JP2000273263A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition which contains a maleimide-based copolymer, a graft copolymer, a polyamide resin, an acrylate ester-based copolymer, and a vinylic copolymer as effective components and has high heat resistance, high impact resistance, excellent chemical resistance and excellent dimensional stability. SOLUTION: This thermoplastic resin composition comprises (A) 5-55 wt.% of a maleimide-based copolymer comprising 30-70 mol.% of an aromatic vinyl monomer, 25-50 mol.% of a maleimide-based monomer, 1-30 mol.% of an unsaturated dicarboxylic acid anhydride monomer, and 0-40 mol.% of one or more other monomers, (B) 10-50 wt.% of a graft copolymer obtained by graft- copolymerizing 35-65 pts.wt. of a mixture comprising 35-70 mol.% of an aromatic vinyl monomer, 30-60 mol.% of a vinyl cyanide monomer and 0-30 mol.% of a vinylic monomer to 35-65 pts.wt. of a rubbery polymer, (C) 3-20 wt.% of a polyamide resin, (D) 2-12 wt.% of an acrylate ester-based copolymer comprising 0.1-10 mol.% of an unsaturated dicarboxylic acid and/or its anhydride, 30-94 mol.% of an olefinic monomer, and the like, and (E) 0-50 mol.% of a vinylic copolymer comprising 35-70 mol.% of an aromatic vinyl monomer, and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic resin composition having excellent heat resistance, impact resistance, chemical resistance, dimensional stability, moldability, and appearance of a molded article. More specifically, a maleimide-based copolymer containing a maleimide-based monomer group and an unsaturated dicarboxylic anhydride monomer group at a specific ratio, a specific graft copolymer, a polyamide resin, and a specific ratio The present invention relates to a thermoplastic resin composition containing an acrylate copolymer having a saturated dicarboxylic acid and / or an anhydride monomer group as an essential component. The thermoplastic resin composition of the present invention is used for automobile parts, electric / electronic parts,
It can be preferably used for office equipment parts, heating appliances such as electric rice cookers, microwave ovens and microwave ovens, tableware, electric refrigerator parts, bathtub parts, shower parts, water purifier parts, toilet seats and the like.

[0002]

2. Description of the Related Art Conventionally, a method for producing a copolymer having a maleimide-based monomer group is known (US Pat. No. 38).
No. 40499, U.S. Pat. No. 3,998,907). However, although the copolymer having a maleimide-based monomer group is excellent in heat resistance and dimensional stability, it has a problem in that impact resistance, chemical resistance, and moldability are poor.

Therefore, a resin composition in which an ABS resin is blended with a copolymer having a maleimide-based monomer group to improve impact resistance is also known (US Pat. No. 3,642,294).
No. 9, U.S. Pat. No. 3,652,726, JP-A-57-98536, JP-A-57-125241.
No.). However, the resin composition obtained by blending these ABS resins has a disadvantage that although the impact resistance is improved, the chemical resistance is not sufficient.

For the purpose of improving the chemical resistance of a copolymer having a maleimide-based monomer group, a resin composition obtained by blending a polyamide resin with the copolymer has been proposed (Japanese Patent Application Laid-Open No. 58-1983). No. 71952, JP-A-63-179
49, JP-A-3-277648, JP-A-1
-2155843). By blending polyamide resin, chemical resistance can be improved,
Various problems have arisen.

For example, in Japanese Patent Application Laid-Open (JP-A) No. 58-71952, this resin composition has excellent chemical resistance, but has insufficient compatibility between blended resins, and has a drawback that a molded product is peeled off. . In addition, when the amount of polyamide resin is 20
When the content exceeds 20% by weight, the impact resistance is improved. When the content is less than 20% by weight, the impact resistance and the chemical resistance are extremely reduced. In addition, examples in which the ABS resin is added to improve the impact resistance are described in the examples. This is the case where the amount of the polyamide resin exceeds 20% by weight, and when the amount of the polyamide resin is 20% by weight or less. Even if an ABS resin is added, the impact resistance is low and is not suitable for practical use at all.

[0006] JP-A-63-17949 proposes a resin composition comprising a copolymer having a maleimide monomer group, a polyamide resin, and a graft copolymer. When the amount of the polyamide resin is large, the impact resistance is improved but the dimensional stability is reduced. When the amount of the polyamide resin is small, the dimensional stability is improved. There is a disadvantage that the chemical property is reduced.

Further, Japanese Patent Application Laid-Open No. 3-277648 discloses a polymer having a maleimide monomer group in order to improve the compatibility of a resin composition of a copolymer having a maleimide monomer group with a polyamide resin. A resin composition comprising a copolymer having an unsaturated dicarboxylic acid anhydride monomer group in a combination thereof and a polyamide resin has been proposed. Although the compatibility of this resin composition is greatly improved, the blending amount of the polyamide resin is 30% by weight or more, so that there is a disadvantage that the dimensional stability is poor. When the amount of the polyamide resin in the resin composition is less than 30% by weight, the impact resistance is significantly reduced.

Further, JP-A 1-215843 discloses a copolymer having a maleimide monomer group, a polyamide resin, and an ethylene-α-olefin elastomer having an unsaturated dicarboxylic acid and / or an anhydride thereof. A resin composition comprising a copolymer has been proposed. This resin composition is very excellent in impact resistance, heat resistance and chemical resistance, but has a drawback that the dimensional stability is inferior since the polyamide resin is 30% by weight or more. If the amount of polyamide resin in the resin composition is less than 30% by weight, the impact resistance is greatly reduced, and it is difficult to actually use the resin composition.

Although it has been known that a polyamide resin and a resin composition containing the polyamide resin are generally excellent in chemical resistance, when the amount of the polyamide resin in the resin composition is large, the dimensional stability due to water absorption is increased. When the amount of polyamide resin is small, the dimensional stability due to moisture absorption is improved, but the chemical resistance is low and the impact resistance is low. There is a disadvantage that it decreases. On the other hand, when the amount of the polyamide resin is small, SBR (styrene-styrene) is used to improve the impact resistance.
It is conceivable to add a rubbery polymer such as butadiene copolymer rubber) or MBS (methyl methacrylate-butadiene-styrene rubber), but in practice, the effect of improving impact resistance was poor.

[0010]

As described above, the present invention relates to a resin composition using a copolymer having a maleimide monomer group, which has high heat resistance, high impact resistance and chemical resistance. However, a resin composition having excellent dimensional stability has not yet been obtained, and at present, there is a strong demand for the development of a high-performance resin composition having these properties. Accordingly, the present invention has been accomplished as a result of intensive studies for the purpose of providing a resin composition having these high performances.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies for the purpose of developing a resin having high heat resistance, high impact resistance, and excellent chemical resistance and dimensional stability. Maleimide-based copolymers, graft copolymers, polyamide resins containing maleimide-based monomer groups and unsaturated dicarboxylic anhydride monomer groups, and unsaturated dicarboxylic acids and / or anhydrides thereof at a specific ratio It has been found that the above object can be achieved when the acrylic ester copolymer having a monomer group is used as an essential component and is blended in a specific ratio, and the thermoplastic resin composition of the present invention has been achieved.

In general, the present invention relates to a thermoplastic resin composition, wherein (A) 30 to 70 mol% of an aromatic vinyl monomer group and 25 to 25% of a maleimide monomer group.
50 mol%, unsaturated dicarboxylic anhydride monomer groups 1 to 3
0 mol% and other copolymerizable vinyl monomer groups 0
5 to 55% by weight of a maleimide-based copolymer composed of 40 to 40% by mole, 35 to 70% by weight of (B) a rubbery polymer, 35 to 70% by mole of an aromatic vinyl monomer, 30 And a monomer mixture of 35 to 65 mol% of a vinyl monomer copolymerizable therewith.
Graft copolymers 10 to 5 obtained by graft polymerization of parts by weight
0% by weight, (C) 3 to 20% by weight of a polyamide resin,
(D) 0.1 to 10% by mole of unsaturated dicarboxylic acid and / or anhydride monomer group, and 30 to 30% of olefin monomer group
94 mol%, 5-69 mol% of acrylate monomer groups, and 0-2 of other copolymerizable vinyl monomer groups.
Acrylic ester copolymers 2-1 comprising 0 mol%
2% by weight, (E) 35 to 70 mol% of aromatic vinyl monomer groups, 30 to 60 mol% of vinyl cyanide monomer groups, and 0 to 30 mol% of other copolymerizable vinyl monomer groups Is a thermoplastic resin composition containing as an active ingredient 0 to 50% by weight of a vinyl copolymer composed of

The present inventors have found that the thermoplastic resin composition according to the present invention is excellent in heat resistance, impact resistance, chemical resistance, dimensional stability and moldability, and the molded article gives a beautiful appearance. I found that.

First, the maleimide copolymer (A) forming the thermoplastic resin composition of the present invention will be described in detail. The (A) maleimide-based copolymer used in the present invention includes 30 to 70
Mole% of an aromatic vinyl monomer group, 25 to 50 mole% of a maleimide monomer group, 1 to 30 mole% of an unsaturated dicarboxylic anhydride monomer group, and 0 to 40 mole% of It can contain other copolymerizable vinyl monomer groups.
If the amount of the aromatic vinyl monomer group is less than 30 mol%, it is difficult to produce a polymer having a homogeneous composition industrially with good reproducibility, and the maleimide polymer is mixed with other components. The resulting thermoplastic resin composition is inferior in properties such as thermal stability, moldability and mechanical strength. When the content of the aromatic vinyl monomer group exceeds 70 mol% or the content of the maleimide monomer group is less than 25 mol%, the obtained thermoplastic resin composition has poor thermal stability, When the amount of the monomer group exceeds 50 mol%, the moldability of the obtained thermoplastic resin composition is poor. If the amount of the unsaturated dicarboxylic anhydride monomer group is less than 1 mol%, the compatibility of the thermoplastic resin composition obtained by mixing with other components is poor, the mechanical strength is poor, and the heat A peeling phenomenon is observed in a molded product of the plastic resin composition. On the other hand, when the amount of the unsaturated dicarboxylic anhydride monomer group exceeds 30 mol%, the moldability of the thermoplastic resin composition is poor, and the thermal stability of the molded product is poor.

The method for producing the (A) maleimide-based copolymer is not particularly limited. For example, an aromatic vinyl monomer, a maleimide-based monomer, an unsaturated dicarboxylic anhydride monomer and, if necessary, It can be produced by radical copolymerization of other copolymerizable monomers.

Specific examples of the aromatic vinyl monomer include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, and substituted products thereof. Is particularly preferred.

Specific examples of the maleimide-based monomer include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-hexylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-toluylmaleimide. Among them, N-phenylmaleimide is particularly preferred.

Specific examples of the unsaturated dicarboxylic anhydride monomers include maleic anhydride, methylmaleic anhydride, 1,2-dimethylmaleic anhydride, ethylmaleic anhydride, phenylmaleic anhydride and the like. Of these, maleic anhydride is particularly preferred.

Specific examples of other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and decyl ( There are meth) acrylate, octadecyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate and the like, and these can be used alone or in combination. Here, methyl (meth) acrylate means methyl acrylate or methyl methacrylate.

The method for copolymerizing these monomers is not particularly limited, and any known radical copolymerization method can be used.

Other methods for producing the maleimide copolymer (A) used in the present invention include aromatic vinyl monomers, unsaturated dicarboxylic anhydride monomers, and other copolymers if necessary. An example is a method in which a copolymer of a possible monomer is reacted with ammonia or a primary amine to imidize an acid anhydride group. The imidization reaction between a polymer substance having an acid anhydride group in a polymer chain and an amine compound is known. For example, according to the method disclosed in JP-B-61-26936 or JP-B-62-8456. By reacting a polymer substance with an amine compound, a maleimide-based copolymer having a target imide group can be produced.

The imidization reaction can be carried out in a solution state, a bulk molten state or a suspension state using an autoclave. It is also possible to carry out the reaction in a molten state using a melt kneading device such as a screw extruder.

The solvent used for the solution reaction is optional.
For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethyl sulfoxide, N-methyl-2 -Pyrrolidone and the like.

The reaction temperature for imidization is preferably in the range of 50 to 350 ° C, particularly preferably in the range of 100 to 300 ° C.

The imidization reaction does not necessarily require the presence of a catalyst, but if used, tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline and N, N-diethylaniline are preferred. .

The graft copolymer (B) used in the present invention comprises 35 to 65 parts by weight of a rubbery polymer and 35 to 70 mol% of an aromatic vinyl monomer and 30 to 60 mol% of vinyl cyanide. Graft polymerizing a monomer and a monomer mixture of 35 to 65 parts by weight of a vinyl monomer copolymerizable with 0 to 30 mol% of an aromatic vinyl monomer and a vinyl cyanide monomer. Can be obtained. When the rubber-like polymer is less than 35 parts by weight, that is, when the monomer mixture exceeds 65 parts by weight, the impact resistance is reduced, and the monomer mixture is less than 35 parts by weight, that is, the rubber-like polymer exceeds 65 parts by weight. In addition, heat resistance and moldability deteriorate. When the amount of the aromatic vinyl monomer in the monomer mixture is less than 35 mol%, the moldability decreases, and when it exceeds 70 mol%, the heat resistance decreases. Furthermore, when the vinyl cyanide monomer in the monomer mixture is 3
If the amount is less than 0 mol% or more than 60 mol%, the compatibility with the component (A) decreases, which causes delamination of the thermoplastic resin composition and a reduction in impact strength.

The method for producing the graft copolymer (B) is not particularly limited. For example, aromatic vinyl monomers,
It can be produced by graft-polymerizing a monomer mixture of a vinyl cyanide monomer and a vinyl monomer copolymerizable therewith with a rubbery polymer. Specifically, conventionally known emulsion polymerization method, suspension polymerization method,
It may be obtained by any method such as a bulk polymerization method and a solution polymerization method, or may be a method obtained by combining these polymerization methods.

The graft copolymer (B) obtained by graft-polymerizing the above monomer mixture to a rubbery polymer may contain an ungrafted copolymer.

Specific examples of the aromatic vinyl monomer include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene as described above, and substituted products thereof. Among them, styrene is particularly preferred.

Specific examples of the vinyl cyanide monomer include:
There are acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, among which acrylonitrile is particularly preferred.

Specific examples of the vinyl monomer copolymerizable with the aromatic vinyl monomer and vinyl cyanide monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and hexyl. There are (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate, octadecyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate and the like. , Or in combination. Here, methyl (meth) acrylate means methyl acrylate or methyl methacrylate.

Specific examples of the rubbery polymer include a butadiene polymer, a copolymer of butadiene with a copolymerizable vinyl monomer, an ethylene-propylene copolymer, and an ethylene-propylene copolymer.
A propylene-diene copolymer, a block copolymer of butadiene and aromatic vinyl, an acrylate polymer, and a copolymer of an acrylate ester and a vinyl monomer copolymerizable therewith are used.

The vinyl monomers copolymerizable with butadiene include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Examples include hexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate, octadecyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, and glycidyl (meth) acrylate. Also,
Examples of the aromatic vinyl monomer include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, and substituted products thereof.

Specific examples of the polyamide resin (C) used in the present invention include nylon-6, nylon-6,6, nylon-4,6, nylon-6,10 and nylon-6,1.
2, nylon-12, nylon-11, etc., and these can be used alone or in combination. Of these, nylon-6 is particularly preferred.

Nylon-6 is produced by adding a ring-opening catalyst to ε-caprolactam, which is a cyclic compound, and heating. As the polymerization method, water addition polymerization, alkali polymerization, and cationic polymerization are known, but water addition polymerization is generally industrially used.

The (D) acrylate copolymer used in the present invention contains 0.1 to 10 mol% of an unsaturated dicarboxylic acid and / or its anhydride monomer group, and 30 to 94
It can contain mole% olefin monomer groups, 5 to 69 mole% acrylate monomer groups, and 0 to 20 mole% of other copolymerizable vinyl monomer groups.
When the content of the unsaturated dicarboxylic acid and / or its anhydride monomer group is less than 0.1 mol%, the compatibility between the resins in the thermoplastic resin composition is insufficient, which causes delamination and causes chemical resistance. Properties and impact strength are not improved. On the other hand, if the content exceeds 10 mol%, a gel or the like is generated in the thermoplastic resin composition. Further, when the olefin monomer group is less than 30 mol% or the acrylate ester monomer group exceeds 69 mol%, the thermal stability is poor and the appearance of the molded article of the thermoplastic resin composition is poor. Worsens. The olefin monomer group is 94
When the content is more than 5 mol% or the content of the acrylate monomer group is less than 5 mol%, the chemical resistance of the present thermoplastic resin composition is not improved or the impact strength is low.

The method for producing the (D) acrylate copolymer is not particularly limited, and for example, a polymerization method such as an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, or a solution polymerization method can be employed.

Specific examples of the unsaturated dicarboxylic acid and / or its anhydride monomer include maleic acid, itaconic acid, citraconic acid, aconitic acid and their acid anhydrides, with maleic anhydride being particularly preferred. .

Specific examples of the olefin monomer include ethylene and propylene.

Specific examples of the acrylate monomer include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methoxymethyl acrylate, methoxyethyl acrylate, and methoxyethyl acrylate. And ethoxymethyl acrylate and ethoxyethyl acrylate.

Specific examples of other copolymerizable vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and decyl. Examples include (meth) acrylate, octadecyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, and glycidyl (meth) acrylate.

The (E) vinyl copolymer in the thermoplastic resin composition of the present invention is not essential, but can be contained in an amount of 50% by weight or less in view of the balance of physical properties.

This (E) vinyl copolymer has a composition of 35 to 35.
It may contain 70 mol% of an aromatic vinyl monomer group, 30 to 60 mol% of a vinyl cyanide monomer group, and 0 to 30 mol% of another copolymerizable vinyl monomer group. it can. When the amount of the aromatic vinyl monomer is less than 35 mol%, the moldability decreases, and when it exceeds 70 mol%, the heat resistance decreases. The vinyl cyanide monomer contained 30 mol%.
If the amount is less than 60 mol% or more, the compatibility with the component (A) decreases, which causes delamination of the thermoplastic resin composition and a decrease in impact strength.

The method for producing the (E) vinyl copolymer is not particularly limited, and for example, a polymerization method such as an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, or a solution polymerization method can be employed.

Specific examples of the aromatic vinyl monomer include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene as described above, and substituted products thereof. Among them, styrene is particularly preferred.

Specific examples of the vinyl cyanide monomer include:
Acrylonitrile, methacrylonitrile,
There are α-chloroacrylonitrile and the like, among which acrylonitrile is particularly preferred.

Specific examples of other copolymerizable vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and cyclohexyl (meth) as described above. ) Acrylate, decyl (meth) acrylate, octadecyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, and the like. These may be used alone or in combination. it can. Here, methyl (meth) acrylate means methyl acrylate or methyl methacrylate.

The thermoplastic resin composition of the present invention comprises (A) 5 to 55% by weight of a maleimide copolymer, (B) 10 to 50% by weight of a graft copolymer, and (C) 3 to 2% of a polyamide resin.
0% by weight, (D) acrylate copolymer 2-1
2% by weight and 0 to 50% by weight of the (E) vinyl copolymer are the active ingredients.

When the amount of the maleimide copolymer (A) in the thermoplastic resin composition of the present invention is less than 5% by weight, the heat resistance is insufficient, and when it exceeds 55% by weight, the impact strength and the formability are reduced. .

If the content of the graft copolymer (B) in the thermoplastic resin composition of the present invention is less than 10% by weight, the impact strength is low,
If it exceeds 50% by weight, heat resistance and molding workability will be reduced.

If the amount of the polyamide resin (C) in the thermoplastic resin composition of the present invention is less than 3% by weight, the chemical resistance is insufficient, and if it exceeds 20% by weight, the dimensional stability decreases.

When the content of the (D) acrylate copolymer in the thermoplastic resin composition of the present invention is less than 2% by weight, the chemical resistance and impact strength are insufficient. And heat resistance falls.

When the amount of the vinyl copolymer (E) in the thermoplastic resin composition of the present invention exceeds 50% by weight, the heat resistance decreases.

(A) A mixture of a maleimide copolymer, (B) a graft copolymer, (C) a polyamide resin and (D) an acrylate copolymer, and (E) vinyl used as necessary The mixing of the system copolymer can be carried out by using a usual melt kneading apparatus. Examples of suitable melt kneading apparatuses include a screw extruder, a Banbury mixer, a co-kneader, and a mixing roll.

The thermoplastic resin composition of the present invention can be made into a composition by adding other additives or modifiers according to the intended use without departing from the purpose of the present invention. Include reinforcing fibers such as glass fibers, carbon fibers, and aramid fibers, fillers such as talc, silica, clay, mica, and calcium carbonate, stabilizers, flame retardants, plasticizers, lubricants, ultraviolet absorbers, and colorants. Can be

The present invention provides heat resistance, impact resistance, chemical resistance,
The present invention relates to a thermoplastic resin composition having excellent dimensional stability and moldability, and also having excellent appearance of a molded article. Therefore, for example, preferably used for automobile parts, electric / electronic parts, office equipment parts, heating appliances such as electric rice cookers / microwave ovens / microwave ovens, tableware, electric refrigerator parts, bathtub parts, shower parts, water purifier parts, toilet seats, etc. It can be used, but is not limited thereto.

[0057]

The present invention will be described in more detail with reference to the following Examples, in which all percentages used in Examples and Comparative Examples are on a weight basis. These are all examples and do not limit the content of the present invention.

(A) Maleimide copolymer The maleimide copolymer was prepared by charging 100 parts of styrene into an autoclave equipped with a stirrer, replacing the system with nitrogen gas, and then heating to 80 ° C. To this, a solution prepared by dissolving 67 parts of maleic anhydride and 0.2 part of benzoyl peroxide in 300 parts of methyl ethyl ketone was added over 8 hours. After the addition, the temperature was kept at 80 ° C. for a further 4 hours. To the above copolymer, 1.2 parts of triethylamine and 44 parts of aniline were added and reacted at a temperature of 130 ° C. for 7 hours. The reaction solution was cooled to room temperature, and methanol
The mixture was poured into 00 parts, filtered and dried to obtain a maleimide-based copolymer (a-3). Other maleimide-based copolymers were similarly prepared. That is, an unsaturated dicarboxylic anhydride-containing copolymer is obtained by changing the amount or type of the aromatic vinyl monomer, unsaturated dicarboxylic anhydride monomer, or other copolymerizable monomer. The maleimide copolymer shown in Table 1 was obtained by further changing the ratio of imidization of the acid anhydride group or the amine compound to be imidized.

[0059]

[Table 1]

(B) Graft copolymer 61.8 parts by weight of butadiene, 54.5 mol% of styrene,
A graft copolymer obtained by graft-polymerizing 38.2 parts by weight of a monomer mixture composed of 45.5 mol% of acrylonitrile was used. Hereinafter, it is referred to as b-1. 50.6 parts by weight of butadiene, 59.7 mol% of styrene, acrylonitrile 4
A graft copolymer obtained by graft polymerization of 49.4 parts by weight of a monomer mixture consisting of 0.3 mol% was used. The following b-
No. 2. 3.4 parts by weight of butadiene, 60.
A graft copolymer obtained by graft-polymerizing 96.6 parts by weight of a monomer mixture consisting of 1 mol% and 39.9 mol% of acrylonitrile was used. Hereinafter, it is referred to as b-3. A graft copolymer obtained by graft-polymerizing 28.0 parts by weight of a monomer mixture composed of 72.0 parts by weight of butadiene, 60.5 mol% of styrene, and 39.5 mol% of acrylonitrile was used.
Hereinafter, it is referred to as b-4.

(C) Polyamide resin Relative viscosity obtained from ε-caprolactam as raw material
Nylon-6 having a concentration of 65 (concentrated sulfuric acid as a solvent, a concentration of 0.5 g / 100 ml, and a temperature of 25 ° C.) was used. Hereinafter, it is referred to as c-1.

(D) Acrylic Ester Copolymer A copolymer comprising 0.6 mol% of maleic anhydride, 88.9 mol% of ethylene and 10.5 mol% of ethyl acrylate was used. Hereinafter, it is referred to as d-1. Maleic anhydride 1.1
A copolymer consisting of mol%, 89.0 mol% of ethylene and 9.9 mol% of ethyl acrylate was used. Hereinafter, it is referred to as d-2. Maleic anhydride 0.0 mol%, ethylene
A copolymer consisting of 5 mol% and 10.5 mol% of ethyl acrylate was used. Hereinafter, it is referred to as d-3. A copolymer consisting of 13.0 mol% of maleic anhydride, 80.5 mol% of ethylene, and 6.5 mol% of ethyl acrylate was used. Below d
-4. A copolymer consisting of 1.1 mol% of maleic anhydride, 28.2 mol% of ethylene and 70.7 mol% of ethyl acrylate was used. Hereinafter, it is referred to as d-5. A copolymer composed of 1.1 mol% of maleic anhydride, 96.2 mol% of ethylene, and 2.7 mol% of ethyl acrylate was used. Hereinafter, it is referred to as d-6.

(E) Vinyl Copolymer A copolymer comprising 60.5 mol% of styrene and 39.5 mol% of acrylonitrile was used. Hereinafter, this is referred to as e-1.

Examples 1 to 18 (A) maleimide copolymer, (B) graft copolymer, (C) polyamide so that the total amount was 8 kg at the mixing ratio (% by weight) shown in Tables 2 and 3. The resin, the (D) acrylate copolymer, and the (E) vinyl copolymer were charged into a 20-liter Henschel and blended.
It was extruded and pelletized at a temperature of 280 ° C. using an M35B extruder (manufactured by Toshiba Machine Co., Ltd., biaxial direction). Using these pellets, test pieces were prepared by an injection molding machine, and various physical properties were measured. The results are shown in Tables 2 and 3.

Comparative Examples 1 to 16 (A) Maleimide copolymer, (B) Graft copolymer, (C) Polyamide so that the total amount was 8 kg at the mixing ratio (% by weight) shown in Tables 4 and 5. The resin, the (D) acrylate copolymer, and the (E) vinyl copolymer were charged into a 20-liter Henschel and blended.
It was extruded and pelletized at a temperature of 280 ° C. using an M35B extruder (manufactured by Toshiba Machine Co., Ltd., biaxial direction). Using these pellets, test pieces were prepared by an injection molding machine, and various physical properties were measured. Tables 4 and 5 show the results.

In Comparative Examples 1 and 2, the amount of the unsaturated dicarboxylic anhydride monomer group in the maleimide-based copolymer (A) was out of the range. In Comparative Examples 3 and 4, the amount of the rubbery polymer in the (B) graft copolymer was out of the range. Comparative Examples 5 and 6
(D) The amount of the unsaturated dicarboxylic acid and / or its anhydride monomer group in the acrylate copolymer is out of the range. In Comparative Examples 7 and 8, the amount of the olefin monomer group or the acrylate monomer group in the (D) acrylate copolymer was out of the range. Comparative Examples 9 and 10
(A) The content of the maleimide-based copolymer is out of the range. In Comparative Examples 11 and 12, the content of (B) the graft copolymer was out of the range. In Comparative Examples 13 and 14, the content of the polyamide resin (C) was out of the range. Comparative Examples 15 and 16 are (D)
This is an example in which the content of the acrylate copolymer is out of the range.

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5]

The physical properties in Tables 2 to 5 were measured by the following methods. (1) The heat resistance was measured at a heat deformation temperature (HD) of 1/4 kg / cm ² using a 1/4 "thick injection molded product molded at a molding temperature of 260 ° C. in accordance with ASTM D-648.
T) was measured (no annealing).

(2) The impact strength was measured according to ASTM D-256.
Notched Izod impact strength (IZO) using a 1/4 "thick injection molded product molded at a molding temperature of 260 ° C.
D) was measured.

(3) The flowability was determined according to ASTM D-1238.
The melt flow rate (MFR) was measured at a temperature of 265 ° C. and a load of 10 kg according to.

(4) The chemical resistance was 330 × 2
0x2mm, major radius 248mm, minor radius 148mm
The critical strain amount after 48 hours at a temperature of 23 ° C. was measured by the 楕 円 ellipse method. In addition, in order to eliminate the influence of molding distortion, the test piece was formed by pressing a pellet at a temperature of 260 ° C. and cut out. Gasoline and methanol were used as chemicals.

(5) Dimensional stability is as per ASTM D-63
According to No. 8, the No. 1 dumbbell molded at a molding temperature of 260 ° C. was immersed in warm water of 80 ° C. for 24 hours, and the longitudinal dimensional change of the dumbbell before and after immersion was measured. The case where the dimensional change rate was 0.5% or less was evaluated as ○, and the case where it exceeded 0.5% was evaluated as ×.

(6) Appearance was measured using a 5 ounce injection molding machine. The molded product was a square plate having a length of 127 mm, a width of 127 mm, and a thickness of 2 mm, and a boss (having an opening) at the center of the back surface. Was molded at a molding temperature of 260 ° C. with a side gate (2 points), and the molded product was visually evaluated. A molded product having no defective phenomenon (flow mark, silver stripe, flash) on the surface is indicated by ○, and a defective phenomenon (flow mark, silver stripe,
A molded product in which flash was generated was evaluated as x.

From the results of the examples and comparative examples, it is found that the maleimide copolymer (A) in the thermoplastic resin composition contains 30 to 70 mol% of an aromatic vinyl monomer group and 25 to 25% of a maleimide monomer group. 50 mol%, 1 to 30 mol% of unsaturated dicarboxylic anhydride monomer groups and 0 to 40 mol% of other copolymerizable vinyl monomer groups.
And the graft copolymer (B) is composed of 35 to 65 parts by weight of the rubbery polymer and 35 to 65 parts by weight of the aromatic vinyl monomer 35.
７０70 mol%, 30 to 60 mol% of vinyl cyanide monomer, and 0 to 30 of vinyl monomer copolymerizable therewith.
35 to 65 parts by weight of a monomer mixture consisting of mol% is composed of a graft-polymerized polymer, and the content of itself is 10 to
50% by weight, and the content of the polyamide resin (C) is 3
-20% by weight, and (D) the acrylate-based copolymer contains 0.1 to 10% by mole of unsaturated dicarboxylic acid and / or anhydride monomer group, and 30 to 94% of olefin monomer group. Mol%, acrylic acid ester monomer group 5-6
9 to 20 mol%, and 0 to 20 mol% of other copolymerizable vinyl monomer groups.
(E) 35 to 70 mol% of an aromatic vinyl monomer group and 30 to 6
Heat resistance, impact resistance, moldability only when the vinyl copolymer comprising 0 mol% and 0-30 mol% of other copolymerizable vinyl monomer groups is 0-50 wt%. It can be seen that the chemical resistance, dimensional stability and appearance of the molded product are excellent.

[0078]

As described above, a maleimide-based copolymer, a graft copolymer, a polyamide resin containing a specific proportion of maleimide-based monomer groups and unsaturated dicarboxylic anhydride monomer groups, and The thermoplastic resin composition containing an acrylic acid ester copolymer having an unsaturated dicarboxylic acid and / or an anhydride monomer group in an essential component at a ratio of, and blending these at a specific ratio, has heat resistance and resistance to heat. It can be seen that the impact resistance, chemical resistance, dimensional stability, moldability, and appearance of the molded product are excellent. Therefore, the thermoplastic composition of the present invention, automotive parts, electric and electronic parts, office equipment parts, heating appliances such as electric rice cookers, microwave ovens, microwave ovens, tableware, electric refrigerator parts, bathtub parts, shower parts, The industrial utility value is extremely large as a material for water purifier parts, toilet seats and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 77/00 C08L 77/00 F term (reference) 4J002 BB044 BB074 BB114 BC065 BG044 BG054 BG064 BH01W BN06X BN12X BN15X BN16X BN21 CL013 CL033 FA040 FD010

Claims (1)

[Claims] (A) an aromatic vinyl monomer group of 30 to 70
Mol%, maleimide monomer groups 25 to 50 mol%, unsaturated dicarboxylic anhydride monomer groups 1 to 30 mol%, and other copolymerizable vinyl monomer groups 0 to 40 mol%. The aromatic vinyl monomer 3 was added to 5 to 55% by weight of the maleimide copolymer and 35 to 65 parts by weight of the rubbery polymer (B).
5 to 70 mol%, 30 to 60 mol% of a vinyl cyanide monomer, and 0 to 30 of a vinyl monomer copolymerizable therewith.
10 to 50% by weight of a graft copolymer obtained by graft polymerization of 35 to 65 parts by weight of a monomer mixture consisting of
(C) 3 to 20% by weight of a polyamide resin, (D) 0.1 to 10% of an unsaturated dicarboxylic acid and / or an anhydride monomer group thereof.
Acrylic ester comprising 10 mol%, 30 to 94 mol% of olefin monomer groups, 5 to 69 mol% of acrylate monomer groups, and 0 to 20 mol% of other copolymerizable vinyl monomer groups 2 to 12% by weight of a copolymer, (E) 35 to 70% by mole of an aromatic vinyl monomer group, 30 to 60% by mole of a vinyl cyanide monomer group, and other copolymerizable vinyl monomers A thermoplastic resin composition comprising, as an active ingredient, 0 to 50% by weight of a vinyl copolymer comprising 0 to 30% by mole of a base group.