JPH0496957A - Polypropylene composition for part having high impact resistance - Google Patents

Abstract

PURPOSE:To obtain a polypropylene composition suitable for interior and exterior automative trims such as fender, etc., having excellent rigidity, heat resistance, etc., by blending a polypropylene with a reinforced elastomer and an inorganic filler into which a modified polyamide hybridized with clay minerals is finely dispersed. CONSTITUTION:100 pts.wt. total amounts of (A) 98-30wt.% modified polypropylene prepared by at least partially subjecting a crystalline polypropylene to graft modification with an unsaturated carboxylic acid and (B) 2-70wt.% reinforced elastomer composition comprising (B1: 40-95wt.% modified elastomer prepared by at least partially subjecting ethylene.alpha-olefin copolymer rubber and/or styrene-based hydrogenated rubber to graft modification with an unsaturated carboxylic acid (derivative) and B2: 60-5wt.% polyamide modified with clay minerals are mixed with (C) 1-15 pts.wt. inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a high-impact polypropylene composition suitable for use in large-scale high-impact parts such as automobile bumpers.

More specifically, the present invention is obtained by blending polypropylene with a reinforcing elastomer in which a modified polyamide hybridized with clay minerals is finely dispersed in advance and an inorganic filler, and in particular, it has excellent rigidity, heat resistance, impact resistance, This invention relates to a polypropylene composition for high-impact parts that has excellent scratch resistance and dimensional stability.

[Conventional technology]

Crystalline polypropylene has been widely used for various purposes because it has excellent rigidity, surface gloss, heat resistance, scratch resistance, and mechanical strength, and is easy to injection mold. However, impact resistance, heat resistance, rigidity, etc. were insufficient for use in large parts such as automobile bumpers. For this reason, polypropylene compositions in which crystalline polypropylene is combined with inorganic fillers such as talc and ethylene/α-olefin copolymer rubber and styrene elastomer components have been developed for use in large impact-resistant parts.

However, this polypropylene composition has the problem that the balance between impact resistance, rigidity, and heat resistance has not been significantly improved, and furthermore, the surface hardness is low, resulting in poor scratch resistance.

Therefore, various methods have been attempted to obtain polypropylene compositions that have excellent rigidity, heat resistance, impact resistance, and scratch resistance. For example, polypropylene-polyamide compositions in which polyamide, etc. and modified elastomers are blended with crystalline polypropylene have been developed (JP-A-59-149940, JP-A-60-110740, JP-A-62 (Refer to publications such as No.-54743). This polypropylene-polyamide composition has high surface hardness and improved scratch resistance in addition to rigidity, heat resistance, and impact resistance.

[Problem to be solved by the invention]

However, even the above-mentioned polypropylene-polyamide compositions cannot be said to have sufficient rigidity, heat resistance, and impact resistance for use in large parts, and furthermore, this composition is suitable for use in plastics and elastomers such as crystalline polypropylene, polyamides, and modified elastomers. Consists only of ingredients,
Since it does not contain an inorganic filler, it has the disadvantage of a large coefficient of linear expansion.

For this reason, molded articles using this polypropylene-polyamide composition have large dimensional changes due to changes in the temperature of the environment in which they are used. This problem is particularly noticeable when used in large parts.

It is generally known that the dimensional stability of polypropylene and compositions thereof can be improved by incorporating inorganic fillers such as talc. However, it has been found that simply adding an inorganic filler to the polypropylene-polyamide composition described above destroys the dispersed structure of the polyamide, modified elastomer, etc. in the polypropylene matrix, resulting in a significant drop in impact resistance. For this reason, it has been difficult to apply the material to large-sized parts simply by adding an inorganic filler.

In order to simultaneously and significantly improve the rigidity, heat resistance, impact resistance, scratch resistance, and dimensional stability of polypropylene and its compositions, it is necessary to select an elastomer that has a high impact resistance improvement effect and to use the polypropylene matrix. distribution technology is very important.

The impact modifier must have a high impact improving effect and must not cause the dispersion structure in the polypropylene matrix to be destroyed by the inorganic filler.

In view of this situation, the present inventors have earnestly investigated an impact modifier for polypropylene whose dispersion structure is not destroyed by inorganic fillers and the like, and a dispersion technique for the same. As a result, when a thermoplastic reinforced elastomer made by preliminarily 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, the dispersion into the polypropylene matrix is strengthened. In addition to dispersion due to the compatibility of modified polyamide and modified polypropylene, which are one component of the elastomer, in this reinforced elastomer, the polyamide molecular chain spreads three-dimensionally around the clay mineral, and due to graft bonding with the elastomer, Sem1-IPN-like When blended with polypropylene, the elastomer is dispersed in the polypropylene matrix in a ceramic-like form surrounding fine particles of modified polyamide, greatly increasing impact resistance and reducing the high aggregation of modified polyamide. Even when inorganic fillers such as talc are added to the composition due to force, its dispersed structure is not destroyed, and its rigidity, heat resistance, impact resistance, scratch resistance, and dimensional stability are far superior to previous compositions. It was discovered that a polypropylene composition for high-impact parts can be obtained, leading 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.
Its major features include improved heat resistance, impact resistance, scratch resistance, and dimensional stability.

[Means for solving the problem] That is, according to the present invention, modified polypropylene (a) 98
~30% by weight and reinforced elastomer composition (b) 2~70
Polypropylene resin composition (c) consisting of 100% by weight
A polypropylene composition for high-impact parts is provided, which contains 1 part by weight or more and less than 15 parts by weight of an inorganic filler (d) per part by weight.

In the above-mentioned polypropylene composition for high-impact parts, component (a) is preferably a modified polypropylene obtained by graft-modifying at least a portion of crystalline polypropylene (e) with an unsaturated carboxylic acid or a derivative thereof.

Furthermore, according to a preferred embodiment of the present invention, component (b) is
A modified elastomer (g) in which at least a portion of an ethylene/α-olefin copolymer rubber and/or hydrogenated styrene rubber is graft-modified with an unsaturated carboxylic acid or a derivative thereof (40 to 95% by weight) and modified with a clay mineral. There is provided a polypropylene composition for high impact parts comprising 60 to 5% by weight of polyamide (h).

Furthermore, preferably, in the polypropylene composition for high impact parts of the present invention, component (b) is a modified elastomer component (g).
Copolymer (i) 1 to 1 of ethylene and/or α-olefin and unsaturated carboxylic acid or its derivative and/or unsaturated epoxy compound to 100 parts by weight of the composition consisting of and modified polyamide component (h) 20 parts by weight are blended.

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

Crystalline polypropylene (e) has a melt index (
ASTM 01238.230°C, 2160g) is 0
．． Any crystalline polypropylene of 3 to 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/lO min and an ethylene content of 3 to 10% by weight.

Unsaturated carboxylic acids and derivatives thereof are used as monomers for graft modification raw materials.

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, and N-methylolmethacrylamide. , calcium methacrylate, γ-methacryloxypropyltrimethoxysilane, acrylamide, methacrylamide, etc., maleic anhydride, itaconic anhydride,
Use citraconic anhydride or the like. 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 decomposition temperature of 250°C or less to obtain a half-life of 1 minute. 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 t-butyl peroxybenzoate, cyclohexanone peroxide, 2,5-dimethyl 2,5-di(benzoylperoxy)hexane, t-butyl peroxyacetate, methyl ethyl ketone peroxide, dicumyl Examples include peroxide, 2.5-dimethyl-2,5-di(t-butylperoxy)hexane, and the like. When used, it can be appropriately selected depending on the reaction conditions and the like.

Graft-modified crystalline polypropylene can 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 kneader such as a twin-screw press ratio machine, a kneader, or a Banbury mixer, but it can usually be carried out using a single-screw extruder. 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 3.0 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. The seven-point mark is about 0.
If it is less than 0.05 parts by weight, no modification effect can be obtained,
On the other hand, if it exceeds 5 parts by weight, the grafting efficiency of the monomer will be extremely reduced and the amount of unreacted molecules 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 1000% by weight and a melt index of about 0.5 to 200 g/10 minutes.

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 modified polypropylene and unmodified crystalline polypropylene may be used in combination with polypropylene 100 times more! The amount of unsaturated carboxylic acid or its derivative monomer grafted to ffl is 0.0
It can be used in combination in an amount exceeding 3 parts by weight.

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

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−
The olefin component includes those having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-decene.

The α-olefin component may be used alone (or a mixture of two or more types may be used). Furthermore, in some cases, a trace amount of Geno component may be included.

The modified ethylene/α-olefin copolymer rubber can be obtained by graft-modifying the above-mentioned ethylene/α-olefin copolymer rubber. The same unsaturated carboxylic acid and its derivatives as the graft-modified monomer of the modified polypropylene are used as the graft-modified raw material. 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 raw material monomer grafting ratio of about 0.01 to 10% by weight, preferably about 0.1 to 3.0% by weight, and is melt indensified. about 0.01 to 50 g/10 minutes, preferably 0.05 to 15
The ratio of each raw material and the reaction conditions are appropriately selected so that the reaction rate is 100 g/10 minutes.

If the monomer grafting rate of the modified ethylene/α-olefin copolymer rubber is less than 0.05% by weight, no modification effect will be obtained, and if it exceeds 5.0% by weight, the degree of crosslinking of the rubber will increase during graft modification, resulting in poor modification. Melt mixing with polyamide becomes difficult.

In addition, styrene-based hydrogenated rubber has - dilation of A (B-A),
It is a hydrogenated derivative obtained by hydrogenating a block copolymer represented by . Here, in the above general 2, 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 α-methylstyrene, vinyltoluene, other lower alkyl-substituted styrenes, and vinylnaphthalene groups may also be used.

The conjugated diene monomer in polymer B is preferably butane diene or isoprene, or may be a mixture of the two. When butadiene is used as the single conjugated diene monomer to form polymer block B, the block copolymer retains elastomeric properties after being hydrogenated to saturate the double bonds. In order to achieve this, 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. More preferably, the 1,2-micron structure is 35 to 45
%belongs to.

The weight average molecular weight of polymer block A in the block copolymer is 5.000 to 125,000,
is preferably 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 described, for example, in Japanese Patent Publication No. 42-8704, No. 43-6636, or No. 46
This is carried out by hydrogenation in the presence of a catalyst in an inert solvent according to the methods described in various publications such as No. 20814. In this hydrogenation, at least 50%, preferably 8%, of the olefinic group double bonds in polymer block B are
0% or more of the aromatic unsaturated bonds in the polymer block A are hydrogenated, and 25% or less of the aromatic unsaturated bonds in the polymer block A are hydrogenated. Specifically, the above block copolymers include hydrogenated copolymers (SEBS) of styrene-butylene-styrene copolymers (SBS) and hydrogenated styrene-isoprene-styrene copolymers (SIS). Examples include copolymers (SEPS) and the like.

In addition, the graft modification raw material monomer, graft modification reaction initiator, manufacturing method, graft modification raw material monomer, grafting ratio, etc. of the modified hydrogenated block copolymer obtained by graft modification of the above styrene-based hydrogenated block copolymer are This is the same as the 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 the ethylene/α-olefin copolymer rubbers and/or the styrene-based hydrogenated block copolymer rubbers may be used alone. A composite rubber can be used in combination with the unsaturated carboxylic acid or its derivative monomer in an amount exceeding 0.01 part by weight based on 100 parts by weight of the elastomer.

Furthermore, the modified polyamide resin (h) constituting the reinforced elastomer (b) is 0% based on 100 parts by weight of the polyamide.
．． 05 to 10 parts by weight, preferably 0.1 to 7 parts by weight of a specific clay mineral is uniformly dispersed, and the composite heat resistance, rigidity, etc. are greatly improved. If the proportion of clay minerals is less than 0.05 parts by weight, no improvement effect on heat resistance or rigidity will be observed, and if it exceeds 15 parts by weight, fluidity during melting will decrease significantly and injection molding will become impossible. There is.

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.

Specific examples include nylon-6, nylon-6,6, nylon-6,10, nylon-9, nylon-11, nylon-12, nylon-6/6.6, and nylon 12.12.

The clay minerals used to modify the above polyamide resins are mainly layered silicates, whose shape is usually - side length 0.0
The size is 02-Ium and the thickness is 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, there are smectite 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 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 interlayers in advance and create 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 a high cohesive force centered on clay minerals, with the polyamide molecular chains being three-dimensionally shaped from the eyebrows of individual clay minerals, and has significantly improved heat resistance and rigidity. .

Furthermore, 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 onto 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-hexane, 4-methyl-
Examples include 1-pentene, -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 copolymerized using a radical initiator. It can be produced by a method of copolymerizing ethylene and/or an α-olefin (co)polymer, or a method of grafting an unsaturated epoxy compound onto an ethylene and/or α-olefin (co)polymer.

Among these, particularly preferred are modified ethylene and/or α-
Olefin copolymers include ethylene/ethyl methacrylate/maleic anhydride copolymers, ethylene/glycidyl methacrylate copolymers, and the modified polypropylene (a
) can be mentioned.

The amount of grafting of the unsaturated carboxylic acid or its derivative or the unsaturated epoxy compound is preferably 0.3 to 5% by weight. If the amount of grafting is less than 0.1% 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,
Decrease the surface appearance and moldability of the composition.

In the present invention, the inorganic filler used as component (d) is a powder filler such as oxides such as alumina, magnesium oxide, calcium oxide, zinc white, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, etc. Hydrated metal oxides such as calcium carbonate, carbonates such as magnesium carbonate, silicates such as talc, clay, pentonate, etc., borates such as barium borate, phosphates such as aluminum phosphate, sulfuric acid. Sulfates such as barium 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 hygiene, etc., other glass peas, glass Examples include flakes, mica, and the like.

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 high-impact parts of the present invention is a modified polypropylene (e) in which at least a portion of crystalline polypropylene (e) is modified with an unsaturated carboxylic acid or a derivative thereof.
a) Reinforced elastomer composition (b) 2 consisting of 98-30% by weight, preferably 90-50% by weight of a modified elastomer (g) and a polyamide (h) modified with clay minerals
70% by weight, preferably 10 to 50% by weight of the inorganic filler (d) per 100 parts by weight of the polypropylene resin composition (c), 1 part by weight or more and less than 15 parts by weight, preferably 5 parts by weight or more and 15 parts by weight. Consists of less than.

The inorganic filler of component (d) is a polypropylene resin composition (
For c), if the amount is less than 1 part by weight, there will be no improvement in dimensional stability, and if it is more than 15 parts by weight, there will be problems with appearance quality such as deterioration of scratch resistance due to filler and occurrence of flow marks in injection molded products. occurs.

Furthermore, if the reinforcing elastomer (b) is less than 2% by weight in the polypropylene resin composition (c), a sufficient effect of improving impact resistance cannot be obtained as a polypropylene composition for high impact components.

On the other hand, when the reinforcing elastomer (b) exceeds 70% by weight, the dispersed structure of the polypropylene resin composition (c) becomes a sea-island structure with the elastomer as the sea, and depending on the filler blend, the stiffness, heat resistance, and Vulnerability is significantly reduced.

Furthermore, 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.
% by weight, preferably 40-80% by weight, and 60-5% by weight, preferably 60-20% by weight of a modified polyamide (h) modified with a clay mineral, with the modified polyamide of component (h) being 60% by weight. In the above case, 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 impact resistance due to the addition of the reinforced elastomer (b) cannot be said to be sufficient; In the following cases, the effect of improving rigidity and heat resistance is small even by adding fillers.
In particular, there is no improvement effect on scratch resistance.

The present invention also provides a composition (b) consisting of the above component (g) and component (h), in which ethylene and/or α-olefin, an unsaturated carboxylic acid or a derivative thereof, and/or an unsaturated epoxy compound are added to 100 parts by weight of the composition (b). ) of copolymer with 1
~20 parts by weight. component (i
) is less than 1 part by weight, the effect of improving the physical properties of the reinforced elastomer (b) by improving the dispersion of the modified polyamide does not appear, and if it exceeds 20 parts by weight, the moldability is significantly reduced, making it impossible to obtain favorable results.

In order to obtain the polypropylene composition for high-impact parts of the present invention, there is no particular restriction other than first producing the reinforced elastomer composition (b) and then producing the present composition (using a conventional known method). I can do it.

To obtain the reinforced elastomer (b), a modified elastomer (
g) and the modified polyamide (h), and the copolymer (1) of ethylene and/or α-olefin with an unsaturated carboxylic acid or its derivative and/or an unsaturated epoxy compound in the above range. Various known methods can be used, such as tri-blending using a Henschel mixer, blender, ribbon blender, tumbler blender, etc., melt-mixing using a screw extruder, twin screw extruder, kneader, Banbury mixer, etc., and then pelletizing. can be adopted.

Next, the reinforced elastomer (b), the modified polypropylene (a), and the 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 (b) in advance into the manufacturing process of the composition of the present invention. That is, the reinforced elastomer (b) is produced in the first step, and the modified polypropylene (a) and the inorganic filler are added to the molten state of the reinforced elastomer (b) in the second step. In addition, in the first step, modified polypropylene (
It is also possible to adopt a manufacturing method in which a) and the inorganic filler (d) are sufficiently melted and mixed, and the reinforcing elastomer (b) 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 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. General additives such as , slip agents, etc. may be blended within the range that does not impair the purpose of the present invention.

〔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/cnl): 8STM 0638 Flexural strength (FS) (kg/c++1): ASTM D2584 Flexural modulus (FM) (kg/cIIN): ASTM D2584 Izoot impact strength (IZoo) (kg - cm/cm): 8 STM D
256 Heat Deformation Temperature (HDT) (''C): ASTM D648 Surface Hardness (RH) (R Scale): ASTM D785 High Velocity Impact Strength (HSI) (kg-cm): Thickness 1.6 mm, Diameter 100 m
A round missile is dropped onto this disk at a speed of 2.5 ttm/sec at -10°C using the disk as a test piece, and the area of the stress-strain curve at failure is calculated. The fracture energy was calculated using the scratch surface impact measurement method (LJBE method).

: A flat plate (injection molded) with a thickness of 2 mm and 100 mm x 100 mm was used as a test piece, and the test piece was rubbed back and forth with #80 sandpaper with a load of 1 kg, and the scratched portion 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.

Linear expansion coefficient (mm/mm/”C): ASTM D696(-
30°C to 30°C) The above test piece for physical property evaluation was molded at 240°C, mold temperature was 50°C, injection time was 15 seconds, and cooling time was 30 seconds.
This was done by injection molding under the following conditions. Moreover, each raw material used in the examples and comparative examples is as follows.

1) Polypropylene (hereinafter abbreviated as PP) melt index 15 g/10 min, ethylene content 10% by weight
Crystalline ethylene-propylene copolymer: Ube Industries J
815HK 2) Modified polypropylene (hereinafter abbreviated as MPP) melt index 1. Og/10 min, crystalline ethylene/propylene block copolymer 1 with ethylene content 10% by weight
00 parts by weight, 0.2 parts by weight of maleic anhydride, t-
Tri-blend 0.2 parts by weight of butyl peroxybensoate in a ■-blender, and heat at 220°C in a single-screw extruder.
After melting and mixing, the mixture was pelletized.

3) Furthermore, the reinforced elastomer (hereinafter abbreviated as RE) is prepared by tri-blending the polyamide component, elastomer component, and other components in the composition ratio shown in Table 1 in a V-blender, and then using a twin-screw extruder (two-thread type screw , L/D40)
After melt-mixing at 240° C., the mixture was made into pellets.

4) Polyamide Component As a normal polyamide (hereinafter abbreviated as PA), nylon-61013B manufactured by Ube Industries was used.

Modified polyamide (hereinafter abbreviated as MPA) was produced and used by the following method. Layered silicate - The average thickness of the unit is 9.5 mm and the average side length is approximately 0.1 m. 100 g of montmorillonite is dispersed in 101 parts of water, and 51.2 m of montmorillonite is dispersed in 101 parts of water.
g of 12-aminododecanoic acid and 24d of concentrated hydrochloric acid were added, stirred for 5 minutes, and then filtered.

Furthermore, this was thoroughly washed and then vacuum dried.

Through this operation, a complex of ammonium 12-aminododecanoate ion and montmorillonite was prepared. Next, 10 kg of ε-force prolactam was added to a reaction vessel equipped with a stirrer.
1 kg of water and 200 g of the dried pre-composite were added and stirred at 100°C so that the inside of the reaction system was in a uniform state. Furthermore, the temperature was increased to 260°C, and 15kg/c
The mixture was stirred for 1 hour under a pressure of m. Thereafter, the pressure was released to volatilize water from the reaction vessel, and the reaction was carried out at normal pressure for 3 hours. After the reaction was completed, the reaction product taken out in the form of a strand from the lower nozzle of the reaction vessel was cooled with water and cut to obtain modified polyamide pellets consisting of polyamide with 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 in a vacuum dryer.

5) Elastomer component The following elastomer components were used.

EPR (abbreviation): Mooney viscosity ML. 470, ethylene-propylene copolymer rubber modified EPR with ethylene content of 73% by weight (hereinafter abbreviated as MEPR): EPR1
A modified ethylene-propylene copolymer rubber obtained by adding 0.8 parts by weight of maleic anhydride and 0.4 parts by weight of dicumyl peroxide to 00 parts by weight, and modifying the rubber in a varaxylene solution at 100°C.

5EBS-1 (abbreviation) Clayton G manufactured by Nigel Chemical Co., Ltd.
1650 SEBS-2 (abbreviation) Clayton G manufactured by Nigel Chemical Co., Ltd.
1657 M5EBS (abbreviation) Clayton G manufactured by Nigel Chemical Co., Ltd.
1901x 6) Inorganic filler Talc with an average particle size of 2 feet was used.

As a polypropylene resin composition on Urababan, MPP 10% by weight
60% by weight of PP, 120% by weight of RE-1, and 11.1 parts by weight of talc per 100 parts by weight of the polypropylene resin composition were tri-blended in a ■-blender, and then mixed in a different direction twin screw extruder (2FCM-65φ single screw extruder). ) at 250℃
After melting and mixing, the mixture was pelletized. This pellet was heated at 80°C.
A test piece was prepared by drying with hot air and injection molding at 230°C.

Backing material 10% by weight of MPP and 55% by weight of PP as a polypropylene resin composition and reinforced elastomer (RE-2 to 5)
) 25% by weight, and this polypropylene resin composition 10
0 parts by weight and 11.1 parts by weight of talc were pelletized in the same manner as in Example 1 to obtain test pieces.

The polypropylene resin composition used was 10% MPP, 30% by weight of PP, and 50% by weight of RE-6, and 11% of talc per 100 parts by weight of this polypropylene resin composition.
．． 1 part by weight was pelletized in the same manner as in Example I to obtain a test piece.

This Jd soup polypropylene resin composition contains 80% by weight of PP and EP.
R25% by weight, and this polypropylene resin composition 10
0 parts by weight and 11.1 parts by weight of talc were tri-blended using a V-blender, and then mixed using a twin-screw extrusion method in different directions (2FCM-6
After melt-mixing at 220°C using a 5φ single-screw extruder, the mixture was pelletized. The pellets were dried with hot air at 80°C and
A test piece was prepared by injection molding.

Comparison I A polypropylene resin composition containing 10% by weight of MPP, 70% by weight of PP, and 20% by weight of RE-1 was pelletized in the same manner as in Example 1 to obtain a test piece.

The main polypropylene resin composition was MPP 10% by weight, PP 60% by weight, EPR 4% by weight, 5EBS-23% by weight, MSEBS 3% by weight and MPA 10% by weight, and Tal based on 100 parts by weight of this polypropylene resin composition. 911.1 parts by weight was pelletized in the same manner as in Example 1 to obtain a test piece.

The same procedure as in Examples 2 to 4 was carried out except that elastomer (E-1) was used instead of this 1d soil RE-2.

The base polypropylene resin composition was 10% by weight of MPP, 40% by weight of PP, 225% by weight of RE-2, and 33.3 parts by weight of talc per 100 parts by weight of this polypropylene resin composition.
Parts by weight were pelletized in the same manner as in Example 2 to obtain test pieces.

The results obtained are shown in Table 1.

1 [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, making it perfect for fenders.
, various interior and exterior parts for automobiles such as bumpers, hubcaps, spoilers, instrument panels, and trims, various industrial parts such as home appliance parts, mechanical parts, and other applications that require heat resistance, impact resistance, and scratch resistance. It is suitably used for.

Claims (1)

[Claims] 1. (i) Modified polypropylene (a) 98 to 30% by weight
and (ii) 100 parts by weight of a polypropylene resin composition (c) consisting of 2 to 70% by weight of a reinforced elastomer composition (b), and 1 part by weight or more and less than 15 parts by weight of an inorganic filler (d). Polypropylene composition for high impact parts. 2. The polypropylene composition for high-impact parts according to claim 1, wherein the modified polypropylene (a) is a modified polypropylene obtained by graft-modifying at least a portion of the crystalline polypropylene (e) with an unsaturated carboxylic acid or a derivative thereof. . 3. The reinforced elastomer composition (b) is an elastomer (f
) Modified elastomer (g) 40~
Polyamide (h) 60 modified with 95% by weight and clay minerals
5. The polypropylene composition for high impact parts according to claim 1, comprising 5% by weight. 4. The polypropylene composition for high impact components according to any one of claims 1 to 3, wherein the elastomer (f) is an ethylene/α-olefin copolymer rubber and/or a hydrogenated styrene rubber. 5. The reinforced elastomer composition (b) is added to 100 parts by weight of a composition consisting of a modified elastomer and a modified polyamide,
Further, 1 to 20 parts by weight of a copolymer (i) of ethylene and/or α-olefin and unsaturated carboxylic acid or its derivative and/or unsaturated epoxy compound are blended. The polypropylene composition for high impact parts according to any one of the items. 6. Claims 1 to 5, wherein the grafting amount of the modified elastomer (g) is 0.01 to 10% by weight based on the modified elastomer.
The polypropylene composition for high impact parts according to any one of the above.