noblene D-501: trade name), poly (2,6-dimethylphenylene) ether (Sumitomo Chemical Co., Ltd.), hydrogenated styrene-isoprene block copolymer ( Hereinafter, abbreviated as hydrogenated SI.) (Kreton G1701 X: trade name, manufactured by Shell Chemical Co., Ltd.), and the styrene-grafted copolymer modified ethylene-propylene copolymer obtained in Reference Example 1 in the proportions shown in Table 1. After mixing with a super mixer, melt kneading at 260-280 ° C using a twin-screw extruder (TEM-50 manufactured by Toshiba Machine Co., Ltd.),
Pellets were obtained. The physical property measurement results are shown in Table 1.

Comparative Example 1 Instead of the hydrogenated styrene-isoprene block copolymer of Example 1, hydrogenated styrene-butadiene-styrene block copolymer (hereinafter abbreviated as hydrogenated SB) (Shell Chemical Co., Ltd., Kraton 1650: Pellets were obtained in the same manner as in Example 1 except that (trade name) was used. The physical property measurement results are shown in Table 1.

Comparative Example 2 Styrene-graft copolymer modified ethylene of Example 1
Pellets were obtained in the same manner as in Example 1 except that an unmodified ethylene-propylene copolymer (Supren E-120: trade name, manufactured by Sumitomo Chemical Co., Ltd.) was used in place of the propylene copolymer. The physical property measurement results are shown in Table 1.

Comparative Example 3 Pellets were obtained in the same manner as in Example 1 except that the styrene graft copolymer-modified ethylene-propylene copolymer of Example 1 was not used. The physical property measurement results are shown in Table 1.

As is clear from a comparison between Example 1 and Comparative Examples 1 to 3, the hydrogenated styrene-isoprene block copolymer and the styrene-geraft copolymer modified ethylene-propylene copolymer, which are the compositions of the present invention, are combined. In particular, it shows good physical properties.

Examples 2 to 5 Pellets were obtained by molding in the same manner as in Example 1 with the compounding ratios shown in Table 2, and the physical properties were evaluated. Table 2 shows the results. The components used in Table 2 are as follows.

Polypropylene homopolymer: Sumitomo Chemical Co., Ltd., Sumitomo Noblen D-501
(Brand name) Random copolymer: Propylene-ethylene random copolymer [Sumitomo Chemical Co., Ltd., Sumitomo Noblene S-131 (Brand name)] Block copolymer: Propylene-ethylene block copolymer [Sumitomo Chemical Co., Ltd. Sumitomo Noblene AS-171A (trade name)] Polyphenylene ether: poly- (2,6-dimethylphenylene) ether [Sumitomo Chemical Co., Ltd.] Hydrogenated SI: Shell Chemical Co. [Clayton G-1701 X (trade name)] Modified Ethylene-α-olefin copolymer S-EP: Styrene graft copolymer modified ethylene-propylene copolymer (obtained in Reference Example 1) S-EPD: Styrene graft copolymer modified ethylene-propylene-ethylidene norbornene copolymer Combined (using Esprene E-501A instead of Esprene E-120 in Reference Example 1) S-EB: Styrene graft copolymerization modified ethylene-butene Copolymer (instead of ethylene Esprene E-120 of Reference Example 1 - butene-1 copolymer (using butene content 15 wt%)) [Effects of the Invention] As described above, the resin composition of the present invention exhibits an excellent balance of mechanical strength, solvent resistance and molding processability.

The resin composition according to the present invention is a molding method applied to a general thermoplastic resin composition, for example, injection molding, extrusion molding,
A product that can be easily processed into a molded product by blow molding or the like, has a very good balance of physical properties such as impact resistance, heat resistance, and solvent resistance, and has excellent appearance uniformity and smoothness.

Claims (1)

(57) [Claims] 1. A polyolefin resin 20 to 95% by weight
And (b) 80 to 5% by weight of polyphenylene ether resin, and (c) partially hydrogenated alkenyl aromatic compound-isoprene block co-weight based on 100 parts by weight of the total of the components (a) and (b). Ethylene-α-olefin copolymer elastomer 3 modified by graft-copolymerizing 3 to 45 parts by weight of the compound and (d) a styrene compound
A resin composition characterized by containing up to 45 parts by weight.