JPH0611833B2 - Transparent and heat resistant thermoplastic resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition which is transparent and has excellent heat resistance, and the composition of the present invention relates to automobiles, home appliances, precision instruments and the like. Can be used as a material for the equipment or parts thereof.

(Prior Art) A composition comprising a copolymer of an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride and a polycarbonate resin has been known (Japanese Patent Publication No. 57-27133). A composition comprising a copolymer of a rubber-modified aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride and a polycarbonate resin has also been proposed for the purpose of improving impact strength (JP-A-56-92950). .

However, the composition of the copolymer obtained by copolymerizing these unsaturated dicarboxylic acid anhydrides and the polycarbonate resin has an acid anhydride group derived from the unsaturated dicarboxylic acid anhydride in the copolymer chain, and therefore, at a high temperature. Of course, it easily decomposes due to chemical changes not only with water but also with heat, and is subject to significant restrictions during injection or extrusion processing. Also, the processed product is exposed to water or steam or exposed to high temperatures. However, there is a drawback that the mechanical properties are deteriorated. Polycarbonate resin has excellent mechanical and thermal properties, but it has been pointed out that it has a high melt viscosity, poor moldability and poor oil resistance and hot water resistance. When manufacturing, high injection pressure and high molding temperature are required, which causes molding distortion and thermal deterioration. When the molded product is immersed in oil such as gasoline or brake oil or boiling water, cracking occurs and the strength is remarkably reduced.

(Problems to be Solved by the Invention and Means for Solving the Problems) As a result of repeated studies to solve the above-mentioned drawbacks, the present invention shows that heat resistance and transparency are improved by mixing an unsaturated dicarboxylic acid imide derivative with an epoxy resin and a polycarbonate resin. A composition having excellent properties is obtained, and the unsaturated dicarboxylic acid anhydride monomer residue 1-2 present in the imidized copolymer is obtained.
By reacting 0% by weight with the epoxy resin, the impact resistance could be improved significantly. Furthermore, they have succeeded in improving the drawbacks of the polycarbonate resin, such as poor oil resistance, hot water resistance and moldability.

That is, the present invention comprises: Component A: aromatic vinyl monomer residue 30 to 90% by weight, unsaturated dicarboxylic acid imide derivative residue 3 to 70% by weight, unsaturated dicarboxylic acid anhydride monomer residue 1 to 20. 5 to 70% by weight of an imidized copolymer composed of 0 to 40% by weight of vinyl monomer residues other than the above groups, B component: 0.1 to 20% by weight of epoxy resin, and C component: Polycarbonate resin 94.9-15% by weight
And a transparent thermoplastic resin composition having heat resistance.

The imidized copolymer of the component A and its manufacturing method will be described.

As the method for producing the component A copolymer, the first production method is an aromatic vinyl monomer, an unsaturated dicarboxylic acid imide derivative, an unsaturated dicarboxylic acid anhydride monomer, and a vinyl monomer copolymerizable therewith. A method of copolymerizing the mixture, and as a second production method, an aromatic vinyl monomer, an unsaturated dicarboxylic acid anhydride, and a polymer obtained by copolymerizing a vinyl monomer mixture copolymerizable therewith 0.
Examples thereof include a method of reacting 8 to 0.99 molar equivalents of ammonia and / or a primary amine to convert an acid anhydride group into an imide group, and any method can give an imidized polymer. it can.

As the aromatic vinyl monomer used in the first production method of the component A copolymer, styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and chlorostyrene, and substituted monomers thereof Among these, styrene is particularly preferable.

Maleimide as the unsaturated dicarboxylic acid imide derivative,
N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N
-Hydroxyphenyl maleimide, N-methoxyphenyl maleimide, N-chlorophenyl maleimide, N-carboxyphenyl maleimide, N-nitrophenyl maleimide, N-cyclohexyl maleimide, N-methyl imide and other maleimide derivatives, N-methyl Examples thereof include itaconic acid imide derivatives such as itaconic acid imide and N-phenylitaconic acid imide, and among these, N-phenylmaleimide is particularly preferable.

Examples of unsaturated dicarboic acid anhydrides include anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid.
Maleic anhydride is especially preferred.

As vinyl monomers copolymerizable with these, vinyl cyanide monomers such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile, and acrylic acid ester monomers such as methyl acrylic acid ester and ethyl acrylic acid ester. Acrylic acid ester monomers such as ester, methacrylic acid ester monomers such as methyl methacrylic acid ester, ethyl methacrylic acid ester, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amide, methacrylic acid amide, etc. Therefore, of these, monomers such as acrylonitrile, methacrylic acid ester, acrylic acid and methacrylic acid are preferable.

As the aromatic vinyl monomer, unsaturated dicarboxylic acid anhydride and vinyl monomer copolymerizable with these used in the second production method, those used in the first production method can be used.

Further, the ammonia and the primary amine used in the imidization reaction may be in either anhydrous or aqueous solution, and examples of the primary amine include methylamine, ethylamine,
Examples thereof include alkylamines such as butylamine and cyclohexylamine, and aromatic amines such as chloro- or bromine-substituted alkylamines, aniline, tolylamine, naphthylamine, and allogen-substituted aromatic amines such as chloro- or bromo-substituted aniline.

Furthermore, when the imidization reaction is carried out in a solution state or a suspension state, it is preferable to use an ordinary reaction vessel, for example, an autoclave, and the rate of carrying out in a bulk molten state can be obtained by using an extruder equipped with a devolatilization device. Good. A catalyst may be present during imidization, and for example, a tertiary amine or the like is preferably used.

The temperature of the imidization reaction is about 80 to 350 ° C, preferably 100 to 300 ° C.

When the temperature is lower than 80 ° C, the reaction rate is slow and the reaction requires a long time, which is not practical. On the other hand, when the temperature exceeds 350 ° C, the physical properties are deteriorated due to thermal decomposition of the polymer.

As the solvent for imidization in a solution state, there are acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, tetrahydrofuran, dimethylformamide and the like. Among these, methyl ethyl ketone and methyl isobutyl ketone are preferable. Particularly, the non-aqueous medium which is imidized in the non-aqueous medium in a substituted state includes aliphatic hydrocarbons such as hebutane, hexane, pentane, octane, 2-methylpentane, cyclopentane and cyclohexane.

The component A copolymer has an aromatic vinyl monomer residue of 30 to 90.
% By weight, preferably 40-70% by weight, unsaturated dicarboxylic acid imide derivative residue 3-70% by weight, preferably 10-6
0% by weight, unsaturated dicarboxylic acid anhydride monomer residues 1-2
0% by weight, preferably 2-15% by weight and vinyl monomer residues other than the above groups, 0-40% by weight, preferably 0-30
It is an imidized copolymer composed of wt%. When the amount of the aromatic vinyl monomer residue is less than 30% by weight, moldability and dimensional stability are impaired, and when it exceeds 90% by weight, impact strength and heat resistance are impaired. When the amount of the unsaturated dicarboxylic acid imide derivative residue is less than 3% by weight, the effect of improving the heat resistance is not sufficient, while when it exceeds 70% by weight, the resin composition becomes brittle and the moldability is remarkably deteriorated. If the amount of vinyl monomer residues other than these groups exceeds 40% by weight, dimensional stability and heat resistance are impaired.

The epoxy resin used for component B has the general formula [In the formula, R represents a hydrogen atom or a methyl group, and n is 0 to
It is a rational number of 100,000. ] Bisphenol type epoxy resin represented by [Wherein R represents a hydrogen atom or a methyl group, and R ′ represents C ₁ -R
₉ represents an alkyl group, and m is a rational number of 0 to 100. ] There is a novolak type epoxy resin represented by the following, and specific examples are bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, Heterocyclic epoxy resins, such as triglycidyl isocyanate and hydantoin epoxy resins,
Of hydrogenated bisphenol A type epoxy resin, epoxy resin obtained by reaction of aromatic or aliphatic or alicyclic carbamic acid with epichlorohydrin, spiro ring-containing epoxy resin, orthoallyl-phenol novolak compound and epichlorohydrin A glycidyl ether type epoxy resin which is a reaction product, a glycidyl ether type epoxy resin which is a reaction product of a diallyl bisphenol compound having an allyl group at an ortho position and epichlorohydrin and a halogen derivative thereof, each of which may be used alone or in a complex system. Used in.

The polycarbonate resin used for the C component is generally represented by the formula And has a repeating unit of, for example, a phosgene method or a transesterification method. Preferred as the polycarbonate resin are bis (hydroxyaryl) alkane-based polycarbonate resins such as bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane, 2,2-bis (4-hydroxy-)
It is obtained from bis (hydroxyaryl) alkane such as 3,5-dichlorophenylpropane or bis (4-hydroxyphenyl) phenylmethane and phosgene or diaryl carbonate, which may be used alone or in a mixture.

In the present invention, the proportions of the A component, B component and C component are: A component 5 to 70% by weight, preferably 10 to 60% by weight; B component 0.1 to 20% by weight, preferably 0.5 to 15%
% By weight; C component 94.9-15% by weight, preferably 89.5-
It is 20% by weight.

If the proportion of the component A is less than 5% by weight, the effect of improving heat resistance, oil resistance and hot water resistance is not sufficient, and if it exceeds 70% by weight, impact strength is lowered and moldability is deteriorated.

If the proportion of the component B is less than 0.1% by weight, the impact strength is not sufficiently improved, and if it exceeds 20% by weight, the heat resistance is lowered.

When the proportion of C component is less than 15% by weight, the impact strength is inferior.
If it exceeds 4.9% by weight, moldability, oil resistance and hot water resistance are deteriorated.

In the present invention, the mixing method of the components A, B and C is not particularly limited, and known means can be used. Examples of such means include a Banbury mixer, a tumbler mixer, a mixing roll, a single-screw or two-hour extruder.
As a mixing form, there are a usual melt mixing method, a multi-step melt kneading method using a master pellet, and a method of obtaining a composition by blending in a solution.

(Example) All parts and% in the examples are expressed on a weight basis.

Experimental Example (1) Production of a polymer obtained by imidizing a copolymer obtained by polymerizing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride 100 parts of styrene in an autoclave equipped with a stirrer,
And 50 parts of methyl isobutyl ketone were charged and the contents were replaced with nitrogen gas. After the temperature was raised to 83 ° C., a solution prepared by dissolving 67 parts of maleic anhydride and 0.2 part of benzoyl peroxide in 400 parts of methyl isobutyl ketone was added over 8 hours. A part of the viscous reaction liquid was sampled and the amount of unreacted monomer was quantified by gas chromatography. As a result, the polymerization rate was 99% for styrene and 99% for maleic anhydride. To the copolymer solution obtained here, 57.2 parts of aniline and 1 part of triethylamine, which are 0.9 molar equivalents to maleic anhydride, were added and reacted at 140 ° C. for 7 hours. The imidized polymer obtained by the degassing treatment is referred to as polymer A-1.

Experimental Example (2) Production of a polymer obtained by imidizing a copolymer obtained by polymerizing an aromatic vinyl, an unsaturated dicarboxylic acid, and a vinyl monomer copolymerizable therewith, instead of 100 parts of styrene in Experiment (1) Styrene 100
And 17 parts of acrylonitrile, maleic anhydride 6
The same operation as in Experimental Example (1) was carried out except that 7 parts was changed to 50 parts and 57.2 parts of aniline was changed to 42.7 parts to obtain an imidized polymer. This is designated as Polymer A-2. The polymerization rate of this polymer was 98% styrene and 98% maleic anhydride.

Experimental Example (3) Production of polymer composed of aromatic vinyl monomer and N-substituted maleimide 100 parts of styrene in an autoclave equipped with a stirrer,
After charging 50 parts of methyl isobutyl ketone and replacing the inside of the system with nitrogen, the temperature was raised to 83 ° C. and N-phenylmaleimide 85 was added.
Parts, 15 parts of maleic anhydride and 0.2 parts of benzoyl peroxide were dissolved in 400 parts of methyl isobutyl ketone in 8 hours, and the same operation as in Experimental Example (1) was performed to obtain a copolymer. Polymerization rate is 96% styrene, N-
It was 95% phenylmaleimide. This is polymer A-
Set to 3.

Example 1 135 parts of the polymer A obtained in Experimental Example (1), 5 parts of epoxy resin (Epicoat 1001 manufactured by Ciel Chemical Co., Ltd.) Polycarbonate resin (Panlite K-1 manufactured by Teijin Chemicals)
300 W) 60 parts were blended, and this blended product was blended with 30 parts.
It was extruded into pellets by a screen extruder equipped with a mmφ devolatilizer.

Examples 2 to 3 Example 1 was repeated except that the blend ratio of the polymer A-1, the epoxy resin and the polycarbonate resin was changed.

Examples 4 to 5 In the same manner as in Example 1 except that the polymer A-1 in Example 1 was replaced with the polymer A-2 in Experimental Example (2) and the polymer A-3 in Experimental Example (3). Done.

Comparative Example 1 In Example 1, only the polycarbonate resin was molded without using the polymer A-1.

Comparative Example 2 The procedure of Example 1 was repeated except that the styrene-maleic anhydride copolymer obtained in Experimental Example (1) was used without imidization.

Comparative Example 3 In Example 1, molding was performed using only the polymer A-1.

Comparative Example 4 Example 1 was repeated except that no epoxy resin was used.

The physical properties of the compositions obtained in the above Examples and Comparative Examples are shown in Table 1.

The physical properties were measured by the following methods.

(1) Bicat softening temperature: ASTM D-1 with 5 kg excess
According to 525.

(2) Izod impact strength: with notch, 1/4 inch,
According to ASTM D-256.

(3) Molding processability: “X” indicates that a molding temperature and / or injection pressure equal to or higher than that of the polycarbonate resin is required by performing the sharpening process with an injection molding machine.
Those that can be molded at a molding temperature and injection pressure lower than those of the polycarbonate resin are indicated by “◯”.

(4) Oil resistance: The test pieces were immersed in gasoline at room temperature for 24 hours, and those with cracking were indicated by "x", and those without cracking were indicated by "○".

(5) Hot water resistance: Test pieces were immersed in boiling water for 24 hours, and those with crack generation were indicated by "x", and those without crack generation were indicated by "○".

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display area C08L 69:00) 9363-4J (C08L 69/00 35:06 7921-4J 63:00) 8830- 4J

Claims (1)

[Claims] 1. Component A: aromatic vinyl monomer residue 30 to 9
0% by weight, unsaturated dicarboxylic acid imide derivative residues 3 to 7
0% by weight, unsaturated dicarboxylic acid anhydride monomer residues 1-2
0% by weight and 0 to 40 vinyl monomer residues other than the above groups
5 to 70% by weight of imidized copolymer consisting of 10% by weight, B component: 0.1 to 20% by weight of epoxy resin, C component: 94.9 to 15% by weight of polycarbonate resin
A transparent and heat-resistant thermoplastic resin composition comprising: