JPH06883B2 - Heat resistant resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a heat-resistant thermoplastic resin composition containing an imidized copolymer having improved impact resistance. It can be preferably used for electronic parts, office equipment parts, household electric parts, medical equipment parts, camera parts and the like.

(Prior Art) Conventionally, a method for producing a copolymer comprising an aromatic vinyl monomer, maleic anhydride and another vinyl monomer (Japanese Patent Publication No. Sho 40).
-15,829, JP-B-45-31,953, and JP-B-49-10,156) are known. Further, a method for producing a thermoplastic copolymer having improved impact resistance by graft-polymerizing an aromatic vinyl monomer, maleic anhydride and a vinyl monomer copolymerizable therewith with a rubber-like polymer has also been proposed. There is. (JP-A-48-42,091, JP-A-49)
-28,693, JP-A-53-78,252, JP-A-53-80490) However, the polymers obtained by copolymerizing these maleic anhydrides have a high heat distortion temperature. Has insufficient impact resistance, and the copolymer is easily decomposed by hot water,
In addition, it has a drawback that it easily gels and foams due to heat, so there are significant restrictions on injection or extrusion processing, and mechanical properties when the processed product is contacted with water or steam or exposed to high temperatures. In particular, there is a drawback that the impact resistance is lowered.

For the purpose of improving these drawbacks, a method and a composition for producing a copolymer in which maleic anhydride is replaced with a maleimide derivative have also been proposed. (USP 3,651,171, USP
No. 3,652,726, JP-A-57-98,536) (Problems to be solved by the invention) However, although these copolymers or compositions are improved in heat stability and hot water resistance, they are still resistant. It has the drawback of insufficient impact resistance.

(Means for Solving the Problems) The present invention solves the above-mentioned drawbacks, that is, an aromatic vinyl monomer in the presence of a copolymer containing an aromatic vinyl / vinyl cyanide monomer residue, Improving impact resistance as well as heat resistance by using an imidized acid anhydride group copolymer of unsaturated dicarboxylic acid anhydride and copolymerizable vinyl monomer It is intended to provide a composition.

That is, the present invention comprises: Component A: 0 to 40 parts by weight of a rubbery polymer, 40 to 80% by weight of an aromatic vinyl monomer residue, 15 to 40% by weight of a vinyl cyanide monomer residue, and a copolymerization thereof. Copolymers 3 to 50 consisting of 0 to 40% by weight of possible vinyl monomer residues
Aromatic vinyl monomers, unsaturated dicarboxylic acid anhydrides and vinyl monomers copolymerizable with them, if necessary, are polymerized in the presence of parts by weight, and the total of the monomer residues is 30.
10 to 90 parts by weight of an imidized copolymer having an imide group obtained by reacting ammonia and / or a primary amine with the copolymer, which is ˜97 parts by weight, and component B: a rubbery polymer 3 to 70% by weight. A graft copolymer comprising 30 to 80% by weight of an aromatic vinyl monomer residue, 0 to 40% by weight of a vinyl cyanide monomer residue, and 0 to 40% by weight of a vinyl monomer residue copolymerizable therewith. Polymer 0-9
0 parts by weight, C component: 40 to 90% by weight of aromatic vinyl monomer residue, 0 to 40% by weight of vinyl cyanide monomer residue, and 0 to 0% of vinyl monomer residue copolymerizable therewith It is a thermoplastic resin composition containing 0 to 90 parts by weight of a copolymer consisting of 40% by weight.

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

As the method for producing the component A, an aromatic vinyl monomer and an unsaturated dicarboxylic acid are added in the presence of a copolymer containing an aromatic vinyl monomer residue and a vinyl cyanide monomer residue and, if necessary, a rubbery polymer. A polymer obtained by polymerizing a mixture of an anhydride and a vinyl monomer copolymerizable therewith, which is further added if necessary, is reacted with ammonia and / or a primary amine to imidize part or all of the acid anhydride group. A method of obtaining an imidized copolymer by converting it into a group is used.

The copolymer containing an aromatic vinyl monomer residue and a vinyl cyanide monomer residue used in the production of the component A copolymer is a styrene-acrylonitrile copolymer or a styrene-acrylonitrile-methyl methacrylate copolymer. , Styrene-α-methylstyrene-acrylonitrile copolymer, α-methylstyrene-acrylonitrile copolymer and the like.

The rubbery polymer may be a butadiene polymer, a copolymer of butadiene and a vinyl monomer copolymerizable therewith, an ethylene-propylene copolymer, an ethylene-propylene-polymer.
Diene copolymers, block copolymers of butadiene and aromatic vinyl, acrylic acid ester polymers, and copolymers of acrylic acid esters and vinyl monomers copolymerizable therewith are used.

Styrene, α-methylstyrene, vinyltoluene, as an aromatic vinyl monomer that is polymerized in the presence of a copolymer containing an aromatic vinyl monomer residue and a vinyl cyanide monomer residue,
There are styrene monomers such as t-butylstyrene and chlorostyrene and substituted monomers thereof, and among these, styrene is particularly preferable.

Examples of unsaturated dicarboxylic 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. , Methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amide, methacrylic acid amide, and the like, among which acrylonitrile, Monomers such as methacrylic acid ester, acrylic acid and methacrylic acid are preferred.

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

Further, 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 when it is carried out in a bulk molten state, an extruder equipped with a devolatilization device is used. Good. A solvent 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.

The amount of ammonia and / or primary amine used is preferably 0.8 to 1.05 molar equivalent, particularly 0.9 to 1.0 molar equivalent, based on the unsaturated dicarboxylic acid anhydride. If it is less than 0.8 molar equivalent, the imidized copolymer will have a large amount of acid anhydride groups, and the thermal stability and the hot water resistance will decrease, which is not preferable.

The rubber-like polymer as the component A is 0 to 40 parts by weight, preferably 0.
To 30 parts by weight, and aromatic vinyl monomer residues 40 to 8
0% by weight, vinyl cyanide monomer residue 15-40% by weight
And vinyl monomer residues 0 to 40 copolymerizable therewith
The copolymer composed of wt% is 3 to 50 parts by weight, preferably 5 to 30 parts by weight. When the amount of the rubber-like polymer exceeds 40 parts by weight, heat resistance, moldability and dimensional stability are impaired. If the amount of the copolymer containing the aromatic vinyl monomer residue and the vinyl cyanide monomer residue is less than 3 parts by weight, the impact resistance is not sufficiently improved, while if it exceeds 40 parts by weight, the heat resistance is impaired. Be done. The total of the monomer residues to be polymerized in these polymers is 30 to 97 parts by weight, and the composition of the monomer residues is 30 to 90% by weight of aromatic vinyl monomer residues and unsaturated dicarboxylic acid anhydride. 10 to 50% by weight of the compound residue and 0 to 40% by weight of the vinyl monomer residue copolymerizable therewith.

Next, the component B and its manufacturing method will be described. The rubber-like polymer used as the component B is a polymer composed of a vinyl monomer which is homopolymerizable with butadiene or copolymers thereof, ethylene-
There are propylene copolymers, ethylene-propylene-diene copolymers, and polymers of acrylic acid ester homopolymers or vinyl monomers copolymerizable therewith.

The aromatic vinyl monomer used as the component B is a styrene monomer such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, or a substituted monomer thereof. And α-
Monomers such as methylstyrene are particularly preferred.

Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc., and acrylonitrile is particularly preferable. Further, as vinyl monomers copolymerizable with these, acrylic acid esters such as methyl acrylic acid ester, ethyl acrylic acid ester, butyl acrylic acid ester, etc., methacrylic acid ester such as methyl methacrylic acid ester, ethyl methacrylic acid ester, etc. Body, vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amide, and methacrylic acid amide. Of these, methyl methacrylic acid ester and acrylic acid methacrylic acid are particularly preferable.

The method for producing the graft copolymer of the component B is rubber-like polymer 3 to
Amount consisting of 30-80% by weight of aromatic vinyl monomer, 0-40% by weight of vinyl cyanide monomer and 0-40% by weight of vinyl monomer copolymerizable with these in the presence of 70% by weight. It is obtained by graft copolymerizing a body mixture. Polymerization
Any known polymerization technique can be adopted, for example,
Aqueous heterogeneous polymerization such as suspension polymerization and emulsion polymerization, bulk polymerization,
There are solution polymerization and precipitation polymerization of the produced polymer in a non-solvent.

Emulsion polymerization is particularly preferable because the rubber particle size can be easily controlled.

Further, the copolymer which can be used as the component C preferably has good compatibility with the imidized copolymer which is the component A and the graft copolymer which is the component B.

The aromatic vinyl monomer used as the C component is a styrene monomer such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, or chlorostyrene and a substituted monomer thereof. And α-
Methylstyrene is especially preferred.

Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc., and acrylonitrile is particularly preferable.

Examples of vinyl monomers copolymerizable with them include acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester, and butyl acrylic acid ester, and methacrylic acid ester such as methyl methacrylic acid ester and ethyl methacrylic acid ester. Examples thereof include monomers, vinylcarboxylic acid monomers such as acrylic acid and methacrylic acid, acrylic acid amides, methacrylic acid amides, acenaphthylene, N-vinylcarbazole, N-alkyl-substituted maleimides, and N-aromatic-substituted maleimides.

In the present invention, the ratio of A component, B component and C component is A
Component 10 to 90 parts by weight, preferably 20 to 60 parts by weight, component B 0 to 90 parts by weight, preferably 10 to 60 parts by weight, component C 0 to 90 parts by weight, preferably 0 to 60 parts by weight. Is. If the amount of the component A is less than 10 parts by weight, the effect of improving heat resistance is insufficient. On the other hand, when the amount of the component A exceeds 90 parts by weight, the impact resistance decreases and the formability also deteriorates. The component B may be 0 part by weight, but when impact resistance is more required, it is preferably used in an amount of 10 parts by weight or more. On the other hand, the B component is 9
If it exceeds 0 parts by weight, heat resistance is impaired. If the amount of C component also exceeds 90 parts by weight, the heat resistance of the present composition will be impaired as well.

In the present invention, in addition to the components A, B and C, usual additives and reinforcing agents such as stabilizers, lubricants, plasticizers, fillers, colorants, ultraviolet absorbers, flame retardants, glass fibers, carbon fibers, etc. It can be blended.

There is no particular limitation on the method of blending the resin composition of the present invention,
Known means can be used. Examples of the means include a Banbury mixer, a tumbler mixer, a Henschel mixer, a mixing roll, a single-screw or twin-screw extruder, and the like. As the mixing form, there are methods such as ordinary melt mixing, multi-step melt kneading using a master pellet, etc., solution blending, or mixing in a reaction solution to obtain the composition.

(Example) All parts and% in the examples are represented by weight.

Experimental Examples 1 to 3 Polymers obtained by imidizing a copolymer obtained by polymerizing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride in the presence of a rubbery polymer and an aromatic vinyl-cyanide vinyl copolymer. Manufacturing of.

Experimental Example 1 100 parts of styrene in an autoclave equipped with a stirrer,
100 parts of methyl ethyl ketone, 25 parts of polybutadiene cut into small pieces, and 13 parts of an aromatic vinyl-vinyl cyanide copolymer (AS-S manufactured by Denki Kagaku Kogyo Co., Ltd., hereinafter referred to as AS) were charged, and the inside of the system was charged. After purging with nitrogen gas, the mixture was stirred overnight at room temperature to dissolve rubber and AS.
After adjusting the temperature to 85 ° C., 67 parts of maleic anhydride and 0.2 part of benzoyl peroxide are added to 100 parts of methyl ethyl ketone.
The solution dissolved in 1 part was continuously added in 6 hours. The temperature was kept at 85 ° C. for a further 4 hours after the addition. As a result of sampling a part of the viscous reaction liquid and quantifying the unreacted monomer by gas chromatography, the polymerization rate was 97%. To the copolymer solution obtained here, 63.6 parts of aniline and 0.5 parts of triethylamine, which are equivalent to maleic anhydride, were added and reacted at 140 ° C. for 6 hours. Methyl ethyl ketone (150 parts) was added to the reaction solution, cooled to room temperature, poured into 1,000 parts of vigorously stirred methanol, precipitated, filtered and dried to obtain an imidized polymer. From the C ₁₃ NMR analysis, the conversion rate of acid anhydride groups to imide groups was 97%. A-
It was set to 1.

As the polybutadiene rubber in the text, Asahi Kasei Gen NF55AS was used.

(Experimental example 2) Except that the AS addition amount of 13 parts of Experimental example-1 was changed to 25 parts,
The same thing as Experimental Example 1 was performed. The polymerization rate of the copolymer is 9
6% and the conversion rate to an imide group was 97%. This polymer was designated as A-2.

(Experimental Example 3) The same operation as in Experimental Example 1 was performed except that the AS addition amount of 13 parts in Experimental Example-1 was changed to 13 parts of HAS obtained in Experimental Example-11. The polymerization rate of the copolymer was 98%, and the conversion rate to an imide group was 98%. This polymer was designated as A-3.

Experimental Examples 4 to 5 Production of a polymer obtained by imidizing a copolymer obtained by polymerizing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride in the presence of an aromatic vinyl-cyanide copolymer.

(Experimental Example 4) 100 parts of styrene, 100 parts of methyl ethyl ketone, 25 parts of polybutadiene cut into small pieces and 13 parts of AS were charged into the autoclave of Experimental Example 1, and 100 parts of styrene and 100 parts of methyl ethyl ketone were charged into the autoclave.
Example, except that the parts and AS 25 parts were charged and replaced
Did the same as. The copolymerization rate was 98%, and the conversion rate to imide groups was 98%. A-
It was set to 4.

(Experimental example 5) Exactly the same thing was performed except having replaced AS25 part preparation of Experimental example-4 with AS54 part preparation. The polymerization rate of the copolymer was 96%, and the conversion rate to the imide group was 97%. This polymer was designated as A-5.

Experimental Example 6 A copolymer obtained by polymerizing an aromatic vinyl monomer, an unsaturated dicarboxylic acid and a vinyl monomer copolymerizable therewith in the presence of an aromatic vinyl-cyanide copolymer was imidized. Manufacture of coalescence.

100 parts of styrene in an autoclave equipped with a stirrer,
After 25 parts of acrylonitrile, 100 parts of methyl ethyl ketone and 22 parts of AS were charged and the system was replaced with nitrogen gas, the mixture was stirred overnight at room temperature to dissolve AS. Temperature 85
After the temperature was adjusted to ° C, a solution prepared by dissolving 42 parts of maleic anhydride and 0.2 part of benzoyl peroxide in 100 parts of methyl ethyl ketone was continuously added over 6 hours. The temperature was kept at 85 ° C. for a further 4 hours after the addition. The polymerization rate of this copolymer is 95
It was in%. 40 parts of aniline equivalent to maleic anhydride was added to the copolymer solution obtained here, and triethylamine was adjusted to 0.
5 parts was added and reacted at 140 ° C. for 6 hours. The subsequent operations were the same as in Experimental Example-1. The conversion rate of the obtained copolymer into imide groups was 97%. This polymer was designated as A-6.

Experimental Example 7 In Experimental Example-1, 100 parts of styrene, 100 parts of methyl ethyl ketone, 25 parts of polybutadiene cut into small pieces and 13 parts of an aromatic vinyl-vinyl cyanide copolymer were charged, and styrene 1 was added to the autoclave.
The same procedure as in Experimental Example 1 was carried out except that 00 parts, 100 parts of methyl ethyl ketone, and 25 parts of polybutadiene cut into small pieces were charged and replaced. The obtained copolymer had a polymerization rate of 98% and a conversion rate to an imide group of 98%.
This polymer was designated as A-7.

Experimental Example 8 100 parts of styrene in an autoclave equipped with a stirrer,
100 parts of methyl ethyl ketone was charged and the system was replaced with nitrogen gas. After adjusting the temperature to 85 ° C, maleic anhydride 6
A solution of 7 parts and 0.2 part of benzoyl peroxide dissolved in 100 parts of methyl ethyl ketone was continuously added over 6 hours. The subsequent operations were the same as in Experimental Example-1.
The obtained copolymer had a polymerization rate of 99% and a conversion rate to an imide group of 98%. This polymer was designated as A-8.

Experimental Example 9 100 parts of styrene in an autoclave equipped with a stirrer,
25 parts of acrylonitrile and 100 parts of methyl ethyl ketone were charged, and the system was replaced with nitrogen gas. Subsequent operations are
Exactly the same as Experimental example-6 was performed. The resulting copolymer had a polymerization rate of 96% and a conversion rate to an imide group of 98%. This polymer was designated as A-9.

Experimental Example 10 Acrylonitrile-butadiene-styrene copolymer (A
BS) Polybutadiene latex 80 parts (solid content 50%, average particle size 0.35μ, gel content 90%), sodium stearate 1 part, sodium formaldehyde sulfoxylate 0.1
Parts, tetrasodium ethylenediaminetetraacetic acid 0.03 parts, ferrous sulfate 0.003 parts and water 200 parts 6 parts
After heating to 5 ° C., 60 parts of a monomer mixture consisting of 30% acrylonitrile and 70% styrene, 0.3 part of t-dodecylmeralptan and 0.2 part of cumene hydroperoxide were continuously added over 4 hours, and after the addition was completed. 65
Polymerization was carried out at 0 ° C for 2 hours. The polymerization rate was 96%. An antioxidant was added to the obtained latex, coagulated with calcium chloride, washed with water and dried to obtain a white powdery polymer.
This is indicated as ABS.

Experimental Example 11 Production of α-methylstyrene-acrylonitrile copolymer 70 parts of α-methylstyrene, 20 parts of acrylonitrile, 12.5 parts of a 20% aqueous solution of sodium dodecylbenzenesulfonate, 0.05 parts of potassium chloride in a nitrogen-substituted polymerization solution.
After charging 0.5 part of t-dodecyl mercaptan and 213 parts of water and raising the temperature to 70 ° C., 6.7 parts of a 1% potassium persulfate aqueous solution was added to initiate polymerization. Also, after 6 hours, 3.3 parts of a 1% aqueous solution of potassium persulfate was added. After 1 hour from the initiation of polymerization, 10 parts of acrylonitrile was continuously added over 6 hours. The polymerization was stopped in 10 hours, and a latex having a final polymerization rate of 98.5% was obtained. The latex was coagulated with calcium chloride, washed with water, filtered and dried to obtain a white powdery copolymer. This is indicated as H-AS.

Examples 1 to 8 and Comparative Examples 1 to 6 Maleimide copolymers (A-1) prepared in Experimental Examples 1 to 9
To A-9) are the acrylonitrile-butanediene-styrene graft copolymer (ABS) obtained in Experimental Example 10.
And acrylonitrile-styrene copolymer (AS, manufactured by Denki Kagaku Kogyo Co., Ltd. AS-S) in the proportions shown in Table-1, and further added with 1 part of an antioxidant (Ciba Geigy, Irganox 1076). After mixing with a sill mixer, melt extrusion pelletization was performed with a 30 mmφ screw extruder equipped with a devolatilizer. The test pieces for evaluation of physical properties were injection-molded with an injection molding machine manufactured by Arburg Co., Ltd., and the measured values are shown in Table 1 together with the compounding ratio in accordance with the following test method.

Example 9 The same procedure as in the other examples was carried out except that 50 parts of the maleimide copolymer A-1 and 50 parts of the acrylonitrile-styrene copolymer AS-S were blended. The measured values are shown in the attached table.
1 together with the compounding ratio.

Comparative Example 7 The procedure of Comparative Example 7 was repeated, except that 50 parts of the maleimide copolymer A-7 and 50 parts of the acrylonitrile-styrene copolymer AS-S were blended. The measured values are shown in the attached table.
1 together with the compounding ratio.

Physical property measurement test method (1) Vicat softening temperature (VSP) Load 5 kg / cm ^{2 According to} ASTM D-1525.

(2) Izod impact strength Notched with 1/4 inch width, conforming to ASTM D-256.

(3) Drop weight impact strength Injection molding of 30 or more 8 cm × 8 cm × 0.1 cm test pieces at a molding temperature of 280 ° C. was performed according to JISK-7211, and 50
% Destruction energy was calculated.

(4) Melt flow index Temperature 280 ° C., load 5 kg, according to ASTM D-1238.

The meanings of the components -I, -II and -III of the component (A) in Table-1 are shown below.

Component-I is the total amount of the polymer obtained by imidizing a copolymer of an aromatic vinyl monomer, an unsaturated dicarboxylic acid anhydride, and a copolymerizable vinyl monomer.

Component-II refers to the amount of polybutadiene present during polymerization.

Component-III represents the amount of aromatic vinyl-vinyl cyanide copolymer present during polymerization.

(Effects of the Invention) As shown in Table 1, the imidized copolymer of the present invention has markedly improved impact strength. This is
The aromatic vinyl-cyanide vinyl copolymer in the component A is added during the graft polymerization so that the loss of heat resistance is small and the impact strength is effectively improved.

Claims (1)

[Claims] 1. Component A: 0 to 40 parts by weight of a rubbery polymer, 40 to 80% by weight of an aromatic vinyl monomer residue, 15 to 40% by weight of a vinyl cyanide monomer residue, and a copolymerization thereof. Aromatic vinyl monomer, unsaturated dicarboxylic acid anhydride and, if necessary, further copolymerizable with them in the presence of 3 to 50 parts by weight of a copolymer composed of 0 to 40% by weight of possible vinyl monomer residues. An imidized copolymer having an imide group obtained by polymerizing a vinyl monomer and reacting a copolymer having a total of 30 to 97 parts by weight of the monomer residues to be polymerized with ammonia and / or a primary amine. 10 to 90 parts by weight of the combined product, B component: 3 to 70% by weight of rubbery polymer, 30 to 80% by weight of aromatic vinyl monomer residue, 0 to 40% by weight of vinyl cyanide monomer residue, and these 0-40 weight of vinyl monomer residue copolymerizable with % Graft copolymer 0-9
0 parts by weight, C component: 40 to 90% by weight of aromatic vinyl monomer residue, 0 to 40% by weight of vinyl cyanide monomer residue, and 0 to 0% of vinyl monomer residue copolymerizable therewith A thermoplastic resin composition containing 0 to 90 parts by weight of a 40% by weight copolymer and 100 parts by weight of A component + B component + C component.