JPH0680833A - Copolymer and thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a thermoplastic resin composition which has excellent impact resistance and heat resistance, has a good appearance when molded and does not cause delamination. [Structure] A thermoplastic resin composition comprising the following components A, B and C. (A) Polymer component having a functional group capable of reacting with an amino group
(A-1) or a composition of a component B, which is different from the resin used in the component B below, and a component (A-1) (A-2) (B) an amino group under molding and processing conditions. A graft copolymer obtained by graft-reacting a compound (I) represented by the general formula 1 with a thermoplastic polymer (C) which does not substantially react with the compound (I), or a repeating unit (II) represented by the general formula 1. ) Or a repeating unit (III) and a repeating unit of an ethylenically unsaturated monomer in the molecule

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel thermoplastic resin composition which can be used as molded articles, sheets, films and the like by injection molding or extrusion molding. The present invention also relates to a novel copolymer added to the thermoplastic resin composition as a compatibilizer.

[0002]

BACKGROUND ART Engineering plastics such as polyamide, polyacetal, polyphenylene ether, polybutylene terephthalate, polycarbonate and polyphenylene sulfide are generally excellent in mechanical properties such as impact resistance and thermal properties such as heat resistance. On the other hand, there is a problem that the moldability is poor and a high manufacturing cost is required. Further, properties other than mechanical properties and thermal properties, such as chemical resistance and low water absorption, cannot be satisfied by a single kind of the above engineering plastic.

On the other hand, polyolefin resins typified by polypropylene, polystyrene resins typified by polystyrene, and ABS resins are excellent in molding processability and manufacturing cost, but in physical properties such as impact resistance and heat resistance. Not as good as engineering plastics.
Further, the polystyrene resin and the ABS resin are non-crystalline resins and therefore have poor solvent resistance.

Therefore, engineering plastics having different characteristics are blended or alloyed, engineering plastic and a polyolefin resin or polystyrene resin are blended or alloyed, or a polyolefin resin and a polystyrene resin are blended or alloyed. As a result, attempts have been actively made to obtain resin compositions that complement each other's drawbacks and have new functional characteristics.

However, the engineering plastics are not well mixed with each other or the engineering plastics and the polyolefin resin or the polystyrene resin are simply blended, and the resin composition obtained as a result has a reduced impact resistance. Will be things. Further, when they are formed into molded products, there is a problem that the appearance itself is bad and delamination occurs.

It is known that impact resistance can be improved to some extent by adding an elastomer component to such a resin composition, but on the contrary, there is a problem that the rigidity of the resin is lowered. It was 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 a compatibilizer.

For example, for polyamide, a graft polymer formed by reacting the polyamide with a maleic anhydride-modified polyolefin in an extruder is used as a compatibilizing agent (Polymer Chemistry, Vol. 29, p. 259).
(1972)). Further, a compatibilizing agent is known in which a polyfunctional compound capable of reacting with a carboxyl group, a carboxylic acid anhydride group, an amino group and the like is added to this system and reacted to partially crosslink (JP-A-64- No. 31864). 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).

Further, when the polyphenylene ether resin and the polyolefin resin are blended, a functionalized polyphenylene ether having a carboxyl group or an epoxy group capable of reacting with an amino group is used as the polyphenylene ether resin, and the polyolefin resin is t-
It has been proposed to use a modified polyolefin obtained by graft-reacting a carbamic acid ester of a tertiary alcohol such as butyl N-allyl carbamate (N-allylcarbamic acid t-butyl ester) with a polyolefin (JP-A-3-33151). . Then, as its mechanism of action, the grafted t-butyl N-allyl carbamate is decarboxylated at a temperature of 225 ° C. or higher to be converted into an amino group, and the generated amino group is converted to a carboxyl group or an epoxy group of the functionalized polyphenylene ether. Proposes to react.

[0011]

However, even if the above-mentioned conventional known compatibilizers are used, the miscibility between the resins has not yet been sufficiently solved, and therefore the impact strength of the resulting resin composition is unsatisfactory. Was enough. Further, when the resin composition is formed into a molded article, there are problems such as poor appearance and delamination. Further, depending on the type of the compatibilizer used, a new problem that the resin composition itself is colored due to the high temperature during the molding process may be caused (for example, three disclosed in JP-A-3-33151). (When a compatibilizer modified with a carbamic acid ester of a primary alcohol is used, the rate at which the carbamic acid ester group is converted to an amino group by heat is too fast, so the resin composition itself is colored due to the high temperature during molding.) .

The present invention has been invented in view of the above-mentioned problems of the prior art, and an object thereof is to have excellent impact resistance and heat resistance, and to provide a good appearance and delamination during molding. It is to provide such a thermoplastic resin composition. Another object of the present invention is to provide a novel copolymer to be added as a compatibilizer in a thermoplastic resin composition.

[0013]

Means for Solving the Problems The present inventors have found that when a graft copolymer or copolymer having a formamide group or a copolymer having a carbamate group is used as a compatibilizing agent, it is possible to achieve the above object. The present invention has been completed by finding that a plastic resin composition can be obtained.

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

(A) A polymer component having a functional group capable of reacting with an amino group, (B) a thermoplastic resin component which does not substantially react with an amino group under molding and processing conditions, and (C) a graft having a formamide group. A copolymer or a copolymer,
Alternatively, a copolymer having a carbamate group.

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

(A) A polymer component having a functional group capable of reacting with an amino group, and a thermoplastic resin which does not substantially react with an amino group under molding and processing conditions and which is different from the resin used in the component B below. Composition with a plastic resin, (B) a thermoplastic resin component that does not substantially react with an amino group under molding and processing conditions, and (C) a graft copolymer or copolymer having a formamide group, or a carbamate group A copolymer having

As described above, the A component in the thermoplastic resin composition of the present invention is roughly classified into the following two components (A-1) and (A-2).

(A-1): a polymer component having a functional group capable of reacting with an amino group (A-2): a polymer component having a functional group capable of reacting with an amino group, and an amino group under molding and processing conditions A composition of a thermoplastic resin that does not substantially react with a thermoplastic resin different from the resin used in the component B, wherein the amino group used in the component (A-1) and the component (A-2) is reacted. The polymer component having a functional group capable of
Further, they are classified into the following two types of components (A-a) and (A-b).

(A-a): 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, Component B in the thermoplastic resin composition of the present invention As described above, a thermoplastic resin component that does not substantially react with an amino group under the molding and processing conditions as described above is used, and specific examples thereof include a polyolefin resin, a polystyrene resin, an ABS resin, and a polyether resin.

As the C component in the thermoplastic resin composition of the present invention, a graft copolymer or copolymer having a formamide group or a copolymer having a carbamic acid ester group is used as described above.

That is, the above graft copolymer having a formamide group is a graft copolymer obtained by graft-reacting a formamide compound (I) represented by the general formula 4 with a thermoplastic polymer.

[0023]

[Chemical 4]

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carbon atom having 6 to 10 carbon atoms.
Is a cycloalkyl group, an aryl group having 6 to 10 carbon atoms or an arylalkyl group having 6 to 10 carbon atoms. The copolymer having a formamide group is a copolymer containing a formamide repeating unit (II) represented by the general formula 5 and a repeating unit of an ethylenically unsaturated monomer in the molecule. is there.

[0025]

[Chemical 5]

(In the formula, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and a carbon atom having 6 to 10 carbon atoms.
Is a cycloalkyl group, an aryl group having 6 to 10 carbon atoms or an arylalkyl group having 6 to 10 carbon atoms. Further, the above-mentioned copolymer having a carbamate group contains in the molecule a carbamate repeat unit (III) represented by the general formula 6 and an ethylenically unsaturated monomer repeat unit. It is a copolymer.

[0027]

[Chemical 6]

(In the formula, R ⁵ is a hydrogen atom and has 1 carbon atom.
To an alkyl group having 8 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ⁶ is a primary or secondary alkyl group having 1 to 8 carbon atoms, a phenyl group or benzyl. Indicates a group. In addition, R ⁵ and R ⁶ may be the same or different for each repeating unit. ) 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): Polymer component having functional group capable of reacting with amino group, and amino group under molding and processing conditions A composition of a thermoplastic resin that does not substantially react with a thermoplastic resin different from the resin used in the component B, wherein the amino group used in the component (A-1) and the component (A-2) is reacted. The polymer component having a functional group capable of
Furthermore, it is classified into two types, a component (Aa) and a component (Ab).

That is, the component (Aa) 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, and as such a bonding group, Bonding groups such as ester bond, carbonic acid ester bond, amide bond, urethane bond, and imide bond are mentioned. (A-a)
Specific examples of the component include a polyester resin, a polycarbonate resin, and a 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 preferable from the viewpoint 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. 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 is preferably 9/1 to 1/9.

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 (PE
T), polybutylene terephthalate (PBT), polycyclohexadimethyl terephthalate (PCT), and further polyarylate.

The polycarbonate resin as the component (Aa) may be 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. There is no particular limitation on the molecular weight,
Considering the moldability and physical properties of the resulting composition, the number average molecular weight is 4,000 to 50,000, preferably 5,000 to 30,000.

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.

The other component (Ab), which is a polymer component having a functional group capable of reacting with an amino group, has a functional group capable of reacting with an amino group at the side chain or molecular end of the polymer. It is a polymer component (side chain or end reaction type). 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. Of these, important and preferred functional groups are succinic anhydride group, carboxyl group, epoxy group, and cyclic iminoether group. (A
The component (b) may contain only one kind of the above-mentioned polymer having a functional group, or may contain two or more kinds thereof.

More specifically, 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) includes, 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 acrylic acid alkyl ester, 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-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide 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 or 2-vinyloxazine and another ethylenically unsaturated monomer is used. Styrene-as a typical example.
2-vinyl oxazoline copolymer can be 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 on the side chain of the component (Ab) include N-phenylmaleimide and N-.
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.

The component (A-2) used as the component A in the thermoplastic resin composition of the present invention is a polymer component (Aa) having a functional group capable of reacting with an amino group as described above.
Alternatively, it is a composition of (Ab) and a thermoplastic resin that does not substantially react with an amino group under molding and processing conditions.

The thermoplastic resin which does not substantially react with the amino group under the above-mentioned molding and processing conditions belongs to the thermoplastic resin of the component B, which will be described in detail later. It is a thermoplastic resin different from the resin used as the B component of the thermoplastic resin composition containing. Moreover, it is desirable that the component (A-a) or the component (A-b) should be well compatible with or compatible with the component.

The proportion of the component (A-a) or component (A-b) in the component (A-2) and the thermoplastic resin which does not substantially react with the amino group under the above molding and processing conditions is ,
(Thermoplastic resin) / [(A-a) or (A-b)] is 9
The range is 9 parts / 1 part to 50 parts / 50 parts, preferably 97 parts / 3 parts to 60 parts / 40 parts.

When the blending ratio is larger than 99/1, the compatibility of the obtained thermoplastic resin composition is insufficient, and when the blending ratio is smaller than 50/50, it is economically disadvantageous. Not only that, but the mechanical properties of the obtained thermoplastic resin composition may deteriorate.

[2] Component B: As described above, as the component B in the thermoplastic resin composition of the present invention, a thermoplastic resin component which does not substantially react with an amino group under molding and processing conditions is used. . Specific examples of such thermoplastic resin components include polyolefin resins, polystyrene resins, AB
Examples of the S resin and the polyether resin include one type or two or more types of these resins, which are used as the B component.

More specifically, the component B polyolefin resin is a polyolefin or its oligomer, a polyolefin elastomer, a polyolefin thermoplastic elastomer, an ethylene-vinyl ester copolymer, an ethylene-acrylic ester copolymer. Etc., and blends of these various polyolefins and copolymers are also included.

Specific examples of the component B polyolefin resin include polyethylene [linear low density polyethylene (LLDP
E), low density polyethylene (LDPE), ultra low density polyethylene (VLDPE), medium density polyethylene, high density polyethylene (HDPE), etc.], homopolymers of polypropylene, polybutene, polyisobutene, etc .; ethylene-propylene copolymer, low Crystalline ethylene-propylene copolymer, ethylene-propylene copolymer rubber (EPR),
Ethylene-α-olefin copolymers such as ethylene-butene copolymer (EBM), ethylene-propylene-diene copolymer (EPDM), ethylene-propylene-butene copolymer, ethylene-butylene copolymer; propylene-
Copolymers of propylene and other α-olefins such as butene copolymers; further, various ethylene copolymers [ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVOH)] , Ethylene-alkyl acrylate copolymer, ethylene-alkyl methacrylate copolymer, etc.], poly (4-methyl-1-pentene), butyl rubber, butadiene rubber, and polyolefin-based heat mainly composed of a blend of polypropylene and ethylene-propylene rubber. Examples include plastic elastomers and the like, and mixtures thereof. The term "copolymer" as used herein includes random copolymers, block copolymers, random block copolymers, and further graft copolymers.

Of these polyolefin resins, polypropylene, polyethylene, ethylene-propylene rubber and EPDM are preferred. The average molecular weight is usually 5,000 to 300,000,
It is preferably 10,000 to 200,000.

Examples of the polystyrene resin as the component B include homopolymers or copolymers of styrene, α-methylstyrene and p-methylstyrene. Specific examples include general-purpose polystyrene (GPPS) and high-impact polystyrene (H
IPS), and so-called styrene thermoplastic elastomer, SEBS resin (hydrogenated styrene-butadiene-styrene copolymer), SEPS resin (hydrogenated styrene-isoprene-styrene block copolymer), SEP Resins (hydrogenated products of styrene-isoprene copolymer) may be mentioned.

Among such polystyrene resins, general-purpose polystyrene (GPPS) and high-impact polystyrene (HI)
PS) is preferable, and its average molecular weight is 20,000.
0 to 300,000, preferably 30,000 to 20
30,000 are suitable.

The type of the ABS resin as the component B is not particularly limited, and those obtained by a grafting method or a polymer blending method can be used. Further, AS resin (acrylonitrile-styrene resin), AES resin (acrylonitrile-EPDM-styrene resin) and the like can be used, but ABS resin is preferable.

There are various types of polyether resin as the component B. For example, polyoxymethylene (POM)
Polyacetal homopolymers such as polyacetal homopolymers and polyacetal copolymers having mixed polyether structures such as trioxane-ethylene oxide copolymers, polyphenylene ethers (PPE), and polyether sulfones having mixed ether groups and sulfone groups (PES). ), Polyetherketone (PEK) in which ether groups and carbonyl groups are mixed,
Further, they can be roughly classified into polyphenylene sulfide (PPS) and polysulfone (PSO) having a thioether group. Among these, polyacetal [polyoxymethylene (POM)] and polyphenylene ether (PPE) are preferable.

The above polyphenylene ether contains
A composition containing polystyrene for the purpose of molding processability is also included.

[3] Component C: As described above, as the component C (compatibilizing agent) in the thermoplastic resin composition of the present invention, a polymer having a formamide group or a carbamic acid ester group is used. There are two types of polymers, a graft type and a copolymer type. These will be described in detail below.

[3]-(1) Graft type The graft copolymer having a formamide group used as the component C in the thermoplastic resin composition of the present invention is a formamide compound represented by the general formula 7 in the thermoplastic polymer.
It is a graft copolymer obtained by subjecting (I) to a graft polymerization reaction by a known method.

[0066]

[Chemical 7]

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 6 to 10 carbon atoms.
Is a cycloalkyl group, an aryl group having 6 to 10 carbon atoms or an arylalkyl group having 6 to 10 carbon atoms. ) That is, from a temperature sufficient to produce free radicals up to 250
In the presence of a free radical generating catalyst at temperatures up to ° C, the average molecular weight is 5,000 to 500,000, preferably 1
It is produced by reacting a thermoplastic polymer having a molecular weight of 20,000 to 200,000 with a formamide compound (I) (allylformamide derivative).

Here, the above-mentioned thermoplastic polymer graft-reacted with the formamide compound (I) is substantially reacted with the amino group under the molding processing conditions in the thermoplastic resin component of the component B and the component (A-2). Not compatible with or compatible with the thermoplastic resin.

Explaining such a thermoplastic polymer, the thermoplastic polymers having an affinity for the polyolefin resin include polyolefins and their oligomers, polyolefin elastomers and their oligomers, and ethylene-vinyl ester copolymers. And its oligomers,
Examples include ethylene-acrylic ester copolymers and oligomers thereof, and blends of these various polyolefins and oligomers are also included.

More specifically, as the above-mentioned polyolefins, 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 can be mentioned. Examples of the polyolefin-based elastomers include ethylene-propylene rubber, ethylene-propylene-diene copolymer (EPDM) and ethylene- Examples thereof include vinyl acetate copolymer (EVA), butyl rubber, butadiene rubber, low crystallinity ethylene-propylene copolymer or propylene-butene copolymer and oligomers thereof, and further polypropylene and ethylene-propylene rubber. Polyolefin-based thermoplastic elastomers mainly composed of the blend of Among these olefin polymers and olefin copolymers described above, polypropylene, ethylene-propylene rubber, EPDM and their oligomers are preferable.

As the thermoplastic polymer having an affinity for polystyrene resin, ABS resin and polyether resin, polystyrene, styrene-α-methylstyrene copolymer, styrene-p-methylstyrene copolymer, styrene- Butadiene copolymer and its hydrogenated product (SEB
S), styrene-isoprene copolymers and hydrogenated products thereof (SEPS), polyphenylene ethers, polyphenylene sulfides and the like, and thermoplastic polymers having an aromatic group in the molecule are preferably used. Of these, SEB
S, SEPS and polyphenylene ether are preferred.

On the other hand, the above-mentioned formamide compound used as a graft monomer in the production of the graft copolymer of the component C
Examples of (I) include N-alkenylformamide compounds and N-alkyl-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,
Examples thereof include N- (1-cyclohexyl-2-propenyl) formamide and N- (1-benzyl-2-propenyl) formamide. As the N-alkyl-N-alkenylformamide compound, N-methyl-N-allylformamide is used. , 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 and the like can be 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 above-mentioned formamide compound (I) is used as a mixture with a small amount of a free radical generating catalyst, and at a temperature high enough to allow the graft reaction to proceed at an appropriate rate.
Moreover, by heating the reaction mixture to a temperature not high enough to cause destructive decomposition of the reactants or products,
It is grafted to a thermoplastic polymer.

Grafting reaction is carried out with peroxide, dialkyl-
, Diacyl-, alkyl-acyl peroxides or azo compounds are contacted by using free radical generating catalysts in a suitable temperature range, or by cocatalysts such as metal salts or complexes, or by irradiation of light. The reaction is started externally.

As a typical example of the above-mentioned free radical generating catalyst, di-
There are t-butyl peroxide, dicumyl peroxide, t-butyl perbenzoate, benzoyl peroxide, cyclohexanone peroxide, lauryl peroxide, azobisisobutyronitrile and the like, and 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 forming catalyst may be a catalytic amount, and a useful range is the thermoplastic polymer 1k.
1 to 200 g per g, preferably 1 k thermoplastic polymer
It is 1 to 100 g per g. Further, the catalyst may be added all at the start of the graft reaction or may be added little by little as the reaction progresses.

The thermoplastic polymer is stirred at a suitable reaction temperature in the form of a mixture containing the formamide compound (I) and a free radical generating catalyst. Useful reaction temperatures vary depending on the type of catalyst used, but range from room temperature to 250 ° C. When di-t-butyl peroxide or dicumyl peroxide is used as the catalyst, a reaction temperature of 100 to 200 ° C. is preferable.

The thermoplastic polymer generally becomes very viscous when the molecular weight is 2,000 or more, and it may be impossible to stir or it may be rubber-like. In that case, it is preferable to carry out the reaction in an inert solvent. Useful solvents include nonane, decane and similar aliphatic hydrocarbons, chlorobenzene, dichlorobenzene, dichlorotoluene and similar chlorinated hydrocarbons.

Among the formamide compound graft copolymers obtained as described above, those which are preferably used in the present invention include thermoplastic polymers such as polypropylene, polyethylene, ethylene-propylene copolymer and ethylene-propylene rubber. Polyolefins, olefin copolymers, thermoplastic polymers such as SEBS, SEPS, polyphenylene ether, etc. are used, and N-allylformamide, N- (1-methyl-2-propenyl) formamide, N-methyl are used for these thermoplastic polymers. It is a graft copolymer obtained by graft reaction of -N-allylformamide or N-methyl-N- (1-methyl-2-propenyl) formamide.

The amount of the formamide compound (I) grafted in the C component graft copolymer cannot be determined unconditionally because it depends on the target physical properties and appearance of the thermoplastic resin composition, but it cannot be determined unconditionally. A thermoplastic polymer 1
Formamide compound (I) is usually added to 100 parts by weight,
The graft reaction may be carried out in the range of 0.05 to 20 parts by weight, preferably 0.2 to 10 parts by weight. Graft amount is 0.
If it is less than 05 parts by weight, the miscibility of the resins in the finally obtained thermoplastic resin composition will be poor, and if the graft amount exceeds 20 parts by weight, it will be difficult to produce the thermoplastic resin composition. Not only is it uneconomical, but it may deteriorate the physical properties of the resin composition obtained on the contrary.

[3]-(2) Copolymerization Type The copolymers used as the C component in the thermoplastic resin composition of the present invention include those having a formamide group and those having a carbamic acid ester group.

The copolymer having a formamide group used as the C component in the thermoplastic resin composition of the present invention is a formamide repeating unit (II) represented by the general formula 8 and an ethylenically unsaturated monomer repeating unit. It is a copolymer containing a unit in the molecule.

[0085]

[Chemical 8]

(In the formula, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carbon atom having 6 to 10 carbon atoms.
Is a cycloalkyl group, an aryl group having 6 to 10 carbon atoms or an arylalkyl group having 6 to 10 carbon atoms. ) Such a formamide group-containing copolymer is obtained by radical polymerization, ionic polymerization or coordination polymerization of an ethylenically unsaturated monomer and a formamide compound (monomer) by a known method.

The ethylenically unsaturated monomer as a raw material for the formamide group-containing copolymer of the component C is a monomer copolymerizable with the formamide compound, and specific examples include styrene, α-methylstyrene, Aromatic unsaturated monomers such as p-methylstyrene, ethylene, propylene, 1-
Α-olefins such as butene, 1-hexene, 1-octene, 1-dodecene, vinyl esters such as vinyl acetate and vinyl propionate, acrylic esters such as ethyl acrylate, propyl acrylate and methyl methacrylate, or methacryl Acid esters are mentioned. Of these, styrene and α-olefin are more preferable.

As the formamide compound which is copolymerized with the ethylenically unsaturated monomer in the production of the C component formamide group-containing copolymer, N-alkenylformamide compounds and N-alkyl-N-alkenylformamide compounds are mentioned. Can be mentioned.

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,
Examples thereof include N- (1-cyclohexyl-2-propenyl) formamide and N- (1-benzyl-2-propenyl) formamide. As the N-alkyl-N-alkenylformamide compound, N-methyl-N-allylformamide is used. , 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 and the like can be mentioned.

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

On the other hand, the copolymer having a carbamic acid ester group used as the C component in the thermoplastic resin composition of the present invention contains the carbamic acid ester repeating unit (III) represented by the general formula 9 It is a copolymer containing a repeating unit of a saturated monomer in the molecule.

[0092]

[Chemical 9]

(In the formula, R ⁵ is a hydrogen atom and has 1 carbon atom.
To an alkyl group having 8 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ⁶ is a primary or secondary alkyl group having 1 to 8 carbon atoms, a phenyl group or benzyl. Indicates a group. In addition, R ⁵ and R ⁶ may be the same or different for each repeating unit. ) Examples of the carbamic acid ester compound used as a raw material monomer in the C component carbamic acid ester group-containing copolymer include methyl N-allyl carbamate, ethyl N-allyl carbamate, and iso-propyl N-.
Allyl carbamate, sec-butyl N-allyl carbamate, n-hexyl N-allyl carbamate, 2
-Ethylhexyl 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, sec -Butyl
N- (1-methyl-2-propenyl) carbamate, phenyl N- (1-methyl-2-propenyl) carbamate, benzyl N- (1-methyl-2-propenyl)
Carbamate, ethyl N- (1-cyclohexyl-2-
Propenyl) carbamate, ethyl N- (1-benzyl-2-propenyl) carbamate and the like can be mentioned.
Of these, more preferred are ethyl N-allyl carbamate, iso-propyl N-allyl carbamate, sec-butyl N-allyl carbamate, phenyl N-allyl carbamate and benzyl N-allyl carbamate.

The ethylenically unsaturated monomer used as a raw material monomer in the C-containing carbamate ester group-containing copolymer is a monomer copolymerizable with the carbamate ester compound. Examples thereof include styrene, ethylene, vinyl acetate, ethyl acrylate and butyl acrylate. Of these, styrene is more preferable.

The formamide group-containing copolymer and carbamic acid ester group-containing copolymer used as the component C described above are obtained by copolymerizing the formamide compound or carbamic acid ester compound described above with the ethylenically unsaturated monomer. Obtained by reacting. These copolymers are addition polymers produced by solution polymerization, emulsion polymerization, precipitation polymerization, suspension polymerization or bulk polymerization. It is preferably produced by solution polymerization or bulk polymerization.

The method of the copolymerization reaction is not particularly limited, but a radical copolymerization method using a free radical generating catalyst such as a peroxide or an azo compound in an appropriate temperature range is used, or titanium trichloride is used. -Ziegler-Natta using triethylaluminum-based ionic polymerization catalyst (Zie
It is convenient to use the Geller-Natta method.

Examples of the free radical generating catalyst used in the radical copolymerization method 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.
It is 1 to 5.0% by weight. The reaction temperature needs to be high enough for the catalyst to generate free radicals. The useful temperature range is from room temperature to 1 depending on the type of catalyst used.
Up to 50 ° C.

As the ionic polymerization catalyst used in the Ziegler-Natta method, in addition to titanium tetrachloride-triethylaluminum system and titanium trichloride-triethylaluminum system,
A combination of an alkylated compound of various metals of Groups 1, 2, and 3 and a transition metal compound of Groups 4 to 7 is used.

The reaction solvent used in these copolymerization reactions is preferably an inert solvent, and specific examples thereof include heptane, octane, benzene, toluene, xylene and chlorobenzene.

Further, the composition ratio of each repeating unit in the C component formamide group-containing copolymer and the carbamic acid ester group-containing copolymer can be determined by measuring the infrared absorption spectrum. That is, ethylenically unsaturated absorption of specific 1450～1500Cm ^-1 or 710～730Cm ^-1 to repeat units of the monomer, absorbing or carbamate of specific 1650～1700Cm ^-1 formamide recurring units (II) 1720 peculiar to repeating unit (III)
The composition ratio of each repeating unit can be determined by the ratio of the absorbance at the absorption of -1730 cm ^-1 .

In the C-formamide group-containing copolymer and the carbamic acid ester group-containing copolymer, the repeating unit of the ethylenically unsaturated monomer is 80 to 99.9 in the molecule.
5%, preferably 90 to 99.8%. Further, the formamide repeating unit (II) in the formamide group-containing copolymer and the carbamic acid ester repeating unit (III) in the carbamic acid group-containing copolymer are each 0.05 to 20%, preferably 0. 2-1
Contains 0%.

When the content ratio of the formamide repeating unit (II) and the carbamic acid ester repeating unit (III) in the above-mentioned copolymer is less than 0.05%, the thermoplastic resin composition finally obtained is Poor miscibility between resins. Further, when the content ratio exceeds 20%, the copolymerizability of the formamide compound and the carbamic acid ester compound is not so high, so that it is not economical to manufacture the copolymer, and the thermoplastic resin composition is manufactured. However, it is not economical, and on the contrary, it may deteriorate the physical properties of the resin composition.

[4] About composition ratio of thermoplastic resin composition: The thermoplastic resin composition of the present invention has the above-mentioned [1] to
The component A, the component B, and the component C described in [3] are essential constituent components, but if necessary, other additives (reinforcing material such as glass fiber and carbon fiber, inorganic filler, Heat stabilizer, antistatic agent, antioxidant, light stabilizer, flame retardant, weathering agent, etc.) may be added.

The blending ratios of the components A, B and C in the thermoplastic resin composition of the present invention are 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 rather the impact strength of the resin composition tends to decrease. Moreover, it is economically disadvantageous in producing the resin composition.

[5] 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 not 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 single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader such as 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.

[0109]

In the thermoplastic resin composition of the present invention, the C component (the graft copolymer or copolymer having a formamide group, or the copolymer having a carbamate group) is the A component [(A-1)]. Component or (A-2) Component]
It has the function of increasing the miscibility of B component (thermoplastic resin component that does not substantially react with amino groups), but the mechanism of its action is estimated as follows in consideration of the polymer structure of C component. To be done. That is, first, the formamide group portion or carbamic acid ester group portion in the C component is decomposed by the action of heat during kneading and converted into an amino group. Next, as a result of combining the C component and the A component through a chemical reaction such as an amidation reaction, an esterification reaction, a transesterification reaction, or a transamidation reaction with a functional group capable of reacting the amino group with the amino group in the A component, It is considered that a solubilizer is formed, and thereby the miscibility of the resins of the A component and the B component is enhanced.

It is presumed that the thermoplastic resin composition of the present invention has improved various physical properties such as impact resistance due to the improved miscibility of the resins of the component A and the component B.

[0111]

According to the present invention, by using a graft copolymer or copolymer having a formamide group or a copolymer having a carbamate group as a compatibilizer (component C), engineering plastics can be separated from each other. The miscibility and the miscibility of the engineering plastic with the polyolefin resin, the polystyrene resin and the like are enhanced, whereby the thermoplastic resin composition of the present invention has the following remarkable effects.

A thermoplastic resin composition having excellent impact resistance can be obtained.

It is possible to obtain a thermoplastic resin composition which has a good appearance even after molding and does not cause delamination.

It is possible to obtain a thermoplastic resin composition which is not colored even when molded at a high temperature and has a good hue of a molded product.

[0115]

EXAMPLES Examples of the present invention will be described below.
The invention is not limited to these examples.

[1] Graft type (formamide group) An example in which a graft copolymer having a formamide group is used as the C component (compatibilizer) of the thermoplastic resin composition will be described.

<Polymer (1)> (Graft copolymer having formamide group) 2.0 g of N-allylformamide (graft monomer) and ethylene-propylene rubber having a weight average molecular weight of 50,000 (ethylene / propylene = 6) / 4) (raw material polymer) 40 g
Was dissolved in 160 g of chlorobenzene, and 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 completion of 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. A propylene rubber [polymer (1)] was obtained. Infrared absorption spectrum of the obtained grafted product was measured, and 166 based on amide was measured.
Due to the absorption near 0 cm ^{−1 and} the absorption at 720 cm ⁻¹ based on the alkyl group of ethylene-propylene rubber, the graft amount of N-allylformamide is 2.7% by weight based on 100% by weight of ethylene-propylene rubber. Was decided.

<Polymer (2) to (8)> A graft copolymer having another formamide group [polymers (2) to (8)] is prepared in the same manner as in the above polymer (1), The results are shown in Table 1.
It was shown to.

Table 1 shows the raw materials of the polymers (1) to (8), the graft monomer and the graft amount thereof, Mw is the weight average molecular weight, and Mn is the number average molecular weight.

[0120]

[Table 1]

Examples 1 to 15 First, as the component (Aa) used for the component A, those listed in Table 2 were used.
As the component (Ab) used in the component, those described in Table 3 are used, and as the component B, those described in Table 4 are used. As the C component (graft copolymer), the above polymers (1) to (8) are used. Tables 2 and 4 show the resin names, their abbreviations, product names, and manufacturers. In addition, Table 3 shows the types of resins, their abbreviations and types of functional groups. Mw represents a weight average molecular weight and Mn represents a number average molecular weight.

[0122]

[Table 2]

[0123]

[Table 3]

[0124]

[Table 4]

Thermoplastic resin compositions of Examples 1 to 15 were obtained by using these components A, B and C in the prescribed proportions shown in Tables 5 and 6.

In Examples 1 to 8, the component (A-1) [component (Aa) or component (Ab)] and component C were dry blended in a predetermined ratio in advance and dried, It was melt-kneaded using a shaft extruder (KRC kneader, manufactured by Kurimoto Iron Works), taken out, and then pelletized. Next, the component B was mixed in a predetermined amount, melt-kneaded again using a twin-screw extruder, taken out, and then pelletized to obtain a thermoplastic resin composition.

In Examples 9 to 15, the resin as the component (A-2) and the component C were dry blended in a predetermined ratio and dried, and then the twin-screw extruder (KRC kneader, manufactured by Kurimoto Iron Works) was used. The mixture was melt-kneaded, and then taken out and pelletized. Next, the component B was mixed in a predetermined amount, melt-kneaded again using a twin-screw extruder, taken out, and then pelletized to obtain a thermoplastic resin composition.

The thermoplastic resin composition thus obtained was processed by using an injection molding machine (Hippershot 3000, manufactured by Niigata Iron Works) to obtain a molded product. By examining the Izod impact strength of this molded product, the presence or absence of delamination and the appearance,
The results are shown in Tables 5 and 6.

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 temperatures were 23 ° C and -30 ° C.

The presence or absence of delamination of the molded product was examined by a cross-cut test. That is, a notch is made on the surface of the test piece using a knife to form 100 1 mm × 1 mm rectangles in a grid pattern. Then, after the cellophane tape is pressure-bonded, the cellophane tape is peeled off with a strong force to count the number of rectangles which are not attached to the cellophane tape and are not peeled off from the test piece. The larger the number is, the more difficult the layered peeling is.

Further, 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 and Table 6, 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 15 Comparative Examples 1 to 15 in which the component C (compatibilizer) was not blended
The results are shown in Tables 5 and 6 as -15.

[0133]

[Table 5]

[0134]

[Table 6]

From Tables 5 and 6, the impact strength of the molded articles of Examples 1 to 15 is superior to the corresponding impact strength of the molded articles of Comparative Examples 1 to 15 at both measurement temperatures of 23 ° C and -30 ° C. ing. Further, regarding the layered releasability of the molded products by the cross-cut test, the molded products of Examples 1 to 15 were 100/10.
It was 0 and did not cause delamination at all, but the molded articles of Comparative Examples 1 to 15 caused considerable delamination. Furthermore, the appearances of the molded products of Examples 1 to 15 were all good, but the appearances of the molded products of Comparative Examples 1 to 15 were poor.

[2] Copolymerization Type (Formamide Group) An example using a copolymer having a formamide group as the C component (compatibilizer) of the thermoplastic resin composition will be described.

<Polymer (9)> (Copolymer Having Formamide Group) Purified n-heptane (40 mL) was charged into an autoclave equipped with a catalyst chamber and having an inner volume of 200 mL and equipped with a magnetic stirrer, and the autoclave was cooled with ice. After replacing the system with nitrogen, propylene 42.0 g
(1 mol) and 4.25 g of N-allylformamide (0.
(05 mol) was charged. The contents were heated to 70 ° C., the opening of the catalyst chamber was opened, and under a nitrogen stream, 65 mg of titanium trichloride and 0.74 mmol of diethylaluminum chloride were added.
% N-heptane solution. Close the mouth of the catalyst chamber, drive the stirrer, and set the internal pressure (about 19.5 kg) in the reaction system.
Nitrogen gas at a pressure slightly higher than / cm ² ) was instantaneously fed into the catalyst chamber, the Teflon cap at the lower end of the catalyst chamber was removed, and the catalyst was added.

When polymerized at 70 ° C. for 1 hour, the internal pressure is 11.0.
It decreased to kg / cm ² . After cooling the autoclave to purge unreacted monomer, the content was put into 200 mL of methanol to obtain a white powder. This powder was filtered off, washed with 100 mL of methanol and dried to obtain a propylene-N-allylformamide copolymer [polymer (9)
] 19.8g was obtained. By an infrared absorption spectrum of the copolymer is measured and compared with the absorption intensity based on formamide with propylene absorption intensity and 1450 cm ^-1 in 1685 cm ^-1, the composition of the copolymer,
(Propylene) / (N-allylformamide) = 97.
It was determined to be 9 / 2.1 (mol / mol). Also, GPC
When the molecular weight of the above copolymer is measured by (gel permeation chromatography), the weight average molecular weight (Mw) is 65,000 and the number average molecular weight (Mn) is 3
It was 1,500.

<Polymer (10) and (11)> A copolymer having another formamide group in the same manner as the polymer (9) [polymer
(10) and (11)] were prepared, and the results are shown in Table 7.

Table 7 shows the kinds and amounts of the raw material monomers of the copolymer and the polymerization conditions, and also shows the yield, molecular weight and N-allylformamide content of the obtained copolymer.

[0141]

[Table 7]

<Polymer (12)> (Copolymer Having Formamide Group) Azobisisobutyronitrile (AIBN) 5 was placed in a flask having an internal capacity of 2,000 mL equipped with a condenser, a thermometer and a nitrogen introducing tube. 0.5 g
500 g of toluene in which was dissolved was charged, and subsequently, 336.0 g (4.0 mol) of hexene-1 and 19.8 g (0.1% of N- (1-methyl-2-propenyl) formamide).
(2 mol), 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 [polymer (12)] was 285.1 g. In addition, the infrared absorption spectrum of the copolymer was measured to be 1450 cm ^-1 based on hexene- ^1.
And 1685 cm ⁻¹ based on the amide group of N- (1-methyl-2-propenyl) formamide,
The molar ratio of the hexene-1 repeating unit to the N- (1-methyl-2-propenyl) formamide repeating unit is 96.0 / 4.
It was decided to be 0. The copolymer had a weight average molecular weight (Mw) of 25,000 and a number average molecular weight (Mn) of 11,000.
Met.

<Polymers (13) to (16)> Using the ethylenically unsaturated monomer, the formamide compound and the radical initiator shown in Table 8 under the polymerization conditions shown in Table 8, the polymer (12) Other formamide group-containing copolymers [polymers (13) to (16)] were prepared in the same manner as in. The results are shown in Table 8.

Table 8 shows the yield, molecular weight and formamide repeating unit content of the obtained copolymer.

[0146]

[Table 8]

Examples 16 to 30 First, as the component (A-a) used in the component A, those listed in Table 2 above were used, and as the component (A-b) used in the component A, the above-mentioned components were used. The one shown in Table 3 is used, and the one shown in Table 4 is used as the B component. As the C component (copolymer), the above polymers (9) to (16) are used.

The components A, B and C are shown in Tables 9 and 10.
The thermoplastic resin compositions of Examples 16 to 30 were obtained by using the above-mentioned predetermined proportions.

In Examples 16 to 23, (A-1)
The components [(A-a) component or (A-b) component] and C component are previously dry-blended in a predetermined ratio and dried, and then 26 using a twin-screw extruder (KRC kneader, manufactured by Kurimoto Iron Works).
The mixture was melt-kneaded at 0 ° C., taken out, and pelletized. Next, the component B was mixed in a predetermined amount, melt-kneaded again using a twin-screw extruder, taken out, and then pelletized to obtain a thermoplastic resin composition.

In Examples 24 to 30, (A-2)
The component resin and the C component were previously dry-blended in a predetermined ratio and dried, and then melt-kneaded at 260 ° C. using a twin-screw extruder (KRC kneader, manufactured by Kurimoto Iron Works), taken out, and pelletized. Next, the component B was mixed in a predetermined amount, melt-kneaded again using a twin-screw extruder, taken out, and then pelletized to obtain a thermoplastic resin composition.

The thermoplastic resin composition thus obtained was processed using an injection molding machine (Hipershot 3000, manufactured by Niigata Iron Works) to obtain a molded product. By examining the Izod impact strength of this molded product, the presence or absence of delamination and the appearance,
The results are shown in Tables 9 and 10.

The above molded products were evaluated in Examples 1 to 15
The same method was used.

<Comparative Examples 1 to 15> In Examples 16 to 30, examples in which the component C (compatibilizer) was not added were Comparative Examples 1 to 15, and the results are shown in Tables 9 and 10.

[0154]

[Table 9]

[0155]

[Table 10]

From Tables 9 and 10, the impact strength of the molded articles of Examples 16 to 30 is superior to that of the corresponding molded articles of Comparative Examples 1 to 15 at both measurement temperatures of 23 ° C and -30 ° C. ing. Moreover, regarding the layered releasability of the molded products by the cross-cut test, the molded products of Examples 16 to 30 had 100% peelability.
/ 100, which did not cause delamination at all,
The molded articles of Comparative Examples 1 to 15 caused considerable delamination. Furthermore, the appearances of the molded articles of Examples 16 to 30 were all good, but the appearances of the molded articles of Comparative Examples 1 to 15 were poor.

[3] Copolymerization Type (Carbamic Acid Ester Group) An example using a copolymer having a carbamic acid ester group as the C component (compatibilizer) of the thermoplastic resin composition will be described.

<Polymer (17)> (Copolymer Having Carbamic Acid Ester Group) Cooler,
Azobisisobutyronitrile (AIBN) was placed in a flask with a volume of 2,000 mL equipped with a thermometer and a nitrogen inlet tube.
400 g of toluene in which 3.6 g was dissolved was charged, followed by 221 g of styrene (ethylenically unsaturated monomer), i
143 g of so-propyl N-allyl carbamate (carbamic acid ester compound) was 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 poured into methanol, and the precipitated copolymer was filtered and dried.

The yield of the obtained copolymer [polymer (17)] was 259.1 g. Further, by measuring the infrared absorption spectrum of the copolymer, the molar ratio of the styrene repeating unit and the carbamate repeating unit was determined to be 90/10. The weight average molecular weight (Mw) of the copolymer is 37.0.
And the number average molecular weight (Mn) was 21,200.

<Polymer (18) and (19)> Another carbamic acid ester group-containing copolymer [polymers (18) and (19)] was prepared in the same manner as in the polymer (17). The results are shown in Tables 11 and 12.

Table 16 shows the types and amounts of the raw material monomers of the copolymer, the types and amounts of the solvents and catalysts used, and the reaction conditions. Table 12 shows the composition and molecular weight of each repeating unit in the obtained copolymer.

[0162]

[Table 11]

[0163]

[Table 12]

<Polymer (20)> Using N-allylcarbamic acid t-butyl ester, which is a carbamic acid ester compound of a tertiary alcohol, as a raw material carbamic acid ester compound, a polymer (20) was prepared in the same manner as in the polymer (17). The styrene- (N-allylcarbamic acid t-butyl ester) copolymer used in Comparative Example (20) described later (molar ratio 90/10, M
w = 36,000, Mn = 21,000) (polymer (20))
Was prepared.

<Examples 31 to 40> First, as the component (A-a) used for the component A, those listed in Table 2 above were used, and as the component (A-b) used for the component A, the components described above were used. The one shown in Table 3 is used, and the one shown in Table 4 is used as the B component. As the C component (copolymer), the above polymers (17) to (19) are used.

The components A, B and C are shown in Table 13 and Table 1.
The thermoplastic resin compositions of Examples 31 to 40 were obtained by using them in the predetermined proportions shown in FIG.

In Examples 31 to 38, (A-1)
After dry blending the components [(A-a) component or (A-b) component], B component and C component in a predetermined ratio and drying,
A thermoplastic resin composition was obtained by melt-kneading at 260 ° C. using a twin-screw extruder (KRC kneader, manufactured by Kurimoto Iron Works).

In Examples 39 and 40, (A-
2) Component resin, B component and C component are dry blended at a predetermined ratio and dried, and then melt-kneaded at 260 ° C. using a twin-screw extruder (KRC kneader, Kurimoto Iron Works) to form a thermoplastic resin. A composition was obtained.

After the thermoplastic resin composition thus obtained was pelletized, it was injected into an injection molding machine (Hippersho).
t3000, manufactured by Niigata Iron Works) 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 Tables 13 and 14.

The above-mentioned molded products were evaluated in Examples 1 to 15
The same method was used.

<Comparative Examples 16 to 19> Examples 31 to 34
Examples in which the C component (compatibilizer) was not mixed in Comparative Examples 16 to 19 are shown in Table 13.

<Comparative Example 20> Component C in Example 35
An example in which the polymer (20) was used as the (compatibilizer) instead of the polymer (17) was set as Comparative Example 20, and the results are shown in Table 13. The thermoplastic resin composition obtained in this comparative example was markedly colored brown.

<Comparative Examples 21 to 25> Examples 36 to 40
Examples in which the component C (compatibilizer) was not blended in Comparative Examples 21 to 25 are shown in Tables 13 and 14.

[0174]

[Table 13]

[0175]

[Table 14]

From Table 13 and Table 14, Examples 31 to 40
The impact strength of the molded articles of No. 1 is superior to the impact strength of the corresponding molded articles of Comparative Examples 16 to 25 at both measurement temperatures of 23 ° C and -30 ° C. Further, regarding the layered releasability of the molded product by the cross-cut test, the molded products of Examples 31 to 40 had
It was 00/100 and did not cause delamination at all, but the molded articles of Comparative Examples 16 to 25 caused considerable delamination. Furthermore, the appearances of the molded articles of Examples 31 to 40 were all good, but the appearances of the molded articles of Comparative Examples 16 to 25 were poor or slightly poor.

In particular, in the comparison between Example 35 and the corresponding Comparative Example 20, although the molded article of Comparative Example 20 showed some compatibilizing effect in terms of impact strength and delamination property, the resin composition obtained was obtained. The coloring of the product was remarkable and there was a problem in practical use.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 55/02 LME 7142-4J 59/00 LMP 8215-4J 67/00 LNZ 8933-4J 69/00 LPP 9363-4J 71/10 LQK 9167-4J 71/12 LQP 9167-4J 77/00 LQS 9286-4J 101/02 LSZ 7242-4J (72) Inventor Yutaka Nakayama 21 Kamigamomogemachi, Kita-ku, Kyoto-shi, Kyoto Prefecture Address (72) Inventor Kaku Hideyuki 3-7-12 Yamazaka, Higashisumiyoshi-ku, Osaka City, Osaka Prefecture

Claims (26)

[Claims] 1. A thermoplastic resin composition comprising the following components A, B and C: Generalized to (A) a polymer component having a functional group capable of reacting with an amino group, (B) a thermoplastic resin component that does not substantially react with an amino group under molding and processing conditions, and (C) a thermoplastic polymer. A graft copolymer obtained by a graft reaction of the formamide compound (I) represented by 1. [Chemical 1] (In Chemical Formula 1, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon atom. (Indicates an arylalkyl group of the number 6 to 10.) 2. The thermoplastic resin component of the component B contains at least one resin selected from the group consisting of a polyolefin resin, a polystyrene resin, an ABS resin and a polyether resin. The thermoplastic resin composition. 3. The polymer component having a functional group capable of reacting with an amino group of the component A contains at least one resin selected from the group consisting of polyester resins, polycarbonate resins and polyamide resins. Claim 1
Or the thermoplastic resin composition described in 2. 4. The polymer component having a functional group capable of reacting with the amino group of the component A is a succinic anhydride group, a carboxyl group, an epoxy group, an ester group, an amide group, a cyclic iminoether group, a cyclic iminoamino group, Having a functional group selected from the group consisting of a halogen group and an imide group in the molecule 1
The thermoplastic resin composition according to claim 1 or 2, which contains at least one polymer. 5. A thermoplastic resin composition comprising the following A component, B component and C component. (A) a polymer component having a functional group capable of reacting with an amino group, and a thermoplastic resin that does not substantially react with an amino group under molding and processing conditions and is different from the resin used in the component B below. (B) a thermoplastic resin component which does not substantially react with an amino group under molding and processing conditions, and (C) a thermoplastic polymer with the formamide compound (I) represented by the general formula 1 Graft copolymer obtained by reaction. 6. The thermoplastic resin component of the component B contains at least one resin selected from the group consisting of a polyolefin resin, a polystyrene resin, an ABS resin and a polyether resin. The thermoplastic resin composition. 7. The polymer component having a functional group capable of reacting with an amino group in the component A contains at least one resin selected from the group consisting of polyester resins, polycarbonate resins and polyamide resins. The thermoplastic resin composition according to claim 5 or 6. 8. The polymer component having a functional group capable of reacting with an amino group in the component A is a succinic anhydride group, a carboxyl group, an epoxy group, an ester group, an amide group, a cyclic iminoether group or a cyclic iminoamino group. 6. One or more polymers having in the molecule thereof a functional group selected from the group consisting of a halogen group and an imide group.
Or the thermoplastic resin composition according to item 6. 9. A copolymer comprising a formamide repeating unit (II) represented by the general formula 2 and an ethylenically unsaturated monomer repeating unit in the molecule. [Chemical 2] (In the formula 2, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon atom. (Indicates an arylalkyl group of the number 6 to 10.) 10. A thermoplastic resin composition comprising the following components A, B and C: The (A) polymer component having a functional group capable of reacting with an amino group, (B) a thermoplastic resin component which does not substantially react with an amino group under molding and processing conditions, and (C) the copolymer according to claim 9. . 11. The thermoplastic resin component of the component B contains at least one resin selected from the group consisting of a polyolefin resin, a polystyrene resin, an ABS resin and a polyether resin. The thermoplastic resin composition. 12. The polymer component having a functional group capable of reacting with an amino group of the component A contains at least one resin selected from the group consisting of a polyester resin, a polycarbonate resin and a polyamide resin. The thermoplastic resin composition according to claim 10 or 11. 13. The polymer component having a functional group capable of reacting with the amino group of the component A is 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 polymer containing one or more polymers having a functional group selected from the group consisting of a halogen group and an imide group in the molecule.
The thermoplastic resin composition according to 0 or 11. 14. A thermoplastic resin composition comprising the following A component, B component and C component. (A) a polymer component having a functional group capable of reacting with an amino group, and a thermoplastic resin that does not substantially react with an amino group under molding and processing conditions and is different from the resin used in the component B below. The composition according to claim 1, (B) a thermoplastic resin component which does not substantially react with amino groups under molding and processing conditions, and (C) the copolymer according to claim 9. 15. The thermoplastic resin component of the component B contains at least one resin selected from the group consisting of polyolefin resin, polystyrene resin, ABS resin and polyether resin. The thermoplastic resin composition. 16. The polymer component having a functional group capable of reacting with an amino group in the component A contains at least one resin selected from the group consisting of polyester resins, polycarbonate resins and polyamide resins. The thermoplastic resin composition according to claim 14 or 15. 17. The polymer component having a functional group capable of reacting with an amino group in the component A is a succinic anhydride group, a carboxyl group, an epoxy group, an ester group, an amide group, a cyclic iminoether group or a cyclic iminoamino group. 16. The thermoplastic resin composition according to claim 14 or 15, which contains one or more polymers having a functional group selected from the group consisting of a halogen group and an imide group in the molecule. 18. A copolymer comprising a carbamic acid ester repeating unit (III) represented by the general formula 3 and an ethylenically unsaturated monomer repeating unit in the molecule. [Chemical 3] (However, in the chemical formula 3, R ⁵ is a hydrogen atom and has 1 to 8 carbon atoms.
Represents an alkyl group having 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 ⁶ has 1 to 1 carbon atoms.
8 represents a primary or secondary alkyl group, a phenyl group or a benzyl group. In addition, R ⁵ and R ⁶ may be the same or different for each repeating unit. ) 19. A thermoplastic resin composition comprising the following A component, B component and C component. The polymer component having (A) a functional group capable of reacting with an amino group, (B) a thermoplastic resin component which does not substantially react with an amino group under molding and processing conditions, and (C) the copolymer according to claim 18. . 20. The thermoplastic resin component of the component B contains at least one resin selected from the group consisting of polyolefin resin, polystyrene resin, ABS resin and polyether resin. The thermoplastic resin composition. 21. The polymer component having a functional group capable of reacting with an amino group of the component A contains at least one resin selected from the group consisting of polyester resins, polycarbonate resins and polyamide resins. The thermoplastic resin composition according to claim 19 or 20. 22. The polymer component having a functional group capable of reacting with the amino group of the component A is 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 polymer containing one or more polymers having a functional group selected from the group consisting of a halogen group and an imide group in the molecule.
The thermoplastic resin composition according to 9 or 20. 23. A thermoplastic resin composition comprising the following A component, B component and C component. (A) a polymer component having a functional group capable of reacting with an amino group, and a thermoplastic resin that does not substantially react with an amino group under molding and processing conditions and is different from the resin used in the component B below. The composition according to claim 1, (B) a thermoplastic resin component which does not substantially react with amino groups under molding and processing conditions, and (C) the copolymer according to claim 18. 24. The thermoplastic resin component of the component B contains at least one resin selected from the group consisting of a polyolefin resin, a polystyrene resin, an ABS resin and a polyether resin. The thermoplastic resin composition. 25. The polymer component having a functional group capable of reacting with an amino group in the component A contains at least one resin selected from the group consisting of polyester resins, polycarbonate resins and polyamide resins. The thermoplastic resin composition according to claim 23 or 24. 26. The polymer component having a functional group capable of reacting with an amino group in the component A is a succinic anhydride group, a carboxyl group, an epoxy group, an ester group, an amide group, a cyclic iminoether group or a cyclic iminoamino group. 25. The thermoplastic resin composition according to claim 23 or 24, comprising one or more polymers having a functional group selected from the group consisting of a halogen group and an imide group in the molecule.