JPH06228383A - Propylene resin composition - Google Patents

Abstract

PURPOSE:To provide a compsn. which is excellent in impact resistance, bending modulus, and tensile yield strength. CONSTITUTION:100 pts.wt. resin compsn. comprising 70-98wt.% propylene homopolymer and 30-2wt.% reaction product of an olefin resin modified with a polymer having isocyanate groups with an ethylene copolymer having at least one kind of group selected from amino, hydroxyl, carboxyl, and acid anhydride groups is compounded with 5-40 pts.wt. noncrosslinked rubber to give the desired compsn.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel resin composition, and more particularly to a propylene resin composition which is useful as a raw material for moldings having excellent impact resistance and mechanical properties.

[0002]

2. Description of the Related Art Polypropylene resin is inexpensive and excellent in various mechanical properties, heat resistance, surface glossiness, chemical resistance, acid resistance and alkali resistance, and various types such as injection molding, blow molding and various types of film molding. Since it can be easily molded by a molding method, it is used in large amounts in a very wide range of applications such as interior / exterior parts of automobiles, home electric appliance parts, household products and film fields. However, the impact resistance is not always satisfactory.

Therefore, various methods have been attempted in order to eliminate the drawbacks of the polypropylene resin. For example, a method of blending a polyethylene resin (Japanese Patent Publication No. 37-6975) or a method of block-polymerizing propylene and ethylene or other α-olefins (Kuroda: Kogaku Kogaku, Vol. 23, No. 10, 714).
and so on. In addition, ethylene-propylene rubber (EP
R), a method of mechanically blending a rubber component such as styrene-butadiene rubber (JP-B-35-7088,
35-10640) is also known.

[0004]

However, although these methods improve impact resistance as compared with propylene homopolymers, they are still insufficient. On the other hand, the impact resistance is improved by allowing the rubber component to be present in polypropylene, but there is a problem that the mechanical properties (for example, tensile strength and bending strength) decrease as the rubber component increases. . In view of the above situation, the present invention has been made for the purpose of providing a propylene-based resin composition having excellent impact resistance, less decrease in flexural modulus, and excellent fluidity.

[0005]

As a result of intensive studies, the present inventors have blended a propylene homopolymer with a reaction-treated product of a specific olefin resin and an ethylene copolymer, and a non-crosslinked rubber. By doing so, they have found that the object can be achieved, and have completed the present invention.

That is, the present invention provides (A) a propylene homopolymer, (B) (a) a modified olefin resin graft-modified with a polymerizable compound having an isocyanate group, and (b) an amino group, a hydroxyl group and a carboxyl group. A reaction product with an ethylene-based copolymer having at least one group selected from the group consisting of a group and an acid anhydride group, and (C) a non-crosslinked rubber, and a component (A) and a component (B). And the proportion of the component (B) in the total amount of the component (B) is 2 to 30% by weight, and the total amount of the component (A) and the component (B) is 10
The present invention provides a propylene-based resin composition in which the amount of the component (C) is 5 to 40 parts by weight relative to 0 parts by weight.

The structure of the present invention will be described in detail below. In the present invention, examples of the propylene homopolymer of the component (A) constituting the propylene resin composition include, for example, Ziegler
It is produced by a known method using a Natta catalyst. The MFR (JIS K 7210, of the propylene homopolymer of the component (A) used in the present invention,
230 ℃, load 2.16kg) is usually 0.01-30
It is 0 g / 10 minutes, preferably 0.05 to 200 g / 10 minutes, and particularly preferably 0.1 to 100 g / 10 minutes.
If the MFR is less than 0.01 g / 10 minutes, the moldability is poor, while if it is 300 g / 10 minutes or more, the mechanical strength of the obtained composition is insufficient. These propylene homopolymers may be used alone or in combination of two or more.

In the propylene resin composition of the present invention, the component (B) is composed of (a) a modified olefin resin graft-modified with a polymerizable compound having an isocyanate group, and (b) an amino group, a hydroxyl group and a carboxyl group. It is a reaction-treated product with an ethylene-based copolymer having at least one kind of group selected from the group consisting of a group and an acid anhydride group.

The modified olefin resin as the component (a) is
It is obtained by graft-polymerizing a polymerizable compound having an isocyanate group on an olefin resin. Examples of the olefin resin as the component (a) include low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene random copolymer, ethylene-propylene block copolymer, propylene and α.
-Olefins, for example 1-butene, 1-pentene, 1
-Hexene, copolymers with 4-methyl-1-pentene and the like and mixtures thereof. Among these, crystalline polypropylene resins such as polypropylene homopolymer, ethylene-propylene block copolymer and ethylene-propylene random copolymer (the copolymerization ratio of α-olefin is at most 20% by weight) are preferable. These may be used alone or in combination of two or more.

On the other hand, as the polymerizable compound having an isocyanate group, a radical polymerizable monomer having an isocyanate group is used. Specific examples of the radical-polymerizable monomer containing an isocyanate group include isopropenyl isocyanate, m-isopropenyl-α,
α-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, 2-isocyanatomethyl acrylate, 2-isocyanatomethyl methacrylate, 2-isocyanatopropyl acrylate, 2-
Isocyanate hexyl acrylate, lauryl isocyanate, methacryl isocyanate, vinyl isocyanate and the like can be mentioned. The proportion of the grafting amount of the grafting monomer in the component (a) is usually 0.05 to 5% by weight, preferably 0.1 to 3% by weight.
If the graft amount is less than 0.05% by weight, the impact strength will be reduced. On the other hand, if it exceeds 5% by weight, it is obtained (B).
It is not preferable because the moldability of the reaction-treated product of the components is significantly reduced.

As a method of grafting a polymerizable compound having an isocyanate group onto the above-mentioned olefin resin, for example, a method using a radical initiator such as an organic peroxide is generally used. Specifically, for example, a method of suspending or dissolving in a suitable solvent and adding a graft monomer and a radical initiator to the polyolefin and heating and stirring, a polyolefin and a graft monomer and a radical initiator are mixed in advance, an extruder, There is a method of melt-kneading using a Banbury, a kneader or the like. Generally, the latter is easier. In the latter case of melt kneading,
Usually, a single-screw extruder, a twin-screw extruder, etc. are charged with a polyolefin-based resin, a polymerizable isocyanate compound, a radical initiator and, if necessary, a by-product catcher agent, and the type of olefin-based resin (melting point) Depending on, usually 120 ~
It may be melted at a temperature of 300 ° C. and kneaded for 30 seconds to 30 minutes. The radical polymerization initiator is usually used in a proportion of 0.01 to 3 parts by weight with respect to 100 parts by weight of the olefin resin.

The radical initiator used is not particularly limited as long as it is a compound that generates radicals.
For example, dibenzoyl peroxide, p-chlorobenzoyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 1,3-bis (t-butylperoxy) isopropylbenzene, 2,5-bis (t-butyl) Peroxy) -2,5-dimethylhexane, 2,5 bis (t-butylperoxy) -2,5-dimethyl-3-hexane, 1,1-bis (t-butylperoxy) -3,3,3. 5-trimethylcyclohexane, t
Organic peroxides such as butyl peroxybenzoate are preferably used, and they may be diluted with an inert substance such as a plasticizer, calcium carbonate and white carbon. The organic peroxide may be a combination of two or more kinds. Further, as a pretreatment for graft modification, the olefin resin may be previously irradiated with an electron beam.

MFR of the resulting modified olefin resin
(JIS K-7210 230 ° C, load 2.16k
It is desirable that g) is usually 0.01 to 500 g / 10 minutes, preferably 0.1 to 300 g / 10 minutes.

Next, the ethylene copolymer as the component (b) is usually obtained by radically polymerizing ethylene and a polymerizable compound having an amino group, a hydroxyl group, a carboxyl group and an acid anhydride group under high pressure. It may be obtained, and is also copolymerized with α-olefins such as low density polyethylene, high density polyethylene, linear low density polyethylene, 1-butene, 1-pentene, 1-hexene and 4-methyl-1-pentene. An ethylene-based copolymer and a mixture thereof, or an amino group, a hydroxyl group, or a copolymer of ethylene and a third-component monomer obtained under high pressure.
The thing which graft-polymerized the polymerizable compound which has a carboxyl group and an acid anhydride group by 0.1 weight% or more can also be used.

As the polymerizable compound containing an amino group, for example, aminomethyl acrylate, aminoethyl acrylate, aminopropyl acrylate, amino-
n-butyl acrylate, aminohexyl acrylate, aminomethyl methacrylate, aminoethyl methacrylate, amino-n-butyl methacrylate,
Amino group-containing (meth) acrylate compounds such as Nt-butylaminoacrylate, N-methylaminoacrylate, N-methylmethacrylate, N-ethylaminoethylmethacrylate and aminohydroxypropylacrylate, and further crotonamine, allylamine, Methacrylamine, N-methylacrylamine,
In addition to laurylamine, oleylamine, etc., N-vinylacetamide, which can be hydrolyzed after copolymerization to give vinylamine, etc. can be mentioned. These amino group-containing compounds may be used alone or in combination of two or more.

Examples of the hydroxyl group-containing polymerizable compound include hydroxyalkyl (meth) acrylate [(meth) acrylate means methacrylate and acrylate). The same shall apply hereinafter], hydroxyalkylalkoxy (meth) acrylate, hydroxyalkyldialkoxy (meth) acrylate, hydroxyalkylpolyalkoxy (meth) acrylate, hydroxyalkylvinylether, hydroxyalkylalkoxyvinylether, hydroxyalkylpolyalkoxyvinylether and the like. More specifically, 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethylethoxy (meth) acrylate, dipropylene glycol mono (meth) acrylate, 2-hydroxyethyl vinyl ether, Examples include diethylene glycol monovinyl ether and allyl alcohol. These hydroxyl group-containing compounds may be used alone or in combination of two or more.

The carboxyl group-containing polymerizable compound is not particularly limited, but is preferably one having 20 or less carbon atoms, particularly 3 to 18 carbon atoms. Typical examples are acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, fumaric acid, monomethyl maleate, monobutyl maleate, monomethyl itaconate, monobutyl itaconate; 3,6-endo. Methylene-cyclohexane-4-ene-1,2-carboxylic acid and the like can be mentioned.

Examples of the polymerizable compound having an acid anhydride group include maleic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, fumaric acid anhydride, endic acid anhydride, and at most carbon atoms. Examples thereof include alkenyl succinic anhydride having a double bond at the terminal of 18 and alkadienyl succinic anhydride having a double bond at the terminal having at most 18 carbon atoms. These carboxyl group- or acid anhydride group-containing compounds may be used alone or in combination of two or more.

In the ethylene copolymer as the component (B), the polymerization amount of the polymerizable compound containing at least one selected from an amino group, a hydroxyl group, a carboxyl group and an acid anhydride group is usually 0. 0.05 to 20% by weight, preferably 0.1 to 10% by weight. If the amount of polymerization is 0.05% by weight or less, the impact strength will not be improved.
On the other hand, even if it exceeds 20% by weight, no further improvement is obtained.

Further, the ethylene-based copolymer as the component (b) may contain a polymerizable third component monomer in addition to the above-mentioned polymerizable compound at the time of copolymerization. Examples of the third component monomer include polymerizable compounds such as ester compounds, amide compounds, ether compounds, and hydrocarbon compounds. Examples of the ester compound of the polymerizable third component monomer include vinyl acetate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, benzyl acrylate, and acrylic. Acid N, N-dimethylaminoethyl, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, N, N methacrylate
-Dimethylaminoethyl, methyl fumarate, ethyl fumarate, propyl fumarate, dibutyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, methyl maleate, ethyl maleate, propyl maleate, malein Examples thereof include butyl acid, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate and the like.

Specific examples of the amide compound of the third component monomer include acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-propyl acrylamide, N-butyl acrylamide and N-.
Hexyl acrylamide, N-octyl acrylamide, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, N, N-dimethyl methacrylamide, N, N-diethyl acrylamide, etc. can be illustrated. Examples of the ether compound include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octidecinyl vinyl ether, phenyl vinyl ether and the like.

Specific examples of the hydrocarbon compound as the third component monomer include styrene, norbornene, butadiene and the like, and in addition thereto, acrylonitrile, acrolein, crotonaldehyde, trimethoxyvinylsilane, vinyl chloride, Examples thereof include vinylidene chloride. These third component monomers may be used alone, depending on the intended use of the composition,
Moreover, you may use it in combination of 2 or more type.

The copolymerization rate of the third component is at most 45% by weight. The total amount with the polymerizable compound having the functional group is preferably 50% by weight. If the copolymerization ratio of the third component exceeds 45% by weight, the bending elasticity may decrease. MF of ethylene copolymer thus obtained
R (190 ° C, load 2.16kg, JIS K721
0) is usually 0.01 to 500 g / 10 minutes, preferably 0.1 to 300 g / 10 minutes.

In the present invention, the reaction-treated product of the component (B) is obtained by reacting the modified olefin resin of the component (a) and the ethylene copolymer of the component (b). In this reaction treatment, the mixing ratio of the component (a) and the component (b) is not particularly limited, but the weight ratio of (a) :( b) is 5:95 to 95: 5, preferably 10:90. ~ 90: 10. If the amount of the component (a) is less than 5, the impact strength will not be improved. On the other hand, if it exceeds 95, the flexural modulus may decrease.

The reaction-treated product of the components (A) and (B) of the component (B) of the present invention is obtained by mixing the component (B) and the component (B) by a solution method or a melting method. Obtained by However, the treatment by the solution method requires a step of removing the solvent or water after the treatment or drying. From the above, it is desirable to carry out the melting method. The mixing processing temperature when carrying out by the melting method is (a)
And, depending on the melting point of the component (b) and the type of comonomer, the treatment is carried out in a temperature range of 130 ° C to 300 ° C. When the treatment temperature exceeds 300 ° C, it depends on the residence time,
It is not preferable because the reaction proceeds too much and the strands coming out of the extruder are not only bad, but also cause deterioration.

The blending ratio of the component (B) in the total amount of the component (A) and the component (B) of the present invention is 2 to 30% by weight, preferably 2 to 20% by weight. (B) component is 2
If it is less than wt%, the impact strength is not improved. On the other hand, if it exceeds 30% by weight, the mechanical strength may decrease.

The non-crosslinked rubber as the component (C) of the present invention is specifically an ethylene-α-olefin copolymer rubber such as an ethylene-propylene copolymer rubber or an ethylene-propylene-diene copolymer rubber. , Polybutadiene, polyisobutylene, polyisochloroprene and other diene rubbers, isobutylene-isoprene copolymer rubber (butyl rubber), chlorinated butyl rubber, styrene-butadiene rubber,
Acrylic rubber etc. are mentioned. Among these, ethylene-propylene copolymer rubbers, ethylene-α-olefin copolymer rubbers such as ethylene-propylene-diene copolymer rubbers, butyl rubbers, chlorinated butyl rubbers and styrene-butadienes from the viewpoint of weather resistance and compatibility. Copolymer rubbers are especially preferred. You may use these individually or in combination of 2 or more types. The propylene content of the ethylene-propylene copolymer rubber or the ethylene-propylene-diene copolymer rubber may be in the range having properties as a rubber, and generally, the range of 20 to 80% by weight is preferable, and the more preferable range. It is 20 to 70% by weight.

The MFR of these non-crosslinked rubbers (230 ° C.,
Load 2.16 kg, JIS K-7210) is 0.01
To 100 g / 10 minutes, preferably 0.05 to 5
It is preferably 0 g / 10 minutes. The amount of non-crosslinked rubber is 5 to 40 parts by weight with respect to 100 parts by weight of the components (A) and (B).
Parts by weight, preferably 5 to 35 parts by weight. If it is less than 5 parts by weight, the impact resistance is not improved, and if it exceeds 40 parts by weight, the flexural modulus and the tensile strength are lowered.

The resin composition of the present invention comprises the above (A),
It can be obtained by uniformly blending the components (B) and (C). The compounding method is not particularly limited, and a method generally used in the field of synthetic resins may be applied. Specifically, for example, a method of dry blending using a mixer such as a Henschel mixer, a tumbler and a ribbon mixer, a method of mixing while melting using a mixer such as an oven roll extrusion mixer, a kneader and a Banbury. Can be given. Two or more of these methods may be used in combination. Further, in producing the resin composition, two or a part of the components (A), (B) and (C) may be premixed and the resulting mixture may be mixed with the remaining components. Good. The temperature for melt kneading is usually 170 to 300 ° C., preferably 180 to 28.
It is 0 ° C. At a temperature of 300 ° C or higher, the composition may deteriorate.

Further, if necessary, an antioxidant, an infrared absorber, a lubricant, an antistatic agent, an electrical property improving agent, a flame retardant, a processing improving agent, a pigment and the like are added to the propylene resin composition of the present invention. Agent, talc, calcium carbonate, barium sulfate,
Inorganic fillers such as mica and calcium silicate can also be added.

Although the mechanism by which the olefin resin composition of the present invention exhibits impact resistance is not clear, the following facts are presumed. Modified olefin resin of component (a) of (B) and (b)
During the mixing treatment with the ethylene copolymer as the component, a part of the functional groups reacts between the functional groups contained in the components (a) and (b) to form a crosslinked structure, which results in rubber elasticity. That the particles of the treated product are finely dispersed, and by blending the non-crosslinked rubber as the component (C), the components (B) and (A) and It is possible that it has increased affinity with (b) and absorbs shock because it is rubber.

[0032]

EXAMPLES Next, the present invention will be described in more detail by way of examples. The physical properties were measured according to the following methods. (1) MFR (230 ° C, 2.16kg load); JIS
K7210 (2) Tensile yield strength; JIS K7113 (3) Izod impact strength; ASTM-D256 notched (4) Flexural modulus; ASTM-D790 The comonomer composition was determined by nuclear magnetic resonance and infrared spectrophotometer. . Production Example 1 Production of Modified Olefin Resin of (A) Component (B) (A-1) Propylene homopolymer (MFR = 0.5 g / 10 min) manufactured by Showa Denko KK and dicumyl peroxide 1.0 PHR , M-isopropenyl-α, α dimethylbenzyl isocyanate (m-TMI) 3.0 PHR and hexamethylene diisocyanate 0.5 PHR as a by-product catcher agent were dry-blended to give uniaxial 4
0 m / mφ extruder (C ₁ = 180 ° C., C ₂ = 210 ° C., C
₃ = 220 ° C., dice = 220 ° C.) was used to graft m-TMI. This sample was melted at the boiling point of xylene, reprecipitated with acetone to remove unreacted monomers, and the amount of graft was examined by an infrared spectrophotometer.
% MFR was 68 g / 10 min.

(A-2) Showa Denko KK ethylene-
Propylene random copolymer (MFR 0.8 g / 10
Min, ethylene concentration: 2.0 wt%) was irradiated with 2 Mrad at an accelerating voltage of 750 KV in a nitrogen atmosphere using an electron beam irradiation device of Nisshin High Voltage Co., Ltd. 2-Isocyanatomethylmethacrylate 3.
0 PHR was added, and the mixture was reacted in toluene at 40 ° C. for 5 hours in a nitrogen atmosphere. This sample was dissolved and reprecipitated in the same manner as in Production Example A-1 to remove unreacted monomers, and the graft amount was examined. As a result, the MFR was 0.82 wt% and the MFR was 17 g / 10 minutes.

(A-3) Using the propylene homopolymer of Production Example (A-1), electron beam irradiation was carried out under the same conditions as in Production Example (A-2) to obtain m-isopropenyl-α, α-dimethyl. Benzyl isocyanate 3.0PHR was added, and the mixture was reacted in toluene at 50 ° C. for 5 hours in a nitrogen atmosphere. This sample was dissolved and reprecipitated in the same manner as in Production Example A-1 to remove the unreacted monomer, and the graft amount was examined.
The MFR at 28 wt% was 28 g / 10 minutes.

Production Example 2 (B) Production of Component (B) Ethylene Copolymer [Ethyl Copolymer of Amino Group, Hydroxyl Group, Carboxyl Group and Anhydride Group or These and Third Component Monomer] At least one selected from ethylene and a polymerizable amino group compound, a polymerizable hydroxyl group compound, a polymerizable carboxyl group compound and an acid anhydride group, or a copolymer of these with a third component monomer has the composition as described above. It refers to an ethylene radical copolymer produced from a raw material in the temperature range of 700 to 3000 atm and 100 to 300 ° C. The preferred pressure and temperature range is 1000 to 250
The pressure is 0 atm and the average temperature in the reactor is 150 to 270 ° C. In manufacturing, generally, ordinary low-density polyethylene manufacturing equipment and technology can be used. It can also be produced by grafting to polyethylene or a copolymer containing ethylene and a third component comonomer. A copolymer of ethylene (E), aminoethyl acrylate (AEA) and vinyl acetate (VAc) was manufactured using the above-mentioned low-density polyethylene manufacturing equipment. Comonomer composition was determined by nuclear magnetic resonance and infrared spectrophotometer. The composition (wt%) and MI (190 ° C, 2.16 load, JIS K7210, g / 10 min) of the obtained copolymer are shown. The comonomer composition is wt%.

(B-1) E / AEA / VAc = 89 /
2.3 / 8.7 MI = 16 Similarly, a hydroxyl group, a carboxyl group and an acid anhydride group or a third component monomer was produced in the same manner as in Production Example 2. (B-2) E / HEA / BA = 87.6 / 3.6 / 8.
8 MI = 7.9 g / 10 minutes (b-3) E / MAA / MMA = 89.2 / 4.3 /
6.5 MI = 11 g / 10 minutes (b-4) E / MAH / EA = 87.7 / 2.7 / 9.
6 MI = 8.6 g / 10 min However, the above symbols represent the following compounds. HEA = 2-hydroxyethyl acrylate, MMA = methyl methacrylate, BA = butyl acrylate, MAA = methacrylic acid, EA = ethyl acrylate

(B-5) Ethylene-1-butene copolymer (1-butene content = 17.7 wt%, MI 16 g / 1
(0 minutes), electron beam irradiation was performed under the same conditions as in (a-2) of Production Example 1 and 3.0 PHR of allylamine was added, and
The reaction was carried out at 40 ° C. for 5 hours under a nitrogen atmosphere. This sample was dissolved and reprecipitated in the same manner as in Production Example 1 (E1) to remove the unreacted monomer, and the amount of allylamine grafted was examined. As a result, it was 0.42 wt% and MI was 0.2 g / 10 min. It was

(B-6) Low density polyethylene (MI16
g / 10 minutes, 2.16 kg), and maleic anhydride (MAH) (2.0 PHR) was added under the conditions of Production Example 1-A-1 for graft reaction (however, without catcher agent), Production Example 1 (A-). As in 1), dissolution and reprecipitation were carried out to remove unreacted monomers and the graft amount was examined. As a result, the graft amount was 0.47 wt% and the MI was 0.9 g / 10 minutes.

As the propylene homopolymer of the component (A), the following one manufactured by Showa Denko KK was used. MFR = 8.3 g / 10 min Homopolymer (a-1) MFR = 12 g / 10 min Homopolymer (a-2)

(C-1) Ethylene-propylene rubber (ethylene content; 62% by weight, MFR 0.5 g / 10 minutes) (C-2) Ethylene-propylene rubber (ethylene content;
62% by weight, MFR 1.2 g / 10 minutes) (C-3) ethylene-propylene rubber (ethylene content;
70% by weight, MFR 10.5 g / 10 minutes) (C-4) Styrene-butadiene rubber (styrene content;
25% by weight)

Examples 1 to 21 Component (A) of (B) which is a modified olefin resin obtained by grafting an isocyanate compound on the above olefin resin and ethylene and an amino group, a hydroxyl group, a carboxyl group or an acid anhydride group. A 20 mmφ single-screw extruder (C ₁ = 170 ° C., C ₂ = 200 ° C., C ₃ = 2) with the (B) component of (B) which is an ethylene-based copolymer containing
Pelletization was performed at 10 ° C., die = 220 ° C., retention time of about 3 minutes) to obtain the reaction-treated product shown in Table 1.

[0042]

[Table 1]

The obtained MFR is 0.08 to 2.0 g / 1.
It was in the range of 0 minutes. The reaction-treated product of the component (B) and the components (A) and (C) having the composition shown in Table 2 were used at 230 ° C. using a KTX-37 type twin-screw vent extruder manufactured by Kobe Steel. Melt mixing was performed to obtain a resin composition. The obtained resin composition was injected using a mini mat 7/8 ounce injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. at an injection temperature of 230 ° C. and a mold temperature of 40.
A flat plate for tensile yield test, a test piece for measuring Izod impact strength and flexural modulus were prepared under the condition of ° C. Next, these test pieces were left in a thermostatic chamber at a temperature of 23 ° C. and a relative humidity of 50% for 2 days, and the tensile yield strength, Izod impact strength (notched) and flexural modulus were measured. The results are shown in Table 2.

Comparative Examples 1 to 13 (B) Component (a), (A) and (C) Component, (B) Component (b), (A) Component and (C) Component, which have been previously subjected to a reaction treatment. Component (A), component (B), component (A) and component (C), which are not contained in component (B), are melt-mixed in the same manner as in the example to obtain a resin composition and injection is performed in the same manner as in the example. Molded. At the same time, the case of only the component (A) was similarly performed. The test piece was conditioned in the same manner as in the example, and the tensile yield strength, Izod impact strength and flexural modulus were measured. The results are shown in Table 3. From these results, (B) component (A), (A) and (C) component, (B)
Component (b), component (A) and component (C), (B) component (a) that has not been previously subjected to reaction treatment, and melt mixture of component (b), component (A) and component (C) are carried out. It can be seen that the Izod impact strength is low compared to the example.

Comparative Examples 14 to 18 In Comparative Examples 14 to 17, the amount (% by weight) of the reaction-treated product of (B) was outside the range of the present invention (2 to 30% by weight), that is, 1 For the case of 40% by weight and the case of 40% by weight, melt mixing was performed in the same manner as in the example to obtain a resin composition and injection molding was performed. The tensile yield strength, Izod impact strength and flexural modulus were measured under the same conditions as in the examples. Further, in Comparative Example 18, when the compounding amount of the component (C) is out of the range of the present invention (5 to 40% by weight), that is, in the case of 50% by weight, injection molding is performed in the same manner as in Example, The tensile yield strength, Izod impact strength and flexural modulus were measured under the same conditions as in the examples. The above results are shown in Table 4. From these results, the impact resistance strength was not improved when the content of the reaction-treated product was 2% by weight or less, and the impact resistance strength was almost the same as that of the examples when it was 30% by weight or more, but the flexural modulus and the tensile yield strength were Is reduced. On the other hand, if the content of the component (C) exceeds 40% by weight, the flexural modulus and the tensile yield strength decrease.

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4] From the results of the above examples and comparative examples, by melt-mixing the reaction-treated product of the component (B) with the component (A) and the component (C), the impact resistance is improved, the flexural modulus and the tensile yield are increased. It is clear that not only mechanical strength such as strength is excellent, but also fluidity is excellent.

[0049]

The propylene resin composition of the present invention is excellent in impact resistance, flexural modulus and tensile yield strength, and a molded product having these characteristics can be obtained from the propylene resin composition. it can. The olefin resin composition of the present invention can be used mainly in fields such as automobile bumpers and motorcycle fenders, helmets, furniture, home appliances, sports equipment, etc. where impact resistance is required and various hose parts.

Claims (1)

[Claims] 1. A modified olefin resin graft-modified with (A) a propylene homopolymer, (B) (a) a polymerizable compound having an isocyanate group, and (b) an amino group, a hydroxyl group, a carboxyl group and an acid. A reaction-treated product with an ethylene-based copolymer having at least one group selected from the group consisting of anhydride groups, and (C) a non-crosslinked rubber, the total of (A) component and (B) component The blending ratio of the component (B) in the amount is 2 to 30% by weight, and the total amount of the component (A) and the component (B) is 10
A propylene resin composition in which the amount of the component (C) is 5 to 40 parts by weight relative to 0 parts by weight.