JP2885507B2 - High rigidity parts made of polypropylene resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a high-rigid component made of a polypropylene resin composition suitably used for a large-sized high-rigid component far from an instrument panel or a center console of an automobile.

More specifically, the present invention comprises a polypropylene, a thermoplastic reinforced elastomer in which a modified polyamide hybridized with a clay mineral has been finely dispersed in advance, and an inorganic filler, and has rigidity, heat resistance, scratch resistance, and resistance to heat. Related to high-rigidity parts with excellent impact properties.

[Conventional technology]

Crystalline polypropylene has been widely used in various applications since it has excellent surface gloss, heat resistance, damage resistance, and mechanical strength, and is easy to perform injection molding.

However, rigidity, heat resistance, dimensional stability, and the like are insufficient for use in industrial parts, particularly for large industrial parts. In order to improve the rigidity, heat resistance, and dimensional stability of polypropylene, a method of blending an inorganic filler such as talc or glass fiber with crystalline polypropylene is known. In particular, the surface impact is significantly reduced. Also, a polypropylene composition using an inorganic filler in combination with an ethylene / α-olefin copolymer rubber or a styrene-based elastomer is known.

However, the composition containing these ordinary rubber components has a disadvantage that the effect of improving the impact resistance is small and the surface hardness is reduced, so that the surface of the molded product is easily damaged and the appearance is impaired. .

[Problems to be solved by the invention]

In order to simultaneously and significantly improve the rigidity, heat resistance, damage resistance and impact resistance of polypropylene and its composition, select elastomers with high impact resistance and disperse them in a polypropylene matrix. Were so important that they needed to be improved.

Therefore, the present inventors have intensively studied an impact modifier having a large impact resistance improving effect and a very small decrease in rigidity in a composition comprising polypropylene and an inorganic filler, and a dispersion technique thereof. As a result, when the modified polyamide hybridized with the viscous mineral is finely and uniformly dispersed in the elastomer in advance, and the hard and toughened thermoplastic reinforced elastomer is used as the impact modifier, the dispersion in the polypropylene matrix is reduced. In addition to the dispersion due to the compatibility of the modified polyamide and the modified polypropylene, which are one component of the reinforced elastomer, the polyamide molecular chain of the reinforced elastomer is three-dimensionally spread around the clay mineral, and the semi-IPN is grafted to the elastomer. When the polypropylene is blended, the elastomer is dispersed in the polypropylene matrix in a salami-like form surrounding the fine particles of the modified polyamide, greatly improving the impact resistance and the high cohesion of the modified polyamide. Inorganic charge such as talc by force A polypropylene composition for high-rigidity parts, which has a much better balance of rigidity, heat resistance, damage resistance and impact resistance than conventional compositions without dispersing its structure even by the addition of filler. Can be obtained, which has led to the present invention.

The polypropylene composition of the present invention has much better dispersibility in a polypropylene modified with an unsaturated carboxylic acid and / or a derivative thereof than ordinary elastomers, and its dispersed form is not destroyed even by blending an inorganic filler. A major feature is that rigidity, heat resistance, damage resistance, and impact resistance are improved by using a hard and tough reinforced elastomer.

[Means for solving the problem]

According to the present invention, (i) a polypropylene resin
100 parts by weight of (ii) (a) 40 to 95 parts by weight of an elastomer and (b) 5 to 60 parts by weight of a modified polyamide modified with a clay mineral, and (c) ethylene and / or α-
To a total amount of 100 parts by weight of 2 to 50 parts by weight of a thermoplastic reinforced elastomer obtained by mixing 1 to 20 parts by weight of a copolymer of an olefin and an unsaturated carboxylic acid and / or a derivative thereof, (i)
ii) A high-rigidity component provided by forming a polypropylene composition containing 15 parts by weight or more and less than 70 parts by weight of an inorganic filler is provided.

The modified polypropylene used in the present invention can be obtained by graft-modifying a binding polypropylene.

Crystalline polypropylene has a melt index (ASTM
D1238, 230 ° C., 2160 g) may be a crystalline homopolymer of polypropylene of 0.3 to 70 g / 10 min, a random or block copolymer with ethylene, or a mixture thereof. The ethylene / propylene copolymer preferably has an ethylene content of 6% by weight or less for a random copolymer and 3 to 15% by weight for a block copolymer.

Among the crystalline polypropylenes, particularly preferred is an ethylene / propylene block copolymer having a melt index of 0.3 to 50 g / 10 minutes and an ethylene content of 3 to 10% by weight.

Unsaturated carboxylic acids and derivatives thereof are used as monomers for the graft-modified raw materials.

Examples of unsaturated carboxylic acids and derivatives thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid, crotonic acid, glycidyl methacrylate, 2-hydroxyethyl methacrylate, polyethylene glycol dimethacrylate, and N-methylol methacrylamide. , Calcium methacrylate, γ-methacryloxypropyltrimethoxysilane, acrylamide,
Use methacrylamide or the like, maleic anhydride, itaconic anhydride, citraconic anhydride, or the like. Preferred are acid anhydrides such as maleic anhydride and itaconic anhydride.

As a graft modification reaction initiator, a radical generating compound such as an organic peroxide can be used. In some cases, graft modification may be caused by heat treatment without using a reaction initiator. The reaction initiator is not particularly limited, and may have a half-life of 1 minute and a decomposition temperature for obtaining the half-life of 250 ° C. or less. Examples of such a reaction initiator include organic peroxides such as hydroperoxide, dialkyl peroxide, and peroxyester. As the organic peroxide used in the present invention, for example, t-butylperoxybenzoate, cyclohexanone peroxide, 2,5-dimethyl-
Examples thereof include 2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, methyl ethyl ketone peroxide, dicumyl peroxide, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane. At the time of use, it can be appropriately selected according to reaction conditions and the like.

The graft-modified crystalline polypropylene can be obtained by mixing the crystalline polypropylene with the modified raw material monomer and the reaction initiator, and melt-kneading the mixture in a nitrogen atmosphere or in the air. It can also be obtained by dissolving under pressure and heat in xylene, stirring and mixing while dropping the modified starting monomer and the reaction initiator. Melt kneading is 2
A kneader such as a screw extruder, an eder, and a Banbury mixer may be used, but usually, a single screw extruder can be used. The mixing temperature is not lower than the melting point of the raw material polypropylene and is usually from 175 to 280 ° C. The melting and mixing time varies depending on the raw materials and the like, but can be generally performed for about 1 to 20 minutes.

The mixing ratio of the raw materials is about 0.05 to 5 parts by weight of the raw material modified monomer and about 0.1 part by weight of the reaction initiator based on 100 parts by weight of the raw material polypropylene.
002 to 1 part by weight. When the amount of the monomer is less than about 0.05 part by weight, the effect of modification is not obtained, while when the amount is more than 5 parts by weight, the grafting efficiency of the monomer is extremely lowered and the amount of unreacted monomer is undesirably increased.

The modified polypropylene obtained as described above has a monomer graft ratio of about 0.03% by weight or more, preferably about 0.1 to
5% by weight and the melt index is about 0.5-200g /
What is 10 minutes is good. Melt index 0.5 ~ 10
If it is smaller, the moldability may be reduced, while if it exceeds 200 g / 10 minutes, the material having the desired performance cannot be obtained because the molecular weight is too low.

These modified polypropylenes may be used alone,
Alternatively, an unmodified crystalline polypropylene containing at least 2% by weight of a modified polypropylene may be used.

The thermoplastic reinforced elastomer composition used in the present invention comprises an elastomer and a clay mineral-modified polyamide or an elastomer and a clay mineral-modified polyamide with ethylene and / or
Alternatively, it comprises a copolymer of an α-olefin and an unsaturated carboxylic acid and / or a derivative thereof. The elastomer constituting these compositions is a hydrogenated rubber obtained by hydrogenating an ethylene / α-olefin copolymer rubber or a diene rubber, or a modified rubber obtained by modifying these with an unsaturated carboxylic acid or a derivative thereof. Alternatively, it may be either a mixture or a mixture.

The ethylene / α-olefin copolymer rubber is an ethylene / α-olefin copolymer rubber having an ethylene content of 30 to 95% by weight, preferably 60 to 90% by weight. The α-olefin component includes one having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene,
4-methyl-1-pentene, 1-decene and the like can be mentioned. The α-olefin component may be used alone or 2
A mixture of more than one type may be used. In some cases, a trace amount of a diene component may be contained.

The modified ethylene / α-olefin copolymer rubber can be obtained by graft-modifying the above-mentioned ethylene / α-olefin copolymer rubber. As the monomer for the graft-modified raw material, the same unsaturated carboxylic acid and its derivative as those used for the graft-modified monomer of the modified polypropylene are used. In addition, a radical-generating compound such as the above-mentioned organic peroxide can also be used for the graft modification reaction initiator. In some cases, graft modification may be caused by heat treatment without using a reaction initiator.

The modified ethylene / α-olefin copolymer rubber is prepared by heating and mixing and stirring the raw material ethylene / α-olefin copolymer rubber and the graft-modified raw material monomer in a solution in the presence of an initiator, or It is manufactured by heat-melting and kneading an olefin copolymer rubber and a graft-modified raw material monomer. The modified ethylene / α-olefin copolymer rubber produced in this manner has a raw material monomer ratio of about 0.01 to 10% by weight, preferably about 0.1 to 10% by weight.
3.0% by weight and melt index is about 0.01-50g / 1
0 minutes, preferably 0.05-15 g / 10 minutes each raw material ratio,
Reaction conditions are appropriately selected.

If the modified ethylene / α-olefin copolymer rubber has a monomer graft ratio of less than 0.01% by weight, the effect of modification cannot be obtained. If it exceeds 10% by weight, the degree of cross-linking of the rubber at the time of graft modification increases, and melting with the modified polyamide occurs. Mixing becomes difficult.

The diene-based hydrogenated rubber has, for example, a general formula of A- (B
-A) A hydrogenated derivative obtained by subjecting a block copolymer represented by _n to a hydrogenation treatment. Here, in the above general formula, A is a polymer block of a monovinyl-substituted aromatic hydrocarbon, B is an elastomeric polymer block of a conjugated diene, and n is an integer of 1 to 5.

The monovinyl-substituted aromatic hydrocarbon of the monomer constituting the polymer block A is preferably styrene,
Methylstyrene, vinyltoluene and other lower alkyl-substituted styrene and vinylnaphthalene groups are also used.

The conjugated diene monomer in the polymer B is preferably butadiene or isoprene, or a mixture of both. When butadiene is used as a single conjugated diene monomer to form polymer block B, the block copolymer retains elastomeric properties after hydrogenation and saturation of the double bonds. For this purpose, it is preferable to employ polymerization conditions in which the 1,2-microstructure in the microstructure of the polybutadiene block is 20 to 50%. More preferably, the 1,2-microstructure is 35-45%.

The weight average molecular weight of the polymer block A in the block copolymer is 5,000 to 125,000, and that of the polymer block B is 15,0
Preferably in the range of 00 to 250,000.

Numerous methods have been proposed for producing these block copolymers. As a typical method, for example, there is a method described in JP-B-40-23798,
The block copolymerization is performed in an inert solvent using a lithium solvent or a Ziegler type catalyst.

The hydrogenation treatment of these block copolymers can be carried out, for example, by the method described in JP-B-42-8704, JP-B-43-6636 or JP-B-46-20814, in the presence of a catalyst in an inert solvent. This is done by hydrogenation below. In this hydrogenation, at least 50%, preferably 80% or more of the olefin group double bonds in the polymer block B are hydrogenated, and 25% or less of the aromatic unsaturated bonds in the polymer block A are hydrogenated. Is done. As the above block copolymer, specifically, a styrene / butadiene / styrene copolymer (SBS) hydrogenated copolymer (SEBS) and a styrene / inprene / styrene copolymer (SIS) were hydrogenated. And copolymers (SEPS).

Further, the graft-modified starting monomer, the graft-modifying reaction initiator, the production method and the graft-modified starting monomer of the modified hydrogenated block copolymer obtained by graft-modifying the above diene-based hydrogenated block copolymer, It is the same as the above-mentioned modified ethylene / α-olefin copolymer rubber.

These modified diene-based hydrogenated block copolymer rubbers and modified ethylene / α-olefin copolymer rubbers may be used alone, or ethylene / α-olein copolymer rubbers and / or diene-based hydrogenated block copolymer rubbers may be used alone. The polymer rubber can be used in combination with the unsaturated carboxylic acid or its derivative monomer in a range of more than 0.01 part by weight based on 100 parts by weight of the elastomer.

Further, the clay mineral-modified polyamide resin constituting the reinforced elastomer is 0.05 to 1 with respect to 100 parts by weight of the polyamide.
0 parts by weight, preferably 0.1 to 7 parts by weight, of a specific clay mineral is uniformly dispersed and compounded to greatly improve heat resistance, rigidity and the like. If the proportion of the clay mineral is less than 0.05 part by weight, no improvement effect such as heat resistance and rigidity is recognized, and if it exceeds 15 parts by weight, the fluidity at the time of melting is significantly reduced and injection molding may be impossible. .

As the polyamide resin used for the modified polyamide of the present invention, an aliphatic, alicyclic, polyamide obtained by polycondensation of an aliphatic or alicyclic aromatic dicarboxylic acid with an aliphatic or alicyclic aromatic dicarboxylic acid, or a lactam Polyamide,
Examples thereof include polyamides obtained by condensation of aminocarboxylic acids and copolymerized polyamides composed of these components. Specific examples include nylon-6, nylon-6,6, nylon-6,10, nylon-9, nylon-11, nylon-12, nylon-6 / 6,6, nylon-12,12 and the like.

The clay mineral for modifying the polyamide resin is mainly a layered silicate, the shape of which usually has a side length of 0.00.
It is 2-1 μm thick and 6-20 mm thick. As a raw material of such a layered silicate, there is, for example, a layered phyllosilicate mineral composed of a layer of magnesium silicate or aluminum silicate.

Specific examples include smectite-based clay minerals such as montmorillonite, saponite, beidellite, nontronite, hectorite, and stevensite, vermiculite, halloysite, and the like. These may be natural or synthetic. Among them, montmorillonite is particularly preferred.

Preferably, each layered silicate is uniformly dispersed in the polyamide at an average distance of 20 ° or more. There is no particular limitation on the method of dispersing the layered silicate in the polyamide resin.However, when the raw material of the layered silicate is a multilayer clay mineral, the layered silicate is brought into contact with a swelling agent, and the layers are expanded in advance and between the layers. A method in which a monomer is easily incorporated and then mixed with a polyamide monomer and polymerized (JP-A-62-64827, JP-A-62-64827).
-72723, JP-A-62-74957, etc.). Alternatively, a method may be used in which a polymer compound is used as a swelling agent, the interlayer is expanded to 100 ° or more in advance, and this is melt-mixed with a polyamide resin.

The modified polyamide modified by clay mineral has a polyamide molecule chain three-dimensionally spread between the layers of each clay mineral, and has a high cohesive force centered on clay mineral, greatly improving heat resistance and rigidity. ing.

The copolymer of ethylene and / or α-olefin and unsaturated carboxylic acid and / or derivative thereof used in the present invention is ethylene and / or α-olefin having 3 to 20 carbon atoms.
It can be produced by grafting an unsaturated carboxylic acid or a derivative thereof or an unsaturated epoxy compound to a (co) polymer with an olefin. Α- other than ethylene
As the olefin, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-
Octene, 1-decene and the like can be exemplified.

As the unsaturated carboxylic acid or its acid derivative, specifically, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, unsaturated carboxylic acid such as tetrahydrophthalic acid, maleic anhydride, itaconic anhydride And anhydrides of unsaturated carboxylic acids such as citraconic anhydride and tetrahydrophthalic anhydride, and esters of unsaturated carboxylic acids such as methyl acrylate, methyl methacrylate, dimethyl maleate and monomethyl maleate.

Examples of the unsaturated epoxy compound include glycidyl esters of unsaturated monocarboxylic acids such as glycidyl acrylate and glycidyl methacrylate; monoglycidyl esters and polyglycidyl esters of unsaturated polycarboxylic acids such as maleic acid, itaconic acid and citraconic acid. No.

The unsaturated carboxylic acid or its acid derivative is converted to ethylene and / or
Or the method of copolymerizing into an α-olefin (co) polymer,
For example, various known methods such as melting the (co) polymer and adding a graft monomer to carry out graft copolymerization, or dissolving in a solvent and adding the graft monomer to carry out copolymerization can be employed.

The copolymerization with the unsaturated epoxy compound is carried out by using one or two kinds of the α-olefin and an unsaturated epoxy monomer having one ethylenically unsaturated bond and one epoxy group in one molecule as a radical initiator. It can be produced by a method of using and copolymerizing or a method of grafting an unsaturated epoxy compound to an ethylene and / or α-olefin (co) polymer.

Among these, particularly preferred modified ethylene and / or α
-Examples of the olefin copolymer include an ethylene / ethyl methacrylate / maleic anhydride copolymer, an ethylene / glycidyl methacrylate copolymer, and the above-mentioned modified polypropylene.

The amount of grafting of the unsaturated carboxylic acid or derivative thereof or the unsaturated epoxy compound is preferably 0.5 to 5% by weight. When the graft amount is less than 0.5% by weight, the effect of improving the compatibility with the modified polyamide resin is extremely low, so that there is no effect of improving the mechanical strength. On the other hand, if it exceeds 10% by weight, partial crosslinking occurs, and the surface appearance and moldability of the composition are reduced.

In the present invention, the inorganic filler used, as a powdery filler, for example, alumina, magnesium oxide, calcium oxide, oxides such as zinc white, aluminum hydroxide,
Magnesium hydroxide, hydrated metal oxides such as calcium hydroxide, calcium carbonate, carbonates such as magnesium carbonate,
Silicates such as talc, clay, bentonite, etc .; borates such as barium borate; phosphates such as aluminum phosphate; sulfates such as barium sulfate; mixtures of two or more of these; fibrous fillers As, for example, glass fiber,
Potassium titanate fiber, ceramic fiber, wollastonite, carbon fiber, SUS fiber, moss heidi, etc., as well as glass beads, glass flakes, mica and the like can be mentioned. Further, the surface of the inorganic filler may be treated with a silane compound, for example, vinylethoxysilane, 2-aminopropyltriethoxysilane, 2-glycidoxypropylmethoxysilane, or a titanate compound. Of these, talc is particularly preferred as the powdery filler, and glass fiber is preferred as the fibrous filler.

The polypropylene composition for high-rigidity parts of the present invention is 98 to 50 parts by weight of a polypropylene resin, preferably 90 to 60 parts by weight, and a thermoplastic reinforced elastomer composition of a polyamide and an elastomer modified with a clay mineral and 2 to 50 parts by weight. 15 parts by weight or more of an inorganic filler to 100 parts by weight of a polypropylene resin composition comprising 100% by weight, preferably 10 to 40% by weight.
It is constituted by blending less than parts by weight. If the inorganic filler is less than 15 parts by weight with respect to 100 parts by weight of the polypropylene resin composition, heat resistance, rigidity, and dimensional stability are insufficient for large high-rigidity parts such as automobile instrument pulses and center consoles, If the amount is more than 70 parts by weight, the effect of improving the impact resistance by the incorporation of the reinforced elastomer cannot be sufficiently obtained, and a problem such as deterioration of the damage resistance occurs.

When the reinforced elastomer is less than 2% by weight in the polypropylene composition, a sufficient effect of improving impact resistance cannot be obtained.

Conversely, if the reinforced elastomer exceeds 50% by weight, the rigidity and heat resistance are greatly reduced even in the case of a filler, which is insufficient for large, high-rigidity parts.

Further, in the polypropylene resin composition, the reinforced elastomer composition is a modified elastomer modified with an unsaturated carboxylic acid or a derivative thereof in an amount of 40 to 95% by weight, preferably 40 to 95% by weight.
Modified polyamide 60 to 5 which is modified with clay mineral by 80% by weight
% By weight, preferably 60 to 20% by weight. If the modified polyamide is 60% by weight or more, the dispersed structure of the reinforced elastomer composition exhibits a sea-island structure with the modified polyamide as the sea, and the effect of improving the impact resistance by blending the reinforced elastomer with polypropylene cannot be said to be sufficient. When the content is 5% by weight or less, the effect of improving the rigidity and heat resistance is small even when the filler is blended, and there is no particular effect on the damage resistance.

The present invention also relates to 100 parts by weight of a composition comprising a modified elastomer and a modified polyamide, ethylene and / or α
A mixture of 1 to 20 parts by weight of a copolymer of an olefin and an unsaturated carboxylic acid or a derivative thereof and / or an unsaturated epoxy compound. If the amount of the copolymer is less than 1 part by weight, the effect of improving the properties of the modified polyamide in the reinforced elastomer will not be improved, and if it exceeds 20 parts by weight, the reaction between the modified compound component and the modified polyamide will proceed and the moldability will be remarkable. To obtain favorable results.

In order to obtain the polypropylene composition for a high-rigidity component of the present invention, there is no particular limitation other than the production of the reinforced elastomer composition and then the production of the present composition, and any ordinary known method can be used.

In order to obtain a reinforced elastomer, a modified elastomer and a modified polyamide are used, and ethylene and / or α
-Olefins and unsaturated carboxylic acids or their derivatives and / or
Or a copolymer with an unsaturated epoxy compound in the above-mentioned range by various known methods such as a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, etc., and a single-screw extruder, a twin-screw extruder, a kneader, A method of pelletizing after melt mixing with a Banbury mixer or the like can be adopted.

Next, the reinforced elastomer, the modified polypropylene and the inorganic filler can be produced in the above-mentioned range by melt-mixing and pelletizing by the above-mentioned method.

In order to further simplify the kneading step, the step of producing the reinforced elastomer composition in advance can be incorporated into the production step of the composition of the present invention. That is,
In the first step, the reinforced elastomer composition can be prepared, and in the second step, the polypropylene resin and the inorganic filler can be charged into a state where the reinforced elastomer is in a molten state. In addition, a method in which the polypropylene resin and the inorganic filler are sufficiently melt-mixed in the first step, and the reinforced elastomer composition is charged and manufactured in the second step can also be adopted. In order to make this method more effective, it is preferable to use a twin-screw extruder having a long L / D and having a raw material supply port in a cylinder in addition to a normal raw material supply port.

The thermoplastic resin composition of the present invention includes an antioxidant, an ultraviolet absorber, a lubricant, a pigment, an antistatic agent, a copper damage inhibitor, a flame retardant, a neutralizing agent, a plasticizer, a nucleating agent, a dye, and a foaming agent. And the like may be blended within a range that does not impair the purpose of the present invention.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to these Examples. The measuring method used in the examples of the present invention is as follows.

Tensile strength (TYS) (kg / cm ² ): ASTM D638 Flexural strength (FS) (kg / cm ² ): ASTM D2584 Flexural modulus (FM) (kg / cm ² ): ASTM D2584 Izod impact strength (IZOD) ( kg ・ cm / cm): ASTM D256 Heat Deformation Temperature (HDT) (℃): ASTM D648 Surface Hardness (RH) (R Scale): ASTM D785 High Speed Impact Strength (HSI) (kg ・ cm): 1.6mm Thickness A disc having a diameter of 100 mm was formed, and the disc was used as a test piece to drop a round missile of 2.54 cmφ at −10 ° C. onto this disc at a speed of 2.5 m / sec.
It was performed by the surface impact measurement method (UBE method) that calculates the fracture energy from the area of the stress-strain curve at the time of fracture.

Scratchability: A flat plate (injection molding) with a thickness of 2 mm and 100 mm x 100 mm was used as a test piece and a load of 1 kg was applied to this test piece.
0 The paper was rubbed back and forth once with side paper, and the scratched portion was visually observed and evaluated. When the scratch was not conspicuous: O, and when it was conspicuous: X.

Coefficient of linear expansion (mm / mm / ° C): ASTM 696 (-30 ° C to 30 ° C) The above test pieces for physical property evaluation have a molding temperature of 240 ° C and a mold temperature of 50.
C., an injection time of 15 sec, and a cooling time of 30 sec. The raw materials used in Examples and Comparative Examples are as follows.

<Modified polypropylene> A crystalline ethylene / propylene block copolymer having a melt index of 1.0 g / 10 minutes and an ethylene content of 10% by weight, 10
A modified polypropylene (hereinafter, referred to as MPP) obtained by adding 0.2 parts by weight of maleic anhydride and 0.2 parts by weight of t-butylperoxybenzoate to 0 parts by weight and melt-mixing the mixture at 220 ° C. in a single screw extruder was used.

The melt index of this modified polypropylene is 25 g /
After 10 minutes (230 ° C.), the grafted amount of maleic anhydride was 0.18% by weight. The amount of maleic anhydride grafted to MPP is determined by dissolving MPP in P-xylene, mixing with cold acetone equivalent to 3 times the amount of P-xylene, cooling and reprecipitating MPP.
The solvent containing this reprecipitated MPP was filtered and dried, dissolved again in P-xylene, KOH was added while heating, and titration was performed with HCl using thymol blue as an indicator.

<Polypropylene> Melt index 15g / 10 minutes, ethylene content 10% by weight
Crystalline ethylene-propylene copolymer made by Ube Industries “J8
15HK "<Reinforced elastomer> The following elastomer components are used in the reinforced elastomer (RE).

EPR: Ethylene / propylene copolymer rubber having an ethylene content of 73% by weight MEPR: Modified ethylene / propylene modified in a 100 ° C para-xylene solution by adding 0.8 parts by weight of maleic anhydride and 0.4 parts by weight of dicumyl peroxide to 100 parts by weight of EPR Copolymer Rubber This MEPR has a melt index of 0.7 g / 10 min (230
C), and the grafted amount of maleic anhydride was 0.6% by weight. The measurement of the graft amount was determined by the same method as the above-described method for measuring the graft amount of MPP.

SEBS-1: "Creton G1650" manufactured by Shell Chemical Company SEBS-2: "Creton G1657" manufactured by Shell Chemical Company MSEBS: "Creton FG1901X" manufactured by Shell Chemical Co., Ltd.
1901X "was used. The amount of maleic anhydride grafted on FG1901X was 2.0% by weight as determined by the above method.

Modified polyamide in reinforced elastomer (MPA)
As components, molecular weight 15,000, montmorillonite content 2
% By weight. In addition, usually as nylon,
"Nylon-6 1013B" manufactured by Ube Industries was used.

Other components in the reinforced elastomer include 15 parts by weight of maleic anhydride and t-butyl par with 100 parts by weight of a polypropylene homopolymer (B101H manufactured by Ube Industries) having a melt flow index of 1 g / 10 minutes (230 ° C.). 1 part by weight of oxybenzoate was added, and modified polypropylene (PO) modified in P-xylene at 130 ° C. was used. MF of the PO
R was 60 g / 10 minutes (230 ° C.), and the grafted amount of maleic anhydride was 6% by weight.

The reinforced elastomers were obtained by melt-mixing them at 240 ° C. in a twin-screw extruder and pelletizing them with the compositions shown in Table 2.

<Inorganic filler> Talc having an average particle size of 2 µm was used.

<Example 1> 12.5% by weight of modified polypropylene (MPP), 75% by weight of polypropylene (PP) and reinforced elastomer (RE-1) 1
2.5 parts by weight and 25 parts by weight of talc for 100 parts by weight of the total of MPP, PP and RE-1 were dry-blended in a V-blender and melt-mixed in a two-way twin-screw extruder "2FCM-65φEXT." Pelletized. The pellets were dried with hot air at 80 ° C. and injection-molded at 230 ° C. to prepare test pieces for measuring physical properties.

<Example 2> MPP 12.5% by weight, PP 62.5% by weight and RE-2 25% by weight
And 25 parts by weight of talc with respect to 100 parts by weight of the total amount of MPP, PP and RE-2 were pelletized in the same manner as in Example 1,
I got a test piece.

<Example 3> 12.5% by weight of MPP, 62.5% by weight of PP, and 25% by weight of RE-3
And 25 parts by weight of talc with respect to 100 parts by weight of the total amount of MPP, PP and RE-3 were pelletized in the same manner as in Example 1,
I got a test piece.

<Example 4> A method similar to that of Example 1 except that MPP 15.4% by weight, PP 38.4% by weight, RE-2 46.2% by weight, and MPP, PP and RE-2 total 100 parts by weight and talc 53.8 parts by weight were used. To obtain a test piece.

<Example 5> 12.5% by weight of MPP, 62.5% by weight of PP and 25% by weight of RE-4
A test piece was obtained by pelletizing 25 parts by weight of talc in the same manner as in Example 1 with respect to 100 parts by weight of the total amount of MPP, PP and RE-4.

<Comparative Example 1> 87.5% by weight of polypropylene (PP), 12.5% by weight of ethylene / propylene copolymer rubber (EPR), and 25 parts by weight of talc were added to 100 parts by weight of PP and EPR with 2FCM-65φEX.
T. Melted and mixed at 220 ° C, pelletized, and injection molded at 230 ° C to produce a test piece.

<Comparative Example 2> Instead of EPR, a styrene elastomer (SEBS-
Except using 1), it carried out similarly to the comparative example 1.

Comparative Example 3 75% by weight of PP as polypropylene resin composition, EPR
12.5% by weight, 12.5% by weight of SEBS-1 and 25 parts by weight of talc based on 100 parts by weight of this polypropylene resin composition were pelletized in the same manner as in Comparative Example 1 to obtain a test piece.

<Comparative Example 4> 11.1% by weight of MPP as a polypropylene resin composition,
Based on 66.7% by weight of PP, 22.2% by weight of RE-2 and 100 parts by weight of this polypropylene resin composition, 11.1 parts by weight of talc were pelletized in the same manner as in Example 1 to obtain a test piece.

<Comparative example 5> It carried out like Example 2 except having used elastomer (E-1) instead of RE-2.

<Comparative Example 6> 15.4% by weight of MPP as a polypropylene resin composition,
38.5% by weight of PP, 11.5% by weight of EPR, 7% by weight of modified ethylene / propylene copolymer rubber (MEPR), 4.6% by weight of SEBS-2, 23.0% by weight of MPA and 53.8% by weight of talc based on 100 parts by weight of this polypropylene resin composition The portion was pelletized in the same manner as in Example 1 to obtain a test piece.

 The results are shown in Table 1.

(Effects of the Invention) The present invention is to finely disperse the modified polyamide hybridized with a clay mineral in advance in an elastomer,
Hard and toughened reinforced elastomer is used as an impact modifier for polypropylene, and by adding an inorganic filler, it can be used without impairing the rigidity, heat resistance, damage resistance and mechanical strength of the polypropylene composition. It has improved impact characteristics and dimensional accuracy.

The novel composition provided by the present invention can be molded by ordinary molding methods such as injection molding and extrusion molding, and is excellent in rigidity, heat resistance, damage resistance and impact resistance, and is suitable for automobile instrument panels. Suitable for industrial parts such as interior parts such as center consoles and trims, home electric parts parts, machine parts and other large and high rigid parts that require rigidity, heat resistance, impact resistance and dimensional accuracy. .

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 23/26 C08L 23/26 51/06 51/06 77/00 77/00 (72) Inventor Akane Okada Nagakute, Aichi-gun, Aichi Prefecture 41, No. 41, Yokomichi, Chomachi, Chuo-cho, Toyoda Central Research Laboratories Co., Ltd. 3-1 Chikko Shinmachi, Sakai City, Osaka Ube Industries, Ltd. Sakai Plant (72) Inventor Tomohiko Akakawa 3-1 Chikko Shinmachi, Sakai City, Osaka Prefecture Ube Industries, Ltd. Sakai Plant (72) Inventor Ikunori Sakai Osaka 3-1 Chikko Shinmachi, Sakai City Inside the Sakai Plant of Ube Industries, Ltd. (72) Inventor Takashi Exit 1978-10, Ogushi, Obe-shi, Ube, Yamaguchi Prefecture Inside the Ube Chemical Plant of Ube Industries, Ltd. 14 854 (JP, A) JP-A-4-96957 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 23/00-23/26 C08L 9/04 C08L 77/00- 77/12 C08L 51/06

Claims (3)

(57) [Claims] (1) 98 to 50 parts by weight of a polypropylene resin and (ii) 40 to 95 parts by weight of an elastomer (a) and (b)
100 parts by weight of a total of 5 to 60 parts by weight of a modified polyamide modified with a clay mineral, (c) 1 to 20 parts by weight of a copolymer of ethylene and / or an α-olefin and an unsaturated carboxylic acid and / or a derivative thereof (Iii) a polypropylene composition comprising (iii) an inorganic filler in an amount of 15 parts by weight or more and less than 70 parts by weight in a total amount of 100 parts by weight of 2 to 50 parts by weight of a thermoplastic reinforced elastomer comprising High rigidity parts. 2. The polypropylene resin is (a) a modified polypropylene graft-modified with an unsaturated carboxylic acid and / or a derivative thereof and / or (b) a crystalline polypropylene containing at least 2% by weight of the modified polypropylene. The high-rigidity component according to claim 1. 3. The thermoplastic reinforced elastomer comprises: (a) an ethylene / α-olefin copolymer rubber, (b)
A modified ethylene / α-olefin copolymer rubber obtained by modifying the above-mentioned ethylene / α-olefin copolymer rubber with an unsaturated carboxylic acid and / or a derivative thereof, (c) a hydrogenated rubber obtained by hydrogenating a diene rubber, 3. The high-rigidity component according to claim 1, wherein d) is at least one elastomer selected from the group consisting of a modified hydrogenated rubber obtained by modifying the hydrogenated rubber with an unsaturated carboxylic acid and / or a derivative thereof.