JP2885492B2 - Polypropylene composition for high impact parts - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a high impact polypropylene composition suitably used for large high impact parts such as automobile bumpers.

More specifically, in the present invention, a modified polyamide hybridized with a clay mineral and a copolymer of ethylene and / or an α-olefin with an unsaturated carboxylic acid or a derivative thereof and / or an unsaturated epoxy compound are blended with polypropylene. The present invention relates to a polypropylene composition for high impact parts, which is obtained by blending an inorganic filler and an inorganic filler, and is particularly excellent in rigidity, heat resistance, impact resistance, damage resistance and dimensional stability.

[Conventional technology]

Crystalline polypropylene has excellent rigidity, surface gloss, heat resistance, damage resistance, and mechanical strength, and is easy to injection mold.
Conventionally, it has been widely used for various applications. However, for applications for large parts such as automobile bumpers, impact resistance,
Heat resistance, rigidity, etc. were insufficient. For this reason, crystalline polypropylene and an inorganic filler such as talc and ethylene / α-
A polypropylene composition blended with an olefin copolymer rubber or a styrene-based elastomer has been developed for use in large impact resistant parts.

However, this polypropylene composition has a problem in that the balance between impact resistance, rigidity and heat resistance is not so much improved, and furthermore, the surface hardness is low, so that the polypropylene composition is inferior in damage resistance.

Therefore, various methods for obtaining a polypropylene composition having excellent rigidity, heat resistance, impact resistance, and excellent damage resistance have been attempted. For example, a polypropylene in which a polyamide or the like and a modified elastomer are blended with a crystalline polypropylene-
Polyamide-based compositions and the like have been developed so far (JP-A-59-149940, JP-A-60-110740, JP-A-62-54743).
No. etc.). This polypropylene-polyamide composition has high surface hardness as well as improved scratch resistance in addition to rigidity, heat resistance and impact resistance.

[Problems to be solved by the invention]

However, even the above-mentioned polypropylene-polyamide composition cannot be said to have sufficient rigidity, heat resistance and impact resistance for large parts, and furthermore, this composition contains plastics and elastomers such as crystalline polypropylene, polyamide and modified elastomer. Since it is composed only of components and does not contain an inorganic filler, there is a disadvantage that the coefficient of linear expansion is large.

For this reason, the molded article using this polypropylene-polyamide composition had a large dimensional change accompanying a temperature change in the use environment. This problem is particularly noticeable when used for large parts.

It is generally known that the dimensional stability of polypropylene and its composition can be improved by blending an inorganic filler such as talc. However, it has been found that simply adding an inorganic filler to the above-mentioned polypropylene-polyamide composition destroys the dispersion structure of a polypropylene matrix such as a polyamide or a modified elastomer, and significantly reduces impact resistance. For this reason, it was difficult to apply it to the use of large parts simply by blending the inorganic filler.

In order to simultaneously and significantly improve the rigidity, heat resistance, impact resistance, damage resistance and dimensional stability of polypropylene and its composition, select elastomers with a high effect of improving impact resistance and its polypropylene matrix. Dispersion technology is very important. The impact modifier must have a high impact modifying effect and must not destroy the dispersed structure in the polypropylene matrix due to the inorganic filler.

In view of such circumstances, the present inventors have diligently investigated an impact modifier for polypropylene whose dispersion structure is not destroyed by an inorganic filler or the like and a dispersion technique thereof. As a result, the modified polyamide hybridized with the clay mineral is finely and uniformly dispersed in the elastomer in advance,
When a toughened thermoplastic reinforced elastomer is used as an impact modifier, the dispersion in the polypropylene matrix is not only the dispersion due to the compatibility of the modified polyamide and the modified polypropylene as one component of the reinforced elastomer, but also the reinforced elastomer. In the case, the polyamide molecular chain spreads three-dimensionally around the clay mineral and forms a semi-IPN-like dispersed structure by graft bonding with the elastomer. It is dispersed in a polypropylene matrix in the form of a ceramic surrounding it, greatly improving impact resistance, and the high cohesive force of the modified polyamite prevents the dispersion structure from being destroyed by the addition of an inorganic filler such as talc. , Heat resistance, impact resistance, damage resistance and dimensional stability It found to be able to get this to high impact parts for polypropylene compositions much better than composition, leading 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. There is a great feature in that rigidity, heat resistance, impact resistance, damage resistance, and dimensional stability are improved by using a hard and tough reinforced elastomer.

[Means for solving the problem]

According to the present invention, (i) the modified polypropylene (a) 98
-30% by weight, modified elastomer (g) obtained by graft-modifying at least a part of elastomer (f) with unsaturated carboxylic acid or its derivative, 40-95% by weight, and polyamide (h) 60-5% by weight modified with clay mineral And 100 parts by weight of the total of components (f) and (h), ethylene and / or α-
The copolymer (i) of an olefin and an unsaturated carboxylic acid or a derivative thereof and / or an unsaturated epoxy compound is
1 to 15 parts by weight of an inorganic filler (d) based on 100 parts by weight of a polypropylene resin composition (c) comprising 2 to 70% by weight of a reinforced elastomer composition (b) blended with 20 to 20 parts by weight. And a polypropylene composition for high impact parts comprising:

The modified polypropylene of the component (a) used in the present invention comprises:
It can be obtained by graft-modifying the crystalline polypropylene (e).

The crystalline polypropylene (e) may be any of a crystalline homopolymer of polypropylene having a melt index (ASTM D1238, 230 ° C., 2160 g) of 0.3 to 70 g / 10 min, a random or block copolymer with ethylene, and a mixture thereof. Crystalline polypropylene may be used. The ethylene / propylene copolymer has an ethylene content of 6 in a random copolymer.
% By weight or less, and preferably 3 to 15% by weight of the 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, as long as the decomposition temperature for obtaining a one-minute half-life is 250 ° C. or less. Examples of such a reaction initiator include organic peroxides such as hydroperoxide, dialkyl peroxide, and peroxyester. Examples of the organic peroxide used in the present invention include t-butylperoxybenzoate, cyclohexanone peroxide, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, methyl ethyl ketone peroxide, Milperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and the like can be mentioned. 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 starting 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, and stirring and mixing while dropping the modified starting monomer and the reaction initiator. Melt kneading may be performed using a kneader such as a twin-screw extruder, a kneader, or a Banbury mixer, but it can usually be performed with a single-screw extruder. 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 3.0 parts by weight of the raw material modified monomer and about 100 parts by weight of the raw material polypropylene,
0.002 to 1 part by weight. If the amount of the monomer is less than about 0.05 part by weight, the effect of the modification cannot be obtained.

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 1%.
0.0% by weight, melt index about 0.5-200g
10 minutes is better. Melt index 0.5 / 10
If it is smaller than 200 minutes, the moldability may be reduced. On the other hand, 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,
Further, a modified polypropylene and an unmodified crystalline polypropylene can be used in combination in a range where the graft amount of the unsaturated carboxylic acid or its derivative monomer exceeds 0.03 part by weight with respect to 100 parts by weight of polypropylene.

In the present invention, the modified elastomer (g) constituting the reinforced elastomer component (b) is a modified rubber obtained by modifying an ethylene / α-olefin copolymer rubber or a styrene-based hydrogenated rubber with an unsaturated carboxylic acid or a derivative thereof, and / or Or a mixture with the elastomer component (f).

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. Examples of the α-olefin component include those having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene,
-Methyl-1-pentene, 1-decene and the like. The α-olefin component may be used alone or as a mixture of two or more. 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 obtained by mixing and heating the raw material ethylene / α-olefin copolymer rubber and the graft-modified raw material monomer in a solution in the presence of an initiator while heating or mixing the raw material. 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 thus produced has a raw material monomer graft 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
/ 10 minutes, preferably 0.05 to 15 g / 10 minutes, the ratio of each raw material and the reaction conditions are appropriately selected.

If the monomer graft ratio of the modified ethylene / α-olefin copolymer rubber is less than 0.01% by weight, the effect of modification cannot be obtained, and 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. Mixing becomes difficult.

The styrene-based hydrogenated rubber is a hydrogenated derivative obtained by subjecting a block copolymer represented by the general formula A- (BA) _n to 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
It is 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 Japanese Patent Publication No. 40-23798, in which block copolymerization is carried out 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, by 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 bond in the polymer block B is hydrogenated,
Up to 25% of the aromatic unsaturated bonds in polymer block A are hydrogenated. As the above block copolymer, specifically, styrene / butadiene / styrene copolymer (SB
Examples include a copolymer (SEBS) obtained by hydrogenating S) and a copolymer (SEPS) obtained by hydrogenating styrene / isoprene / styrene copolymer (SIS).

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 styrene-based hydrogenated block copolymer, It is the same as the above-mentioned modified ethylene / α-olefin copolymer rubber.

These modified styrene-based hydrogenated block copolymer rubbers and modified ethylene / α-olefin copolymer rubbers may be used alone, or ethylene / α-olefin copolymer rubbers and / or styrene-based hydrogenated block copolymer rubbers may be used alone. Polymer rubber can be used in combination with an 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 modified polyamide resin (h) constituting the reinforced elastomer (b) is added in an amount of 0.0
5 to 10 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 not be possible. .

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. Specifically, 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, and halloysite. These may be natural or synthetic. Among these, 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-62-7
2723, 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.

Modified polyamide modified by clay mineral has a high cohesive force centered on clay mineral with polyamide molecular chains spreading three-dimensionally between the layers of individual clay minerals, greatly improving heat resistance and rigidity. I have.

Further, component (i) is a modified ethylene and / or α-olefin copolymer having one or more groups as functional groups.

The modified ethylene and / or α-olefin copolymer is obtained by grafting an unsaturated carboxylic acid or a derivative thereof or an unsaturated epoxy compound to a (co) polymer of ethylene and / or an α-olefin having 3 to 20 carbon atoms. It can be manufactured by Α-olefins other than ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene,
-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 a method in which a (co) polymer is melted and a graft monomer is added to carry out graft copolymerization, or a method in which the polymer is dissolved in a solvent and the graft monomer is added to carry out copolymerization, can be used.

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 ethylene / ethyl methacrylate / maleic anhydride copolymer, ethylene, glycidyl methacrylate copolymer, and the above-mentioned modified polypropylene (a).

The graft amount of the unsaturated carboxylic acid or its derivative or the unsaturated epoxy compound is preferably from 0.3 to 5% by weight. When the graft amount is less than 0.1% 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 the component (d) may be a powdery filler such as an oxide such as alumina, magnesium oxide, calcium oxide, zinc oxide, aluminum hydroxide, magnesium hydroxide, and calcium hydroxide. Hydrated metal oxides such as calcium carbonate, magnesium carbonate, etc., silicates such as talc, clay, bentonite, etc., borates such as barium borate, phosphates such as aluminum phosphate, and sulfuric acid Sulfates such as barium and mixtures of two or more of these, as fibrous fillers, for example, glass fiber, potassium titanate fiber, ceramic fiber, wollastonite, carbon fiber, SUS fiber, moss heidi, etc., other glass beads, glass Flakes, mica and the like can be mentioned. 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 impact parts according to the present invention comprises 98 to 30% by weight, preferably 90 to 50% by weight of a modified polypropylene (a) obtained by modifying at least a part of a crystalline polypropylene (e) with an unsaturated carboxylic acid or a derivative thereof. % Of a modified elastomer (g) and a polyamide (h) modified with a clay mineral (h).
1 part by weight or more and less than 15 parts by weight, preferably 5 parts by weight or more and less than 15 parts by weight based on 100 parts by weight of the polypropylene resin composition (c) consisting of 10% by weight, preferably 10 to 50% by weight. Composed of

When the amount of the inorganic filler of the component (d) is less than 1 part by weight with respect to the polypropylene resin composition (c), there is no effect of improving the dimensional stability. The appearance quality problem such as the occurrence of flow marks in the injection molded product occurs.

When the reinforced elastomer (b) is less than 2% by weight in the polypropylene resin composition (c), a sufficient impact resistance improvement effect cannot be obtained as a polypropylene composition for high impact parts. Conversely, if the reinforced elastomer (b) exceeds 70% by weight, the dispersion structure of the polypropylene resin composition (c) becomes a sea-island structure in which the elastomer is the sea, and the rigidity, heat resistance, and heat resistance can be improved by the addition of the filler. The susceptibility is greatly reduced.

Further, in the polypropylene resin composition (c), the reinforced elastomer composition (b) is a modified elastomer (g) modified with an unsaturated carboxylic acid or a derivative thereof in an amount of 40 to 95% by weight, preferably 40 to 80% by weight, and a clay mineral. And 60 to 20% by weight, preferably 60 to 20% by weight of the modified polyamide (h).
If the content is more than 5% by weight, the dispersed structure of the reinforced elastomer composition exhibits a sea-island structure with the modified polyamide (h) as the sea, and the effect of improving the impact resistance by the addition of the reinforced elastomer (b) cannot be said to be sufficient. When the content is less than 10% by weight, 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.

Further, the present invention relates to 100 parts by weight of the composition (b) comprising the above-mentioned component (g) and component (h), and ethylene and / or α
The copolymer (i) of an olefin and an unsaturated carboxylic acid or a derivative thereof and / or an unsaturated epoxy compound is
It is composed by mixing 20 parts by weight. If the amount of component (i) is less than 1 part by weight, the effect of improving the properties of the modified polyamide in the reinforced elastomer (b) will not be improved, and if it exceeds 20 parts by weight, the moldability will be remarkably deteriorated, and a favorable result will not be obtained.

In order to obtain the polypropylene composition for high-impact parts of the present invention, there is no particular limitation except that the reinforced elastomer composition (b) is first produced and then this composition is used, and a usual known method is used. it can.

In order to obtain the reinforced elastomer (b), the modified elastomer (g) and the modified polyamide (h) are added to the composition, and ethylene and / or an α-olefin and an unsaturated carboxylic acid or a derivative thereof and / or an unsaturated epoxy compound are added to the composition. And the copolymer (i) are dry-blended in the above-mentioned range by various known methods, for example, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, and the like, and a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer are used. After melt-mixing as described above, a method of pelletizing can be adopted.

Next, the reinforced elastomer (b), the modified polypropylene (a), and the inorganic filler can be produced by melt-mixing and pelletizing in the above-described range within the above-described method.

In order to further simplify the kneading step, the step of producing the reinforced elastomer composition (b) may be incorporated in the production step of the composition of the present invention in advance. That is, the reinforced elastomer (b) can be produced in the first step, and the modified polypropylene (a) and the inorganic filler can be charged into the molten state of the reinforced elastomer (b) in the second step. Further, a method in which the modified polypropylene (a) and the inorganic filler (d) are sufficiently melt-mixed in the first stage, and the reinforced elastomer (b) is charged in the second stage to produce the same. 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 usual 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. A general additive such as a slip agent may be blended within a range that does not impair the object 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 distortion temperature (HDT) (℃): ASTM D648 Surface hardness (RH) (R scale): ASTM D785 High-speed impact strength (HSI) (kg ・ cm): thickness 1.6mm A 100 mm diameter disk was formed, and a round missile was dropped on this disk at −10 ° C. at a speed of 2.5 mm / sec as a test piece. The energy was calculated by the surface impact measurement method (UBE method).

Scratch resistance: 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.
The paper was rubbed back and forth with a sandpaper of 0, 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 D696 (-30 ° C to 30 ° C) Molding temperature 240 ° C, mold temperature 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.

1) Polypropylene (hereinafter abbreviated as PP) melt index 15 g / 10 minutes, crystalline ethylene-propylene copolymer having an ethylene content of 10% by weight: J815HK manufactured by Ube Industries, Ltd. 2) Modified polypropylene (hereinafter abbreviated as MPP) melt index 1.0 g / 10 minutes, 0.2 part by weight of maleic anhydride and 0.2 part by weight of t-butylperoxybenzoate are dry-blended with a V-blender based on 100 parts by weight of a crystalline ethylene / propylene block copolymer having an ethylene content of 10% by weight. After melt mixing at 220 ° C. with a single screw extruder, the mixture was pelletized.

3) Further, a reinforced elastomer (hereinafter abbreviated as RE) is dry-blended with a polyamide component, an elastomer component, and other components at a composition ratio shown in Table 1 by a V-blender, and is then subjected to a twin-screw extruder (two-section type screw). , L / D40) at 240 ° C., and then pelletized.

4) Polyamide component As the ordinary polyamide (hereinafter abbreviated as PA), nylon-6 1013B manufactured by Ube Industries was used.

Modified polyamide (hereinafter abbreviated as MPA) was produced and used by the following method. Disperse 100 g of montmorillonite having an average length of about 0.1 μm per side in 10 l of water, and 51.2 g of 12-aminododecanoic acid and 24 ml of concentrated hydrochloric acid. The mixture was stirred for 5 minutes and filtered. After sufficiently washing this, it was vacuum-dried. Through this operation, a complex of ammonium 12-aminododecanoate ion and montmorillonite was prepared. Next, into a reaction vessel equipped with a stirrer, 10 kg of ε-caprolactam, 1 k
g of water and 200 g of the dried complex were added and stirred at 100 ° C. so that the inside of the reaction system became uniform. More temperature
The temperature was raised to 260 ° C., and the mixture was stirred under a pressure of 15 kg / cm for 1 hour.
Thereafter, the reaction was carried out at normal pressure for 3 hours while the pressure was released to evaporate the water from the reaction vessel. After completion of the reaction, the reaction product taken out in a strand form from the lower nozzle of the reaction vessel is water-cooled,
Cutting was performed to obtain a modified polyamide pellet comprising a polyamide having an average molecular weight of 15,000 and 2% by weight of montmorillonite. The pellets were immersed in hot water to extract and remove unreacted monomers, and then dried with a vacuum dryer.

5) Elastomer component The following elastomer components were used.

EPR (abbreviation): Mooney viscosity ML _{1 +} 470, ethylene-propylene copolymer rubber having an ethylene content of 73% by weight Modified EPR (hereinafter abbreviated as MEPR): 100 parts by weight of EPR
Modified ethylene / propylene copolymer rubber modified by adding 0.8 parts by weight of maleic anhydride and 0.4 parts by weight of dicumyl peroxide in a paraxylene solution at 100 ° C.

SEBS-1 (abbreviation): Clayton G1650 manufactured by Shell Chemical Co. SEBS-2 (abbreviation): Clayton G1657 manufactured by Shell Chemical Co., Ltd. MSEBS (abbreviation): Clayton G1901X manufactured by Shell Chemical Co., Ltd. 6) Inorganic filler Use talc with an average particle size of 2 μm Was.

Example 1 As a polypropylene resin composition, MPP 10% by weight and PP
Dry blending of 11.1 parts by weight of talc with a V-blender with respect to 60% by weight, 20% by weight of RE-1 and 100 parts by weight of a polypropylene resin composition, and using a bidirectional twin screw extruder (2FCM-65φ)
After melt-mixing at 250 ° C. using a single screw extruder), the mixture was pelletized. The pellets were dried with hot air at 80 ° C. and injection molded at 230 ° C. to produce test pieces.

Examples 2 to 5 As a polypropylene resin composition, 10% by weight of MPP and PP55
The talc (11.1 parts by weight) was pelletized in the same manner as in Example 1 with respect to 100% by weight of the reinforced elastomer (RE-2 to 5) and 25 parts by weight of the polypropylene resin composition.
A test piece was obtained.

Example 6 10% by weight of MPP and PP30 as a polypropylene resin composition
Example 1 was 11.1 parts by weight of talc based on 100% by weight of this polypropylene resin composition and 50% by weight of RE-6.
A pellet was obtained by pelletizing in the same manner as described above.

Comparative Example 1 As a polypropylene resin composition, 80% by weight of PP and EPR 25
% By weight and dry blending of 11.1 parts by weight of talc with 100 parts by weight of this polypropylene resin composition using a V-blender, and then melt-mixing at 220 ° C. using a biaxial twin screw extruder (2FCM-65φ single screw extruder). Pelletized. The pellets were dried with hot air at 80 ° C. and injection-molded at 230 ° C. to produce test pieces.

Comparative Example 2 10% by weight of MPP and PP70 as a polypropylene resin composition
By weight, 20% by weight of RE-1 and pellets of RE-1 were pelletized in the same manner as in Example 1 to obtain test pieces.

Comparative Example 3 10% by weight of MPP and PP60 as a polypropylene resin composition
Wt%, EPR 4 wt%, SEBS-2 3 wt%, MSEBS 3 wt%
And 10% by weight of MPA and this polypropylene resin composition
A test piece was obtained by pelletizing 11.1 parts by weight of talc with respect to 100 parts by weight in the same manner as in Example 1.

Comparative example 4 It carried out like Example 2-4 except having used elastomer (E-1) instead of RE-2.

Comparative Example 5 10% by weight of MPP and PP40 as a polypropylene resin composition
33.3 parts by weight of talc were pelletized in the same manner as in Example 2 with respect to 100% by weight of the polypropylene resin composition, and a test piece was obtained.

 Table 1 shows the obtained results.

(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 tough reinforced elastomers are used as impact modifiers for polypropylene, and by adding inorganic fillers, they 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 has excellent rigidity, heat resistance, damage resistance and impact resistance, and is suitable for fenders, bumpers and wheels. Automotive interior and exterior parts such as caps, spoilers, instrument panels, trims, etc.
It is suitably used for various industrial parts such as home electric parts and machine parts, and other applications requiring heat resistance, impact resistance, and damage resistance.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 23/16 C08L 23/16 51/06 51/06 77/00 77/00 (72) Inventor Akane Okada Nagakute, Aichi County, Aichi Prefecture 41, No. 41, Yokomichi, Chomachi, Chuo-machi, Toyota Toyota Central R & D Laboratories Co., Ltd. (72) Inventor Osamu Fukui Ark Mori Building Ube Industries, Ltd. Tokyo Head Office, 1-212-32 Akasaka, Minato-ku, Tokyo (72) Inventor Kiyoshi Tsutsui 3-1 Chikko Shinmachi, Sakai City, Osaka Ube Industries, Ltd. Sakai Factory (72) Inventor Tomohiko Akakawa 3-1 Chikko Shinmachi, Sakai City, Osaka Prefecture Ube Industries, Ltd. Sakai Factory (72) Inventor Ikunori Sakai Osaka 3-1 Chikko Shinmachi, Sakai City Ube Industries, Ltd. Sakai Plant (72) Inventor Takashi Exit Takashi 1978-10 Ogushi, Ube City, Yamaguchi Prefecture Ube Chemical Plant Ube Chemical Plant (56) References JP-A-3-3 14 854 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 23/00-23/36 C08L 77/00-77/12 C08L 51/06 C08L 7/06

Claims (4)

(57) [Claims] (1) 98 to 30% by weight of a modified polypropylene (a) and 40 to 95% by weight of a modified elastomer (g) obtained by graft-modifying at least a part of the elastomer (f) with an unsaturated carboxylic acid or a derivative thereof. 60-5% by weight of polyamide (h) modified with clay mineral and components (f) and (h)
Is mixed with 1 to 20 parts by weight of a copolymer (i) of ethylene and / or an α-olefin and an unsaturated carboxylic acid or a derivative thereof and / or an unsaturated epoxy compound to 100 parts by weight of Reinforced elastomer composition (b) 2
Polypropylene resin composition (c) 10
A polypropylene composition for high impact parts, comprising 1 part by weight or more and less than 15 parts by weight of an inorganic filler (d) based on 0 part by weight. 2. The high impact component according to claim 1, wherein the modified polypropylene (a) is a modified polypropylene obtained by graft-modifying at least a part of the crystalline polypropylene (e) with an unsaturated carboxylic acid or a derivative thereof. Polypropylene composition. 3. The polypropylene composition for high impact parts according to claim 1, wherein the elastomer (f) is an ethylene / α-olefin copolymer rubber and / or a styrene-based hydrogenated rubber. 4. The grafted amount of the modified elastomer (g) is 0.01 to 10% by weight based on the modified elastomer.
4. The polypropylene composition for high impact parts according to any one of 3.