JPH07100755B2 - Thermoplastic resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition having excellent heat resistance, impact strength and hot water resistance. More specifically, it relates to a thermoplastic resin composition containing an imidized copolymer and a graft copolymer as essential components and further containing a thermoplastic polymer.

(Prior art and problems) So-called ABS resin obtained by graft-copolymerizing a mixture of styrene and acrylonitrile on a rubber-like polymer has been known, but has heat resistance, for example, low heat distortion temperature and large heat shrinkage. It has drawbacks, and for example, it is required to improve heat resistance in automobile parts and the like, and various improvement methods have been proposed.

For example, aromatic vinyl monomers and vinyl cyan monomers have N-
A resin composition comprising a copolymer containing an aromatic-substituted maleimide and a graft copolymer obtained by copolymerizing an aromatic vinyl monomer and a vinylcyan monomer in the presence of a conjugated diolefin rubber. Is proposed. (USP 3642
949) However, as the ratio of the N-aromatic substituted maleimide increases, the heat resistance of the resulting resin composition improves but the impact resistance decreases.

Further, a graft copolymer composed of a rubber-like polymer, an aromatic vinyl compound and an unsaturated dicarboxylic acid anhydride and a graft copolymer composed of a rubber-like polymer, an aromatic vinyl compound and a methacrylic acid ester-based monomer and an aromatic compound. A resin composition composed of polycarbonate has been proposed (JP-A-60-
112848) has improved impact strength but insufficient heat resistance, and in particular, it has the drawback that the acid anhydride group makes hot water resistance and heat stability extremely poor.

(Means for Solving the Problems) The present invention has been studied extensively in order to solve such drawbacks, and as a result, an imidized copolymer and a graft copolymer containing a methacrylic acid ester monomer are essential components. As a result, a resin composition excellent not only in impact strength but also in heat resistance, hot water resistance, and heat stability could be obtained.

That is, the present invention comprises (A) component: 40% by weight or less of a rubber-like polymer (however, not including 0), 30 to 90% by weight of an aromatic vinyl monomer residue, 3% by weight of an unsaturated dicarboxylic acid imide derivative residue. % Or more 70% by weight
Less than 10 to 90% by weight of an imidized copolymer comprising 0 to 20% by weight of a maleic anhydride monomer residue and 0 to 40% by weight of a vinyl monomer residue copolymerizable therewith, and (B) component. : 50 to 95% by weight of a monomer mixture consisting of 20 to 80% by weight of an aromatic vinyl monomer and 20 to 80% by weight of a methacrylic acid ester monomer with respect to 5 to 50% by weight of a rubber-like polymer.
5 to 60% by weight of a graft copolymer obtained by copolymerizing the above and (C) component: 10 to 80% by weight of a rubber-like polymer, and 60 to 80% by weight of an aromatic vinyl monomer and a vinyl cyanide monomer. 20
A thermoplastic resin containing 20 to 90% by weight of a monomer mixture of 40 to 40% by weight and a graft copolymer of 5 to 60% by weight, and a component (D): ( A thermoplastic resin composition comprising 0 to 80% by weight of a thermoplastic resin other than the components A), (B) and (C).

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

As the method for producing the component (A) copolymer, an aromatic vinyl monomer, an unsaturated dicarboxylic acid imide derivative and a vinyl monomer mixture copolymerizable with these in the presence of the rubbery polymer in the first production method can be used. In the second production method, in the presence of a rubbery polymer, an aromatic vinyl monomer, an unsaturated dicarboxylic acid anhydride and a vinyl monomer mixture copolymerizable therewith are copolymerized. Ammonia and /
Alternatively, a method of reacting a primary amine to convert 40 to 100 mol% of an acid anhydride group into an imide group can be mentioned, and an imidized copolymer can be obtained by any method.

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

As the unsaturated dicarboxylic acid imide derivative, maleimide, N-methylmaleimide, N-butylmaleimide, N
-Cyclohexylmaleimide, N-arylmaleimide (aryl groups include, for example, phenyl, 4-diphenyl, 1-naphthyl, 2-chlorophenyl, 4-bromophenyl and other mono- and dihalophenyl isomers, 2,4,
Examples thereof include 6-tribromophenyl and methoxyphenyl. ) And other maleimide derivatives, N-methylitaconic acid imides, and N-phenylitaconic acid imides and other itaconic acid imide acid conductors.

The aromatic vinyl monomer used in the second production method is as described above, and as the unsaturated dicarboxylic acid anhydride, there are anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid. Maleic anhydride is especially preferred.

The maleic anhydride monomer residue may be 0% by weight,
Up to 20% by weight is acceptable. If it exceeds 20% by weight, thermal stability and hot water resistance are deteriorated, which is not preferable.

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.

Further, the ammonia and the primary amine used for 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 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. May be. 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. If the temperature is lower than 80 ° C, the reaction rate is slow and the reaction takes 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.

Further, the rubber-like polymer used in the first or second production method includes a butadiene polymer, a copolymer of a vinyl monomer copolymerizable with butadiene, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer. A polymer, a block copolymer of butadiene and aromatic vinyl, an acrylic acid ester polymer, a copolymer of an acrylic acid ester and a vinyl monomer copolymerizable therewith, and the like are used.

The component A copolymer is 40% by weight or less of a rubbery polymer (however,
0 is not included) preferably 30% by weight or less (however, 0 is not included), aromatic vinyl monomer residue 30 to 90% by weight, preferably 40 to 70% by weight, unsaturated dicarboxylic acid imide derivative residue 3 An imidized copolymer comprising at least 3 wt% but less than 70 wt%, preferably at 3 to 60 wt% and a vinyl monomer residue copolymerizable with these at 0 to 40 wt%, preferably 0 to 30 wt%, a rubber Heat resistance when the amount of the polymer is more than 40% by weight,
Formability and dimensional stability are impaired. 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. If the amount of the unsaturated dicarboxylic acid imide derivative residue is less than 3% by weight, the effect of improving heat resistance decreases.

On the other hand, when the amount of the unsaturated dicarboxylic acid imide residue is 70% by weight or more, the resin composition becomes brittle and the moldability is significantly deteriorated. When the amount of the vinyl monomer residue copolymerizable with these exceeds 40% by weight, dimensional stability and heat resistance are impaired.

The graft copolymer which is the component (B) of the present invention is a rubber-like polymer obtained by graft-copolymerizing a mixture of an aromatic vinyl monomer and a methacrylic acid ester-based monomer. Is a diene rubber polymer in the polymer used as the component (A). For example, butadiene polymer, butadiene-styrene copolymer, butadiene-
Acrylic copolymers, isoprene polymers, isoprene-styrene copolymers, styrene-butadiene block copolymers and the like can be used.

Aromatic vinyl monomers include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, and substituted monomers thereof.

Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate and the like are used as the methacrylic acid ester-based monomer. (B)
The component graft copolymer can be produced by a known method.

Next, the component (C) and its manufacturing method will be described. (C)
The rubber-like polymer used as the component is a polymer of a vinyl monomer copolymerizable with butadiene alone or a copolymer thereof, an ethylene-propylene copolymer, an ethylene-propylene-cyene copolymer, or an acrylic acid ester alone or this. There is a polymer composed of a vinyl monomer copolymerizable with.

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

As the vinyl cyanide monomer used as the component (C), there are acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc., and acrylonitrile is particularly preferable.

The method for producing the graft copolymer as the component (C) is a rubber-like polymer.
Aromatic vinyl monomer 60-80% by weight against 10-80% by weight
And 20 to 90% by weight of a monomer mixture consisting of 20 to 40% by weight of a vinyl cyanide monomer. For the polymerization, any known polymerization technique can be adopted, for example, suspension polymerization, aqueous heterogeneous polymerization such as emulsion polymerization, bulk polymerization,
For example, precipitation polymerization in a non-solvent for solution polymerization. Emulsion polymerization is particularly preferable from the viewpoint of easily controlling the rubber particle size.

In the present invention, the proportion of component (A), component (B) and component (C) is 10 to 90% by weight of component (A), preferably 20 to 80% by weight, 5 to 60% by weight of component (B), preferably 10 to 50% by weight, component (C) 5 to 60% by weight, preferably 10 to 50% by weight
Is preferred.

If the proportion of the component (A) is less than 10% by weight, the heat resistance improving effect is small, and if it exceeds 90% by weight, the impact strength of the resin composition comprising the components (A), (B) and (C) is insufficient. To do. If the proportion of the component (B) and the component (C) is less than 5% by weight, the effect of reinforcing the impact strength by the graft copolymer is insufficient, and if it exceeds 60% by weight, heat resistance and moldability are impaired.

The thermoplastic resin other than the components (A), (B) and (C) which is the component (D) of the present invention is, for example, an aromatic vinyl monomer 30-
90% by weight, 0 to 50% by weight of a vinyl cyanide monomer, and 0 to 50% by weight of a vinyl monomer copolymerizable therewith, a copolymerized copolymer, a polycarbonate or a poly. Butylene terephthalate, polyethylene terephthalate, polysulfone, polyether sulfone, polyether ether ketone, polyether imide, 6,6-
Examples thereof include nylon, 6-nylon, 12-nylon, polyphenylene oxide, polyphenylene oxide obtained by graft-polymerizing styrene, and polyphenylene oxide, and one or more kinds of these resins can be used.

The aromatic vinyl monomer used as the component (D) is a styrene monomer such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene or chlorostyrene and a substituted monomer thereof. Particularly preferred are styrene and α-methylstyrene.

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 butylactyl acid ester, and methacrylic acid ester monomers 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 blending ratio of the thermoplastic resin composed of the components (A), (B) and (C) and the thermoplastic resin composed of the component (D) is the same as that composed of the components (A), (B) and (C). Plasticity is 20 to 100% by weight, component (D) is 0 to 80% by weight, and the fluidity and impact strength are improved by the inclusion of component (D), but heat resistance when component (D) exceeds 80% by weight. Run out.

The mixing method of the thermoplastic resin composition of the present invention is not particularly limited, and known means can be used. Examples of the means include a Banbury mixer, a tumbler mixer, a mixing roll, a single-screw or twin-screw extruder, and the like.
Examples of the mixing form include ordinary melt mixing, multi-stage melt mixing using master pellets, and solution blending.

Further, an antioxidant, a flame retardant, an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, a glass fiber, a carbon fiber, a filler such as calcium carbonate, a coloring agent, a metal powder and the like are further added to the composition of the present invention. It is also possible.

(Example) Hereinafter, the present invention will be further described with reference to examples. All parts and% in the examples are expressed on a weight basis.

Experimental Example- (1) (A) Component (A) Manufacture 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 a rubbery polymer A stirrer was provided. In an autoclave, 100 parts of styrene, 50 parts of methyl ethyl ketone, and 24 parts of polybutadiene rubber (NF35AS manufactured by Asahi Kasei Co., Ltd.) cut into small pieces were charged, and the atmosphere in the system was replaced with nitrogen gas, followed by stirring at room temperature for one day to dissolve the rubber.
After adjusting the temperature to 80 ° C., a solution prepared by dissolving 67 parts of maleic anhydride and 0.3 part of benzoyl peroxide in 400 parts of methyl ethyl ketone was continuously added over 8 hours. After addition 3.
Hold at 80 ° C for 5 hours. A portion of the viscous reaction liquid was sampled, unreacted monomers were quantified by gas chromatography, and the polymerization rate and the content rate of maleic anhydride in the polymer were calculated. The polymerization rate was 98%, the polymerization rate of maleic anhydride was 99%, and the content rate of maleic anhydride in the copolymer was 35.2%. Then, 63 parts of aniline (100% molar equivalent of added maleic anhydride), 2 parts of triethylamine and 1 part of Irganox 1076 (Ciba Geigy) as an antioxidant were added to the polymerization solution, and the mixture was heated at 140 ° C and reacted for 7 hours. An imidization reaction was performed. The reaction solution was cooled to 100 ° C. and the stainless vat was purged with the reaction solution.
Further, it was vacuum dried at 180 ° C. for 3 hours, desolvated and then pulverized to obtain a yellowish white powder copolymer. C-13 NMR
From the analysis, the conversion rate of acid anhydride groups to imide groups was 95%. This copolymer was designated as Polymer A-1.

Experimental Example- (2) Component (A) In the presence of a rubber-like polymer, aromatic vinyl, unsaturated dicarboxylic acid anhydride, and a copolymer obtained by polymerizing a vinyl monomer copolymerizable therewith are imidized. Manufacture of coalescence Instead of 100 parts of styrene in Experimental Example- (1), 100 parts of styrene and 17 parts of acrylonitrile were used, and 67 parts of maleic anhydride was added.
Except for using 50 parts and using 47 parts instead of 63 parts of aniline, the same operation as in Experimental Example (1) was performed to obtain an imidized polymer. This is designated as Polymer A-2. The average conversion at this time was 95% and the conversion to imide groups was 94%.

Experimental Example- (3) Production of a polymer obtained by imidizing a copolymer obtained by polymerizing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride in the absence of the component (A) rubbery polymer- (1) ) Except for not using the polybutadiene of Experimental Example- (1), the same operation as in Experimental Example- (1) was performed to obtain an imidized polymer. This is polymer A-3. At this time, the average polymerization rate was 99% and the conversion rate to an imide group was 98%.

Experimental Example- (4) Production of a polymer obtained by imidizing a copolymer obtained by polymerizing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride in the absence of the component (A) rubbery polymer- (2 ) An imidized polymer was obtained by performing the same operation as in Experimental Example- (1) except that 54 parts (85% molar equivalent of added maleic anhydride) was used instead of 63 parts of aniline in Experimental Example- (3). .
The conversion rate of acid anhydride groups to imide groups was 83%. This is designated as Polymer A-4.

Experimental Example- (5) Component (C): Production of Graft Copolymer 80 parts of polybutadiene latex (solid content 50%, average particle size)
0.35μ, gel content 90%), 1 part sodium stearate,
0.1 part of sodium formaldehyde sulfoxylate, 0.03 part of tetrasodium ethylenediamine atraacetic acid, 0.003 part of ferrous sulfate and 200 parts of water were charged into an autoclave substituted with nitrogen gas. After heating to a temperature of 65 ° C., 60 parts of a monomer mixture consisting of 30% acrylonitrile and 70% styrene, t-dodecyl mercaptan 0.
3 parts and 0.2 part of Kyumen hydroperoxide were continuously added over 4 hours, and after the addition was completed, polymerization was carried out at 65 ° C. for 2 hours.
The polymerization rate was 96%. After adding an antioxidant to the obtained latex, salting out with calcium chloride, washing with water and drying were carried out to obtain a white powdery polymer.

This is designated as ABS resin.

Experimental Example- (6) A copolymer was obtained in the same manner as in Experimental Example- (1) except that the styrene-maleic anhydride copolymer was not imidized in Experimental Example- (1). This is designated as Polymer A-5.

Example-1 45 parts of the polymer A-1 obtained in Experimental Example- (1) and 15 parts of a graft copolymer (KM-330 manufactured by Rohm and Haas Company) containing a methacrylic acid ester-based monomer; Experimental example
40 parts of the ABS resin obtained in (5) was blended, and this mixture was extruded at 260 ° C. with an extruder with a vent to form pellets.
Injection molding was performed at 60 ° C to prepare a test piece, and the physical properties were measured, and the results shown in Table 1 were obtained.

Example-2 It carried out like Example-1 except having used A-2 instead of polymer A-1 in Example-1.

Examples-3 to 6 Polymer A-1 was used as the component (A), the following thermoplastic resin was used as the component (D), and blended in the proportions shown in Table 1 and carried out in the same manner as in Example-1. It was

AS resin (AS-XGB manufactured by Denki Kagaku Kogyo KK), PC (Panlite L-1250 manufactured by Teijin Chemicals Ltd.), and nylon-6 (1030B manufactured by Ube Industries, Ltd.) were used.

Comparative example-1 It carried out like Example-1 except having used the polymer A-5 which did not imidize the styrene-maleic anhydride copolymer in Example-1.

Comparative Example-2 The procedure of Example-1 was repeated except that the component (B) was not used in Example-1.

Comparative Example-3 In Example-1, the component (B) was not used and ABS was 55
The same procedure as in Example 1 was performed except that the weight part was used.

Comparative example-4 It carried out like Example-3 except having used A-5 instead of A-1 in Example-3.

Comparative Example-5 The procedure of Example-4 was repeated, except that the polymer A-1 was used in place of the polymer A-1 and the component (B) was not used in Example-4.

Comparative Examples-6 to 7 The procedure of Example 1 was repeated, except that the polymer A-1 was replaced with the polymers A-3 to A-4.

Comparative Examples-8 to 11 Polymer A-3 was used as the component (A), and blended in the proportions shown in Table 2 below as the component (D).
The same procedure as 1 was performed.

Comparative Example 12 45 parts of Polymer A-1 obtained in Experimental Example- (1) and KM-33
55 parts of 0 were blended, the mixture was extruded at 260 ° C. by an extruder with a vent, pelletized, and injection-molded at 260 ° C. to prepare test pieces, and the physical properties were measured, and the results shown in Table 2 were obtained.

Comparative Example 13 45 parts of A-1 was used as the component (A), the component (B) was not used,
The results shown in Table 2 were obtained in the same manner as in Example 1 except that 45 parts of ABS resin was used as the component (C) and 10 parts of AS resin was used as the component (D).

The physical properties were measured by the following methods.

(1) Vicat softening point (VSP): load 5 kg, ASTM-D
-1525.

(2) Impact strength: Notched Izod impact strength, AS
According to TM-D-256.

(3) Hot water deterioration ... A 1/4 ″ Izod test piece was immersed in hot water at 100 ° C. and taken out on the 1st and 15th days to measure the Izod strength.

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Claims (1)

[Claims] 1. A component (A): 40% by weight or less of a rubber-like polymer (excluding 0), an aromatic vinyl monomer residue of 30 to
90% by weight, unsaturated dicarboxylic acid imide derivative residue 3% by weight or more and less than 70% by weight, maleic anhydride monomer residue 0-20
% By weight and vinyl monomer residue copolymerizable therewith 0 to
10 to 90% by weight of an imidized copolymer consisting of 40% by weight and (B) component: 5 to 50% by weight of a rubbery polymer, 20 to 80% by weight of an aromatic vinyl monomer and a methacrylic acid ester-based monomer. Monomer mixture consisting of 20-80% by weight 50-95% by weight
5 to 60% by weight of a graft copolymer obtained by copolymerizing the above and (C) component: 10 to 80% by weight of a rubber-like polymer, and 60 to 80% by weight of an aromatic vinyl monomer and a vinyl cyanide monomer. 20
A thermoplastic resin containing 20 to 90% by weight of a monomer mixture of 40 to 40% by weight and a graft copolymer of 5 to 60% by weight, and a component (D): ( A thermoplastic resin composition comprising 0 to 80% by weight of a thermoplastic resin other than the components A), (B) and (C).