JPH04136058A - Thermoplastic resin composition excellent in colorability and heat resistance - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition excellent in colorability, heat resistance, impact resistance and moldability by mixing a specified graft copolymer with polyglutarimide and a specified terpolymer. CONSTITUTION:A resin composition comprising 20-60wt.% graft copolymer prepared by polymerizing an aromatic vinyl compound, a vinyl cyanide compound and/or another vinyl compound copolymerizable therewith in the presence of a rubbery polymer, 10-70wt.% polyglutarimide and 10-70wt.% terpolymer comprising 40-80wt.% alpha-methylstyrene, 5-40wt.% acrylonitrile and 1-50wt.% imide compound of an alpha,beta-unsaturated dicarboxylic acid. A particularly desirable aromatic vinyl compound to be used is styrene. A particularly desirable vinyl cyanide compound to be used is acrylonitrile. A particularly desirable another vinyl compound is methyl methacrylate.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is directed to the coloring property and wear resistance of a graft copolymer, a polyimide, and a terpolymer having a specific composition. This invention relates to an excellent thermoplastic resin composition.

<Prior art and problems to be solved by the invention> Graft copolymers based on rubbery polymers or such graft copolymers and aromatic vinyl-vinyl cyanide/L/
Rubber-reinforced resins, which are mixtures with rubber-based copolymers, have excellent moldability, impact resistance, and chemical resistance, and also have a relatively good appearance, so they are used in a wide range of fields. However, on the other hand, it has the disadvantage of poor coloring properties.

As a method to improve the colorability of these rubber reinforced resins,
It has been proposed to blend a copolymer containing an unsaturated carboxylic acid alkyl ester compound as a main component into the graft copolymer resin; When a polymer is blended, there is a drawback that heat resistance is reduced.

On the other hand, as a conventional method for improving the heat resistance of rubber-reinforced resins, α-methylμ-nutylene-acrylonitrile copolymers and α-based graft copolymers have been used.

A method of blending an imide compound copolymer of β-unsaturated dicarboxylic acid is known.

Therefore, it is conceivable to further blend the above-mentioned heat-resistant copolymer into a rubber-reinforced resin made by blending an unsaturated carboxylic acid alkyl ether-based copolymer, but sufficient heat resistance cannot be obtained, and the coloring property is rather increased. decreases.

Means for Solving the Problems> The present inventors have worked diligently to improve both the colorability and heat resistance properties without sacrificing the impact resistance and moldability, which are the characteristics of rubber reinforced resins. As a result of our investigation, we found that by blending polyglutarimide and a ternary copolymer with a specific composition into a rubber-reinforced graft copolymer, colorability, heat resistance,
The present invention was achieved by discovering that a thermoplastic resin composition having excellent impact resistance and moldability can be obtained.

That is, the present invention provides a graft copolymer "(A)" which is obtained by polymerizing an aromatic vinyl compound, a vinyl cyanide compound, and/or another vinyl compound copolymerizable with these in the presence of a rubbery polymer. 20-60% by weight, 10-70% by weight of polyglutarimide (B) and 40-80% by weight of α-methylsulfate, 5-80% by weight of acrylonitrile.
The present invention provides a thermoplastic resin composition that is characterized by 40% by weight and α,β unsaturated dicarboxylic acid and has excellent colorability, heat resistance, impact resistance, and moldability.

The present invention will be explained in detail below.

- Graft copolymer (A) As the rubbery polymer constituting the graft copolymer (A) used in the present invention, polybutadiene, acrylonitrile-butadiene copolymer rubber (NBR), nutylene-butadiene copolymer Diene rubber such as rubber (SBR),
Acrylic rubbers such as polybutyl acrylate and polybutyl acrylate, and ethylene-propylene-diene rubber (EPDM) and ethylene-propylene rubber (EPR)
(7)-1-f-lene-propylene rubber, etc. are exemplified, and one or more types can be used.

Here, in the terpolymer ethylene-propylene-diene rubber (EPDM), non-conjugated cytosite compounds, synchlopentadiene, ethylidene turbornene, 1,4-hexadiene, 1,4-cycloheptadiene, l, 5- Examples include cyclooctadiene. The 7μ ratio of the binary copolymer ethylene-propylene rubber (EIIR) and the terpolymer ethylene-propylene-diene rubber (EPDM) can range from 52 l to l23. preferable. Also, terpolymer ethylene
In propylene-diene rubber (EPDM), it is preferable that the proportion of non-conjugated diene is in the range of 2 to 50 in terms of iodine value.

Examples of aromatic vinyl compounds include styrene, α-methylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene,
- Methylstyrene, t-butylstyrene, α-methyl-vinyltoluene, dimethylstyrene, chlorstyrene, diglomostyrene, bromstyrene, diglomostyrene,
Examples include vinylnaphthalene, and one or more types can be used. Among these, styrene is particularly preferred.

Examples of vinyl cyanide compounds include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, and mercury.
to ! Jt and the like are exemplified, and one type or two or more types can be used. Among these, acrylonitrile is particularly preferred.

Examples of other vinyl compounds that can be copolymerized with these include unsaturated carboxylic acid alkyl ester compounds such as methyl acrylate and methyl methacrylate, and one or more of them can be used. Among these, methyl methacrylate is particularly preferred.

There is no particular restriction on the composition ratio of the rubbery polymer and the above compound in the graft copolymer (A), but rubbery polymer 1
0-80% by weight and 90-20% by weight of compounds (total)
It is preferable that In addition, there is no particular restriction on the composition ratio of the aromatic vinyl compound, vinyl cyanide compound, and other vinyl 1v compounds copolymerizable with these in the compound; Preferably, the content is 50 to 20% by weight of the vinyl compound and 0 to 50% by weight of other vinyl compounds copolymerizable therewith.

The graft copolymer (A) obtained by polymerizing such a compound in the presence of a diene rubber can be obtained by a known polymerization method, such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, etc. .

- Polyglutarimide (B) Polyglutarimide (B) used in the present invention is a polymer or copolymer containing a cyclic imide unit represented by the following formula (I).

Particularly preferred are polymers or copolymers containing 5% by weight or more of cyclic imide units.

However, R1, R2 and R8 in the formula each represent hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or an aryμ group. Any polyglutarimide having any chemical structure can be applied to the present invention as long as it contains the above-mentioned cyclic imide unit, but usually R1 and R2 in the above-mentioned cyclic imide unit are hydrogen or methyl groups,
Those in which R8 is hydrogen, methyl group, ethyl group, propyl group, ethyl group or phenyl group are used for boat fishing.

The method for producing polyglutarimide is not particularly limited, but for example, an unsaturated carboxylic acid alkyl ester compound copolymer is reacted with ammonia or a primary amine such as methylamine or ethylamine in an extruder to form a glutarimide ring. A method of forming is useful.

-Terpolymer (C) The copolymer (C) used in the present invention is a terpolymer of α-methylstyrene, acrylonitrile, and an imide compound of α, β-unsaturated dicarboxylic acid; The copolymer composition is 40-80% by weight of α-methylstyrene, acrylonitrile)! It is important that the amount of J# is 5 to 40% by weight and the imide compound of α,β unsaturated dicarboxylic acid is 1 to 50% by weight. Polymers outside this range cannot achieve the purpose of the present invention.

Here, as an imide compound of α,β-unsaturated dicarboxylic acid, the following formula % formula % (in the formula, R1, R2, R8 are hydrogen, 7μ key group, 7/l/
Indicates a carbonyl group, a cycloalkyl group, a phenyl group, a phenylene group, an alkylene group, etc. ). Specific examples of the compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-(p-methylamine/I/)maleimide, N-(p- Hydroxyphenylene/I/)maleimide, N-(8,5-cimicylpheny/I/)maleimide, N-(p-methoxyphenylene/l)
/) maleimide, N-benzylmaleimide, N-(1-
Examples include naphthi IV)-maleimide and N-hydroxyethylmaleimide. These may be used alone or in combination of two or more. Preferred among these compounds are N-phenylmaleimide and N-cyclohexylmaleimide.

When the copolymerization amount of α-methylstyrene is less than 40% by weight,
The heat resistance of the resulting composition decreases, and conversely, if it exceeds 80% by weight, the impact resistance and melt flowability of the composition decrease. Furthermore, if the copolymerized amount of acrylonitrile is less than 5% by weight, the resulting composition will have poor mechanical properties, and if it exceeds 40% by weight, the composition will become colored and its heat resistance will deteriorate. Furthermore, if the amount of copolymerized imide compound of unsaturated dicarboxylic acid is less than 1% by weight, the heat resistance of the composition will decrease, and if it exceeds 50% by weight, the impact resistance and melt flowability of the composition will decrease, The intended effect of the invention cannot be obtained.

A good balance between colorability, heat resistance, and impact resistance, especially α-
Methylstyrene 50-75% by weight, acrylonitrile/l
Preference is given to terpolymers of 10 to 30% by weight and 5 to 3% by weight of imide compounds of unsaturated dicarboxylic acids.

Moreover, the above-mentioned terpolymer (C) can be obtained by a known polymerization method, such as an emulsion polymerization method, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or a polymerization method using a combination thereof.

・Final composition The thermoplastic resin composition of the present invention contains 20 to 60% by weight of the above-mentioned graft copolymer (A) and 1% by weight of polyglutarimide (B).
0 to 70% by weight and 10 to 70% by weight of the terpolymer (C).

If the amount of the graft copolymer (A) is less than 20% by weight, the impact resistance will be poor, and if it exceeds 60% by weight, the colorability and moldability will be poor. If the content of polyglutarimide (B) is less than 10% by weight, coloring properties will be poor, and if it exceeds 70% by weight, impact resistance and moldability will decrease. Terpolymer (C) is 10% by weight
If it is less than 70% by weight, heat resistance will decrease, and if it exceeds 70% by weight, colorability and moldability will decrease.

Preferably, the content is 20 to 50% by weight of the graft copolymer (A), 10 to 60% by weight of the polyglutarimide, and 20 to 50% by weight of the terpolymer (C). Particularly preferred is a composition in which the content of rubber derived from the graft copolymer (A) is 3 to 25% by weight.

There are no restrictions on the method of mixing the graft copolymer (A), polyglutarimide (B) and terpolymer (C), and the mixing can be carried out using a known mixer. Further, at the time of mixing, it is also possible to mix well-known additives such as dyes and pigments, stabilizers, plasticizers, antistatic agents, ultraviolet absorbers, lubricants, fillers, etc., if necessary.

EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these in any way.

Reference example> Production of graft copolymer (A-1 to A-2)> A-1 = In the presence of 50 parts by weight of polybutadiene rubber, styrene 3
A graft copolymer (Al) was prepared by polymerizing 8 parts by weight and 12 parts by weight of acrylonitrile.

A-2 = ethylene-propylene-diene thread rubber (iodine value 8.5
, Mooney viscosity 61, propylene content 43% by weight, diene component diethylidenenorbornene) in the presence of 50 parts by weight, 33 parts by weight of styrene and 17 parts by weight of acrylonitrile were polymerized to prepare a graft copolymer (A-2). did.

Production of polyglutarimide (B-1-2)> Methyl methacrylate 95% by weight, ethyl acrylate 5% by weight
A pellet of the copolymer was charged into an extruder together with ammonia or methylamine, and extrusion was performed at a resin temperature of 280°C while degassing the generated gas from an exhaust port attached to the extruder. Two types of polyglutarimide were prepared.

Production of ternary copolymer (C-1-C-6)> α-methylstyrene, styrene, acrylonitrile/l/, N-phenylmaleimide, and methyl methacrylate were copolymerized to produce the composition shown in Table 2. Lower margin of 04 binary or ternary copolymers (Examples and comparative examples) The graft copolymer, polyglutarimide and tertiary copolymer were blended in the ratio shown in Table 3, and After melt extrusion, various physical properties were obtained from the test pieces obtained by injection molding.

Pigment formulation (per 100 parts by weight of resin composition) Red: 0.2 parts by weight of Nichrome Phthalate Blue: Ultramarine 52000 0.2 parts by weight Black
k: 0.9 parts by weight of carbon #45 The blending ratio, colorability, heat distortion temperature, Izot impact strength and processability of the composition are shown in Table 3.

Below margin *1 Visually judge sharpness and jet blackness ○ (good), △
(slightly good), × (bad) *fl 1/4', no Annie y, 18.564/-
*3 V notch, 1/4'23℃ (Ij-cWI/i)
*4 Koka type 70-250℃, 60h/cd (cc/
m) <Effects of the Invention> The composition of the present invention, which is composed of a Gofuft copolymer resin, polyglutalimide, and a terpolymer of a specific composition, has significantly superior coloring properties, heat resistance, and heat resistance compared to conventional compositions. r# Impact resistance and moldability.

Claims (1)

[Claims] A graft copolymer (A) obtained by polymerizing an aromatic vinyl compound, a vinyl cyanide compound, and/or another vinyl compound copolymerizable with these in the presence of a rubbery polymer.
20-60% by weight, polyglutarimide (B) 10-7
0% by weight and α-methylstyrene 40-80% by weight
, a terpolymer (C) consisting of 5 to 40% by weight of acrylonitrile and 1 to 50% by weight of an imide compound of an α,β unsaturated dicarboxylic acid (C) 10 to 70% by weight. A thermoplastic resin composition with excellent properties.