JPH0770401A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the resin composition comprising a polymer having functional groups capable of reacting with amino groups, and a graft copolymer produced by grafting a N-substituted amide to an olefinic polymer having a specific weight-average mol. wt., and excellent in impact resistance and rigidity. CONSTITUTION:(A) 50-99.5 pts.wt. of a polymer having functional groups capable of reacting amino groups and (B) 0.5-50 pts.wt. of a graft copolymer produced by grafting a N-substituted unsaturated carboxylic acid amide of the formula (R<1>, R<2> are H, 108C alkyl, 6-10C cycloalkyl, phenyl, 7-18C arylalkyl; R<4> is H, 1-8C alkyl, phenyl, benzyl, 1-18C primary or secondary alkoxy, phenoxy, benzyloxy; R<3> is H, methyl) to an olefinic polymer or copolymer having a weight-average mol. wt. are compounded with each other to obtain the thermoplastic resin composition excellent in impact resistance and rigidity andexhibiting the effects in a small addition amount due to the efficient dispersion of the impact-absorbing component such as the elastomer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition having improved impact resistance.

[0002]

2. Description of the Related Art As a conventional thermoplastic resin composition having improved impact resistance, for example, a method of blending an elastomer component is most commonly used.

[0003]

However, in such a conventional method for improving impact resistance by adding an elastomer, since a relatively large amount is required, the rigidity of the resin is significantly lowered, Further, there is a problem that impact resistance is often lowered due to poor interfacial adhesion between the matrix component and the elastomer component.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of such conventional problems, and is a copolymer which can be an impact absorbing component for suppressing the decrease in strength of a resin which is a matrix component. Efficiently disperse, to disperse the impact absorbing component that becomes the domain component as fine uniform particles in order to obtain the desired impact strength with the smallest possible addition amount, and at the same time decrease the physical properties due to poor adhesion at the macro phase separation interface. From the viewpoint of having to use a method that does not occur, as a result of earnest research, as a result, a copolymer containing an acyl group, an amino group, a formamide group or an alkoxycarbonyl group that can be a shock absorbing component has reactivity with an amino group. The present invention has been completed by finding that a thermoplastic resin composition having a modified impact resistance of a thermoplastic resin containing a functional group can be obtained.

That is, the first invention is a thermoplastic resin composition containing the following components A and B: (A) 50 to 99.5 parts by weight of a polymer having a functional group capable of reacting with an amino group [hereinafter referred to as (A) component]. (B) A graft copolymer obtained by graft-reacting an N-substituted amide represented by the general formula 2 with an olefin polymer or olefin copolymer having a weight average molecular weight of 5,000 to 500,000. (B) component] 0.5 to 50 parts by weight.

[0006]

[Chemical 2]

(In Chemical Formula 2, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or an arylalkyl group having 7 or 8 carbon atoms, and R ³ is a carbon number. 1-18 alkylene group, having 5 carbon atoms
A cycloalkylene group having 17 carbon atoms, an arylene group having 6 to 12 carbon atoms or an arylalkylene group having 7 to 17 carbon atoms, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group, or a carbon number. 1 to 8 primary or secondary alkoxyl group, phenoxy group or benzyloxy group. R ¹ , R ² , R ³ and R ⁴ may be the same or different in each repeating unit. )

As a second invention, the following components A and B
It is a thermoplastic resin composition containing a component. (A) an amino group selected from the group consisting of a succinic anhydride group, a carboxyl group, an epoxy group, an ester group, an amide group, a cyclic iminoether group, a cyclic iminoamino group, a halogen group, an imide group and an isocyanate group in the molecule; A polymer component containing at least one polymer having a reactive functional group, a thermoplastic resin which does not substantially react with an amino group under molding and processing conditions, and which has an affinity with the polymer component. Composition with certain unreactive thermoplastics 50-99.
5 parts by weight. (B) 0.5 to 50 parts by weight of the component (B)

As the component A in the thermoplastic resin composition of the present invention, the following two types of components (A-1) and (A-2) are used. (A-1): Polymer component having functional group capable of reacting with amino group (A-2): Succinic anhydride group, carboxyl group, epoxy group, ester group, amide group, cyclic iminoether group, in the molecule A polymer component containing at least one polymer having a functional group capable of reacting with an amino group selected from the group consisting of a cyclic iminoamino group, a halogen group, an imide group and an isocyanate group, and an amino group under molding and processing conditions. Composition of a thermoplastic resin that does not substantially react with, and an unreactive thermoplastic resin having an affinity with the polymer component

Further, the polymer component having a functional group capable of reacting with an amino group used in the above component (A-1) is represented by the following (A-
It is classified into two kinds of components a) and (Ab). (Aa): Polymer component containing at least one resin selected from the group consisting of polyester resin, polycarbonate resin and polyamide resin (Ab): Succinic anhydride group, carboxyl group, epoxy group, ester group , Amide group, cyclic iminoether group,
Polymer component containing one or more polymers having in the molecule a functional group selected from the group consisting of cyclic iminoamino groups, halogen groups, imide groups and isocyanate groups

That is, the component (A) of the first invention is the component (Aa) or the component (Ab), which is used as the component (A-1). The component (A) of the second invention is a composition of the component (Ab) of the component (A-1) and the unreactive thermoplastic resin. It is used as an ingredient.

As the component B in the thermoplastic resin composition of the present invention, a copolymer having an amino group, an acylamino group, a formamide group or a carbamate group represented by the following chemical formula 3 is used. It

[0013]

[Chemical 3] (In the formula, R ^{1 to} R ⁴ are the same as described above.)

(Requirements Constituting Means) Hereinafter, each component in the thermoplastic resin composition of the present invention will be described in more detail.

[1] Component A: As described above, the component A in the thermoplastic resin composition of the present invention is roughly classified into the following two components (A-1) and (A-2). To be done. (A-1): Polymer component having functional group capable of reacting with amino group (A-2): Succinic anhydride group, carboxyl group, epoxy group, ester group, amide group, cyclic iminoether group, in the molecule A polymer component containing at least one polymer having a functional group capable of reacting with an amino group selected from the group consisting of a cyclic iminoamino group, a halogen group, an imide group and an isocyanate group, and an amino group under molding and processing conditions. Composition of a thermoplastic resin that does not substantially react with, and an unreactive thermoplastic resin having an affinity with the polymer component

(1) Component (A-1) The polymer component having a functional group capable of reacting with an amino group used in the above component (A-1) includes components (Aa) and (A-).
There are two types of component b). (I) Component (A-a) The component (A-a) is a polymer component (main chain reaction type) having a bonding group capable of reacting with an amino group in the main chain of the polymer. Examples of the bonding group include bonding groups such as ester bond, carbonic acid ester bond, amide bond, urethane bond, and imide bond. Specific examples of the component (A-a) include polyester resin, polycarbonate resin, and polyamide resin, and one or more of these resins are used as the component (A-a).

More specifically, the type of the polyester resin as the component (Aa) is not particularly limited, and various types can be used. This polyester resin may be either an aliphatic or aromatic polyester resin, but the latter aromatic polyester resin is preferred in view of physical properties. The molecular weight may be appropriately selected according to the purpose of use, etc., but normally the intrinsic viscosity is 0.2 to 2.0 dl / g, preferably 0.5 to 1.
2 dl / g fits. Furthermore, this polyester resin may have a carboxylic acid terminal or an alcoholic hydroxyl group terminal.

Such polyester resin can be produced by various known methods, and various kinds thereof can be mentioned. Specific examples of the polyester resin as the component (Aa) include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexadimethyl terephthalate (PCT), and polyarylate.

The polycarbonate resin as the component (Aa) may be either an aliphatic or aromatic polycarbonate resin, and examples thereof include 2,2-bis (4-oxyphenyl) alkane-based and bis ( 4-oxyphenyl)
Examples include ether-based and bis (4-oxyphenyl) sulfone, sulfide and sulfoxide-based bisphenol-based polymers or copolymers.

The type of the polyamide resin as the component (Aa) is not particularly limited, and various types can be used, and may be an aliphatic or aromatic polyamide resin.
The molecular weight is not particularly limited, but in consideration of moldability and physical properties of the obtained composition, the number average molecular weight is 4,
000 to 50,000, preferably 5,000 to 30,
000 is suitable. Such a polyamide resin can be manufactured by various known methods. For example, it can be produced by ring-closing (co) polymerization or (co) polycondensation of a lactam having three or more membered rings, a polymerizable ω-amino acid, a dibasic acid and a diamine, or the like.

As the polyamide resin as the component (Aa), various ones can be used, and specific examples thereof include nylon 6; nylon 6,6; nylon 6,10; nylon 11; nylon. 12; nylon 6,
12; Nylon 4, 6 and other aliphatic polyamides, Nylon 6/6; Nylon 6/6, 10; Nylon 6/6, 12
And other aliphatic copolyamides, polyhexamethylenediamine terephthalamide; polyhexamethylenediamine isophthalamide; aromatic polyamides such as xylene group-containing polyamides. Furthermore, polyester amide, polyester ether amide, etc. can be mentioned. Of these, preferred are nylon 6; nylon 6,6.

(Ii) Component (Ab) The other component (Ab), which is a polymer component having a functional group capable of reacting with an amino group, is an amino group at the side chain or molecular end of the polymer. It is a polymer component (side chain or end reaction type) having a functional group capable of reacting with a group. Specific examples of such a functional group include a succinic anhydride group, a carboxyl group, an epoxy group, an ester group, an amide group, a cyclic iminoether group, a cyclic iminoamino group, a halogen group, an imide group, and an isocyanate group. Among them, the important and preferable functional groups are succinic anhydride group, carboxyl group, epoxy group and cyclic iminoether group. The component (Ab) may contain only one type of the above-mentioned polymer having a functional group, or may contain two or more types thereof.

In more detail, does the polymer having a succinic anhydride group in the side chain of the component (Ab) copolymerize maleic anhydride or itaconic anhydride with an ethylenically unsaturated monomer? Alternatively, it can be obtained by graft polymerization of a polymer such as polyolefin with maleic anhydride or itaconic anhydride in the presence of a radical initiator. Specific examples thereof include a styrene-maleic anhydride copolymer, an isobutylene-maleic anhydride copolymer, and an ethylene-maleic anhydride copolymer. Further, as specific examples, polyethylene, polypropylene, SEBS (hydrogenated product of styrene-butadiene-styrene copolymer), ethylene-propylene rubber, EPDM (ethylene-propylene-
Diene copolymers), styrene-isoprene copolymers, polyphenylene ethers, and other polymers grafted with maleic anhydride are also included.

The polymer having a carboxyl group in the side chain of the component (Ab) copolymerizes a carboxylic acid containing an ethylenically unsaturated bond such as acrylic acid and methacrylic acid with an ethylenically unsaturated monomer. Alternatively, it can be obtained by graft-polymerizing an ethylenically unsaturated bond-containing carboxylic acid onto a polymer such as polyolefin. Specific examples include an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, and an ethylene-maleic anhydride-acrylic acid copolymer. Specific examples thereof include acrylic acid graft products and methacrylic acid graft products of polymers such as polyethylene, polypropylene, SEBS (hydrogenated product of styrene-butadiene-styrene copolymer), and ethylene-propylene rubber.

The polymer having an epoxy group in the side chain of the component (Ab) is, for example, a copolymer of glycidyl acrylate or glycidyl methacrylate and an ethylenically unsaturated monomer. Representative examples are ethylene-glycidyl methacrylate copolymer, propylene-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

Examples of the polymer having an ester group in the side chain of the component (Ab) include ester group-containing ethylenically unsaturated monomers such as alkyl acrylate, methacrylic acid alkyl ester and alkyl vinyl ester, and others. The copolymer with the ethylenically unsaturated monomer of can be utilized. Specific examples include ethylene-acrylic acid ester copolymers, ethylene-methacrylic acid ester copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, ethylene-vinyl acetate copolymers, and the like. To be

Examples of the polymer having an amide group in the side chain of the component (Ab) include acrylamide, methacrylamide,
Examples thereof include copolymers of N-methyl acrylamide, N-methyl methacrylamide, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide and other ethylenically unsaturated monomers.

As the polymer having a cyclic iminoether group in the side chain of the component (Ab), a copolymer of 2-vinyloxazoline, 2-vinyloxazine and another ethylenically unsaturated monomer is used. Styrene-as a typical example.
2-vinyl oxazoline copolymer is mentioned.

Examples of the polymer having a cyclic iminoamino group in the side chain of the component (Ab) include a copolymer of 2-vinylimidazoline and another ethylenically unsaturated monomer.

Specific examples of the polymer having a halogen group in the side chain of the component (Ab) include polyvinyl chloride, chlorinated polyolefin, chloroethyl vinyl ether copolymer, chloromethylated polystyrene and the like.

Specific examples of the polymer having an imide group in the side chain of the component (Ab) include N-phenylmaleimide and N-phenylmaleimide.
Examples thereof include copolymers of alkylmaleimide and other ethylenically unsaturated monomers.

As the polymer having a carboxyl group at the molecular end of the component (Ab), for example, a radical initiator having a carboxyl group is used and, if necessary, a chain transfer agent having a carboxyl group is used. Examples of the polymer containing a carboxyl group at one end obtained by polymerization include terminal carboxypolystyrene, terminal carboxypolyisoprene, terminal carboxy-polyacrylic acid ester, and terminal carboxy-polymethacrylic acid ester. Examples of the above-mentioned polymer having a carboxyl group at the molecular end include a terminal carboxypolyester and a terminal carboxypolyamide obtained by reacting with excess dicarboxylic acid in a condensation polymerization reaction.

The polymer having an epoxy group or an ester group at the molecular end of the component (Ab) is, for example, a terminal ester group obtained by esterifying the above-mentioned terminal carboxypolystyrene or the like with a lower alcohol or glycidol. Examples thereof include polystyrene having an end epoxy group.

(2) Component (A-2) The component (A-2) used as the component A in the thermoplastic resin composition of the present invention has a functional group capable of reacting with an amino group as described above. A polymer (Ab) component having a thermoplastic resin that does not substantially react with an amino group under molding and processing conditions, and is an unreactive thermoplastic resin having an affinity with the component (Ab) [hereinafter referred to as (A-c) component].

The non-reactive thermoplastic resin is mixed with the B component (A-
The component (A-c) can be added because the resin composition having improved impact resistance can be obtained even in the state where the graft polymer reacted with the component (b) is dispersed.
Even in the aspect of the composition of the component (-2), the same effect as that of the component (A-1) can be obtained.

Specific combinations of components (Ab) and (Ac) include maleic anhydride-grafted polypropylene and polypropylene, maleic anhydride-grafted polyphenylene oxide and polyphenylene oxide or polystyrene, and styrene-maleic anhydride co-polymer. Examples thereof include polymer and polystyrene or polyphenylene oxide, and styrene-glycidyl (meth) acrylate and polystyrene or polyphenylene oxide.

The mixing ratio of the component (Ab) and the component (Ac) in the component (A-2) is (Ac) / (A-
b) is in the range of 99 parts by weight / 1 part by weight to 50 parts by weight / 50 parts by weight, preferably in the range of 99 parts by weight / 1 part by weight to 70 parts by weight / 30 parts by weight. When the blending ratio is larger than 99/1, the impact resistance of the obtained thermoplastic resin composition is not sufficient, and when the blending ratio is less than 50/50, it is economically disadvantageous. In addition, the physical properties of the obtained thermoplastic resin composition may deteriorate.

[2] Component B: As described above, the component B in the thermoplastic resin composition of the present invention is an olefin polymer or olefin copolymer having a weight average molecular weight of 5,000 to 500,000. A graft copolymer obtained by graft-reacting an N-substituted amide represented by the general formula 4 is used.

[0039]

[Chemical 4]

(However, in the general formula 4, R ¹ and R ² are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and a carbon atom having 6 carbon atoms.
10 represents a cycloalkyl group, a phenyl group or an arylalkyl group having 7 or 8 carbon atoms, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group , A benzyl group, a primary or secondary alkoxy group having 1 to 8 carbon atoms, a phenoxy group or a benzyloxy group. The above R ¹ , R ² , R ³ and R ⁴
May be the same or different for each repeating unit. )

The graft copolymer represented by the above general formula 4 includes a formamide group-containing graft copolymer (I) and an acylamino group-containing graft copolymer (I
I) and a graft copolymer (III) having a carbamate group. That is, the formamide group-containing graft copolymer (I) is represented by the general formula 5.

[0042]

[Chemical 5]

(In the formula 5, R ^{1 to} R ³ are the same as described above.) The acylamino group-containing graft copolymer (II) is represented by the general formula 6.

[0044]

[Chemical 6]

(In the formula 6, R ^{1 to} R ³ are the same as above. R ⁵ is an alkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group. R ^{1 to} R ³ and R ⁵ are repeated. It may be the same or different for each unit.)

The carbamic acid ester group-containing graft copolymer (III) is represented by the general formula (7).

[0047]

[Chemical 7]

[0048] In (Formula 7, R ¹ to R ³ are the same as described above .R ⁶ is .R ¹ to R ³ showing a primary or secondary alkyl group, a phenyl group or a benzyl group having 1 to 8 carbon atoms And R ⁶ may be the same or different for each repeating unit.)

These graft copolymers (I), (II),
A copolymer having any two or more of (III) in the molecule may be used as the component B in the thermoplastic resin composition of the present invention.

Examples of the N-substituted formamide compound (I) represented by the general formula 5 used as a graft monomer in the preparation of the graft copolymer having a formamide group as the component B include N-alkenylformamide compounds and N-alkyl- Examples include N-alkenylformamide compounds.

More specifically, as the N-alkenylformamide compound, N-allylformamide, N-
(1-Methyl-2-propenyl) formamide, N-
(1-Ethyl-2-propenyl) formamide, N-
(1-n-propyl-2-propenyl) formamide,
N- (1-n-butyl-2-propenyl) formamide, N- (1-n-hexyl-2-propenyl) formamide, N- (1-cyclohexyl-2-propenyl)
Formamide, N- (1-benzyl-2-propenyl)
Formamide and the like, and as the N-alkyl-N-alkenylformamide compound, N-methyl-N-
Allylformamide, N-methyl-N- (1-methyl-
2-propenyl) formamide, N-ethyl-N-allylformamide, N-ethyl-N- (1-methyl-2-)
Propenyl) formamide, N-propyl-N- (1-
Benzyl-2-propenyl) formamide, N-butyl-N- (1-cyclohexyl-2-propenyl) formamide, N-hexyl-N- (1-n-hexyl-2-
Propenyl) formamide, N-octyl-N- (1-
n-butyl-2-propenyl) formamide, N-benzyl-N-allylformamide, N-cyclohexyl-
N-allylformamide etc. are mentioned.

Of these, more preferred are N-allylformamide, N- (1-methyl-2-propenyl) formamide, N-methyl-N-allylformamide, N-
-Methyl-N- (1-methyl-2-propenyl) formamide, N-ethyl-N-allylformamide, N-ethyl-N- (1-methyl-2-propenyl) formamide.

The N-substituted amide (II) represented by the general formula 6 used as a graft monomer in a graft copolymer having an acylamino group includes N-allylacetamide and N- (1-methyl-2). -Propenyl) acetamide, N- (1-ethyl-2-propenyl) acetamide, N- (1-n-propyl-2-propenyl)
Acetamide, N- (1-n-butyl-2-propenyl) acetamide, N- (1-n-hexyl-2-propenyl) acetamide, N- (1-cyclohexyl-2)
-Propenyl) acetamide, N- (1-benzyl-2)
-Propenyl) acetamide, N-allylpropionamide, N- (1-methyl-2-propenyl) propionamide, N-allylbutyramide, N- (1-methyl-
2-propenyl) butyramide, N-allylvaleramide, N- (1-methyl-2-propenyl) valeramide, N-allylphenylamide, N-allylbenzylamide and the like. Of these, more preferred are N-allylacetamide and N- (1-methyl-2-propenyl) acetamide.

Further, the N-substituted carbamic acid ester (I) represented by the general formula 7 is used as a grafting monomer in a graft copolymer having a carbamic acid ester group.
II) includes methyl N-allyl carbamate, ethyl
N-allyl carbamate, iso-propyl N-allyl carbamate, sec-butyl N-allyl carbamate, phenyl N-allyl carbamate, benzyl
N-allyl carbamate, ethyl N- (1-methyl-
2-propenyl) carbamate, iso-propyl N
-(1-methyl-2-propenyl) carbamate, se
c-Butyl N- (1-methyl-2-propenyl) carbamate, phenyl N- (1-methyl-2-propenyl) carbamate, benzyl N- (1-methyl-2-)
Propenyl) carbamate, iso-propyl N-
(1-propyl-2-propenyl) carbamate, se
c-Butyl N- (1-propyl-2-propenyl) carbamate, benzyl N- (1-propyl-2-propenyl) carbamate, n-hexyl N-allyl carbamate, 2-ethylhexyl N-allyl carbamate, ethyl N- ( 1-n-heptyl-2-propenyl) carbamate, ethyl N- (1-cyclohexyl-2-propenyl) carbamate, ethyl N- (1-
Phenyl-2-propenyl) carbamate and the like.

Among these, ethyl N is more preferable.
-Allyl carbamate, iso-propyl N-allyl carbamate, sec-butyl N-allyl carbamate, phenyl N-allyl carbamate and benzyl
It is N-allyl carbamate.

The olefin polymer or olefin copolymer grafted in the graft copolymer of the present invention includes polyolefins or oligomers thereof, polyolefin thermoplastic elastomers or oligomers thereof, polyolefin elastomers, ethylene- Examples include vinyl ester copolymers, ethylene-acrylic ester copolymers and oligomers thereof, and blends of these various polyolefins and oligomers are also included.

More specifically, the above-mentioned polyolefins or oligomers thereof include high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, ethylene and α-olefin. Polymers and the like, and the thermoplastic polyolefin-based elastomers or oligomers thereof are ethylene-propylene rubber, ethylene-propylene-diene copolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), butyl rubber, butadiene rubber, A polyolefin thermoplastic elastomer comprising a low crystalline ethylene-propylene copolymer or a propylene-butene copolymer, and the polyolefin-based elastomer is a polyolefin-based thermoplastic elastomer mainly composed of a blend of polypropylene and ethylene-propylene rubber. Mer, styrene - ethylene -
Examples thereof include butylene-styrene block copolymer (SEBS).

Among such olefin polymers and olefin copolymers, polypropylene, ethylene-propylene rubber, ethylene-propylene-diene copolymer (E
PDM) and their oligomers or SEBS are preferred. The average molecular weight thereof is usually 5,000.
Although those of 0 to 500,000 are used, those of 10,000 to 200,000 are suitable.

The method for producing the graft copolymer of the present invention is carried out in the presence of a catalyst for producing free radicals in a temperature range from a temperature sufficient to produce free radicals to 250 ° C. The N-substituted amide is graft-reacted with an olefin polymer or olefin copolymer having 500,000. In the graft reaction, a small amount of a free radical generating catalyst is mixed with the N-substituted amide. When the reaction temperature is within the above temperature range, the graft reaction proceeds at an appropriate rate, and the destructive decomposition of the reaction product and the product does not occur.

The grafting reaction may be catalyzed by a free radical generating catalyst such as a peroxide, dialkyl-, diacyl-, alkyl-acyl peroxide, or azo compound when used in a suitable temperature range, or a metal salt or The reaction is initiated externally by a cocatalyst such as a complex or by irradiation with light.

Typical examples of such a free radical generating catalyst are di-t-butyl peroxide, dicumyl peroxide, t-butyl perbenzoate, benzoyl peroxide, cyclohexanone peroxide, lauryl peroxide and azobisisos. Butyronitrile and the like, as well as mixtures thereof. More preferred of these catalysts are di-t-butyl peroxide, dicumyl peroxide and mixtures thereof.

The amount of the above-mentioned free radical generating catalyst may be a catalytic amount, and a useful range is 1 to 200 g per kg of the olefin (co) polymer, preferably 1 to 1 kg per olefin (co) polymer. It is 100 g. Further, the catalyst may be added all at the start of the graft reaction or added little by little as the reaction progresses.

The mixture containing the olefin polymer or olefin copolymer, the N-substituted amide and the free radical generating catalyst is stirred at an appropriate reaction temperature. The reaction temperature range useful for conducting the experiment varies depending on the type of catalyst used,
From room temperature to 250 ° C. When using di-t-butyl peroxide or dicumyl peroxide as a catalyst,
The preferred reaction temperature range is 100 to 200 ° C.

Further, since the olefin (co) polymer is generally very viscous when the molecular weight is 2,000 or more,
The olefin (co) polymer may be so viscous or rubber that it cannot be stirred. In that case, the reaction is preferably carried out in an inert solvent, and useful nonane,
It is also possible to use decane and similar aliphatic hydrocarbons, and chlorobenzene, dichlorobenzene, dichlorotoluene and similar chlorinated hydrocarbons.

Further, the graft amount of the N-substituted formamide compound (I), N-substituted amide (II), N-substituted carbamic acid ester (III) onto the olefin polymer or olefin copolymer is determined by infrared absorption spectrum. Can be determined by measuring the value of 1400 to 15 based on the alkyl group of the olefin (co) polymer used as a raw material.
Absorption at 00 cm ^-1 and 165 peculiar to formamide compounds
Absorption of 0～1700Cm ^-1, absorption of 1650～1690Cm ^-1 based on the amide group of N- substituted amides, to determine the graft amount by the ratio of the absorbance of absorption peculiar 1720～1730Cm ^-1 carbamic acid ester. The amount of the above compound grafted cannot be uniquely determined because it depends on the target physical properties and appearance of the finally obtained thermoplastic resin composition, but it is usually 100% by weight of the olefin polymer or copolymer used as a raw material. Is 0.2 to 20% by weight. If the graft amount is less than 0.2% by weight, the miscibility of the resins in the finally obtained thermoplastic resin composition will be poor, and if the graft amount exceeds 20% by weight, the thermoplastic resin Not only is it uneconomical to produce the composition, but it may rather deteriorate the physical properties of the resin composition.

[3] About composition ratio of thermoplastic resin composition: The resin composition of the present invention contains the components A and B described in the above [1] and [2] as essential constituent components. However, if necessary, other additives (reinforcing material such as glass fiber and carbon fiber, inorganic filler, heat stabilizer,
Antistatic agents, antioxidants, light stabilizers, flame retardants, weathering agents, etc.) may be added. Further, regarding the mixing ratio of the A and B components in the resin composition of the present invention, the A component is 50 to 99.% with respect to a total of 100 parts by weight of the A component and the B component.
5 parts by weight, preferably 70 to 99 parts by weight, and 0.5 to 50 parts by weight of component B, preferably 1.0 to 30 parts by weight.

If the blending ratio of the component B is less than 0.5 part by weight, the physical properties such as impact strength of the obtained resin composition are not sufficiently improved. Further, when the blending ratio of the component B exceeds 50 parts by weight, the rigidity of the resin composition tends to remarkably decrease. Moreover, it is economically disadvantageous in producing the resin composition.

[4] Method for producing thermoplastic resin composition: There is no particular limitation on the order of addition of the components A and B, the timing of addition, and the method of addition in producing the resin composition of the present invention. Specifically, the resin composition of the present invention is prepared by heating each of the above components using a kneader such as a single-screw extruder, a twin-screw extruder, a burr-barrier mixer, a kneading roll, or a mixer such as a Hensiel mixer. -Manufactured by kneading in a molten state. The kneading temperature differs depending on the type of constituent components used, the amount of the components used, the physical properties of the composition to be produced, and the like, and cannot be uniquely determined.

[0069]

The component A polymer grafted with the elastomer component by the exchange reaction of the formamide group or the like in the component B used in the present invention with the ester bond or amide bond or the like in the component A or the addition reaction to the non-hydroxyl group or oxirane group. Is generated. Since this polymer has the A component in the trunk, it is possible to disperse the elastomer component in the A component very efficiently, and it can be seen that the impact resistance is remarkably improved.

[0070]

EXAMPLE An example of producing the graft copolymer having a formamide group of the present invention is shown below. (Graft copolymer having formamide group) 2.0 g of N-allylformamide (graft monomer), and ethylene-propylene rubber (ethylene / propylene = 6/4) having a weight average molecular weight of 50,000 (raw polymer) 40
g and 160 g of chlorobenzene were dissolved, and a solution of 0.5 g of dicumyl peroxide dissolved in 40 g of chlorobenzene was gradually added dropwise at a temperature of 128 ° C. After the reaction was continued for 3 hours after the dropwise addition of dicumyl peroxide, the reaction mixture was put into methanol to remove unreacted N-allylformamide, and further dried to ethylene-grafted with N-allylformamide. Propylene rubber [graft copolymer (1)] was obtained. The resulting grafts measured for infrared absorption spectrum, the absorption around 1660 cm ^-1 based on the amide, ethylene - the absorption of the 720 cm ^-1 based on alkyl propylene rubber, a graft amount of N- allyl formamide 2.7% by weight based on 100% by weight of ethylene-propylene rubber
Was determined to be.

<Graft Copolymers (2) to (7)> A graft copolymer having another formamide group [graft copolymers (2) to (7) is prepared in the same manner as in the above graft copolymer (1). )] Was prepared and the results are shown in Table 1.
Table 1 shows the raw material polymers of the graft copolymers (1) to (7), the graft monomer and the graft amount thereof, where Mw represents the weight average molecular weight and Mn represents the number average molecular weight.

[0072]

[Table 1]

Next, production examples of the graft copolymer having an acylamino group of the present invention will be shown below. (Graft copolymer containing acylamino group) 7.5 g of N-allylacetamide (graft monomer), weight average molecular weight (Mw) of 50,000, number average molecular weight (M
n) 30,000 ethylene-propylene rubber (ethylene / propylene = 60/40) (raw material polymer) 150 g
Was dissolved in 150 g of chlorobenzene, and 20 g of lauryl peroxide dissolved in 200 g of chlorobenzene was gradually added dropwise thereto at 120 ° C. After the completion of the addition of lauryl peroxide, the reaction was continued for 1 hour, and then the reaction mixture was put into methanol to remove unreacted N-allylacetamide and dried to give ethylene-propylene grafted with N-allylacetamide. A rubber [graft copolymer (8)] was obtained. The yield of the obtained graft copolymer was 154 g. In addition, the infrared absorption spectrum of the graft copolymer was measured, and it was confirmed that the N- ^value was determined by the absorption around 1670 cm ^-1 based on the acetamide group and the absorption at 1500 cm ^-1 based on the alkyl group of ethylene-propylene rubber.
The graft amount of allylacetamide on ethylene-propylene rubber was determined to be 5% by weight.

<Graft Copolymers (9) to (14)> A graft copolymer containing an acylamino group was prepared in the same manner as in the above graft copolymer (8). These graft copolymers are shown in Table 2 together with those of the graft copolymer (8). Table 2 shows the type of the raw material polymer, the graft monomer and the graft amount thereof, where Mw is the weight average molecular weight and Mn is the number average molecular weight.

[0075]

[Table 2]

The production examples of the graft copolymer having a carbamate ester group of the present invention are shown below. (Graft copolymer having a carbamate group)
Ethyl N-allyl carbamate (graft monomer)
7.5 g and 150 g of ethylene-propylene rubber having a molecular weight of 50,000 (ethylene-propylene = 60/40) (raw polymer) were dissolved in 150 g of chlorobenzene,
A solution prepared by dissolving 20 g of lauryl peroxide in 200 g of chlorobenzene was gradually added dropwise at a temperature of 120 ° C. After the reaction was continued for 1 hour after the completion of the addition of lauryl peroxide, the reaction mixture was put into methanol to remove unreacted ethyl N-allyl carbamate, and further dried to graft ethylene with ethyl N-allyl carbamate. -Propylene rubber [graft copolymer (15)] was obtained. The infrared absorption spectrum of the obtained grafted product was measured, and it was based on the carbamate group.
And absorption around 00cm ^-1, ethylene - the absorption of 1500 cm ^-1 based on alkyl propylene rubber, a graft amount of ethyl N- allyl carbamate ethylene - 4.5% by weight relative to propylene rubber 100 wt% It was decided to be.

<Graft copolymers (16) to (21)>
Further, another graft copolymer was synthesized by the same method as the above graft copolymer (15) [Graft copolymers (16) to (21)], and the results are shown in Table 3. In Table 3, the raw material polymers of the graft copolymers (15) to (21), the graft monomer and the graft amount thereof are shown, where Mw is the weight average molecular weight and Mn is the number average molecular weight.

[0078]

[Table 3]

In obtaining a thermoplastic resin composition (A-
a), (A-b) and (A-c) as resins for the components shown in Table 4
The one described in 1. was used. In addition to those listed in Table 4,
As component (Ab), a maleic anhydride polyphenylene oxide (MAH-g-PP), which is a laboratory synthesized product, is used.
O), a styrene-glycidyl methacrylate copolymer (St-GMA), and a reagent polyphenylene oxide (PPO) as the component (A-c).

[0080]

[Table 4]

Examples 1 to 21 These components A and B were used in the proportions shown in Tables 5 and 6 to obtain the thermoplastic resin compositions of Examples 1 to 21 according to the present invention. That is, components A and B are dry-blended in a predetermined ratio and dried, and then melt-kneaded using a twin-screw extractor (KRC kneader, manufactured by Kurimoto Iron Works), and extruded strands are cold-cut. A pelletized composition was obtained.

The pelletized resin composition was processed by using an injection molding machine (Hipershot 3000, manufactured by Niigata Iron Works) to obtain a molded product. The Izod impact strength, surface impact resistance, and flexural modulus of this molded product were investigated and evaluated. The results are also shown in Tables 5 and 6.

Evaluation Method The evaluation method of the above molded article will be described. ○ Izod impact strength It was measured according to JIS K-7110. ○ Surface impact resistance: 6 with a Dyupon-type falling ball impact tester (1 inch φ strike)
The energy (J) when 50% of the test pieces fractured was calculated and shown using 0 × 60 × 3 mm test pieces. Bending elastic modulus 12 obtained by injection molding according to JIS K-7203
It was measured at a distance of 50 mm between fulcrums using a test piece of x125x3 mm.

[0084]

[Table 5]

[0085]

[Table 6]

Comparative Examples 1 to 12 Examples in which the B component was not blended with the resins used in the components (Aa), (Ab) and (Ac) alone, and the blending ratio of the B component was 0. An example in which the amount is out of the range of 5 to 50 parts by weight is Comparative Example 1
No. 12 was evaluated in the same manner as in Example and is shown in Table 7.

[0087]

[Table 7]

[0088]

EFFECTS OF THE INVENTION The thermoplastic resin composition of the present invention exhibits an effect even at a low addition amount due to efficient dispersion of impact absorbing components such as elastomers, and the elastic modulus (rigidity) is relatively slightly reduced, and impact resistance is high. It is possible to improve the sex.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C08L 101/00 LSZ

Claims (6)

[Claims] 1. A thermoplastic resin composition comprising the following component A and component B: (A) Polymer 50 having a functional group capable of reacting with an amino group
~ 99.5 parts by weight. (B) Graft copolymer obtained by graft-reacting an N-substituted amide represented by the general formula 1 with an olefin polymer or olefin copolymer having a weight average molecular weight of 5,000 to 500,000. 5 to 50 parts by weight. [Chemical 1] (In the formula, R ¹ and R ² represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, a phenyl group or an arylalkyl group having 7 or 8 carbon atoms,
R ⁴ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group, a primary or secondary alkoxyl group having 1 to 8 carbon atoms, a phenoxy group or a benzyloxy group. R ³ represents a hydrogen atom or a methyl group. R ¹ , R
² , R ³ and R ⁴ may be the same or different in each repeating unit. ) 2. The polymer having a functional group capable of reacting with an amino group contains at least one resin selected from the group consisting of polyester resins, polycarbonate resins and polyamide resins. The thermoplastic resin composition according to 1. 3. The polymer having a functional group capable of reacting with the amino group is a succinic anhydride group, a carboxyl group, an epoxy group, an ester group, an amide group, a cyclic iminoether group,
A polymer containing one or more polymers having a functional group selected from the group consisting of a cyclic iminoamino group, a halogen group and an imide group in the molecule [hereinafter referred to as (Ab) component]. The thermoplastic resin composition described. 4. A thermoplastic resin composition comprising the following component A and component B: (A) A thermoplastic resin which does not substantially react with an amino group under molding and processing conditions with the component (Ab) according to claim 3, and which has no affinity with the component (Ab). 50-99.5 parts by weight of a composition with a hydrophilic thermoplastic resin. (B) 0.5 to 50 parts by weight of the graft copolymer according to claim 1. 5. The polymer having a functional group capable of reacting with an amino group contains at least one resin selected from the group consisting of a polyester resin, a polycarbonate resin and a polyamide resin. 4. The thermoplastic resin composition according to 4. 6. The polymer having a functional group capable of reacting with the amino group is a succinic anhydride group, a carboxyl group, an epoxy group, an ester group, an amide group, a cyclic iminoether group,
The thermoplastic resin composition according to claim 4, which contains at least one polymer having a functional group selected from the group consisting of a cyclic iminoamino group, a halogen group and an imide group in the molecule.