JPH04183733A - Polypropylene composition for high stiffness part - Google Patents

Abstract

PURPOSE:To obtain a polypropylene composition for high stiffness parts, containing a thermoplastic reinforced elastomer in which a clay mineral-modified polyamide is finely dispersed and inorganic filler and having excellent stiffness, heat resistance, scar resistance and impact resistance. CONSTITUTION:The composition for high stiffness parts is obtained by blending 100 pts.wt. composition consisting of (A) 98-50 pts.wt. polypropylene resin, preferably a polypropylene which is subjected to graft modification with an unsaturated carboxylic acid (derivative) or a crystalline polypropylene containing the above-mentioned modified resin at an amount of >=2wt.% and (B) 2-50 pts.wt. elastomer composition consisting of B1: elastomer, preferably one or more kind of elastomer selected form ethylene-alpha-olefin copolymer rubber, hydrogenated diene rubber and their modification products with an unsaturated carboxylic acid (derivative) and B2: a clay mineral-modified polyamide with (C) >=15 pts.wt. to <70 pts.wt. inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a highly rigid polypropylene composition that is suitably used for large, highly rigid parts such as automobile instrument panels and center consoles.

More specifically, the present invention combines polypropylene with a thermoplastic reinforcing elastomer in which a modified polyamide hybridized with clay minerals is finely dispersed and an inorganic filler, which has high rigidity, heat resistance, scratch resistance, and resistance. This invention relates to a polypropylene composition for highly rigid parts with excellent impact resistance.

[Conventional technology]

Crystalline polypropylene has surface gloss, heat resistance, scratch resistance,
Since it has excellent mechanical strength and is easy to injection mold, it has been widely used for various purposes.

However, rigidity, heat resistance, dimensional stability, etc. are insufficient for use in industrial parts, especially for large-sized industrial parts. In order to improve the rigidity, heat resistance, and dimensional stability of polypropylene, it is known to add inorganic fillers such as talc and glass fiber to crystalline polypropylene. In particular, it significantly reduces surface impact resistance. Polypropylene compositions containing inorganic fillers and ethylene/α-olefin copolymer rubber, styrene elastomers, etc. are also known.

However, compositions containing these ordinary rubber components not only have a small effect on improving impact resistance, but also have the disadvantage that the surface hardness of the molded product is easily scratched and the appearance is impaired. .

[Problem to be solved by the invention]

In order to simultaneously and significantly improve the rigidity, heat resistance, scratch resistance, and impact resistance of polypropylene and its compositions, it is necessary to select an elastomer with a high impact resistance improvement effect and to disperse it into a polypropylene matrix. were very important and needed to be improved.

Therefore, the present inventors have conducted intensive research on an impact modifier that has a large impact improving effect and extremely little decrease in rigidity in a composition consisting of polypropylene and an inorganic filler, and a technique for dispersing the impact modifier. As a result, when a reinforced thermoplastic elastomer made by finely and uniformly dispersing modified polyamide hybridized with clay minerals into an elastomer to make it hard and tough is used as an impact modifier, it is difficult to disperse it into a polypropylene matrix. In addition to dispersion due to the compatibility of the modified polyamide and modified polypropylene, which are one component of the reinforced elastomer, in the reinforced elastomer, the polyamide molecular chain spreads three-dimensionally around the clay mineral, and due to graft bonding with the elastomer, Sem1-I
Because it forms a PN-like dispersion structure, when blended with polypropylene, the elastomer disperses in the polypropylene matrix in a salami-like form surrounding fine particles of modified polyamide, greatly increasing impact resistance.
Due to the high cohesive strength of modified polyamide, its dispersed structure is not destroyed even when inorganic fillers such as talc are added, and the balance of rigidity, heat resistance, scratch resistance, and impact resistance is far greater than that of conventional compositions. discovered that it is possible to obtain a polypropylene composition for highly rigid parts with excellent
This led to the present invention.

The polypropylene composition of the present invention has far better dispersibility in polypropylene modified with unsaturated carboxylic acids and/or derivatives thereof than that of ordinary elastomers, and its dispersion form is not destroyed even by the addition of inorganic fillers. Rigidity is achieved by using a hard and strong reinforced elastomer.
The major feature is that it has improved heat resistance, scratch resistance, and impact resistance.

[Means to solve the problem]

According to the present invention, (a) polypropylene resin 98-5
0 parts by weight and (b) thermoplastic reinforced elastomer composition 2 consisting of clay mineral modified polyamide and elastomer
There is provided a polypropylene composition for highly rigid parts, which contains 15 parts by weight or more and less than 70 parts by weight of (c) an inorganic filler with respect to 100 parts by weight of a polypropylene resin composition comprising 50 parts by weight.

In a preferred embodiment of the polypropylene composition for highly rigid parts according to the present invention, the polypropylene resin contains at least 2% by weight of a modified polypropylene graft-modified with an unsaturated carboxylic acid and/or a derivative thereof and/or the modified polypropylene described above. Use crystalline polypropylene containing.

In addition, as thermoplastic reinforced elastomer compositions, ethylene/α-olefin copolymer rubber, the above-mentioned ethylene/α-olefin copolymer rubber,
Modified ethylene/α-olefin copolymer rubber obtained by modifying olefin copolymer rubber with unsaturated carboxylic acid and/or its derivatives, hydrogenated rubber obtained by hydrogenating diene rubber, hydrogenated rubber obtained by hydrogenating the above hydrogenated rubber with unsaturated carboxylic acid and/or at least one elastomer selected from the group consisting of modified hydrogenated rubber modified with a derivative thereof and a clay mineral modified polyamide, or (i) Elastomer 40
~95 parts by weight and polyamide 5-6 modified with clay minerals
To 100 parts by weight of the elastomer composition containing 0 parts by weight, further (ii) ethylene and/or α-olefin,
Copolymer with unsaturated carboxylic acid and/or its derivative 1
~20 parts by weight is used.

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

Crystalline polypropylene has a melt index (AST
M 01238.230°c, 2160g) is 0.
Any crystalline polypropylene of 3-70 g/10 min polypropylene homopolymer, random or block copolymer with ethylene, and mixtures thereof may be used. The ethylene/propylene copolymer preferably has an ethylene content of 6% by weight or less in the case of a random copolymer, and 3 to 15% by weight in the case of a block copolymer.

Among the above crystalline polypropylenes, particularly preferred are ethylene-propylene block copolymers 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 the graft-modified raw material.

Unsaturated carboxylic acids and their derivatives include acrylic acid,
Methacrylic acid, maleic acid, itaconic acid, fumaric acid,
Citraconic acid, crotonic acid, glycidyl methacrylate, 2-hydroxyethyl methacrylate, polyethylene glycol dimethacrylate, N-methylolmethacrylamide, calcium methacrylate, T-methacryloxypropyltrimethoxysilane, acrylamide, methacrylamide, etc., maleic anhydride, anhydride, etc. Itaconic acid, citraconic anhydride, etc. are used. Preferred are acid anhydrides such as maleic anhydride and itaconic anhydride.

As a reaction initiator for graft modification, 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 it has a half-life of 1 minute and the decomposition temperature for obtaining the half-life is 250° C. or lower. Examples of such reaction initiators include organic peroxides such as hydroperoxides, dialkyl peroxides, and peroxy esters. Examples of the organic peroxide used in the present invention include L-butyl peroxybenzoate,
Cyclohexanone peroxide, 2,5-dimethyl-2
, 5-di(benzoylperoxy)hexane, L-butylperoxyacetate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,
Examples include 5-di(t-butylperoxy)hexane. When used, it can be appropriately selected depending on the reaction conditions and the like.

Graft-modified crystalline polypropylene can also be obtained by mixing the crystalline polypropylene, the modified raw material monomer, and the reaction initiator, and melt-kneading the mixture in a nitrogen atmosphere or air, or by mixing the crystalline polypropylene with toluene or It can also be obtained by dissolving the modified raw material monomer and the reaction initiator in xylene under pressure and heating, and stirring and mixing while dropping the modified raw material monomer and the reaction initiator. Melt-kneading may be performed using a kneading machine such as a twin-screw extruder, a kneader, or a Banbury mixer, but usually a single-screw extruder can be used.

The mixing temperature is usually 175 to 280°C, which is higher than the melting point of the raw material polypropylene. The melt-mixing time varies depending on the raw materials, etc., but it can generally be carried out for about 1 to 20 minutes.

The mixing ratio of the raw materials is approximately 0.05 to 5 parts by weight of the raw material modified monomer and approximately 0.002 to 1 part by weight of the reaction initiator per 100 parts by weight of the raw material polypropylene. Monomer is about 0.05
If it is less than 5 parts by weight, no modification effect can be obtained, while if it exceeds 5 parts by weight, the monomer grafting efficiency will be extremely reduced and the amount of unreacted polymers will increase, which is not preferable.

The modified polypropylene obtained as described above has a monomer graft ratio of about 0.03% by weight or more, preferably about 0.03% by weight or more.
1 to 5% by weight and a melt index of about 0.5
~200 g/10 minutes is preferable.

If the melt index is smaller than 0.5/10 minutes, molding processability may be reduced;
If the heating time exceeds 10 minutes, the molecular weight decreases too much, making it impossible to obtain a material with the desired performance.

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

The thermoplastic reinforced elastomer composition used in the present invention is a copolymer of an elastomer and a clay mineral-modified polyamide, or an elastomer and a clay mineral-modified polyamide, ethylene and/or α-olefin, and an unsaturated carboxylic acid and/or a derivative thereof. Consists of a combination of. The elastomers constituting these compositions include hydrogenated rubbers obtained by hydrogenating ethylene/α-olefin copolymer rubbers and diene rubbers, and modified rubbers obtained by modifying these with unsaturated carboxylic acids or derivatives thereof, alone and/or or a mixture.

The ethylene/α-olefin copolymer rubber has an ethylene content of 30 to 95% by weight, preferably 60 to 90% by weight.
This is an ethylene/α-olefin copolymer rubber. α−
There are olefin components with 3 to 20 carbon atoms,
Examples include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-decene.

The α-olefin component may be used alone or in a mixture of two or more types. Furthermore, depending on the case, it may contain a trace amount of a diene component.

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

The modified ethylene/α-olefin copolymer rubber is produced by heating 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 by heating and stirring the raw material ethylene/α-olefin copolymer rubber in a solution in the presence of an initiator. It is produced by heating, melting, and kneading an olefin copolymer rubber and a graft-modified raw material monomer. The modified ethylene/α-olefin copolymer rubber produced in this way has a Zimmer graft ratio of about 0.01 to 10% by weight based on the raw material, preferably about 0.
．． 1 to 3.0% by weight and a melt index of approximately 0
．． 01-50g/10 minutes, preferably 0.05-15g
The ratio of each raw material and reaction conditions are appropriately selected so that the reaction time is 10 minutes.

If the monomer graft ratio of the modified ethylene/α-olefin copolymer rubber is less than 0.01% by weight, no modification effect will be obtained, and if it exceeds 10% by weight, the degree of crosslinking of the rubber will increase during graft modification, resulting in a modified polyamide It becomes difficult to melt mix with the metal.

In addition, diene-based hydrogenated rubber, for example, has the formula A-(B-
It is a hydrogenated derivative obtained by hydrogenating a block copolymer represented by A). Here, in the above formula, A is a monovinyl-substituted aromatic hydrocarbon polymer block, B is a conjugated diene elastomeric polymer block, and n is an integer from 1 to 5.

The monovinyl-substituted aromatic hydrocarbon monomer constituting the polymer block A is preferably styrene, but lower alkyl-substituted styrenes other than α-methylstyrene and vinyltoluene, and vinylnaphthalene groups can also be used.

The conjugated diene monomer in Polymer B is preferably butadiene or isoprene, or may be a mixture of both. When butadiene is used as the single conjugated diene monomer to form polymer Pro-Tsuk B, the elastomeric properties are obtained after the Pro-Tsuk copolymer is hydrogenated to saturate the double bonds. In order to maintain this property, it is preferable to adopt polymerization conditions such that the 1,2-microstructure accounts for 20 to 50% of the microstructure in the polybutadiene block. Preferably 1.2-microstructural force 35-45
%belongs to.

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

Many methods have been proposed for producing these block copolymers. A typical method is, for example, the 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.

Hydrogenation treatment of these block copolymers is carried out by the method described in Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, or Japanese Patent Publication No. 46-20814, etc., in the presence of a catalyst in an inert solvent. This is done by hydrogenating the bottom. In this hydrogenation, at least 50%, preferably 80% or more of the olefin group double bonds in polymer block B are hydrogenated, and polymer block A is hydrogenated.
Up to 25% of the aromatic unsaturated bonds in the polyester are hydrogenated. Specifically, the above-mentioned Pro-Tsuku copolymers include a copolymer obtained by hydrogenating styrene-butadiene-styrene copolymer (SBS) (SEBS), and a hydrogenated copolymer obtained by hydrogenating styrene-isoprene-styrene copolymer (SIS). Examples include added copolymers (SEPS) and the like.

In addition, a graft-modified raw material monomer, a graft-modified reaction initiator, a manufacturing method, and a graft-modified raw material monomer of a modified hydrogenated PRO-TSUK copolymer obtained by graft-modifying the above-mentioned diene-based hydrogenated PRO-TSUK copolymer, The graft ratio and the like are the same as those of the 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 they may be used together with ethylene/α-olefin copolymer rubbers and/or diene-based hydrogenated block copolymer rubbers. Polymer rubber may be used in combination with the unsaturated carboxylic acid or its derivative monomer in an amount exceeding 0.01 part by weight per 100 parts by weight of the elastomer.

Further, the clay mineral-modified polyamide resin constituting the reinforced elastomer is 0.0 parts by weight per 100 parts by weight of the polyamide.
5 to 10 parts by weight, preferably 0. It is made by uniformly dispersing and compounding 1 to 7 parts by weight of a specific clay mineral, and has greatly improved heat resistance, rigidity, etc. The proportion of clay minerals is 0.05
If the amount is less than 1 part by weight, no improvement effect on heat resistance or rigidity will be observed, and if it exceeds 15 parts by weight, fluidity during melting may be markedly reduced and injection molding may become impossible.

Polyamide resins used in the modified polyamide of the present invention include polyamides obtained by polycondensation of aliphatic, alicyclic, aromatic, etc. diamines and aliphatic, alicyclic aromatic dicarboxylic acids, and lactams. Polyamides obtained by condensation of aminocarboxylic acids, copolyamides made of these components, and the like can be mentioned.

Specifically, nylon-6, nylon-6, 6, nylon-6, 10, nylon-9, nylon-11, nylon-12, nylon-6/6, 6, nylon-12.1
2nd prize is mentioned.

The clay minerals used to modify the above polyamide resins are mainly layered silicates, whose shape is usually - side length 0.0
02-1- with a thickness of 6-20 people. Examples of raw materials for such layered silicates include layered phyllosilicate minerals composed of layers of magnesium silicate or aluminum silicate.

Specifically, smectite clay minerals such as montmorillonite, sabonite, beidellite, nontronite, hectorite, stevensite, vermiculite,
There are halloy sites, etc.

These may be natural or synthetic. Among these, montmorillonite is particularly preferred.

Preferably, each layered silicate is uniformly dispersed in the polyamide with an average separation of 20 Å or more. There are no particular restrictions on the method of dispersing the layered silicate in the polyamide resin, but if the raw material for the layered silicate is a multilayered clay mineral, the layered silicate is brought into contact with a swelling agent to expand the glabella in advance to form a layer between the layers. It is also possible to use a method in which the monomer is made easy to incorporate, and then mixed with a polyamide monomer and polymerized (see Japanese Patent Application Laid-open Nos. 62-64827, 62-72723, and 62-74957). Alternatively, a method may be used in which a polymer compound is used as the swelling agent, the interlayer gap is expanded to 100 Å or more, and the mixture is melt-mixed with the polyamide resin.

Modified polyamide modified with clay minerals has polyamide molecular chains that spread out three-dimensionally from the eyebrows of individual clay minerals, and has high cohesive strength centered on clay minerals, greatly improving heat resistance and rigidity. are doing.

The copolymer of ethylene and/or α-olefin and unsaturated carboxylic acid and/or its derivative 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 its derivative or an unsaturated epoxy compound onto a (co)polymer with an olefin. α− other than ethylene
Examples of olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-
Examples include octene and 1-decene.

Specific examples of unsaturated carboxylic acids or acid derivatives thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid,
Unsaturated carboxylic acids such as itaconic acid, citraconic acid, and tetrahydrophthalic acid, maleic anhydride, itaconic anhydride,
Examples include 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 unsaturated epoxy compounds 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. Can be mentioned.

A method of copolymerizing an unsaturated carboxylic acid or an acid derivative thereof into an ethylene and/or α-olefin (co)polymer includes, for example, a method of melting the (co)polymer and adding a graft monomer to carry out graft copolymerization; Various known methods can be employed, such as dissolving it in a solvent and adding a graft monomer to copolymerize it.

For copolymerization with an unsaturated epoxy compound, one or two of the α-olefins and an unsaturated epoxy monomer having one ethylenically unsaturated bond and one epoxy group in each molecule are combined with a radical initiator. It can be produced by a method in which an unsaturated epoxy compound is grafted onto an ethylene and/or α-olefin (co)polymer, or the like.

Among these, particularly preferred are 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.

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

In the present invention, the inorganic filler used is a powder filler, for example, an oxide such as alumina, magnesium oxide, calcium oxide, zinc white, or a hydrated metal such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide. oxides, carbonates such as calcium carbonate and magnesium carbonate, silicates such as talc, clay, hentonite, etc., borates such as barium borate, phosphates such as aluminum phosphate, sulfates such as barium sulfate. and mixtures of two or more of these, fibrous fillers such as glass fibers, potassium titanate fibers, ceramic fibers, wollastonite, carbon fibers, SUS fibers, moss hygienic fibers, glass peas, glass flakes, mica, etc. can be mentioned. Further, the surface of the inorganic filler may be treated with a silane compound such as vinylethoxysilane, 2-aminopropyltriethoxysilane, 2-glycidoxypropylmethoxysilane, or a titanate compound. Among these, talc is particularly preferred as the powdery filler, and glass fiber is particularly preferred as the fibrous filler.

The polypropylene composition for highly rigid parts of the present invention has a polypropylene resin of 98 to 50 parts by weight, preferably 90 to 60 parts by weight.
parts by weight, thermoplastic reinforced elastomer compositions 2 to 5 consisting of clay mineral-modified polyamide and elastomer.
0% by weight, preferably 10 to 40% by weight of the inorganic filler per 100 parts by weight of the polypropylene resin composition.
It is constituted by blending 5 parts by weight or more and less than 70 parts by weight. The inorganic filler is polypropylene resin composition 10
If the amount is less than 15 parts by weight compared to 0 parts by weight, the heat resistance, rigidity, and dimensional stability will be insufficient for use in large, high-rigidity parts such as automobile instrument panels and center consoles.
If it exceeds 70 parts by weight, the effect of improving impact resistance due to the addition of the reinforcing elastomer cannot be sufficiently obtained, resulting in problems such as deterioration of scratch resistance.

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

On the other hand, if the content of the reinforcing elastomer exceeds 50% by weight, the rigidity and heat resistance will be significantly reduced even by the addition of fillers, making it unsatisfactory for use in large, highly rigid parts.

Furthermore, in the polypropylene resin composition, the reinforced elastomer composition comprises 40 to 95% by weight, preferably 40 to 80% by weight, of a modified elastomer modified with an unsaturated carboxylic acid or a derivative thereof and 60 to 5% by weight of a modified polyamide modified with a clay mineral. %, preferably 60 to 20% by weight. When the modified polyamide content exceeds 60% by weight, 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 impact resistance by blending the reinforced elastomer into polypropylene cannot be said to be sufficient. If the amount is less than 5% by weight, the effect of improving rigidity and heat resistance is small even when the filler is added, and in particular there is no effect of improving scratch resistance.

Further, the present invention provides ethylene and/or α
- It is composed of 1 to 20 parts by weight of a copolymer of an olefin and an unsaturated carboxylic acid or its derivative and/or an unsaturated epoxy compound. If the amount of the copolymer is less than 1 part by weight, the effect of improving the physical properties of the reinforced elastomer by improving the dispersion of the modified polyamide will not appear.
If the amount exceeds 0 parts by weight, the reaction between the modified compound component and the modified polyamide will proceed, resulting in a marked decrease in moldability, making it impossible to obtain favorable results.

In order to obtain the polypropylene composition for highly rigid parts of the present invention, there are no particular limitations, and any conventional known method can be used, except that the reinforced elastomer composition is first produced and then the present composition is produced.

To obtain a reinforced elastomer, a modified elastomer and a modified polyamide are added to the composition, and ethylene and/or α-
A copolymer of an olefin and an unsaturated carboxylic acid or its derivative and/or an unsaturated epoxy compound is dry-blended within the above range using various known methods, such as a Henschel mixer, a ■-blender, a ribbon blender, a tamper blender, etc. However, a method can be adopted in which the mixture is melt-mixed using a screw extruder, twin-screw extruder, kneader, Banbury mixer, etc., and then pelletized.

Next, the reinforcing elastomer, modified polypropylene, and inorganic filler can be melt-mixed in the above range and pelletized by the above method.

In order to further simplify the kneading process, it is also possible to incorporate a step of manufacturing the reinforced elastomer composition in advance into the manufacturing process of the composite acid product of the present invention. That is, a reinforced elastomer composition is prepared in the first step, and a polypropylene resin and an inorganic filler are added to the reinforced elastomer in a molten state in the second step. Alternatively, a method may be adopted in which the polypropylene resin and the inorganic filler are sufficiently melt-mixed in the first step, and the reinforcing elastomer composition is added in the second step. 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 part of the cylinder in addition to the usual raw material supply port.

The thermoplastic resin composition of the present invention includes antioxidants, ultraviolet absorbers, lubricants, pigments, antistatic agents, copper damage prevention agents, flame retardants, neutralizing agents, plasticizers, nucleating agents, dyes, and blowing agents. General additives such as these may be added to the extent that the purpose of the present invention is not impaired.

〔Example〕

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

Tensile strength (TYS) <kg/cd>: AS
TM 0638 bending strength (FS) (kg/cat)
: ASTM 02584 Flexural Modulus (FM)
(kg/cil): ASTM D2584 Heat Distortion Temperature (HDT) (“C): ASTM
D64B surface hardness (RH) (R scale): AST gate D785 high velocity impact strength (H5I) (kg-C1l): thickness 1.6 m,
A disk with a diameter of 100 m+ was formed, and the disk was used as a test specimen. A round missile of 2.54 cmφ was dropped onto this disk at a speed of 2.5 m/sec at 110"C, and the stress-strain at the time of fracture was measured. The surface impact measurement method (UBE method) was used to calculate the fracture energy from the area of the corner curve.

Scratch resistance: Thickness 2am, 100mX 100mm
A flat plate (injection molded) was used as a test piece, and the test piece was rubbed back and forth with #80 sandpaper under a load of 1 kg, and the scratched area was visually observed and evaluated. A score of 20 was given to those with inconspicuous scratches, and a score of × was given to those with noticeable scratches.

The above test pieces for physical property evaluation were injection molded under conditions of molding temperature of 240° C., mold temperature of 50° C., injection time of 15 seconds, and % cooling time of 30 seconds. Moreover, each raw material used in the examples and comparative examples is as follows.

<Modified polypropylene> Melt index 1.0 g/10 minutes, ethylene content 1
0.2 parts by weight of maleic anhydride per 100 parts by weight of 0% by weight crystalline ethylene/propylene block copolymer;
Modified polypropylene (hereinafter referred to as MPP) obtained by adding 0.2 parts by weight of t-butyl peroxybenzoate and melt-mixing in a single screw extruder at 220°C was used.

The melt index of this modified polypropylene is 25
g/10 min (230°C), and the grafting amount of maleic anhydride was 0.18% by weight. The amount of maleic anhydride grafted onto MPP is determined by dissolving MPP in P-xylene, mixing with cold acetone equivalent to three times the amount of P-xylene and cooling to obtain reprecipitated MPP. After filtering and drying the containing solvent, dissolve it in P-xylene again, add KOH while heating, and add HCOH using thymoldel as an indicator.
It was determined by titration using ffi.

Polypropylene> Melt index 15g/10min, ethylene content 10
Weight% crystalline ethylene-propylene copolymer manufactured by Ube Industries, Ltd. r J815HK J <Reinforced elastomer> The following were used as elastomer components in the reinforced elastomer (hereinafter referred to as RE).

EPR: Mooney clay ML, 50, ethylene content 7
3% by weight ethylene-propylene copolymer rubber MEPR: 0.8 parts by weight of maleic anhydride and 0.4 parts by weight of dicumyl peroxide were added to 100 parts by weight of EPR, and modified in a 100'C para-xylene solution. The melt index of this MEPR ethylene-propylene copolymer rubber was 0.7 g/10 min (230°C), and the grafting amount of maleic anhydride was 0.6% by weight. The amount of grafting was determined by the same method as the method for measuring the amount of grafting of MPP.

5EBS-1 Nisiel Chemical Co., Ltd. “Crayton GI650
JSEBS-2 “Crayton G16” manufactured by Nisiel Chemical Co., Ltd.
57 JMSEBS: Sys/E/Kagakusha “
Clayton FG1901X" Maleic Anhydride 5EBS 7FG1901XJ manufactured by Shell Chemical Company was used. The amount of maleic anhydride grafted in FG1901X was determined by the method described above and was 2.0% by weight.

Modified polyamide (MPA) in reinforced elastomer
The components used had a molecular weight of 15,000 and a montmorillonite content of 2% by weight. Further, as the normal nylon, Nylon-61013BJ manufactured by Ube Industries was used.

Other components in the reinforced elastomer include polypropylene homopolymer (BIOIH manufactured by Ube Industries, Ltd.) with a melt flow index of Ig/10 minutes (230°C).
To 100 parts by weight, 15 parts by weight of maleic anhydride, t-
Add 1 part by weight of butyl peroxybenzoate to 130
Modified polypropylene modified in P-xylene at °C (
PO) was used. The MFR of the PO is 60g/10min (2
30'C), the amount of maleic anhydride grafted was 6% by weight.
Met.

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

<Inorganic filler> Talc with an average particle size of 2 pm was used.

<Example 1> Modified polypropylene (MPP) 12.5% by weight, polypropylene (PP) 75% by weight, reinforced elastomer (RE-1) 12.5% by weight, and the total amount of MPP, PP and RE-1 100 parts by weight 25 parts by weight of talc were tri-blended using a blender, melt-mixed using a twin-screw extruder r2FCM-65φEXT, and then pelletized. This pellet was dried with hot air at 80° C. and injection molded at 230° C. to prepare a test piece for measuring physical properties.

<Example 2> MPP 12.5% by weight, PP 62.5% by weight and R
Example 1 25 parts by weight of talc was added to 100 parts by weight of the total amount of E-225% by weight and MPP, PP and RE-2.
A test piece was obtained by pelletizing in the same manner as above.

<Example 3> MPP 12.5% by weight, PP 62.5% by weight and R
Example 1 25 parts by weight of talc was added to 100 parts by weight of the total amount of E-325% and MPP, PP and RE-3.
A test piece was obtained by pelletizing in the same manner as above.

<Example 4> MPP 15.4% by weight and PP 3B, 4% by weight, RE
-246.2% by weight and MPP, PP and RE-2
Based on the total amount of 100 parts by weight, 53.8 parts by weight of talc was pelletized in the same manner as in Example 1 to obtain a test piece.

<Example 5> MPP 12.5% by weight, PP 62.5% by weight and R
Example 1 25 parts by weight of talc was added to 100 parts by weight of the total amount of E-425% and MPP, PP and RE-4.
A test piece was obtained by pelletizing in the same manner as above.

<Comparative Example 1> Polypropylene (PP) 87.5% by weight and ethylene-propylene copolymer rubber (EPR) 12.5% by weight
Also, 25 parts by weight of talc was added to 100 parts by weight of the total amount of pp and EPR, 2FCM-65φEXT, 220
After melt-mixing at °C, the mixture was pelletized and injection molded at 230 °C to prepare a test piece.

<Comparative Example 2> Instead of EPRO, styrene elastomer (Sll:
The same procedure as Comparative Example 1 was conducted except that BS-1) was used.

<Comparative Example 3> PP as a polypropylene resin composition 75% by weight,
EPR12.5% by weight and 5EBS-112.5% by weight
Further, 25 parts by weight of talc was pelletized based on 100 parts by weight of this polypropylene resin composition in the same manner as in Comparative Example 1 to obtain a test piece.

Comparative Example 4> 11.1% by weight of MPP, 66.7% by weight of PP and 2% by weight of RE-222 as a polypropylene resin composition, and 11.1 parts by weight of talc per 100 parts by weight of this polypropylene resin composition. A test piece was obtained by pelletizing in the same manner as in Example 1.

<Comparative Example 5> The same procedure as Example 2 was carried out except that elastomer (E-1) was used instead of RE-2.

Comparative Example 6> MPP as a polypropylene resin composition 15.4% by weight, PP 38.5% by weight, EPR 11.5% by weight,
Modified ethylene propylene copolymer rubber (MEPR)
7% by weight, 5RBS-24, 6% by weight, MPA 23.
0% by weight and 53.8 parts by weight of talc based on 100 parts by weight of this polypropylene resin composition were pelletized in the same manner as in Example 1 to obtain a test piece.

The results are shown in Table 1.

Below is a table with a 1m margin. [Effects of the Invention] The present invention uses a reinforced elastomer made by finely and uniformly dispersing modified polyamide hybridized with clay minerals in an elastomer to make it hard and tough, as an impact modifier for polypropylene. Furthermore, by blending an inorganic filler, the rigidity, heat resistance,
It has improved impact resistance and dimensional accuracy without compromising scratch resistance, mechanical strength, etc.

The novel composition provided by the present invention can be molded by conventional molding methods such as injection molding and extrusion, and has high rigidity and
It has excellent heat resistance, scratch resistance, and impact resistance, and is suitable for interior parts such as automobile instrument panels, center consoles, and trims, various industrial parts such as home appliance parts, mechanical parts, and other lateral and heat resistant parts. Suitable for use in large, high-rigidity parts that require impact resistance and dimensional accuracy.

Claims (1)

[Scope of Claims] 1. A polypropylene resin composition comprising (a) 98 to 50 parts by weight of a polypropylene resin and (b) 2 to 50 parts by weight of a thermoplastic reinforced elastomer composition comprising a clay mineral-modified polyamide and an elastomer. For 100 parts by weight,
(c) A polypropylene composition for highly rigid parts, which contains 15 parts by weight or more and less than 70 parts by weight of an inorganic filler. 2. Claim 1, wherein 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 polypropylene composition for highly rigid parts described in . 3. The thermoplastic reinforced elastomer composition comprises (a) an ethylene/α-olefin copolymer rubber, (b) the above-mentioned ethylene/α-olefin copolymer rubber modified with an unsaturated carboxylic acid and/or a derivative thereof. modified ethylene/α-olefin copolymer rubber, (c) hydrogenated rubber obtained by hydrogenating the hydrogenated rubber, (d) modified hydrogenated rubber obtained by modifying the above hydrogenated rubber with an unsaturated carboxylic acid and/or its derivative. The polypropylene composition for highly rigid parts according to claim 1 or 2, which comprises at least one elastomer selected from the group consisting of rubber and clay mineral-modified polyamide. 4. The thermoplastic reinforced elastomer composition has (i) (a
) 40 to 95 parts by weight of an elastomer and (b) 100 parts by weight of an elastomer composition containing 5 to 60 parts by weight of a polyamide modified with a clay mineral, and further (ii) ethylene and/or α-olefin and an unsaturated carboxylic acid. The polypropylene composition for highly rigid parts according to any one of claims 1 to 3, which contains 1 to 20 parts by weight of a copolymer with a copolymer and/or a derivative thereof.