JPH0772243B2 - Thermoplastic resin composition having excellent transparency, heat resistance and impact resistance - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin having excellent transparency, heat resistance and impact resistance, and more specifically, a diene-acrylic copolymer and methyl methacrylate, The present invention relates to a thermoplastic resin composition containing N-cyclohexylmaleimide and optionally a thermoplastic resin containing an aromatic vinyl compound.

[Prior art]

As a method of obtaining a thermoplastic resin having excellent heat resistance and impact resistance, a graft copolymer obtained by graft-copolymerizing styrene or acrylonitrile onto a diene rubber has been used so far.
A method of mixing a terpolymer composed of α-methylstyrene, methyl methacrylate and acrylonitrile (JP-A-57-70143) or a method of mixing a polycarbonate resin and a diene rubber (JP-B-38-15225). Gazette) is proposed. But with these methods,
It is difficult to obtain a thermoplastic resin having a good balance between heat resistance and impact resistance, and in the case of a mixture of polycarbonate and a diene rubber, there is a problem that flow processability is remarkably reduced. However, all of these methods have inferior optical properties, and the fact is that a material having transparency, heat resistance and impact resistance has not been developed yet.

[Problems to be solved by the invention]

An object of the present invention is to provide a thermoplastic resin composition having good flow processability and a good balance of transparency, heat resistance and impact resistance.

[Means for Solving Problems] The above-mentioned object of the present invention has the following diene-acrylic graft copolymer [II]
2 to 90% by weight, methyl methacrylate 99 to 35% by weight, N-cyclohexylmaleimide 1 to 35% by weight, and aromatic vinyl compound 0 to 30%
A thermoplastic resin [III] of 98% to 10% by weight, which is a polymer by weight, is blended, and the diene-acryl-based graft copolymer [II] in the composition is bloated rubbery copolymer. A thermoplastic resin composition comprising 1 to 50% by weight of [I] '.

Diene-acrylic graft copolymer [II]: The following rubber-like copolymer [I] latex polymer content 100
0.1 to 5 parts by weight of the following acid group-containing copolymer (A) in the form of a polymer latex and / or at least one oxyacid salt (B) below is added to the rubber-like copolymer [I ] The latex was enlarged, the average particle size was adjusted to the range of 0.12 to 0.4 μm, and the following monomer or monomer mixture was added in the presence of 100 parts by weight of the enlarged rubbery copolymer [I] 'latex. (C) 1 to 10 to 1000 parts by weight
A diene-acrylic graft copolymer obtained by polymerization in two or more stages or in different composition ratios.

Rubbery copolymer [I]: 49 to 10% by weight of an alkyl acrylate unit having an alkyl group with 2 to 8 carbon atoms, 51 to 90% by weight of a 1,3-butadiene unit, and copolymerizability therewith Rubber-like copolymer obtained by emulsion polymerization of a monomer mixture consisting of 0 to 10% by weight of a monofunctional or polyfunctional vinyl-based monomer unit (1): an acid group-containing copolymer (A): Acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
3 to 40% by weight of at least one unsaturated unit selected from the group consisting of maleic acid, fumaric acid, cinnamic acid, sorbic acid and p-styrenesulfonic acid, and at least one acryl having 1 to 12 carbon atoms in the alkyl group. An acid group-containing copolymer obtained by emulsion-polymerizing 97 to 35% by weight of an acid alkyl ester unit and 0 to 40% by weight of another copolymerizable monomer unit in one step or in two or more steps with different composition ratios. Polymer Oxygenate (B): Alkali metal of oxyacid mainly composed of elements selected from the group of elements belonging to Group 3 and 4 of Group IA and Group IIA in the periodic table of elements Oxygenate selected from salts or alkaline earth metal salts, zinc, nickel and aluminum salts-Monomer or monomer mixture (C): in methyl methacrylate, N-cyclohexylmaleimide and styrene A monomer or monomer consisting of 50 to 100% by weight of at least one monomer unit selected from the group and 50 to 0% by weight of another monofunctional or polyfunctional monomer unit copolymerizable therewith Achieved by body mixture.

The composition of the present invention is characterized in that the above-mentioned diene-acrylic graft copolymer [II] component and a thermoplastic resin [III] component comprising methyl methacrylate, N-cyclohexylmaleimide and, if necessary, an aromatic vinyl compound. It is because of the synergistic effect of, it is possible to exhibit excellent characteristics with variations in heat resistance, impact resistance and flow processability.

Diene-acrylic graft copolymer [II] has the effect of imparting impact resistance to the intended resin composition,
2 to 90% by weight in the total resin composition is suitable, and more preferably 5 to 50% by weight. If it is less than 2 parts by weight, the impact resistance is poor, and if it exceeds 90% by weight, the heat resistance is poor and both are not preferable.

Further supplementing the enlarged rubber-like copolymer [I] ', it is appropriate that the content is 1 to 50% by weight in the total resin composition.

As described above, the most important feature of the present invention is that, as the rubbery copolymer [I], an acrylic acid alkyl ester having a relatively low glass transition point (Tg) and 1,3-butadiene are major copolymerization components. In order to improve the impact resistance, and in these composition ratios, an inferior amount of an alkyl acrylate unit having excellent weather resistance is used, a predominant amount of 1,3-butadiene having excellent rubber properties is used, and impact resistance is improved. ,
Graft copolymer obtained by enlarging a rubber-like copolymer with a substance having a special structure shown in (A) and (B) above to a specific particle size range and then graft-polymerizing a hard resin component. It is in using the combination [II]. Further, this graft copolymer can also be used by being mixed and dispersed in another hard thermoplastic resin.

The rubbery copolymer [I] is composed of 49 to 10% by weight of an alkyl acrylate having 2 to 8 carbon atoms of an alkyl group, 51 to 90% by weight of 1,3-butadiene, and other copolymerizable mono-components. Body 0
It is obtained by emulsion polymerization of a monomer mixture consisting of 10% by weight. The alkyl acrylate used here is preferably butyl acrylate or 2-ethylhexyl acrylate. Other copolymerizable monomers are
Aromatic vinyl monomers such as acrylonitrile and styrene Monofunctional vinyl monomers represented by methacrylic acid alkyl esters such as methyl methacrylate, divinylbenzene, ethylene glycol dimethacrylate, butylene glycol diacrylate and tri It is a polyfunctional vinyl monomer such as allyl cyanurate, triallyl isocyanurate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate.

The emulsion polymerization itself can be performed according to a known method.
It is also possible to add a chain transfer agent such as mercaptan when obtaining the rubbery copolymer.

The particle size of the rubbery copolymer [I] obtained by emulsion polymerization is preferably in the range of 0.03 to 0.20 μm, and 0.05 to 0.15 μm.
The range of m is more preferable. Outside this range, it becomes difficult to control the polymerization rate and the polymerization temperature, the desired particle size is not obtained at the time of enlargement which is a subsequent step, the polymerization system becomes unstable, and the impact resistance of the final composition and Problems such as deterioration of appearance may occur.

Next, it contains at least one unsaturated acid monomer selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid, sorbic acid and p-styrenesulfonic acid. The copolymer (A) is used to enlarge the rubbery copolymer latex.

It is an essential condition that the copolymer (A) contains the unsaturated acid monomer and the acrylate, and as the acrylate, at least one kind of alkyl acrylate having an alkyl group having 1 to 12 carbon atoms is selected. Be done.

However, in addition to the acrylate, it is possible to jointly use 0 to 40% by weight of other copolymerizable monomers. Examples of such copolymerizable monomers include monomers such as methyl methacrylate, other methacrylic acid esters, styrene, α-methylstyrene and other styrene derivatives, and acrylonitrile.

The unsaturated acid monomer is used in an amount of 3-40% by weight. If it is less than 3% by weight, the enlarging ability is small, and if it exceeds 40% by weight, on the contrary, the enlarging ability is too strong and excessive particles exceeding 1 μm are generated, which is not preferable. On the other hand, if the amount of the alkyl acrylate is less than 35% by weight, the enlarging ability is small and it is not preferable.

Also, the optimum content of unsaturated acid monomer varies depending on the degree of hydrophilicity of the acrylate used, and when the acrylate has high hydrophilicity, the effect of bloat is large in the region where the amount of unsaturated acid monomer is small. On the other hand, when the amount of the unsaturated acid monomer increases, the latex is destroyed, which is not preferable. vice versa,
When the hydrophilicity of the acrylate is low, the effect of enlarging is small in the region where the amount of unsaturated acid monomer is low, and the effect cannot be obtained unless the amount of unsaturated acid monomer exceeds a certain level. For example, in the case of highly hydrophilic acrylate such as methyl acrylate or ethyl acrylate, it is most suitable when the amount of the unsaturated acid monomer is 5 to 10%, whereas the alkyl group has 4 or more carbon atoms. In the case of butyl acrylate or 2-ethylhexyl acrylate, which are hydrophobic alkyl acrylates, it becomes optimum when the amount of unsaturated acid monomer is 13 to 20%. If a highly hydrophilic acrylate is used, even when the amount of the unsaturated acid monomer is 5 to 10%,
While the system is prone to instability and therefore cullets (coarse particles) are likely to occur, the use of the hydrophobic acrylates as described above does not cause the system to become unstable and leads to uniform enlargement. Often, activated particles are obtained.

The acid group-containing copolymer (A) latex used in the present invention is 3 to 40% by weight of at least one unsaturated acid selected from the above-mentioned unsaturated acids, and the alkyl group has 1 carbon atom.
It is also possible to charge at once a monomer mixture consisting of 97 to 35% by weight of at least one alkyl acrylate of 0 to 12 and 0 to 40% by weight of another copolymerizable monomer, Of the body mixture, 5 to 90% by weight of the mixture is first polymerized at a portion not containing the unsaturated acid, and then the remaining 95 to 10% by weight of the monomer containing the unsaturated acid is formed into new particles. It is also possible to obtain a latex having a multi-layer structure of two or more layers by continuously polymerizing without carrying out, that is, by polymerizing in two or more steps.

Alkali metal salt or alkaline earth metal salt of oxyacid mainly containing an element selected from the group of elements belonging to Group 3 and 4 of Group IA and Group IIA in the periodic table of elements, zinc, The oxyacid salt (B) selected from nickel and aluminum salts is also used as a bulking agent for the rubbery copolymer [I] latex. Specific examples of the oxyacid salt include sulfuric acid, nitric acid, phosphoric acid and the like, potassium, sodium, magnesium, calcium, zinc, nickel,
Examples thereof include salts with aluminum and the like. Preferred are potassium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, sodium phosphate, magnesium phosphate and the like.

The acid group-containing copolymer (A) and the salt of oxygen acid (B) described above may be used alone or in combination.

The acid group-containing copolymer (A) latex and the oxyacid salt (B) are added to the rubbery copolymer [I]. When these are used alone, the amount of the acid group-containing copolymer (A) latex added is 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, per 100 parts by weight of the base rubber [I] as a polymer solid content. It is a department. The amount of the oxyacid salt (B) added is 0.1 to 5 parts by weight, preferably 100 parts by weight of the base rubber [I].
It is 0.1 to 4 parts by weight. By adding an appropriate amount, the base rubber is enlarged more efficiently, and the stability of the obtained large particle diameter rubber latex is greatly improved.

When the enlargement treatment of the present invention is carried out using the acid group-containing copolymer (A), the pH of the base rubber [I] latex is preferably 7 or more. When the pH value is on the acidic side, the enlargement efficiency is low even if the acid group-containing copolymer (A) latex is added, and the composition aimed at by the present invention may not be advantageously produced. is there.

When the pH of the base rubber [I] latex is set to 7 or more, the pH may be adjusted during the production of the base rubber, or may be separately performed before the enlargement treatment.

In the presence of 100 parts by weight of the rubbery copolymer [I] 'latex thus treated for enlargement, styrene,
50 to 100% by weight of at least one monomer unit selected from N-cyclohexylmaleimide and methyl methacrylate, and another monofunctional or polyfunctional monomer unit copolymerizable therewith (for example, the aforementioned Monofunctional or bifunctional vinyl monomers) 50 to 0% by weight of a monomer or monomer mixture (C) is polymerized in an amount of 10 to 1,000 parts by weight to obtain a diene-acrylic graft copolymer. A combination [II] is obtained.
Examples of the monomer or monomer mixture (C) to be grafted onto the rubber latex [I] 'include styrene alone, methyl methacrylate alone, N-cyclohexylmaleimide alone, and methyl methacrylate-styrene-N-cyclohexylmaleimide. Monomer mixture, styrene-acrylonitrile monomer mixture, styrene-acrylic acid ester monomer mixture, methyl methacrylate-acrylonitrile monomer mixture, methyl methacrylate-acrylic acid ester monomer mixture, etc. A monomer mixture obtained by mixing two or more kinds of these monomers in a selected combination can be used.

Alternatively, a known polyfunctional monomer (divinylbenzene, 1,2) may be added to a monomer or monomer mixture containing at least one selected from methyl methacrylate, N-cyclohexylmaleimide and styrene as an essential component. 4-butanediol diacrylate, etc.) and then graft polymerization, followed by graft polymerization of a monomer or monomer mixture without adding a polyfunctional monomer. It is also possible to polymerize.

In the emulsion graft polymerization, known emulsifiers and catalysts are usually used, and there are no particular restrictions on the type and amount of addition.

The thermoplastic resin [III] in the present invention comprises 99-35% by weight of methyl methacrylate, N-cyclohexylmaleimide 1-
It is a polymer of 35% by weight and 0 to 30% by weight of an aromatic vinyl compound, and basically has the function of imparting heat resistance and flow processability to the final resin composition. Thermoplastic resin [III]
The composition ratio of the constituent units of methyl methacrylate, N-cyclohexylmaleimide and aromatic vinyl compound is determined from the balance of heat resistance, weather resistance, polymerization rate, fluid processability of the thermoplastic resin [III]. If any of the monomer components is out of the above range, problems such as poor heat resistance and weather resistance and extremely poor productivity occur.

In order to improve the physical properties of the thermoplastic resin composition of the present invention (for example, to reduce the water absorption rate), or the thermoplastic resin [II
In order to improve the productivity of [I], an aromatic vinyl compound can be used, if necessary, in the production of the thermoplastic resin [III]. The amount used is in the range of 0 to 30% by weight, preferably 1 to 30% by weight, based on the total amount of the monomer mixture.

The role of the aromatic vinyl compound in improving the productivity of the thermoplastic resin [III] is explained as follows.

Since the copolymerizability of methyl methacrylate and N-cyclohexylmaleimide is relatively low for N-cyclohexylmaleimide, when a thermoplastic resin [III] is produced from a monomer mixture containing a large amount of N-cyclohexylmaleimide, A large amount of unreacted N-cyclohexylmaleimide remains.

A large amount of residual monomer causes a decrease in moldability and heat resistance of the desired thermoplastic resin composition. Therefore, for example, polymer beads obtained when the thermoplastic resin [III] is produced by aqueous suspension polymerization. Is preferably washed with a solvent insoluble to the polymer beads (eg, methanol) before use. In this case, the amount of remaining monomer is 2%
It is desirable to reduce to below, especially to 1% or less for N-cyclohexylmaleimide. On the other hand, by substituting a part of methyl methacrylate with an aromatic vinyl compound, the copolymerizability of N-cyclohexylmaleimide is improved and the amount of residual monomer is reduced to a desired value. The above-mentioned washing treatment is not necessary for the thermoplastic resin [III] obtained even in the case of a relatively large amount of polymerization system.

In order to further enhance the effect of the aromatic vinyl compound, the molar ratio of N-cyclohexylmaleimide to the aromatic vinyl compound in the monomer mixture is preferably 0.1-5, more preferably 0.5-2.

Typical examples of the aromatic vinyl compound used in the present invention include styrene and aralkylstyrene such as o- and m.
-And p-methylstyrene, 1,3-dimethylstyrene, 2,4-dimethylstyrene, arethylstyrene, p
-Tertiary butyl styrene, α-methyl styrene, α-
Monovinylidene aromatic hydrocarbons such as ethylstyrene, α-methyl-p-methylstyrene, vinylnaphthalene,
Examples thereof include alhalomonovinylidene aromatic hydrocarbons such as o-, m- and p-chlorostyrene, 2,4-dibromostyrene and 2-methyl-4-chlorostyrene. For long-term production using alhalomonovinylidene aromatic hydrocarbons, it is necessary to take measures against equipment corrosion. From the viewpoint of the balance of productivity and physical properties, it is particularly preferable to use at least one selected from the group consisting of styrene, vinyltoluene and α-methylstyrene.

If necessary, 10% or less of another copolymerizable monomer may be used as a fourth component within a range not impairing the gist of the present invention. Preferred examples include acrylic acid alkyl esters having a C1-10 alkyl group, methacrylic acid alkyl esters having a C2-10 alkyl group, and the like. These are used alone or in combination of two or more.

Further, when the thermoplastic resin [III] is mixed with the diene-acrylic copolymer [II] and the other resin [IV] described later, good compatibility is exhibited and favorable fluidity is obtained in the final resin composition. It is preferable that the intrinsic viscosity of the resin [III] in chloroform at 25 ° C. is in the range of 0.3 to 0.8 dl / g in order to impart

The mixing ratio of the thermoplastic resin [III] is 10 in the final resin composition.
~ 98% by weight, preferably 20-90% by weight, 10% by weight
If it is less than 100% by weight, heat resistance and fluid processability are poor, and if it exceeds 98% by weight, impact resistance tends to be poor.

The resin [III] can be produced by a conventional polymerization method such as suspension polymerization, bulk polymerization or solution polymerization of the above-mentioned monomer mixture with a radical polymerization initiator.

1% of the enlarged rubber-like copolymer [I] 'was added to the final resin composition.
It can be contained in an amount of up to 50% by weight, particularly preferably 5 to 40% by weight.

If it is out of this range, defects such as inferior impact resistance and lower heat distortion temperature occur, which is not preferable.

In the series of emulsion polymerizations until the production of the graft copolymer [II], known emulsifiers and catalysts are usually used, and the kind and the addition amount thereof are not particularly limited. The diene-acrylic graft copolymer [II] latex obtained by the emulsion polymerization method is coagulated and dried by a known method.

In the present invention, a diene-acrylic graft copolymer [II]
And a thermoplastic resin [III] depending on the purpose of use in addition to blending, other methacrylic resin, polycarbonate, AS resin, methyl methacrylate-styrene copolymer,
It is also possible to add at least 89% by weight or less, preferably 70% by weight or less of a resin [IV] selected from polystyrene, polyester (polyethylene terephthalate, polybutylene terephthalate), and polyamide to the composition. For example, when extremely good weather resistance is required, methacrylic resin or polyethylene terephthalate resin is suitable, and when high flow processability is required, polystyrene, AS resin and methyl methacrylate-styrene copolymer Coalescence is used.

Further, in the composition of the present invention, if necessary, a stabilizer, a lubricant, a plasticizer, a dye / pigment, a filler, etc. are appropriately added, and after mixing with a V-type blender, a Henshur mixer, a mixing roll, Melt and mix at 150 to 300 ° C. using a screw type extruder or the like.

Hereinafter, the present invention will be described in more detail based on examples.
In the examples, "part" means "part by weight" and "%" means "% by weight".

(1) Production of diene-acrylic graft copolymer [II]: Production of rubbery copolymer [I]: Butyl acrylate 3.5 kg 1,3-butadiene 6.5 kg Diisopropylbenzene hydroperoxide 20 g Beef tallow fatty acid potassium 100 〃 Sodium N-lauroyl sarcosinate 50 〃 Sodium pyrophosphate 50 〃 Ferrous sulphate 0.5 〃 Dextrose 30 Deionized water 20 kg Replace the oxygen contained in it with nitrogen,
The state was set such that the polymerization reaction was not substantially inhibited. Then all materials were charged in 50 autoclave and polymerized at 52 ° C.
Polymerization was completed in 7 hours, conversion rate 98%, particle size 0.08μ
m rubber latex was obtained.

Synthesis of acid group-containing copolymer latex [A-1] for enlargement: The mixture having the above composition was polymerized in a glass round bottom flask of 5 at 70 ° C. for 1.5 hours and then at 70 ° C. Was added dropwise over 1 hour, and the mixture was continuously stirred for 1 hour to obtain a copolymer latex having a conversion of 98%.

Preparation of enlarged rubber-like polymer [I] ': 400 g of [A-1] latex at an internal temperature of 50 ° C. while stirring a 50 autoclave containing a rubber-like copolymer [I] latex containing 10 kg of a polymer solid content. Was added and held for 30 minutes. Add 1kg of 5% aqueous sodium sulfate solution to add 1
Held for hours. The average particle size of the obtained enlarged rubbery polymer [I] 'was 0.20 µm.

Production of Diene-Acrylic Graft Copolymer [II] Latex A degassed reaction vessel containing an enlarged latex containing 10 kg of polymer solids of the enlarged rubbery copolymer [I] ' Ionized water 9 kg, sodium formaldehyde sulfoxylate 20 g, and sodium N-lauroyl sarcosinate 50 g were added to raise the internal temperature to 77 ° C.
Polymerization was carried out by continuously adding over a period of minutes.

Methyl methacrylate 3780 g Styrene 380 g Methyl acrylate 40 g Normal octyl mercaptan 6 g Cumene hydroperoxide 15 g After the addition was completed, the polymerization was continued for another 90 minutes, and the conversion of methyl methacrylate was almost 100%.

Styrenated phenol 58 was added to the obtained polymer latex.
g, dilauryl thiopropionate 44g, Irganox
58 g of 1076 (stabilizer manufactured by Ciba Geigy) was added, and 0.25% sulfuric acid water was added to the latex / water =
Agglomerated at 1/2 and held at 85 ° C for 5 minutes.

The slurry polymer obtained is washed and dehydrated, and the polymer is dried at 65 ° C.
After drying for an hour, a white powder was obtained. This powder resin is [II-
1].

Monomer mixture component constituting rubber-like copolymer [I] and monomer mixture component (C) added during graft polymerization
Powder resins [II-2] and [II-4] were obtained in exactly the same manner as in the case of producing [II-1] except that the composition ratios were shown in Table 1.

[II-5] Contains rubber-like latex copolymer [I] latex (polymer solid content 10 kg) used for producing [II-1]
While stirring the 50 autoclave, 500 g of (A-1) latex was added and the mixture was kept at 50 ° C. for 60 minutes. The average particle size of the obtained enlarged rubbery polymer [I] 'was 0.26 µm. Graft polymerization is carried out in the same manner as in the production of [II-1] to obtain a copolymer [II-5] latex.
Coagulation, washing and dehydration were performed in the same manner as in [II-1] to obtain white powder [II-5].

[II-6] (A-1) Without adding latex, sodium sulfate 50 g
Except for adding 500 g of magnesium sulfate instead of [II-
5) and white powder [II-6] was obtained.
The particle size of [I] 'was 0.15 μm.

(2) Production of thermoplastic resin [III]: [III-1] 27 kg of deionized water using a pressure-resistant polymerization kettle having an internal volume of 50 and a mixture of methyl methacrylate and sodium salt of 2-sulfoethyl methacrylate as a dispersant. Charged with 3 g of polymer and 90 g of sodium sulfate, 85 parts of methyl methacrylate, N-
Cyclohexylmaleimide 9 parts, α-methylstyrene 6
Parts, n-octyl mercaptan 0.14 parts, azobisisobutyronitrile 0.3 parts, stearic acid monoglyceride 0.1
18 kg of monomer solution consisting of 10 parts of nitrogen was bubbled with stirring at 200 rpm for 20 minutes at a rate of 10 / min to remove oxygen in the system, and heated at 80 ° C for 4 hours to carry out suspension polymerization and further heated to 120 ° C. After maintaining for 20 minutes, post-treatment was carried out, followed by cooling, washing with water and drying to obtain a bead-like polymer having an average particle size of 0.3 mm.

[III-2] to [III-4] A beaded polymer having an average particle size of 0.3 mm was obtained in the same manner as in [III-1] except that the monomer solution was changed as follows.

Monomer solution composition In addition, in [III-4], N-
Since the content of cyclohexylmaleimide was 1% or more, 300 parts by weight of methanol was added to 100 parts by weight of the beaded polymer, washed at 40 ° C. for 1 hour, and dried. The residual monomer in the beads after the treatment was 0.3% or less.

Examples 1 to 8 Powder resin [II] and bead-like polymer [III] at a ratio shown in Table 2 and 20 g of an ultraviolet absorber (Tinuvin-p, manufactured by Ciba Geigy) and a stabilizer (Sanol LS770, Sankyo Co., Ltd.) Made) 3
0 g and 20 g of Henschel mixer were mixed, and then a 30 mmφ twin-screw extruder (PCM-30 manufactured by Ikegu Tekko KK)
Pelletized at a temperature of 250-270 ° C. Using a screw type injection molding machine (manufactured by Japan Steel Works; Ankelberg V-17-65 type), this pellet resin is used for various test pieces at a cylinder temperature of 260 ° C and an injection pressure (gauge pressure) of 60 kg / cm ^2. Was prepared and evaluated, and the results shown in Table 4 were obtained.

As can be seen from these results, the composition according to the present invention exhibits excellent low temperature impact resistance, and also has good heat stability, heat colorability and weather resistance.

[Reference example]

Example 5 except that a methacrylic resin (Acrypet VH manufactured by Mitsubishi Rayon Co., Ltd.) was used instead of the thermoplastic resin [III].
The heat resistance was measured in exactly the same manner as above, and the result was 94 ° C. and the Izod impact strength (23 ° C.) was 8.9 kg cm / cm, and the example has excellent properties.

The evaluation was carried out based on the following.

1) Izod impact strength ASTM D-1003 2) Weather resistance test Suga tester Sunshine weather metal WEL-SUN-DCH type used Black panel 63 ℃, rainfall 12 minutes / 60 minutes 1000 hours 3) Heat resistance (HDT) ASTM D- 648 4) Fluidity (MI) ASTM D1238-52T 230 ℃ ・ 10kg load 5) Optical characteristics Specimen thickness 2mm ASTM D-1003 6) Gloss ASTM D673-44 (incident angle 60 °) For the resin powders [II-1] to [II-3], the thermal oxidative decomposability was confirmed as follows for 200 minutes or more.
The thermal stability was satisfied.

[Oxidative decomposition measurement]

Test method and evaluation of polymer materials, edited by Japan Society of Polymer Science (Baifukan) p.
According to 94, measure the time until abruptly absorbing oxygen at 170 ℃.

〔The invention's effect〕

As described in detail above, by molding the thermoplastic resin composition of the present invention using an extrusion molding machine, an injection molding machine, etc., it is possible to obtain a molded article excellent in heat resistance, transparency, and impact resistance. Therefore, it is useful for applications such as vehicle exterior parts, solar system equipment parts, and housings for electrical equipment and OA equipment.

Claims (1)

[Claims] 1. A diene-acrylic graft copolymer [II] 2 to 90% by weight, methyl methacrylate 99 to 35% by weight, N-cyclohexylmaleimide 1 to 35% by weight and an aromatic vinyl compound 0 to 30
A thermoplastic resin [III] of 98% to 10% by weight, which is a polymer by weight, is blended, and the diene-acryl-based graft copolymer [II] in the composition is bloated rubbery copolymer. A thermoplastic resin composition comprising 1 to 50% by weight of [I] '. Diene-acrylic graft copolymer [II]: The following rubber-like copolymer [I] latex polymer content 100
0.1 to 5 parts by weight of the following acid group-containing copolymer (A) in the form of a polymer latex and / or at least one oxyacid salt (B) below is added to the rubber-like copolymer [I ] The latex was enlarged, the average particle size was adjusted to the range of 0.12 to 0.4 μm, and the following monomer or monomer mixture was added in the presence of 100 parts by weight of the enlarged rubbery copolymer [I] 'latex. (C) 1 to 10 to 1000 parts by weight
A diene-acrylic graft copolymer obtained by polymerization in two or more stages or in different composition ratios. Rubbery copolymer [I]: 49 to 10% by weight of an alkyl acrylate unit having an alkyl group with 2 to 8 carbon atoms, 51 to 90% by weight of a 1,3-butadiene unit, and copolymerizability therewith Rubber-like copolymer obtained by emulsion polymerization of a monomer mixture consisting of 0 to 10% by weight of a monofunctional or polyfunctional vinyl-based monomer unit (1): an acid group-containing copolymer (A): Acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
3 to 40% by weight of at least one unsaturated unit selected from the group consisting of maleic acid, fumaric acid, cinnamic acid, sorbic acid and p-styrenesulfonic acid, and at least one acryl having 1 to 12 carbon atoms in the alkyl group. An acid group-containing copolymer obtained by emulsion-polymerizing 97 to 35% by weight of an acid alkyl ester unit and 0 to 40% by weight of another copolymerizable monomer unit in one step or in two or more steps with different composition ratios. Polymer Oxygenate (B): Alkali metal of oxyacid mainly composed of elements selected from the group of elements belonging to Group 3 and 4 of Group IA and Group IIA in the periodic table of elements Oxygenate selected from salts or alkaline earth metal salts, zinc, nickel and aluminum salts-Monomer or monomer mixture (C): in methyl methacrylate, N-cyclohexylmaleimide and styrene A monomer or monomer consisting of 50 to 100% by weight of at least one monomer unit selected from the group and 50 to 0% by weight of another monofunctional or polyfunctional monomer unit copolymerizable therewith Body mixture