JPH061810A - Graft copolymers and copolymers containing N-substituted amide repeating units, and thermoplastic resin compositions containing them - Google Patents

Abstract

(57) [Abstract] [Purpose] Graft copolymers and copolymers that enhance the miscibility between thermoplastic resins such as engineering plastics and polyolefin resins, and thermoplastic resin compositions containing these and having good impact resistance. I will provide a. [Constitution] N represented by the general formula 1 in an olefin polymer
-A graft copolymer obtained by grafting a substituted amide, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer with the N-substituted amide, and these were used as compatibilizers. A resin composition containing an engineering plastic and a polyolefin resin. In addition,
In Chemical formula ¹ , R ¹ represents a hydrogen atom, an alkyl group or the like,
R ² represents an alkyl group. [Chemical 1]

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to novel graft copolymers and copolymers capable of functioning as compatibilizing agents for enhancing the miscibility of thermoplastic resins such as engineering plastics with polyolefin resins, and injection molding and extrusion. The present invention relates to a thermoplastic resin composition containing the above polymer, which can be used as a molded product, a sheet, a film and the like by molding.

[0002]

2. Description of the Related Art Engineering plastics are generally excellent in mechanical properties such as impact resistance and thermal properties such as heat resistance, but on the other hand, they are poor in moldability and require high manufacturing costs. There was a problem.

On the other hand, a polyolefin resin represented by polypropylene is excellent in molding processability and manufacturing cost, but is inferior to engineering plastics in physical properties such as impact resistance and heat resistance.

Therefore, attempts have been made actively to obtain a resin composition having new functional characteristics by complementing the defects of the engineering plastic and the polyolefin resin by blending or alloying them.

However, a simple blend of the engineering plastic and the polyolefin resin does not mix the two resins well, and the resulting resin has a reduced impact resistance. Further, even if it is formed into a molded product, there is a problem that the appearance itself is bad and delamination occurs.

Regarding the impact resistance of the resin, it is known that the impact resistance can be improved to some extent by adding an elastomer component to the resin, but on the contrary, there is a problem that the rigidity of the resin is lowered. there were. Further, it does not essentially solve the problems such as delamination and poor appearance when the resin is used as a molded product.

In order to solve such a problem, attempts have been made to improve the miscibility of resins to be blended with each other by using a compatibilizer.

For example, for polyamide, a graft polymer produced by reacting the polyamide with a maleic anhydride-modified polyolefin in an extruder is used as a compatibilizer (Polymer Chemistry, Vol. 29, p. 259 ( 19
72)). Furthermore, a compatibilizing agent is known in which a polyfunctional compound capable of reacting with a carboxyl group, a carboxylic acid anhydride group, and an amino group is added to this system and reacted to partially crosslink the compound (JP-A-64-31864). Issue). By using this compatibilizer, the heat resistance and impact resistance of the resin composition can be further improved.

Polyamide, polyester, aromatic polyether, polyacetal, polycarbonate, A
When engineering plastics such as BS resin and polypropylene are blended, a product obtained by reacting an unsaturated acid anhydride-modified polyolefin with a low molecular weight diol, diamine, or a low molecular weight compound having a hydroxyl group and an amino group, and if necessary Accordingly, it has been proposed to improve the miscibility of these resins with each other by using a compatibilizer to which a thermoplastic urethane is added (Japanese Patent Laid-Open No. 2-36248).
Issue).

[0010]

In the method of blending the resins with each other by using the conventional known compatibilizer, the miscibility of the resins is still insufficient. Therefore, there are problems that the resulting resin composition has insufficient impact strength, and that when the resin composition is used as a molded product, the appearance is poor and layered peeling occurs.

Further, depending on the type of the compatibilizer used, a new problem may occur in that the resin composition itself is colored due to the high temperature during the molding process.

The present invention has been invented in view of the above-mentioned problems of the prior art, and its object is to provide a compatibilizing agent for increasing the miscibility between a thermoplastic resin such as engineering plastic and a polyolefin resin. It is an object of the present invention to provide a novel graft copolymer and a copolymer that can function. Another object of the present invention is a thermoplastic resin composition containing the graft copolymer or the copolymer, which is excellent in impact resistance and heat resistance and has a good appearance and delamination when molded. It is to provide what does not happen.

[0013]

In order to achieve the above object, the inventors of the present invention have found that a graft copolymer containing an N-substituted amide repeating unit in the molecule and a phase between resins described above in the copolymer. They have found that they function as a solubilizer and have completed the present invention.

The graft copolymers and copolymers containing N-substituted amide repeating units in the molecule according to the present invention will be described below.

The graft copolymer containing the N-substituted amide repeating unit in the molecule according to the present invention is represented by the general formula 3 as an olefin polymer or an olefin copolymer having a weight average molecular weight of 5,000 to 500,000. Is a graft copolymer obtained by a graft reaction of an N-substituted amide represented by:

[0016]

[Chemical 3]

In the general formula 3, R ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms,
R ² represents an alkyl group having 1 to 4 carbon atoms. The above R ¹ and R ² may be the same or different for each repeating unit.

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, examples of the above-mentioned polyolefins or oligomers thereof include high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, and ethylene and α-olefin. Polymers and the like, and the thermoplastic polyolefin 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 mainly composed of a blend of polypropylene and ethylene-propylene rubber, which is made of a low crystalline ethylene-propylene copolymer or propylene-butene copolymer, and which is used as the polyolefin-based elastomer. It is over, and the like.

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

The N-substituted amide represented by the general formula 3 used as a graft monomer in the graft copolymer of the present invention includes N-allylacetamide, 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 and the like.
Of these, more preferred are N-allylacetamide and N- (1-methyl-2-propenyl) acetamide.

The method for producing the graft copolymer of the present invention is carried out in the presence of a free radical-forming catalyst in a temperature range from a temperature sufficient to generate 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 is 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 free radical producing catalysts are di-t-butyl peroxide, dicumyl peroxide, t-butyl perbenzoate, benzoyl peroxide, cyclohexanone peroxide, lauryl peroxide and azobisiso. 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 from 1 to 200 g per 1 kg of olefin (co) polymer, preferably from 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 amide on the olefin polymer or olefin copolymer is
Can be determined by measuring the infrared absorption spectrum, the absorption of 1650～1690Cm ^-1 based on the amide group absorption and N- substituted amides of 1400～1500Cm ^-1 based on alkyl groups of the olefin (co) polymer used as a raw material The amount of grafting is determined by the ratio of the absorbance of. The graft amount of the N-substituted amide cannot be uniquely determined because it depends on the target physical properties and appearance of the finally obtained thermoplastic resin composition, but is not uniquely determined, but is usually an olefin polymer or copolymer used as a raw material. 0.1% for 100% by weight.
It is 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.

Among the N-substituted amide graft copolymers thus obtained, those particularly preferably used in the present invention include polypropylene, polyethylene, ethylene-propylene copolymer, ethylene-acrylic acid ester copolymer, ethylene- Olefin polymers or olefin copolymers such as propylene rubber, N-allylacetamide, N
It is a graft copolymer obtained by graft reaction of-(1-methyl-2-propenyl) acetamide or N-allylpropionamide.

Next, the copolymer containing the N-substituted amide repeating unit according to the present invention in the molecule has, in the molecule, the N-substituted amide repeating unit represented by the general formula 4 and an ethylene-based monomer. It is a copolymer containing a repeating unit of a saturated monomer. This copolymer is an addition polymer produced by solution polymerization, emulsion polymerization, precipitation polymerization, suspension polymerization or bulk polymerization, preferably bulk polymerization.

[0031]

[Chemical 4]

In the general formula 4, R ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms,
R ² represents an alkyl group having 1 to 4 carbon atoms. The above R ¹ and R ² may be the same or different for each repeating unit.

Copolymerizable N in the copolymer of the present invention
The -substituted amide compound is N-allylacetamide, 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 and the like.
Among these, more preferred are N-allylacetamide and N-allylpropionamide.

The ethylenically unsaturated monomer used in the copolymer of the present invention is a monomer copolymerizable with the N-substituted amide compound, and specific examples include styrene,
Vinyl acetate, ethyl acrylate, butyl
Examples thereof include acrylate. Of these, styrene is more preferable.

The copolymer of the present invention can be obtained by subjecting the above ethylenically unsaturated monomer and the N-substituted amide compound to a copolymerization reaction.

The copolymerization reaction may be initiated externally by contact with free radical-forming catalysts such as peroxides or azo compounds when used in a suitable temperature range, or by cocatalysts such as metal salts or complexes. To be done.

Examples of such free radical producing catalysts include benzoyl peroxide, t-butyl benzoate, cyclohexane peroxide, azobisisobutyronitrile and the like, and mixtures thereof. The amount of free radical generating catalyst need only be a catalytic amount, and a useful range is 0.1 to 1.0% by weight, based on the monomer.

The reaction temperature must be high enough for the catalyst to produce free radicals. The useful temperature range is from room temperature to 100 ° C, depending on the type of catalyst used.

As the reaction solvent, it is preferable to use an inert solvent, and specific examples include heptane, octane, benzene,
Toluene, xylene, chlorobenzene, etc. can be mentioned.

Further, the composition ratio of each repeating unit in the copolymer of the present invention can be determined by measuring the infrared absorption spectrum. That is, 1450 to 1500 cm ⁻¹ and 171 peculiar to the repeating unit of the ethylenically unsaturated monomer
And absorption of 0~1730cm ^-1, it is possible to determine the composition ratio of each repeating unit by the ratio of the absorbance of the absorption of 1650～1690Cm ^-1 based on the amide group of N- substituted amides repeating units.

The repeating unit of the ethylenically unsaturated monomer is contained in the copolymer molecule of the present invention in an amount of 80 to 99.8%, preferably 90 to 99.8%, and the N-substituted amide repeating unit is 0. .2 to 20%, preferably 1.0 to 10%.

The content of the N-substituted amide repeating unit is 0.
If it is less than 2%, the miscibility of the resins in the finally obtained thermoplastic resin composition will be poor.

When the content of the N-substituted amide repeating unit exceeds 20%, the copolymerizability of the N-substituted amide compound is not so high and it is not economical to produce the copolymer. Also, it is not economical to manufacture a thermoplastic resin composition. Furthermore, the physical properties of the resin composition may be deteriorated.

The thermoplastic resin composition of the present invention will be described below.

By blending a thermoplastic resin such as an engineering plastic and a polyolefin resin with a graft copolymer or copolymer containing the N-substituted amide repeating unit of the present invention in the molecule as a compatibilizer, The thermoplastic resin composition of the present invention is obtained. That is, the thermoplastic resin composition according to the present invention has the following component A,
It is a resin composition containing B component and C component.

(A) Polycarbonate resin, polyester resin, polyamide resin, polyether resin and AB
At least one thermoplastic resin selected from the group consisting of S resins, (B) a polyolefin resin, and
(C) N-on the olefin polymer or olefin copolymer
The graft copolymer of the present invention obtained by grafting a substituted amide compound.

The thermoplastic resin composition according to the present invention is a resin composition containing the following components A, B and C.

(A) Polycarbonate resin, polyester resin, polyamide resin, polyether resin and AB
At least one thermoplastic resin selected from the group consisting of S resins, (B) a polyolefin resin, and
(C) The copolymer of the present invention obtained by copolymerizing an ethylenically unsaturated monomer and an N-substituted amide compound.

The constitution of the thermoplastic resin composition of the present invention will be described in more detail below.

(1) Component A: As the component A in the thermoplastic resin composition of the present invention, as described above, polycarbonate resin, polyester resin, polyamide resin,
Thermoplastic resins selected from the group consisting of polyether resins and ABS resins can be mentioned.

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

The type of the component A polyester resin is not particularly limited, and various types can be used.
Either an aliphatic or aromatic polyester resin may be used, but the latter aromatic polyester resin is preferable in consideration of physical properties. The molecular weight may be appropriately selected according to the purpose of use and the like, but normally the intrinsic viscosity is 0.2 to
2.0 dl / g, preferably 0.5-1.2 dl / g are suitable. Further, this polyester resin may have a carboxylic acid terminal or an alcoholic hydroxyl group terminal, and the ratio thereof is not particularly limited, but 9/1 to 1 /
9 is preferable.

Such polyester resin can be produced by various known methods, and various kinds thereof can be mentioned.

Specific examples of the polyester resin used in the present invention include polyethylene terephthalate (PET),
Examples include polybutylene terephthalate (PBT), polycyclohexadimethyl terephthalate (PCT), and polyarylate.

Further, the type of the component A polyamide resin is not particularly limited, and various types can be used, and either aliphatic or aromatic polyamide resin may be used.
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 above-mentioned polyamide resin, various ones can be applied.
Nylon 6; Nylon 6,6; Nylon 6,10; Nylon 11; Nylon 12; Nylon 6,12; Aliphatic polyamides such as Nylon 4,6; Nylon 6/6; Nylon 6 / 6,10; Nylon 6/6 , 12 and the like, aliphatic copolyamides, polyhexamethylenediamine terephthalamide; polyhexamethylenediamine isophthalamide; aromatic polyamides such as xylene group-containing polyamides. Furthermore, polyester amide, polyester ether amide, etc. can be mentioned.

Further, the kind of the polyether resin as the component A is not particularly limited, and various kinds can be used.
It may be an aliphatic or aromatic polyether resin.

There are various types of the above-mentioned polyether resin. For example, a polyacetal homopolymer such as polyoxymethylene (POM) or a polyacetal copolymer having a mixed polyether structure such as trioxane-ethylene oxide copolymer, polyphenylene ether (P
PE), polyether sulfone (PES) in which ether groups and sulfone groups are mixed, polyether ketone (PEK) in which ether groups and carbonyl groups are mixed, and polyphenylene sulfide (P) having thioether groups
It can be roughly classified into PS) and polysulfone (PSO).

Here, the polyacetal homopolymer is a polymer having an oxymethylene unit as a molecular main chain, and can be produced by homopolymerizing formaldehyde or trioxane. On the other hand, the polyacetal copolymer, in the main chain consisting of the oxymethylene unit, oxyethylene units, oxypropylene units, oxyalkylene units such as oxytetramethylene units and oxyphenylene ethylene units are randomly mixed. It can be produced by copolymerizing formaldehyde or trioxane with a cyclic ether such as ethylene oxide.

Further, the kind of the ABS resin as the component A is not particularly limited, and those by the graft method or polymer blend method can be used.

As a typical example, a rubber component of butadiene alone or a rubber component obtained by copolymerizing butadiene with styrene and acrylonitrile is mixed with a styrene-acrylonitrile copolymer.

In the thermoplastic resin composition of the present invention,
Although any of the resins of the component A described above is sufficiently mixed with the polyolefin resin of the component B, a more excellent resin composition is obtained when a polycarbonate resin, a polyester resin or a polyamide resin is used as the resin of the component A. be able to.

(2) Component B: The component B in the thermoplastic resin composition of the present invention is a polyolefin resin as described above.
Examples include polyolefin-based thermoplastic elastomers, polyolefin-based elastomers, ethylene-vinyl ester copolymers, ethylene-acrylic ester copolymers, and blends of these various polyolefins and copolymers.

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

Of these B component polyolefin resins, polypropylene, ethylene-propylene rubber and ethylene-propylene-diene copolymer (EPDM) are preferred. The average molecular weight is usually 5,000-
500,000 is used, preferably 1
Those of 10,000 to 200,000 are suitable.

(3) About the composition ratio of the thermoplastic resin composition: The thermoplastic resin composition of the present invention comprises the components A and B described in (1) and (2) above and the N of the present invention described above. A graft copolymer or a copolymer (component C) containing a substituted amide repeating unit in its molecule is an essential constituent component, but other additives (glass fiber, carbon Reinforcing materials such as fibers, inorganic fillers, heat stabilizers,
Antioxidants, light stabilizers, flame retardants, weathering agents, etc.) may be added.

The blending ratio of the components A, B and C in the thermoplastic resin composition of the present invention is as follows.
The component A is mixed in an amount of 5 to 95 parts by weight, preferably 20 to 95 parts by weight, and the component B is 9
The amount is 5 to 5 parts by weight, preferably 80 to 5 parts by weight. A
When the mixing ratio of the component and the component B is out of the above range, there arises a problem that mechanical strength such as rigidity is lowered and molding processability is deteriorated in the obtained resin composition.

The mixing ratio of the component C is 0.05 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the components A and B. If the blending ratio of the component C is less than 0.05 parts by weight, the mixing of the resins of the component A and the component B will be insufficient, and various physical properties such as impact strength of the resulting resin composition will not be sufficiently improved. Further, even if the blending ratio of the C component exceeds 20 parts by weight, the effect of improving various physical properties corresponding to the blending amount of the C component is not recognized, and further, the impact strength of the resin composition tends to decrease. . Moreover, it is economically disadvantageous in producing the resin composition.

(4) Regarding the method for producing the thermoplastic resin composition: In the production of the thermoplastic resin composition of the present invention, the order of addition of the components A, B and C, the timing of addition, and the addition method are particularly limited. There is no.

As the simplest example, the components A, B and C may be heated and melted at the same time, or a mixture of the components A and C previously melted and kneaded may be added to the component B and melted and kneaded. Of course, various combinations of addition order, timing and method can be adopted.

In the method for producing the thermoplastic resin composition of the present invention, specifically, a kneading machine such as a single-screw extruder, a twin-screw extruder, a flash mixer, a kneading roll, or a mixer such as a Henschel mixer is used. Then, the above components may be kneaded in a heat-melted state. The kneading temperature varies depending on the types of constituent components used, the amount of the components used, the physical properties of the resin composition to be produced, and the like, and cannot be unambiguously determined, but it is usually selected in the range of 180 to 340 ° C.

[0073]

The graft copolymer or copolymer (C component) containing the N-substituted amide repeating unit of the present invention is a thermoplastic resin (A component) and a polyolefin resin (B component).
It has the function of increasing the miscibility of C., but its mechanism of action is presumed in consideration of the molecular structure of the C component polymer. That is, the trunk portion of the C component polymer shows affinity with the B component, and the amide group portion corresponding to the branch portion of the C component polymer shows affinity with the A component having a relatively high polarity, or transesterification, As a result of being involved in some chemical reaction such as amide exchange, it seems that the miscibility between the A component and the B component is enhanced.

[0074]

The graft copolymer or copolymer containing the N-substituted amide repeating unit of the present invention in the molecule is effective as a compatibilizer, and is used as a compatibilizing agent in thermoplastic resins such as engineering plastics and polyolefin resins. The thermoplastic resin composition of the present invention having excellent miscibility can be obtained by using it in the blending. Therefore, the thermoplastic resin composition of the present invention is an extremely excellent invention that exhibits the following excellent effects.

The thermoplastic resin composition of the present invention has excellent impact resistance.

Even when the thermoplastic resin composition of the present invention is molded and processed, the appearance and hue are good and no delamination occurs.

[0077]

EXAMPLES Hereinafter, the graft copolymers and copolymers containing the N-substituted amide repeating unit of the present invention in the molecule and the thermoplastic resin compositions of the present invention containing them will be further described by specific examples. explain in detail. The present invention is not limited to these examples.

First, an example of the production of a graft copolymer containing the N-substituted amide repeating unit of the present invention in the molecule is shown below.

Example 1 (Preparation of Graft Copolymer Containing N-Substituted Amide Repeating Unit in the Molecule) N-allylacetamide (graft monomer) 7.5 g and weight average molecular weight (Mw) of 50.0.
150 g of ethylene-propylene rubber (ethylene / propylene = 60/40) (raw material polymer) of No. 00 was dissolved in 150 g of chlorobenzene, and 20 g of lauryl peroxide was dissolved in 200 g of chlorobenzene.
The solution was gradually added dropwise at 20 ° 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. Got rubber. The yield of the obtained graft copolymer was 154 g. In addition, the infrared absorption spectrum of the graft copolymer was measured, and the absorption around 1670 cm ⁻¹ based on the acetamide group and the absorption at 1500 cm ⁻¹ based on the alkyl group of the ethylene-propylene rubber showed that the ethylene-propylene of N-allylacetamide. The amount of graft on the rubber was determined to be 5% by weight.

<Examples 2 to 8> As in Example 1, N-
A graft copolymer containing a substituted amide repeating unit in the molecule was prepared. These graft copolymers are shown in Table 1 together with those in Example 1. Table 1 shows the kinds of raw material polymers, the graft monomers and the graft amounts thereof.

[0081]

[Table 1]

Next, examples of the production of the copolymer containing the N-substituted amide repeating unit of the present invention in the molecule are shown below.

Example 9 (Preparation of Copolymer Containing N-Substituted Amide Repeating Unit in the Molecule) Azobisiso was placed in a flask having an internal capacity of 2 liters equipped with a condenser, a thermometer and a nitrogen introducing tube. 500 g of toluene in which 5.5 g of butyronitrile (AIBN) was dissolved was charged, and subsequently 450 g of styrene (monomer 2) (4.
3 mol) and 100 g (1.0 mol) of N-allylacetamide (monomer 1) were charged, and the inside of the flask was replaced with nitrogen. Then, this was heated at 60 ° C. for 10 hours to obtain a viscous solution. This solution was added to 2,000 g of methanol, and the precipitated copolymer was filtered and dried.

The yield of the obtained copolymer was 350 g. Further, measuring the infrared absorption spectrum of the copolymer, the absorption of 1660 cm ^-1 based on the amide group absorption and N- allyl acetamide 1450 cm ^-1 based on styrene, of styrene repeat units and N- allyl acetamide repeating units The molar ratio was determined to be 9/1. The weight average molecular weight (Mw) of the copolymer was 45,000, and the number average molecular weight (Mw
n) was 25,000.

<Examples 10 and 11> In the same manner as in Example 9, copolymers containing N-substituted amide repeating units in the molecule were prepared. These copolymers are shown in Table 2 together with those of Example 9. Table 2 shows the types and amounts of raw material monomers and catalysts used, reaction conditions (temperature and time), and the composition and molecular weight (Mw) of each repeating unit in the obtained copolymer.
And Mn). As the reaction solvent, 500 g of toluene was used in each of the examples.

[0086]

[Table 2]

Examples of the thermoplastic resin composition of the present invention will be shown below.

Examples 12 to 25 First, as the thermoplastic resin as the component A, those shown in Table 3 were used, as the polyolefin resin as the component B, those shown in Table 4 were used, and further the component C was used. As the graft copolymer or copolymer of the (compatibilizer), those produced in Examples 1 to 11 are used. Tables 3 and 4 show the resin names, their abbreviations, product names, and manufacturers.

[0089]

[Table 3]

[0090]

[Table 4]

The components A, B and C were dry blended in the prescribed proportions shown in Table 5 and dried, and then melted and kneaded using a twin-screw extruder (KRC kneader, Kurimoto Iron Works) to prepare the present invention. A thermoplastic resin composition of was obtained. Table 5
The number of the example was described as the type of the C component.

After pelletizing the resin composition, an injection molding machine (Hippershot 3000, manufactured by Niigata Iron Works)
Was used to obtain a molded product. The Izod impact strength, the presence or absence of delamination and the appearance of this molded product were examined, and the results are shown in Table 5.

The evaluation method of the above-mentioned molded product will be described. Regarding the Izod impact strength, the Izod impact value was measured according to JIS K-7110, and the measurement temperature was 23 ° C and -30 ° C.

The presence or absence of delamination of the molded product was checked by a cross cut test. That is, a 1 mm × 1 mm rectangle 10 is cut into the surface of the test piece using a knife.
Make 0 pieces. Then, after crimping the cellophane tape,
Tear off with a strong force and count the number of rectangles that could not be removed without sticking to the cellophane tape. The larger the number is, the more difficult the layered peeling is.

Furthermore, regarding the appearance and hue of the molded product,
The flow marks, fluffiness, occurrence of silver, and the degree of coloring were visually determined. In Table 5, those having a good appearance are indicated by ◯, those having a somewhat poor appearance are indicated by Δ, and those having a poor appearance are indicated by x.

<Comparative Examples 1 to 14> An example in which the component C (compatibilizer) was not blended in Examples 12 to 25 is Comparative Example 1
The experimental results are shown in Table 5.

[0097]

[Table 5]

From Table 5, the impact strength of the molded articles of Examples 12 to 25 is considerably higher than that of the corresponding molded articles of Comparative Examples 1 to 14 at both measurement temperatures of 23 ° C and -30 ° C. Was excellent. Regarding the presence or absence of layered peeling of the molded articles, the molded articles of Examples 12 to 25 did not cause layered peeling at all, but the molded articles of Comparative Examples 1 to 14 caused layered peeling, and in almost all cases, cross-cut. Was peeled off more than 80%. Further, regarding the hue of the molded product, all of the examples and the comparative examples were white, but regarding the appearance, the appearance of the molded products of Examples 12 to 25 were all good, while the comparative examples 1 to The appearance of all 14 molded products was poor.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C08L 55/02 LME 7142-4J 59/00 LMP 8215-4J 71/10 LQK 9167-4J 71/12 LQP 9167- 4J 77/00 LQS 9286-4J

Claims (4)

[Claims] 1. A weight average molecular weight of 5,000 to 500,0.
A graft copolymer obtained by graft-reacting an N-substituted amide represented by the general formula 1 with an olefin polymer or copolymer having 00. [Chemical 1] (However, in the chemical formula ¹ , R ¹ is a hydrogen atom and has 1 to 8 carbon atoms.
Represents an alkyl group of 6 to 10 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² has 1 to 1 carbon atoms.
4 represents an alkyl group. The R ¹ and R ² may be the same or different for each repeating unit. ) 2. A copolymer containing an N-substituted amide repeating unit represented by the general formula 2 and an ethylenically unsaturated monomer repeating unit in the molecule. [Chemical 2] (However, in the chemical formula 2, R ¹ is a hydrogen atom and has 1 to 8 carbon atoms.
Represents an alkyl group of 6 to 10 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ² has 1 to 1 carbon atoms.
4 represents an alkyl group. The R ¹ and R ² may be the same or different for each repeating unit. ) 3. A thermoplastic resin composition comprising the following components A, B and C: (A) at least one thermoplastic resin selected from the group consisting of polycarbonate resin, polyester resin, polyamide resin, polyether resin and ABS resin;
(B) a polyolefin resin, and further (C).
The graft copolymer described. 4. A thermoplastic resin composition, wherein the C component is the copolymer according to claim 2.